An intrinsic antibacterial powder coating composition, and a preparation method and application thereof

Abstract

The application discloses an intrinsic antibacterial powder coating composition and a preparation method and application thereof. The intrinsic antibacterial powder coating composition comprises an intrinsic antibacterial modified epoxy resin precursor, a second epoxy resin precursor, an epoxy resin curing agent, a curing accelerator and an auxiliary agent; wherein the intrinsic antibacterial modified epoxy resin precursor is obtained by an epoxy ring-opening condensation reaction of thiazole pyridine diacid and a difunctional epoxy resin precursor under the condition of an epoxy ring-opening catalyst. The resin after curing of the intrinsic antibacterial powder coating composition has high glass transition temperature, excellent flexibility and thermodynamic properties; meanwhile, the obtained coating layer has high adhesion and good durability and weather resistance, and more importantly, the powder coating can be endowed with excellent intrinsic antibacterial, bacteriostatic and antiviral properties, so that the safety of electronic appliances, buildings, homes and human bodies is improved, and more durable and efficient protection against microbial contamination is provided.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of antibacterial technology, and particularly relates to an intrinsic antibacterial powder coating composition and a preparation method and application thereof. BACKGROUND

[0002] Powder coating is a new type of dry solid coating variety that is developing rapidly. The biggest difference between powder coating and general liquid coating using solvent or water as the dispersion medium is that powder coating is dispersed only by air during coating and can be uniformly coated on the surface of the workpiece, and then forms a uniform thickness coating film after heating and solidification. Therefore, powder coating can avoid the problems of fire safety, storage and transportation safety, toxicity and environmental pollution caused by organic solvents. At the same time, powder coating can use a closed-loop spraying system, and the oversprayed powder coating can be recycled and reused, having the advantages of energy saving, environmental protection, no three wastes pollution, etc. More importantly, the molecular weight of the resin used in powder coating is larger than that of solvent-based coating, so the performance and durability of the coating film have been greatly improved.

[0003] With the development of science and technology and the improvement of people's living standards, people have higher requirements for the antibacterial and environmental performance of household electronic appliances such as mobile phones, computers, electric fans, air conditioners, humidifiers, and transportation tools such as cars, subways, and ships, as well as building and home coatings. The emergence and application of antibacterial coatings have greatly improved the environmental quality of people's living and reduced the threat of microorganisms and bacteria to human health. Generally, antibacterial agents are added to powder coatings to improve the antibacterial and environmental performance of powder coatings. At present, antibacterial agents are divided into two categories: inorganic and organic. Inorganic antibacterial agents include mercury, cadmium, lead and other metal ions, and silver ion antibacterial agents are the most commonly used antibacterial agents. For example, patent CN113999590A discloses a composite antibacterial agent based on nano-silver and ginkgo tree branch extract, which is used to develop an antibacterial coating that can resist superbugs. However, silver ions are toxic to the human body and water, and have been gradually eliminated; organic antibacterial agents mainly include quaternary ammonium salts, quaternary phosphonium salts, phenolic ethers, phenols, quaternary phosphonium salts, pyridines, biguanides, halogenated amines, thiazoles, pyrroles, etc. For example, patent CN109439095A discloses a weather-resistant antibacterial powder coating prepared by adding a quaternary phosphonium salt antibacterial agent, which replaces inorganic silver ion antibacterial agents to overcome the heavy metal pollution caused by the release of silver ions. However, the safety of current organic antibacterial agents is still under study, and generally organic antibacterial agents have poor heat resistance, are prone to hydrolysis, have a short effective period, and are difficult to promote and use. At the same time, the precipitation pollution problem of added antibacterial agents needs to be considered. Therefore, it is urgent to provide a new intrinsic antibacterial powder coating to avoid secondary pollution to the human body and the environment. SUMMARY

[0004] The main purpose of the present application is to provide an intrinsic antibacterial powder coating composition and its preparation method and application to overcome the shortcomings of the prior art. The resin after curing of the intrinsic antibacterial powder coating composition in the present application has a relatively high glass transition temperature (Tg), excellent flexibility and thermodynamic properties; at the same time, the obtained coating shows a relatively high adhesion and good durability and weathering properties, and more importantly, the present application can impart excellent intrinsic antibacterial and antiviral properties to the powder coating, thereby providing more durable and efficient protection against microbial contamination for electronic appliances, buildings, home safety and personal protection.

[0005] To achieve the aforementioned purposes, the technical solutions adopted by the present application include:

[0006] The present application provides an intrinsic antibacterial powder coating composition, which comprises: an intrinsic antibacterial modified epoxy resin precursor, a second epoxy resin precursor, an epoxy resin curing agent, a curing accelerator and an auxiliary agent.

[0007] The intrinsic antibacterial modified epoxy resin precursor has a structure as shown in formula (I) and / or formula (II):

[0008]

[0009] R is selected from and / or m is selected from 1 to 10; R1 and R2 are independently selected from molecular structures of any one of the above, oligomers formed by polymerization of glycerol esters and / or glycerol ethers, or a combination of two or more thereof; n is selected from 0 to 10; R2, R3, R4 and R5 are independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or C3-C7 cycloalkyl; * represents the bonding position.

[0010] The present application also provides a preparation method of the aforementioned intrinsic antibacterial powder coating composition, which comprises: fully mixing the intrinsic antibacterial modified epoxy resin precursor, the second epoxy resin precursor, the epoxy resin curing agent, the curing accelerator and the auxiliary agent, and then melt-mixing, extruding and finely pulverizing to obtain the intrinsic antibacterial powder coating composition.

[0011] The present application also provides an intrinsic antibacterial powder coating cured product, which is obtained by curing the aforementioned intrinsic antibacterial powder coating composition.

