CN108117831B - Non-migration type antibacterial coating material and preparation method thereof - Google Patents
Non-migration type antibacterial coating material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/08—Polyurethanes from polyethers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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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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Abstract
The invention discloses a non-migration type antibacterial coating material and a preparation method thereof, belonging to the field of materials science. The non-migration type antibacterial epoxy coating material has excellent antibacterial performance, is an environment-friendly non-migration type antibacterial coating material, and can be used for preparing coatings on the inner walls of tap water conveying pipelines, beer and beverage storage tanks, food packaging materials, automotive upholstery or medical equipment.
Description
Technical Field
The invention relates to a non-migration type antibacterial coating material and a preparation method thereof, belonging to the field of materials science.
Background
With the rapid development of modern economic society, people put higher and higher requirements on antibacterial products. The nano zinc oxide is safe, non-toxic, tasteless, low in price and excellent in antibacterial performance, can be directly and widely applied to the inner wall coating of a tap water conveying pipeline, the inner wall coating of a beer and beverage storage tank, the coating of a food packaging material, the coating of an automotive interior part or a medical material coating, and is an ideal material for developing a green antibacterial product.
Patent CN106280955A discloses an elevator coating and a preparation method thereof, the method adopts a two-layer coating structure, the bottom coating is a compact coating, the surface coating is an antibacterial coating, and the surface coating is easy to release nano zinc oxide into the environment, so that the finished coating is short in antibacterial life and causes environmental pollution. Patent CN106047118A discloses an antibacterial environment-friendly paint for furniture, which has poor antibacterial performance and nano zinc oxide in the material is easy to migrate into the environment. Patent CN103073971A discloses a novel solvent-free antistatic antibacterial epoxy self-leveling floor coating, which is easy to release nano zinc oxide into the environment, thereby making the coating antibacterial short-lived and environmental pollution. Patent CN103555133A discloses a dirt-resistant quick-drying building coating, in which the nano zinc oxide also has no migration resistance.
The unmodified nano zinc oxide in the polyurethane/nano zinc oxide or epoxy/nano zinc oxide antibacterial coating material obtained by the above patents is easy to agglomerate, and the specific surface area is reduced, so that the bacteriostatic rate of the coating material is low, and the nano zinc oxide of the antibacterial coating material obtained by the methods can gradually migrate into the environment from a matrix, so that the antibacterial service life of the coating material is short, the problem of environmental pollution exists, and the application range of the coating material is limited. Therefore, it is very necessary to invent a non-migration type antibacterial coating material.
Disclosure of Invention
The first purpose of the invention is to provide a non-migration type antibacterial coating material, which comprises a resin raw material and modified nano zinc oxide capable of chemically bonding with groups on the resin.
In one embodiment of the invention, the antibacterial coating material is an antibacterial polyurethane coating material, and comprises the following raw materials in parts by weight: 40-65 parts of polyisocyanate, 40-65 parts of polyol and 0.01-8 parts of modified nano zinc oxide.
In one embodiment of the invention, the antibacterial polyurethane coating material further comprises the following raw materials in parts by weight: 0.1-2 parts of chain extender, 1-5 parts of cross-linking agent, 0.1-3 parts of plasticizer and 0.1-2 parts of defoaming agent.
In one embodiment of the invention, the modified nano zinc oxide is obtained by modifying nano zinc oxide by using a silane coupling agent.
In one embodiment of the invention, the modified nano zinc oxide is prepared by the following method: mixing the nano zinc oxide and the silane coupling agent in a high-speed mixer for 0.5-10 minutes according to the weight part ratio to obtain the modified nano zinc oxide.
In one embodiment of the present invention, the silane coupling agent is at least one of aminosilane, epoxy silane, sulfur-containing silane, and isocyanatosilane.
In one embodiment of the invention, the ratio of the nano zinc oxide to the silane coupling agent is 1-6: 0.1-2.5 by weight.
In one embodiment of the present invention, the polyisocyanate is at least one of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, tetramethylxylylene diisocyanate, HDI trimer, IPDI trimer, TDI trimer, and MDI trimer.