[0012] The embodiment of the present application also provides a preparation method of the intrinsic antibacterial coating, which comprises: applying the aforementioned intrinsic antibacterial powder coating composition on a substrate and performing a curing treatment to obtain the intrinsic antibacterial coating.

[0013] The embodiment of the present application also provides the intrinsic antibacterial coating prepared by the aforementioned preparation method, wherein the antibacterial rate of the intrinsic antibacterial coating is greater than 91%.

[0014] The embodiment of the present application also provides the application of the aforementioned intrinsic antibacterial powder coating composition, intrinsic antibacterial powder coating solidified product or intrinsic antibacterial coating in household electronic appliances, architectural coatings, home coatings or coatings for rail transit decorative surfaces.

[0015] Compared with the prior art, the present application has the following beneficial effects:

[0016] (1) The two bio-based thiazolylpyridine ring-containing dicarboxylic acid monomers used in the present application are derived from cysteine, dimethyl cysteine (penicillamine) and citric acid, and the present application creatively introduces the bio-based thiazolylpyridine ring-containing dicarboxylic acid monomers into a commercial epoxy resin precursor structure under the action of a catalyst to prepare a series of intrinsic antibacterial epoxy resin precursors, which endow the epoxy resin with antibacterial properties on the basis of renewable resources. A series of intrinsic antibacterial powder coatings and coatings with excellent thermodynamic properties are developed by using the intrinsic antibacterial epoxy resin precursors, and the preparation method is simple and efficient.

[0017] (2) The present application prepares a series of intrinsic antibacterial epoxy resin precursors with linear glycidyl ester type by combining a commercial epoxy resin precursor with thiazolylpyridine derivatives having the effects of killing bacteria, fungi and resisting viruses. The introduction of rigid thiazolylpyridine rings not only greatly enhances the strength and modulus of the epoxy resin material, but also greatly improves the toughness and durability of the coating film by increasing the molecular weight of the epoxy resin precursor. At the same time, the introduction of high-density thiazolylpyridine ring structures can endow the powder coating with excellent antibacterial, antifungal and antiviral properties.

[0018] (3) The intrinsic antibacterial powder coating and coating provided by the present application have excellent thermodynamic properties, antibacterial, antifungal and antiviral functions, and the preparation process is simple and controllable, which is convenient to apply and suitable for large-scale industrial production, and has a very good application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiment or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0020] Figure 1a This is a characterization diagram of the antibacterial ability of the intrinsic antibacterial powder coating in Comparative Example 1 of the present invention against Staphylococcus aureus;

[0021] Figure 1b This is a characterization diagram of the antibacterial ability of the intrinsic antibacterial powder coating against Staphylococcus aureus in Example 1 of the present invention;

[0022] Figure 2a This is a characterization diagram of the antibacterial ability of the intrinsic antibacterial powder coating in Comparative Example 1 of the present invention against Escherichia coli;

[0023] Figure 2b This is a characterization diagram of the antibacterial ability of the intrinsic antibacterial powder coating against Escherichia coli in Embodiment 1 of the present invention;

[0024] Figure 3a This is the 1H NMR spectrum of intrinsic antibacterial modified epoxy resin precursor B in Example 2 of the present invention (solvent is deuterated DMSO);

[0025] Figure 3b This is the infrared spectrum of intrinsic antibacterial modified epoxy resin precursor B in Example 2 of the present invention. Detailed Implementation

[0026] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0027] Specifically, as one aspect of the technical solution of the present invention, the intrinsic antibacterial powder coating composition includes: an intrinsic antibacterial modified epoxy resin precursor, a second epoxy resin precursor, an epoxy resin curing agent, a curing accelerator, and additives.

[0028] The intrinsic antibacterial modified epoxy resin precursor has a structure as shown in formula (I) and / or formula (II):

[0029]

[0030] Where R is selected from and / or m is selected from 1 to 10; R1 and R2 are each independently selected from... a molecule of any one structure, an oligomer of any one structure of polymeric glycerol ester and / or glycerol ether, and / or a combination of two or more; n is selected from 0-10; R2, R3, R4, R5 are independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, or C3-C7 cycloalkyl; * represents the position of bond connection.

[0031] In some preferred embodiments, the intrinsic antibacterial modified epoxy resin precursor is obtained by epoxy ring opening esterification reaction of thiazolopyridine diacid and a di-functional epoxy resin precursor under the condition of an epoxy ring opening catalyst.

[0032] Further, the reaction temperature of the epoxy ring opening esterification reaction is 80-160°C.

[0033] Further, the thiazolopyridine diacid includes 5-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid and / or 5-oxo-2,3-dihydro-2,2-dimethyl-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, and is not limited thereto.

[0034] Further, the di-functional epoxy resin precursor includes any one of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, monoglycol diglycidyl ether, diglycol diglycidyl ether, triglycol diglycidyl ether, polyglycol diglycidyl ether, bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, p-phenylenediamine tetraglycidyl amine, p-phenylmethanol diglycidyl ether, bisphenol S diglycidyl ether, naphthalene benzene diamine tetraglycidyl amine, bisphenol F diglycidyl ether, bisphenol fluorene diglycidyl ether, cyclohexane dimethyl alcohol diglycidyl ether, p-phenol diglycidyl ether, naphthalene diol diglycidyl ether, 4,4'-dihydroxy diphenyl sulfide diglycidyl ether, 4,4'-dihydroxy diphenyl ether diglycidyl ether, 4,4'-dihydroxy diphenyl ether diglycidyl ether, 1,4-diethyl cyclohexane dimethyl alcohol diglycidyl ether, or a combination of two or more, and is not limited thereto.

[0035] Further, the epoxy ring opening catalyst includes any one of an organic phosphine catalyst, an imidazole catalyst, a quaternary ammonium salt catalyst, or a combination of two or more, and is not limited thereto.

[0036] Further, the organic phosphine catalyst includes any one of tributyl phosphine, triphenyl phosphine, tri(p-methylphenyl) phosphine, tri(nonylphenyl) phosphine, triphenyl phosphine benzoquinone adduct, tetraphenyl phosphine tetraphenyl borate, or a combination of two or more, and is particularly preferably triphenyl phosphine and / or tri(p-methylphenyl) phosphine.

[0037] Further, the imidazoles include any one or more than two combinations of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and are particularly preferably 2-ethylimidazole and / or 2-ethyl-4-methylimidazole.

[0038] Further, the quaternary ammonium salts include any one or more than two combinations of tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and benzyltriethylammonium bromide.

[0039] Specifically, the preparation method of the intrinsic antibacterial modified epoxy resin precursor includes: adding thiazolopyridine diacid (5-oxo-2, 3-dihydro-5H-thiazolo [3, 2-a] pyridine-3, 7-dicarboxylic acid, 5-oxo-2, 3-dihydro-2, 2-dimethyl-5H-thiazolo [3, 2-a] pyridine-3, 7-dicarboxylic acid) and the above-mentioned commercial difunctional epoxy resin precursor into a reaction kettle, and heating to 80-160℃ for melt reaction under the action of an epoxy ring-opening catalyst to obtain the intrinsic antibacterial modified epoxy resin precursor through an epoxy ring-opening esterification reaction.

[0040] Further, the molar ratio of the thiazolopyridine diacid, the difunctional epoxy resin precursor, and the epoxy ring-opening catalyst is 1.0:2.0-5.0:0.01-0.1.

[0041] In some preferred embodiments, the second epoxy resin precursor includes a compound having any one of the structures shown in the following formula or an oligomer formed by polymerization of any one of the structures shown in the following formula:

[0042]

[0043] wherein X, Y, and Z are each independently selected from any one or more than two combinations of the above, n is selected from 1-10; R2, R3, R4, and R5 are each independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, or C3-C7 cycloalkyl.

[0044] As some typical examples, the second epoxy resin precursor can be more specifically ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, ethylene glycol mono-diglycidyl ether, ethylene glycol di-diglycidyl ether, ethylene glycol tri-diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, p-phenylene diamine tetra-diglycidyl amine, p-phenylene methanol diglycidyl ether, bisphenol S diglycidyl ether, naphthalene benzene diamine tetra-diglycidyl amine, bisphenol F diglycidyl ether, bisphenol fluorene diglycidyl ether, cyclohexane dimethanol diglycidyl ether, hydroquinone diglycidyl ether, naphthalene diol diglycidyl ether, 4,4'-dihydroxy diphenyl sulfide diglycidyl ether, 4,4'-dihydroxy diphenyl ether diglycidyl ether, 4,4'-dihydroxy diphenyl diglycidyl ether, 1,4-diethyl cyclohexane dimethanol diglycidyl ether, and the like, but are not limited thereto.

[0045] In some preferred embodiments, the epoxy resin curing agent includes an amine-based curing agent and / or an anhydride-based curing agent, and is not limited thereto.

[0046] Further, the amine-based curing agent is selected from any one or a combination of two or more of rigid diamines such as diaminodiphenylmethane, diaminodiphenyl sulfone (DDS), diphenyl diamine, o-phenylene diamine, p-phenylene diamine, p-phenylene methyl amine, decane diamine, dicyandiamide, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-chloro-4-aminophenyl)fluorene, 9,9-bis(3-bromo-4-aminophenyl)fluorene, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)-2-bromofluorene, 9,9-bis(4-aminophenyl)-2,7-dibromofluorene, and the like, but is not limited thereto.

[0047] Further, the anhydride-based curing agent is selected from any one or a combination of two or more of rigid anhydrides such as succinic anhydride, homophthalic anhydride, diphenic anhydride, trimellitic anhydride, phthalic anhydride, phenyl succinic anhydride, pyromellitic dianhydride, 1,8-naphthalic anhydride, 1,2-naphthalic anhydride, 2,3-pyrazine dicarboxylic anhydride, 3-hydroxy phthalic anhydride, 2,3-naphthalene dicarboxylic anhydride, 2,3-pyridine dicarboxylic anhydride, 3,3',4,4'-diphenyl ether tetra carboxylic dianhydride, 3,3',4,4'-benzophenone tetra carboxylic anhydride, 3,3',4,4'-biphenyl tetra carboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and cyclobutane tetra carboxylic dianhydride, and the like, but is not limited thereto.

[0048] In some preferred embodiments, the curing accelerator includes any one or a combination of two or more of Lewis acids, imidazole-based compounds, and organic phosphine compounds, and is not limited thereto.

[0049] Further, the Lewis acid includes any one or a combination of two or more of boron trifluoride, boron trifluoride-ether complex, tin octoate, and preferably boron trifluoride and / or boron trifluoride-ether complex.

[0050] Further, the imidazole compound includes any one or a combination of two or more of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and preferably 2-ethylimidazole and / or 2-ethyl-4-methylimidazole.

[0051] Further, the organic phosphine compound includes any one or a combination of two or more of tributylphosphine, triphenylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine benzoquinone adduct, and tetraphenylphosphonium tetraphenylborate, and preferably triphenylphosphine and / or tri(p-methylphenyl)phosphine.

[0052] In some preferred embodiments, the auxiliary agent includes a leveling agent, a pigment, and a filler.

[0053] Further, the leveling agent includes one or more of a polysiloxane leveling agent, a polyester leveling agent, a polyurethane leveling agent, a polyacrylate leveling agent, and a polyvinyl leveling agent, and is not limited thereto.

[0054] Further, the pigment can be one or more of titanium dioxide, carbon black, red iron oxide, yellow iron oxide, and phthalocyanine blue, and is not limited thereto.