In one embodiment of the present invention, the polyester polyol is at least one of polyether polyol and polyester polyol; the chain extender is at least one of 1, 4-butanediol, diethylene glycol, trimethylolpropane, ethylene glycol, glycerol, 1, 4-cyclohexanediol and resorcinol hydroxyl ether.
In one embodiment of the present invention, the crosslinking agent is at least one of trimethylolpropane, triethanolamine and triethylamine.
In one embodiment of the present invention, the plasticizer is at least one of phthalate, aliphatic diacid ester, dimethyl adipate, dibutyl adipate, dioctyl sebacate and dibutyl sebacate.
In one embodiment of the present invention, the defoaming agent is at least one of polydimethylsiloxane, polysiloxane, and silicone glycol.
In one embodiment of the present invention, the preparation method of the antibacterial polyurethane coating material comprises the following steps:
(1) mixing polyisocyanate and polyatomic alcohol according to the weight part ratio at 60-120 ℃, stirring and reacting under the condition of introducing nitrogen, then adding a chain extender, a cross-linking agent and modified nano zinc oxide, and continuing stirring and reacting to obtain a prepolymer;
(2) and (3) blending the prepolymer, the plasticizer and the defoaming agent according to the weight part ratio at 50-150 ℃ for 1 minute-12 hours to obtain the non-migration type antibacterial polyurethane coating material.
In one embodiment of the invention, the antibacterial coating material is an antibacterial epoxy coating material, and comprises 60-90 parts by weight of epoxy resin and 0.1-10 parts by weight of aminated nano zinc oxide.
In one embodiment of the present invention, the antibacterial epoxy coating material comprises the following two components:
the first component comprises the following components in parts by weight: 60-90 parts of epoxy resin, 0.1-10 parts of aminated nano zinc oxide, 0.1-3 parts of defoaming agent, 0.1-5 parts of diluent, 0.1-5 parts of accelerator and 0.5-70 parts of solvent;
the second component comprises the following components in parts by weight: 0.1-70 parts of solvent and 10-90 parts of curing agent.
In one embodiment of the present invention, the weight ratio of the first component to the second component is 100: 5-30.
In one embodiment of the invention, the aminated nano zinc oxide is obtained by modifying nano zinc oxide with aminated silane.
In one embodiment of the invention, the aminated nano zinc oxide is prepared by mixing nano zinc oxide and aminated silane according to the weight part ratio in a high-speed mixer for 0.5-10 minutes, wherein the weight part ratio of the nano zinc oxide to the aminated silane is 1-5: 0.05-2.0.
In one embodiment of the invention, the aminated nano zinc oxide is obtained by fully mixing nano zinc oxide, aminosilane and a solvent for 0.5-12 hours according to the weight part ratio, wherein the weight part ratio of the nano zinc oxide, the aminosilane and the solvent is 1-5: 0.05-2.0: 9-45.
In one embodiment of the invention, the aminosilane is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- β -aminoethyl-gamma-aminopropyltrimethoxysilane, N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane, N- β -aminoethyl-gamma-aminopropylmethyldiethoxysilane, and gamma-aminoethylaminopropyltrimethoxysilane.
In one embodiment of the present invention, the epoxy resin is at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, and a bisphenol S type epoxy resin.
In one embodiment of the present invention, the solvent is at least one of acetone, xylene, and n-butanol.
In one embodiment of the present invention, the curing agent is at least one of aliphatic polyamine, aromatic polyamine, alicyclic amine, heterocyclic amine, and acid anhydride.
In one embodiment of the present invention, the defoaming agent is at least one of Corongro AC-300, Digao FOAMEX N, silicone and silica.
In one embodiment of the invention, the diluent is at least one of n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, glycidyl methacrylate ether, vinylcyclohexene monoepoxide, diglycidyl ether, styrene oxide, ethylene oxide, and propylene oxide.