[0055] Further, the filler can be one or a mixture of several of nano calcium carbonate, nano silicon dioxide, wollastonite powder, micro silicon powder, precipitated barium sulfate, and ultra-fine barium sulfate, and is not limited thereto.

[0056] In some preferred embodiments, the intrinsic antibacterial powder coating composition includes, by weight parts, 30-60 parts of the intrinsic antibacterial modified epoxy resin precursor, 6-30 parts of the second epoxy resin precursor, 12-50 parts of the epoxy resin curing agent, 1-2 parts of the curing accelerator, and 7-36 parts of the auxiliary agent.

[0057] In some preferred embodiments, the mass ratio of the intrinsic antibacterial modified epoxy resin precursor to the second epoxy resin precursor is 10-90:90-10.

[0058] In some preferred embodiments, the ratio of the sum of the epoxy equivalent values of the intrinsic antibacterial modified epoxy resin precursor and the second epoxy resin precursor to the equivalent value of the active hydrogen or anhydride group of the epoxy curing agent is 100:(10-100).

[0059] Another aspect of the embodiments of the present application also provides a method for preparing the aforementioned intrinsic antibacterial powder coating composition, which includes:

[0060] The intrinsic antibacterial modified epoxy resin precursor, the second epoxy resin precursor, the epoxy resin curing agent, the curing accelerator and the auxiliary agent are mixed, and then are extruded by melt mixing, finely pulverized to obtain the intrinsic antibacterial powder coating composition.

[0061] Specifically, the intrinsic antibacterial powder coating composition adopts the only method internationally used for producing thermosetting powder coating, i.e. melt mixing extrusion method, mixing, melt mixing extrusion and fine pulverization. Specifically, the method comprises the following steps: (1) each raw material is weighed according to the formula ratio, and is mixed in a high-speed mixer for 30-40 min to obtain a mixed material; (2) the mixed material obtained in step (1) is transferred into a screw extruder, and the material is extruded and cooled to room temperature, and then is pressed into a thin sheet by a tablet press to obtain a tablet material; (3) the tablet material obtained in step (2) is coarsely pulverized and then ground to obtain a fine powder; and (4) the fine powder obtained in step (3) is separated by a cyclone separator, classified by sieving and detected to obtain a finished product. Preferably, in step (1), the rotating speed of the high-speed mixer is 280-350 r / min, and the temperature is 35-45 ℃.

[0062] Another aspect of the embodiment of the present application further provides an intrinsic antibacterial powder coating cured product, which is obtained by curing treatment of the aforementioned intrinsic antibacterial powder coating composition.

[0063] Further, the glass transition temperature of the intrinsic antibacterial powder coating cured product is 70-200 ℃, the tensile strength is 60-180 MPa, and the antibacterial rate is >91%.

[0064] Further, the killing rate of the intrinsic antibacterial powder coating cured product on gram-positive bacteria is 100%, and the killing rate on gram-negative bacteria is >91%.

[0065] Another aspect of the embodiment of the present application further provides a preparation method of the intrinsic antibacterial coating, which comprises: applying the aforementioned intrinsic antibacterial powder coating composition to a substrate and performing curing treatment to prepare the intrinsic antibacterial coating.

[0066] Further, the intrinsic antibacterial powder coating composition is applied to the substrate in a dry powder spraying manner.

[0067] Further, the temperature of the curing treatment is 100-200 ℃, and the time is 0.5-10 h.

[0068] Specifically, the intrinsic antibacterial coating is prepared by the following steps: the aforementioned intrinsic antibacterial powder coating composition is sprayed onto a substrate in a dry powder spraying manner to form an antibacterial powder coating dry powder coating layer with a specified thickness, and then the antibacterial powder coating dry powder coating layer is heated and cured at 100-200 ℃ for 0.5-10 h.

[0069] Another aspect of the embodiment of the present application also provides the intrinsic antibacterial coating prepared by the preparation method, and the antibacterial rate of the intrinsic antibacterial coating is greater than 91%.

[0070] Further, the killing rate of the intrinsic antibacterial coating on gram-positive bacteria is 100%, and the killing rate on gram-negative bacteria is greater than 91%.

[0071] Another aspect of the embodiment of the present application also provides the application of the aforementioned intrinsic antibacterial powder coating composition, intrinsic antibacterial powder coating solidified product or intrinsic antibacterial coating in household electronic appliances, building coatings, home coatings or coatings for rail transit decoration surfaces.

[0072] The intrinsic antibacterial powder coating solidified product or intrinsic antibacterial coating provided by the present application has a glass transition temperature of 70-200℃ and a tensile strength of 60-180MPa, the killing rate on gram-positive bacteria is 100%, and the killing rate on gram-negative bacteria is greater than 91%, and the preparation route is short, the raw materials have low toxicity, the preparation method is simple and universal, is suitable for large-scale production, and has a wide application prospect.

[0073] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The present embodiment is implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0074] In the following examples, the experimental materials used in the examples are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0075] The source part structure of the intrinsic antibacterial epoxy resin precursor is a commercialized epoxy resin precursor, wherein the source of the thiazolopyridine ring-containing dicarboxylic acid monomer is mainly prepared according to the method in the literature (Carbon dots with high fluorescence quantum yield: the fluorescence originates from organic fluorophores. Nanoscale, 2016, 8, 14374-14378.).

[0076] Embodiment 1

[0077] This embodiment illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of an intrinsic antibacterial powder coating and a coating layer and its solidified product, which specifically includes the following steps:

[0078] (1) 1 eq. 5-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, 2.1 eq. cyclohexanedimethanol diglycidyl ether and 0.01 eq. catalyst for ring opening of epoxy tetra-n-butylammonium bromide were added into a three-necked flask with mechanical stirring, the temperature was raised to 120°C and the reaction was stirred until the solid was completely dissolved, then the temperature was raised and controlled in the range of 140-160°C, the reaction was stirred for 4 hours, then poured out while hot, and the intrinsic antibacterial epoxy resin precursor A was obtained after cooling to room temperature.

[0079]

[0080] (2) First, the obtained intrinsic antibacterial epoxy resin precursor A was mixed with bisphenol A diglycidyl ether (E20) according to a mass ratio of 50:50, then the obtained mixture 1 was weighed according to the formula ratio (weight parts): epoxy resin 60 parts, phthalic anhydride 12 parts, 2-ethyl-4-methylimidazole 2 parts, titanium dioxide 8 parts, polysiloxane leveling agent 0.1 parts, nano-silicon dioxide 18 parts, each raw material was mixed in a high-speed mixer at a speed of 300 r / min for 30 min, and the temperature was maintained at 35-45°C, to obtain a uniform mixture, then transferred into a screw extruder, and the temperature was controlled in the range of 100-110°C, then extruded and cooled to room temperature, pressed into tablets by a tablet press, coarsely crushed and then ground into fine powder, finally separated by a cyclone separator, sieved, detected, and the intrinsic antibacterial powder coating finished product was obtained.

[0081] (3) The obtained intrinsic antibacterial powder coating finished product was pre-solidified by melting at 130°C, and finally post-solidified at 180°C for 2 hours in a vacuum oven to obtain the intrinsic antibacterial powder coating solidified product. Similarly, the obtained intrinsic antibacterial powder coating finished product was formed into a coating layer of a corresponding thickness by spraying, and was solidified according to the above solidification program to obtain the corresponding intrinsic antibacterial powder coating layer.

[0082] The performance test results show that the glass transition temperature of the obtained antibacterial powder coating and coating solidified product is 162°C, the tensile strength is 136 MPa, the impact resistance of the paint film is 65 kg·cm, and the adhesion test shows that the adhesion grade of the paint film is 4B according to ASTM D 3359 standard.

[0083] Representative and typical test strains were selected: *Escherichia coli* (Gram-negative bacteria) and *Staphylococcus aureus* (Gram-positive bacteria). The antibacterial experiment was conducted using the agar diffusion method. Under aseptic conditions, the strains were inoculated onto slant agar plates, activated twice at 37°C, and then inoculated into an appropriate amount of nutrient broth and incubated for 24 hours. The original bacterial suspension was diluted to 100 CFU / mL using a 10-fold dilution method, and then added dropwise to all cured resin discs wiped with ethanol. After covering with plastic wrap and leveling, the antibacterial effect was measured. The results are as follows: Figure 1b and Figure 2b As shown. The antibacterial powder coating and cured coating prepared in this embodiment have a 100% kill rate against Gram-positive bacteria and a kill rate of over 98% against Gram-negative bacteria.

[0084] Example 2

[0085] This embodiment illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of an intrinsic antibacterial powder coating and coating layer and their cured product, specifically including the following steps:

[0086] (1) 1 eq. of 5-oxo-2,3-dihydro-5H-thiazo[3,2-a]pyridine-3,7-dicarboxylic acid, 2,2 eq. of polyethylene glycol diglycidyl ether, and 0.03 eq. of triphenylphosphine, an epoxy ring-opening catalyst, were added to a three-necked flask equipped with a mechanical stirrer. The mixture was heated to 120°C and stirred until the solid was completely dissolved. The temperature was then increased and controlled within the range of 140-160°C. After stirring for 5 hours, the mixture was poured out while still hot and cooled to room temperature to obtain the intrinsic antibacterial epoxy resin precursor B shown below. Figure 3a This is the 1H NMR spectrum of the intrinsic antibacterial modified epoxy resin precursor B in this embodiment. Figure 3b This is the infrared spectrum of the intrinsic antibacterial modified epoxy resin precursor B in this embodiment.

[0087]

[0088] (2) First, the intrinsic antibacterial epoxy resin precursor B and bisphenol A diglycidyl ether (E12) were mixed evenly at a mass ratio of 60:40. Then, the mixture 1 was weighed according to the formula ratio (parts by weight): epoxy resin 62 parts, diaminodiphenylmethane 12 parts, carbon black 10 parts, polyacrylate leveling agent 0.5 parts, and nano calcium carbonate 16 parts. The raw materials were mixed in a high-speed mixer at a speed of 300 r / min for 30 min, and the temperature was kept at 35-45℃ to obtain a uniform mixture. Then, it was transferred to a screw extruder and the temperature was controlled within the range of 100-110℃. After extrusion, it was cooled to room temperature and pressed into tablets using a tablet press. The tablets were first coarsely crushed and then ground to obtain fine powder. Finally, they were separated by a cyclone separator, graded and sieved, and tested to obtain the intrinsic antibacterial powder coating product.

[0089] (3) The obtained intrinsic antibacterial powder coating product was pre-solidified by melting at 160°C by laying into a stainless steel mold, and finally post-solidified at 180°C for 5 hours in a vacuum oven to obtain an intrinsic antibacterial powder coating solidified product. Similarly, the obtained intrinsic antibacterial powder coating product was formed into a coating layer of a corresponding thickness by spraying, and was solidified according to the above solidification procedure to obtain a corresponding intrinsic antibacterial powder coating layer.

[0090] The performance test results show that the glass transition temperature of the obtained antibacterial powder coating and coating solidified product is 70°C, the tensile strength is 60 MPa, the impact resistance of the paint film is 58 kg-cm, and the adhesion grade of the paint film is 5B.

[0091] The antibacterial test experiment procedure is the same as that of Example 1. The killing rate of the antibacterial powder coating and coating solidified product prepared in this example on gram-positive bacteria is 100%, and the killing rate on gram-negative bacteria is above 99%.