In one embodiment of the invention, the accelerator is at least one of a tertiary amine, a metal acetylacetonate, triphenylphosphine, and an organic carboxylate.
In one embodiment of the present invention, the preparation method of the antibacterial epoxy coating material comprises the following steps:
(1) uniformly mixing epoxy resin, aminated nano zinc oxide, a defoaming agent, a diluent, an accelerant and a solvent at room temperature according to the weight part ratio to obtain a mixture A;
(2) uniformly mixing a curing agent and a solvent at room temperature according to the weight part ratio to obtain a mixture B;
(3) and uniformly mixing the mixture A and the mixture B at room temperature according to the weight part ratio to obtain the non-migration type antibacterial epoxy coating material.
In one embodiment of the present invention, a method for using the antibacterial epoxy coating material comprises the following steps:
(1) coating the non-migration type antibacterial coating material on the surface of a base material;
(2) then curing for 5 minutes to 1.5 days at the first temperature;
(3) then heating to a second temperature and curing for 5 minutes to 2 days;
wherein the first temperature is 10-150 ℃, and the second temperature is 1-100 ℃ higher than the first temperature.
The second purpose of the invention is to provide a method for inhibiting the migration of nano zinc oxide in a resin coating material, which is to modify the nano zinc oxide to obtain modified nano zinc oxide capable of chemically bonding with groups on a resin, and then mix and react with the resin material.
The third purpose of the invention is to provide the application of the non-migration type antibacterial coating material, which can be used for preparing the inner wall coating of the tap water conveying pipeline, the inner wall coating of the beer and beverage storage tank, the coating of the food packaging material, the coating of the automotive interior trim part or the coating of the medical apparatus.
The invention has the beneficial effects that:
the non-migration type antibacterial polyurethane coating material has excellent antibacterial performance and is non-migration type antibacterial, in the preparation process of the coating material, an isocyanate group in ① polyurethane prepolymer is easy to be chemically bonded with an amino group or an epoxy group or a sulfydryl group on the surface of modified zinc oxide or a hydroxyl group in ② polyurethane prepolymer is easy to be chemically bonded with an isocyanate group on the surface of zinc oxide, the nano zinc oxide is grafted to a polyurethane matrix through a chemical bond, the migration of the nano zinc oxide is fixed and inhibited, the nano zinc oxide is more uniformly dispersed in the polyurethane, and the antibacterial effect of the coating material is more remarkable.
The non-migration type antibacterial epoxy coating material has excellent antibacterial performance and non-migration type antibacterial performance, in the curing process of the coating material, an epoxy group on the epoxy resin can be chemically bonded with an amino functional group on the surface of the zinc oxide, the nano zinc oxide is grafted to a matrix of the epoxy resin through a chemical bond, the migration of the nano zinc oxide is fixed and inhibited, the nano zinc oxide is dispersed in the epoxy resin more uniformly, and the antibacterial effect of the coating material is more remarkable.
Detailed Description
The embodiments disclosed herein are examples of the present invention, which may be embodied in various forms. Therefore, specific details disclosed, including specific structural and functional details, are not intended to be limiting, but merely serve as a basis for the claims. It should be understood that the detailed description of the invention is not intended to be limiting but is intended to cover all possible modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims. The word "may" is used throughout this application in an permissive sense rather than the mandatory sense. Similarly, unless otherwise specified, the words "include", "comprises", and "consisting of" mean "including but not limited to". The words "a" or "an" mean "at least one" and the words "a plurality" mean more than one. When abbreviations or technical terms are used, these terms are meant to have the generally accepted meaning known in the art.
Example 1:
a method for preparing a non-migratory antimicrobial polyurethane coating material, the method comprising the steps of:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of modified nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the modified nano-zinc oxide can be obtained by mixing the nano-zinc oxide and the gamma-aminopropyl triethoxysilane for 2.5 minutes in a high-speed mixer according to the weight ratio of 1:0.4, and the grafting ratio of the gamma-aminopropyl triethoxysilane measured after purification is 3.6%.