[0092] Example 3

[0093] This example illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of an intrinsic antibacterial powder coating and a coating layer and its solidified product, which specifically includes the following steps:

[0094] (1) 1 eq. 5-oxo-2,3-dihydro-2,2-dimethyl-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, 2.2 eq. dodecyl glycol diglycidyl ether and 0.03 eq. epoxy ring opening reaction catalyst triphenylphosphine were added to a three-necked flask with mechanical stirring, heated to 120°C and stirred until the solid was completely dissolved, then heated and controlled at a temperature in the range of 140-160°C, stirred for 5 hours, then poured out while hot, and cooled at room temperature to obtain the intrinsic antibacterial epoxy resin precursor C as shown below.

[0095]

[0096] (2) First, the obtained intrinsic antibacterial epoxy resin precursor C is mixed with bisphenol s diglycidyl ether in a mass ratio of 70:30, and then the obtained mixture 1 is weighed according to the formula ratio (weight parts): epoxy resin 50 parts, pyromellitic dianhydride 33 parts, boron trifluoride-ethanol ether complex 1 part, phthalocyanine blue 6 parts, polyester leveling agent 0.1 part, superfine barium sulfate 10 parts. Each raw material is mixed in a high-speed mixer at a speed of 350 r / min for 30 min, and the temperature is maintained at 35-45°C. A uniform mixture is obtained, which is then transferred to a screw extruder, and the temperature is controlled in the range of 100-110°C. After extrusion, it is cooled to room temperature, pressed into tablets by a tablet press, coarsely crushed, then ground into fine powder, and finally separated by a cyclone separator, sieved, and detected to obtain the finished intrinsic antibacterial powder coating.

[0097] (3) The obtained intrinsic antibacterial powder coating product is placed in a stainless steel mold and pre-solidified at 160°C by melting, and finally post-solidified at 180°C in a vacuum oven for 6 hours to obtain the intrinsic antibacterial powder coating solidified product. Similarly, the obtained intrinsic antibacterial powder coating product is formed into a coating layer of a corresponding thickness by spraying, and is solidified according to the above solidification procedure to obtain the corresponding intrinsic antibacterial powder coating layer.

[0098] The performance test results show that the glass transition temperature of the obtained antibacterial powder coating, coating solidified product is 186°C, the tensile strength is 124 MPa, the impact resistance of the paint film is 66 kg·cm, and the adhesion grade of the paint film is 4B.

[0099] The antibacterial test experiment procedure is the same as that of Example 1. The killing rate of the antibacterial powder coating, coating solidified product prepared in this example to gram-positive bacteria is 100%, and the killing rate to gram-negative bacteria is above 96%.

[0100] Example 4

[0101] This example illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of an intrinsic antibacterial powder coating and a coating layer, and its solidified product, which specifically includes the following steps:

[0102] (1) 1 eq. 5-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, 2.1 eq. bisphenol A diglycidyl ether, and 0.03 eq. epoxy ring-opening reaction catalyst benzyl triethyl ammonium bromide are added to a three-necked flask with mechanical stirring. The temperature is raised to 120°C and stirred until the solid is completely dissolved. Then the temperature is raised and controlled in the range of 160-180°C. After stirring for 4 hours, it is poured out while hot and cooled to room temperature to obtain the intrinsic antibacterial epoxy resin precursor D as shown below.

[0103]

[0104] (2) First, the obtained intrinsic antibacterial epoxy resin precursor D is mixed with polyethylene glycol diglycidyl ether 90:10 in a mass ratio, and then the obtained mixture 1 is weighed according to the formula ratio (parts by weight): epoxy resin 65 parts, phenyl succinic anhydride 26 parts, 2-ethyl imidazole 2 parts, iron oxide yellow 1 part, polyester leveling agent 0.1 part, superfine barium sulfate 6 parts. Each raw material is mixed in a high-speed mixer at a speed of 350 r / min for 30 min, keeping the temperature at 35-45°C. A uniform mixture is obtained, which is then transferred to a screw extruder, and the temperature is controlled within the range of 100-110°C. After extrusion, it is cooled to room temperature, pressed into a tablet by a tablet press, coarsely crushed, then ground into fine powder, and finally separated by a cyclone separator, sieved, and detected to obtain the finished intrinsic antibacterial powder coating.

[0105] (3) The obtained intrinsic antibacterial powder coating product is placed in a stainless steel mold and pre-solidified at 120°C by melting, and finally post-solidified at 180°C in a vacuum oven for 6 hours to obtain the intrinsic antibacterial powder coating solidification product. Similarly, the obtained intrinsic antibacterial powder coating product is formed into a coating layer of a corresponding thickness by spraying, and is cured according to the above curing procedure to obtain the corresponding intrinsic antibacterial powder coating layer.

[0106] The performance test results show that the glass transition temperature of the obtained antibacterial powder coating, coating solidification product is 168°C, the tensile strength is 153 MPa, the impact resistance of the paint film is 52 kg·cm, and the adhesion of the paint film is 3B.

[0107] The antibacterial test experiment steps are the same as in Example 1. The antibacterial powder coating, coating solidification product prepared in this example has a killing rate of 100% for gram-positive bacteria and a killing rate of more than 97% for gram-negative bacteria.

[0108] Example 5

[0109] This example illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of intrinsic antibacterial powder coating and coating layer and its solidification product, which specifically includes the following steps:

[0110] (1) 1 eq. of 5-oxo-2,3-dihydro-2,2-dimethyl-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, 3.1 eq. of bisphenol A diglycidyl ether and 0.03 eq. of a catalyst for ring-opening reaction of epoxy, benzyl triethyl ammonium bromide, were added into a three-necked flask with mechanical stirring, the temperature was raised to 120°C, and after the solid was completely dissolved, the temperature was raised and controlled in the range of 140-160°C, and after stirring for 4 hours, the product was poured out while hot, and after cooling at room temperature, a mixture of intrinsic antibacterial epoxy resin precursor E and bisphenol A diglycidyl ether was obtained as shown below.