The bacteriostasis rate of the obtained non-migration type antibacterial polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the migration amount of zinc ions is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Example 2:
a method for preparing a non-migratory antimicrobial polyurethane coating material, the method comprising the steps of:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of modified nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the modified nano-zinc oxide can be obtained by mixing the nano-zinc oxide and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane in a high-speed mixer for 2.5 minutes according to the weight ratio of 1:0.4, and the grafting ratio of the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is measured to be 3.3% after purification.
The bacteriostasis rate of the obtained non-migration type antibacterial polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the migration amount of zinc ions is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Example 3:
a method for preparing a non-migratory antimicrobial polyurethane coating material, the method comprising the steps of:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of modified nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the modified nano-zinc oxide can be obtained by mixing the nano-zinc oxide and the 3-mercaptopropyltrimethoxysilane in a high-speed mixer for 2.5 minutes according to the weight ratio of 1:0.4, and the grafting rate of the 3-mercaptopropyltrimethoxysilane is measured to be 3.2% after purification.
The bacteriostasis rate of the obtained non-migration type antibacterial polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the migration amount of zinc ions is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Example 4:
a method for preparing a non-migratory antimicrobial polyurethane coating material, the method comprising the steps of:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of modified nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the modified nano-zinc oxide can be obtained by mixing the nano-zinc oxide and the 3-isocyanate propyl trimethoxy silane in a high-speed mixer for 2.5 minutes according to the weight ratio of 1:0.4, and the grafting ratio of the 3-isocyanate propyl trimethoxy silane is measured to be 3.5% after purification.
The bacteriostasis rate of the obtained non-migration type antibacterial polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the migration amount of zinc ions is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Example 5:
a method for preparing a non-migratory antimicrobial polyurethane coating material, the method comprising the steps of:
(1) mixing 60 parts of isophorone diisocyanate and 50 parts of polyethylene glycol adipate glycol for reaction for 3 hours at 95 ℃ under the condition of introducing nitrogen, then adding 1 part of diethylene glycol, 1.5 parts of triethanolamine and 1.5 parts of modified nano zinc oxide, and continuing to react for 1.5 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 1 part of dimethyl adipate and 0.5 part of polysiloxane to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the nano zinc oxide and the gamma-aminopropyl triethoxysilane are mixed in a high-speed mixer for 5 minutes according to the weight ratio of 5:1.5 to obtain the aminated nano zinc oxide, and the grafting ratio of the gamma-aminopropyl triethoxysilane measured after purification is 3.1%.
The bacteriostasis rate of the obtained non-migration polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the migration amount of zinc ions is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Example 6:
(1) mixing 55 parts of toluene diisocyanate and 45 parts of polyoxypropylene triol at 100 ℃ for reaction for 2 hours under the condition of introducing nitrogen, adding 0.5 part of trimethylolpropane, 3 parts of trimethylolpropane and 3.5 parts of modified nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 3 parts of dioctyl sebacate and 1 part of silicone glycol to obtain the non-migration type antibacterial polyurethane coating material.
The preparation method of the modified nano zinc oxide comprises the following steps: the modified nano-zinc oxide can be obtained by mixing the nano-zinc oxide and the gamma-aminopropyl triethoxysilane for 1 minute in a high-speed mixer according to the weight ratio of 4:1.5, and the grafting ratio of the gamma-aminopropyl triethoxysilane measured after purification is 2.9%.
The bacteriostasis rate of the non-migration type antibacterial polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Comparative example 1:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol and 2 parts of trimethylolpropane, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the polyurethane coating material.
The bacteriostasis rate of the obtained polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
Comparative example 2:
(1) mixing 50 parts of 1, 6-hexamethylene diisocyanate and 40 parts of polypropylene glycol at 90 ℃ under the condition of introducing nitrogen for reaction for 3 hours, then adding 1.5 parts of 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of nano zinc oxide, and continuing the reaction for 2 hours to obtain a prepolymer;
(2) and uniformly stirring the prepolymer, 0.5 part of phthalate and 1 part of polydimethylsiloxane to obtain the polyurethane coating material.