[0111]

[0112] (2) First, the mixture of intrinsic antibacterial epoxy resin precursor E and bisphenol A diglycidyl ether obtained in step (1) was weighed according to the formula (weight parts): epoxy resin 70 parts, 9,9-bis(4-aminophenyl)fluorene 21 parts, titanium white 1 part, polyester leveling agent 0.5 part, precipitated barium sulfate 8 parts, and each raw material was mixed in a high-speed mixer at a speed of 350 r / min for 30 min while maintaining the temperature at 35-45°C to obtain a uniform mixture, which was then transferred into a screw extruder, and extruded while controlling the temperature in the range of 100-110°C, and then cooled to room temperature, and then pressed into tablets using a tablet press, and then ground after coarse crushing to obtain fine powder, and finally separated by a cyclone separator, classified by sieving, and detected to obtain the finished product of intrinsic antibacterial powder coating.

[0113] (3) The finished product of intrinsic antibacterial powder coating was pre-solidified by melting at 120°C by being laid in a stainless steel mold, and finally post-solidified at 180°C for 6 hours in a vacuum oven to obtain the solidified product of intrinsic antibacterial powder coating. Similarly, the finished product of intrinsic antibacterial powder coating was formed into a coating layer of a corresponding thickness by spraying, and solidified according to the above solidification procedure to obtain the corresponding intrinsic antibacterial powder coating layer.

[0114] The performance test results showed that the glass transition temperature of the obtained antibacterial powder coating and coating solidification product was 178°C, the tensile strength was 161 MPa, the impact resistance of the paint film was 55 kg·cm, and the adhesion of the paint film was 3B.

[0115] The antibacterial test procedure was the same as in Example 1, and the killing rate of the antibacterial powder coating and coating solidification product prepared in this example against gram-positive bacteria was 100%, and the killing rate against gram-negative bacteria was more than 98%.

[0116] Example 6

[0117] This example illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of intrinsic antibacterial powder coating and coating layer, and the preparation process of the solidification product thereof, which specifically includes the following steps:

[0118] (1) 1 eq. of 5-oxo-2,3-dihydro-2,2-dimethyl-5H-thiazolo[3,2-a]pyridine-3,7- dicarboxylic acid, 3.0 eq. of bisphenol F diglycidyl ether and 0.03 eq. of a catalyst for ring-opening reaction of epoxy, benzyl triethyl ammonium bromide, were added into a three-necked flask with mechanical stirring, and the temperature was raised to 120°C. After the solid was completely dissolved, the temperature was raised and controlled in the range of 140-160°C. After stirring for 4 hours, the product was poured out while hot, and cooled at room temperature to obtain a mixture of intrinsic antibacterial epoxy resin precursor F and bisphenol F diglycidyl ether as shown below.

[0119]

[0120] (2) First, the mixture of intrinsic antibacterial epoxy resin precursor F and bisphenol F diglycidyl ether 1 was prepared according to the formula (weight parts): epoxy resin 60 parts, 9,9-bis(3-chloro-4-aminophenyl)fluorene 22 parts, titanium dioxide 1 part, polyester leveling agent 0.5 part, nano-silica 17 parts. Each raw material was mixed in a high-speed mixer at a speed of 350 r / min for 30 min, and the temperature was maintained at 35-45°C to obtain a uniform mixture. Then, the mixture was transferred into a screw extruder, and extruded at a temperature of 100-110°C. After cooling to room temperature, the product was pressed into tablets using a tablet press, and then coarsely crushed and ground into fine powder. Finally, the product was separated by a cyclone separator, and classified by sieving. The intrinsic antibacterial powder coating finished product was obtained by detection.

[0121] (3) The intrinsic antibacterial powder coating finished product was pre-solidified by melting at 140°C, and finally post-solidified at 180°C for 8 hours in a vacuum oven to obtain the intrinsic antibacterial powder coating solidified product. Similarly, the intrinsic antibacterial powder coating finished product was formed into a coating layer of a corresponding thickness by spraying, and solidified according to the above solidification procedure to obtain the corresponding intrinsic antibacterial powder coating layer.

[0122] The performance test results showed that the glass transition temperature of the obtained antibacterial powder coating and coating solidified product was 165°C, the tensile strength was 173 MPa, the impact resistance of the paint film was 54 kg·cm, and the adhesion grade of the paint film was 4B.

[0123] The antibacterial test procedure was the same as that of Example 1. The killing rate of the antibacterial powder coating and coating solidified product prepared in this example against gram-positive bacteria was 100%, and the killing rate against gram-negative bacteria was more than 99%.

[0124] Example 7

[0125] The present embodiment illustrates the synthesis of an intrinsic antibacterial modified epoxy resin precursor, the preparation process of an intrinsic antibacterial powder coating and a coating layer and the cured product thereof, which specifically comprises the following steps:

[0126] (1) 1 eq. of 5-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, 2.1 eq. of bisphenol A diglycidyl ether and 0.03 eq. of an epoxy ring-opening reaction catalyst benzyl triethyl ammonium bromide were added to a three-necked flask with mechanical stirring, the temperature was raised to 120°C and the reaction was stirred until the solid was completely dissolved, then the temperature was raised and controlled in the range of 160-180°C, the reaction was stirred for 4 hours, and then poured out while hot, and the intrinsic antibacterial epoxy resin precursor G was obtained after cooling to room temperature.