The bacteriostasis rate of the obtained polyurethane coating material and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through a zinc ion migration experiment of the coating material, and the test results are shown in table 1.
TABLE 1
TABLE 2
In the above examples, the zinc ion transport was measured by inductively coupled plasma emission spectroscopy (Optima8300, PerkinElmer), and polyurethane was first coatedThe layer material is made into 40x 60mm2The thickness of the coating is 0.4mm, then the coating is respectively soaked in a proper amount of deionized water at 37 ℃ for 2h, 6h, 12h and 24h, and finally the concentration of zinc ions in the deionized water is measured. The coating inhibition zone experiment is determined by a Kirby-Bauer test method (such as am.J. Clin.Pathol.1966,45, 493-286.), and the coating inhibition rate experiment is determined by a plate counting method (J.food Sci.2012,77, 280-286).
As can be seen from the test results listed in tables 1 and 2, the polyurethane coating without zinc oxide (comparative example 1) has no antibacterial function. Compared with a coating (comparative example 2) added with unmodified nano zinc oxide, the coating material added with the same parts of modified nano zinc oxide (such as examples 1-4) has higher antibacterial rate and no bacteriostatic circle, and the 2h zinc ion migration amount is obviously reduced, which indicates that the nano zinc oxide is hardly migrated from the matrix. In addition, with the extension of the test time of the zinc ion migration amount, the zinc ion migration amount of the coating material (examples 1 to 6) added with the modified nano zinc oxide is hardly increased, which shows that the nano zinc oxide in the polyurethane coating obtained by the invention hardly migrates for a long time, and has the advantage of long antibacterial life. It can also be seen from examples 1 to 4 that the effect of modifying zinc oxide with aminosilane is the best regardless of the antibacterial rate or the migration amount, and the amino group is the most reactive with the isocyanate group on polyurethane compared to the reactive group on other silanes.
Therefore, compared with the antibacterial coating material obtained by the existing method, the non-migration type antibacterial polyurethane coating material obtained by the method has the characteristics of high antibacterial rate, no migration of antibacterial agent nano zinc oxide and long antibacterial service life, is an environment-friendly non-migration type antibacterial polyurethane coating material, and can be used for preparing the inner wall coating of a tap water conveying pipeline, the inner wall coating of a beer and beverage storage tank, the coating of a food packaging material, the coating of an automotive interior trim part or the coating of a medical device.
Example 7:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of aminated nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the following steps: the nano zinc oxide and the gamma-aminopropyl triethoxysilane are mixed in a high-speed mixer for 2 minutes according to the weight ratio of 1:0.3 to obtain the aminated nano zinc oxide, and the grafting ratio of the gamma-aminopropyl triethoxysilane measured after purification is 3.5%.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 3 hours at 25 ℃, and is then heated to 200 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Example 8:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of aminated nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the steps of mixing nano zinc oxide and N- β -aminoethyl-gamma-aminopropyltrimethoxysilane for 2 minutes in a high-speed mixer according to the weight ratio of 1:0.3 to obtain the aminated nano zinc oxide, and measuring the grafting rate of the N- β -aminoethyl-gamma-aminopropyltrimethoxysilane to be 3.6% after purification.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 3 hours at 25 ℃, and is then heated to 200 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Example 9:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of aminated nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the following steps: the nano zinc oxide and the gamma-aminopropyl methyl dimethoxy silane are mixed in a high-speed mixer for 2 minutes according to the weight ratio of 1:0.3 to obtain the aminated nano zinc oxide, and the grafting rate of the gamma-aminopropyl methyl dimethoxy silane is measured to be 3.3 percent after purification.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 3 hours at 25 ℃, and is then heated to 200 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Example 10:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of aminated nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the following steps: the nano zinc oxide and the gamma-aminopropyl methyl diethoxy silane are mixed in a high-speed mixer for 2 minutes according to the weight ratio of 1:0.3 to obtain the aminated nano zinc oxide, and the grafting rate of the gamma-aminopropyl methyl diethoxy silane is measured to be 3.2 percent after purification.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 3 hours at 25 ℃, and is then heated to 200 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Example 11:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 65 parts of E31 type epoxy resin, 4 parts of aminated nano-oxide, 2.5 parts of BYK-300 organic silicon defoamer, 3.5 parts of allyl glycidyl ether, 3.5 parts of aluminum acetylacetonate and 60 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 65 parts of hexahydrophthalic anhydride at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 10:3 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the following steps: the nano zinc oxide, the gamma-aminopropyl triethoxysilane and the ethanol are mixed for 2 hours according to the weight ratio of 3:0.8:35 to obtain the aminated nano zinc oxide, and the grafting ratio of the gamma-aminopropyl triethoxysilane measured after purification is 4.1%.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is solidified for 6 hours at 85 ℃, and is then heated to 115 ℃ for solidification for 2 hours to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Example 12:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) 80 parts of E44 type epoxy resin, 2.5 parts of aminated nano-oxide, 0.8 part of silicon dioxide, 3 parts of n-butyl glycidyl ether, 2.5 parts of 2,4, 6-tri (dimethylaminomethyl) phenol and 55 parts of n-butyl alcohol are uniformly mixed at room temperature to obtain a mixture A;
(2) uniformly mixing 45 parts of n-butanol and 70 parts of m-xylene diamine at room temperature to obtain a mixture A;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 5:2 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the aminated nano zinc oxide comprises the steps of mixing nano zinc oxide, N- β -aminoethyl-gamma-aminopropyltrimethoxysilane and methanol for 1 hour according to the weight ratio of 4:1:30 to obtain the aminated nano zinc oxide, and measuring the grafting rate of the N- β -aminoethyl-gamma-aminopropyltrimethoxysilane to be 3.9% after purification.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 24 hours at 25 ℃, and is then heated to 70 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Comparative example 3:
(1) uniformly mixing 75 parts of E51 type epoxy resin, AC-3001 parts, 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain an epoxy coating material;
coating the obtained epoxy coating material on the surface of a steel sheet, curing the steel sheet at 25 ℃ for 3 hours, and then heating to 200 ℃ for curing for 1 hour to form the epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Comparative example 4:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain an epoxy coating material;
coating the obtained epoxy coating material on the surface of a steel sheet, curing the steel sheet at 25 ℃ for 3 hours, and then heating to 200 ℃ for curing for 1 hour to form the epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
Comparative example 5:
a method for preparing a non-migrating antibacterial epoxy coating material, comprising the steps of:
(1) uniformly mixing 75 parts of E51 type epoxy resin, 3 parts of epoxidized nano zinc oxide, AC-3001 parts, 2 parts of 2-ethyl-hexyl glycidyl ether, 2.5 parts of benzyl dimethylamine and 50 parts of acetone at room temperature to obtain a mixture A;
(2) uniformly mixing 50 parts of acetone and 70 parts of triethylene triamine at room temperature to obtain a mixture B;
(3) uniformly mixing the mixture A and the mixture B according to the weight ratio of 6:1 to obtain a non-migration type antibacterial epoxy coating material;
the preparation method of the epoxidized nano zinc oxide comprises the following steps: the nano zinc oxide and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane are mixed in a high-speed mixer for 2 minutes according to the weight ratio of 1:0.3 to obtain the aminated nano zinc oxide, and the grafting ratio of the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is measured to be 3.4% after purification.
The obtained non-migration type antibacterial epoxy coating material is coated on the surface of a steel sheet, is cured for 3 hours at 25 ℃, and is then heated to 200 ℃ for curing for 1 hour to form an epoxy coating.
The bacteriostasis rate of the obtained epoxy coating and the migration behavior of the nano zinc oxide are tested through escherichia coli and staphylococcus aureus bacteriostasis experiments and bacteriostasis zone experiments, the zinc ion migration amount is tested through the zinc ion migration experiments of the epoxy coating, and the test results are shown in table 2.
TABLE 3
TABLE 4
In the above examples, the zinc ion transport amount was measured by inductively coupled plasma emission spectrometer (Optima8300, PerkinElmer), and the epoxy material was first made into 40 × 60mm2The thickness of the coating is 0.4mm, then the coating is respectively soaked in a proper amount of deionized water at 37 ℃ for 2h, 6h, 12h and 24h, and finally the concentration of zinc ions in the deionized water is measured. The coating inhibition zone experiment is determined by a Kirby-Bauer test method (such as am.J. Clin.Pathol.1966,45, 493-286.), and the coating inhibition rate experiment is determined by a plate counting method (J.food Sci.2012,77, 280-286).
As can be seen from the test results listed in tables 3 and 4, the epoxy coating without zinc oxide (comparative example 3) has no antibacterial function. Compared with a coating (comparative example 4) added with unmodified nano zinc oxide, the coating (comparative example 5) added with epoxidized nano zinc oxide has only slightly improved antibacterial rate and zinc ion migration amount, while the coating material (such as examples 7-10) added with the same parts of aminated nano zinc oxide has obviously improved antibacterial rate and no bacteriostatic circle, and the zinc ion migration amount after 2h is obviously reduced, which indicates that the nano zinc oxide hardly migrates from the matrix. Because a large number of epoxy groups in the epoxy resin participate in the curing reaction, a small number of epoxy groups on the epoxidized nano zinc oxide hardly participate in the curing reaction, and a small number of amino groups on the aminated nano zinc oxide easily participate in the reaction of a large number of epoxy groups. It can also be seen from table 4 that, as the test time of the zinc ion migration amount is prolonged, the zinc ion migration amount of the coating material (examples 7 to 12) added with the aminated nano zinc oxide is hardly increased, which indicates that the nano zinc oxide in the epoxy coating obtained by the present invention hardly migrates for a long time, and has the advantage of long antibacterial life. Therefore, compared with the coating material obtained by the existing method, the non-migration type epoxy coating material obtained by the method has the characteristics of high antibacterial rate, anti-migration property of the antibacterial agent nano zinc oxide and long antibacterial service life, is an environment-friendly non-migration type epoxy coating material, and can be used for preparing the coating on the inner wall of a tap water conveying pipeline, the coating on the inner wall of a beer and beverage storage tank, the coating on a food packaging material, the coating on an automotive interior trim part or the coating on a medical device.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that the scope of the invention be defined by the appended claims.
Claims (3)
1. A non-migration type antibacterial coating material is characterized in that the preparation method of the antibacterial coating material comprises the following steps:
(1) mixing 60 parts of isophorone diisocyanate and 50 parts of polyethylene glycol adipate glycol for reaction for 3 hours at 95 ℃ under the condition of introducing nitrogen, then adding 1 part of diethylene glycol, 1.5 parts of triethanolamine and 1.5 parts of modified nano zinc oxide, and continuing to react for 1.5 hours to obtain a prepolymer;
(2) uniformly stirring the prepolymer, 1 part of dimethyl adipate and 0.5 part of polysiloxane to obtain a non-migration type antibacterial polyurethane coating material;
the preparation method of the modified nano zinc oxide comprises the following steps: mixing the nano zinc oxide and the gamma-aminopropyltriethoxysilane according to the weight ratio of 5:1.5 in a high-speed mixer for 5 minutes.
2. The antibacterial coating material according to claim 1, wherein the antibacterial coating material is used by a method comprising the steps of:
(1) coating the non-migratory antimicrobial coating material of claim 1 on the surface of a substrate;
(2) then curing for 5 minutes to 1.5 days at the first temperature;
(3) then heating to a second temperature and curing for 5 minutes to 2 days;
wherein the first temperature is 10-150 ℃, and the second temperature is 1-100 ℃ higher than the first temperature.
3. The use of the non-migratory antimicrobial coating material of claim 1 in the preparation of coatings for the interior walls of water supply lines, beer and beverage containers, food packaging materials, automotive upholstery, or medical devices.
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