[0127]

[0128] (2) First, the obtained intrinsic antibacterial epoxy resin precursor G was mixed with bisphenol fluorene diglycidyl ether at a mass ratio of 60:40, and then the obtained mixture 1 was weighed according to the formula ratio (weight parts): epoxy resin 40 parts, 3,3',4,4'-diphenyl tetracarboxylic dianhydride 50 parts, 2-ethyl imidazole 2 parts, titanium white 1 part, polyacrylate leveling agent 0.2 parts, nano silicon dioxide 7 parts, and each raw material was mixed in a high-speed mixer at a speed of 350 r / min for 30 min, and the temperature was maintained at 35-45°C, to obtain a uniform mixture, which was then transferred to a screw extruder, and extruded at a temperature controlled in the range of 100-110°C, and then cooled to room temperature, and pressed into tablets by a tablet press, and then coarsely crushed and ground to obtain fine powder, and finally separated by a cyclone separator, sieved, detected, and the intrinsic antibacterial powder coating finished product was obtained.

[0129] (3) The obtained intrinsic antibacterial powder coating finished product was pre-solidified by melting at 180°C by laying it in a stainless steel mold, and finally post-solidified at 200°C in a vacuum oven for 5 hours, to obtain the intrinsic antibacterial powder coating cured product. Similarly, the obtained intrinsic antibacterial powder coating finished product was formed into a coating layer of a corresponding thickness by spraying, and cured according to the above curing procedure to obtain the corresponding intrinsic antibacterial powder coating layer.

[0130] The performance test results show that the glass transition temperature of the obtained antibacterial powder coating, coating layer cured product is 200°C, the tensile strength is 169 MPa, the impact resistance of the paint film is 57 kg·cm, and the adhesion grade of the paint film is 4B.

[0131] The antibacterial test experiment steps are the same as those of Example 1, and the killing rate of the antibacterial powder coating, coating layer cured product prepared in the present embodiment to gram-positive bacteria is 100%, and the killing rate to gram-negative bacteria is above 91%.

[0132] Comparative Example 1

[0133] The intrinsic antibacterial epoxy resin precursor A in Example 1 was replaced by E20, and other operation procedures were unchanged. The glass transition temperature of the powder coating cured product prepared was 146°C, and the tensile strength was 133 MPa. The killing rate of the powder coating cured product prepared in this comparative example to gram-positive bacteria was 80%, and the killing rate to gram-negative bacteria was 60%.

[0134] Comparative Example 2

[0135] The intrinsic antibacterial epoxy resin precursor A in Example 1 was replaced by cyclohexane dimethanol diglycidyl ether, and other steps were consistent with those in Example 1. The performance test results showed that the glass transition temperature of the powder coating, coating cured product prepared in this comparative example was 133°C, the tensile strength was 121 MPa, the impact resistance of the paint film was 51 kg·cm, and the adhesion grade of the paint film was 3B.

[0136] Meanwhile, the killing rate of the powder coating, coating cured product prepared in this comparative example to gram-positive bacteria was 46%, and the killing rate to gram-negative bacteria was 45%.

[0137] In addition, the inventors of the present case also conducted tests according to the other raw materials, process operations, process conditions described in the foregoing examples, and all obtained relatively ideal results.

[0138] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above. Any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.

Claims

1. An intrinsically antimicrobial powder coating composition characterized in that, Comprise: The intrinsic antibacterial modified epoxy resin precursor, the second epoxy resin precursor, the epoxy resin curing agent, the curing accelerator and the auxiliary agent; The intrinsic antibacterial modified epoxy resin precursor has a structure as shown in formula (I) and / or formula (II): wherein R is selected from m is selected from 1 to 10; R1, R2 are independently selected from molecules of any one of the structures, oligomers of polymerized glycerol esters and / or glycerol ethers of any one of the structures, or combinations of two or more; n is selected from 0 to 10; R2, R3, R4, R5 are independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, or C3-C7 cycloalkyl; * represents a bond connection position.

2. The intrinsically antimicrobial powder coating composition of claim 1, wherein: The intrinsic antibacterial modified epoxy resin precursor is obtained by epoxy ring opening esterification reaction of thiazolopyridine diacid and difunctional epoxy resin precursor under the condition of epoxy ring opening catalyst.

3. The intrinsically antimicrobial powder coating composition of claim 2, wherein: The reaction temperature of the epoxy ring opening esterification reaction is 80-160℃; And / or, the thiazolopyridine diacid comprises 5-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid and / or 5-oxo-2,3-dihydro-2,2-dimethyl-5H-thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid; And / or, the difunctional epoxy resin precursor comprises any one or a combination of two or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, p-phenylenediamine tetraglycidyl amine, p-phenylenediamine diglycidyl ether, bisphenol S diglycidyl ether, naphthalene benzene diamine tetraglycidyl amine, bisphenol F diglycidyl ether, bisphenol fluorene diglycidyl ether, cyclohexane dimethanol diglycidyl ether, hydroquinone diglycidyl ether, naphthalene diol diglycidyl ether, 4,4'-dihydroxydiphenyl sulfide diglycidyl ether, 4,4'-dihydroxydiphenyl ether diglycidyl ether, 4,4'-dihydroxydiphenyl ether diglycidyl ether, 1,4-diethylcyclohexane dimethanol diglycidyl ether; And / or, the epoxy ring opening catalyst comprises any one or a combination of two or more of organic phosphine catalyst, imidazole catalyst, quaternary ammonium salt catalyst; And / or, the molar ratio of the thiazolopyridine diacid, the difunctional epoxy resin precursor and the epoxy ring opening catalyst is 1.0:2.0-5.0:0.01-0.

1.

4. The intrinsically antimicrobial powder coating composition of claim 1, wherein: The second epoxy resin precursor comprises a compound having any one of the structures as shown in the following formula or an oligomer formed by polymerization of any one of the structures as shown in the following formula: wherein X, Y and Z are each independently selected from n is selected from 1 to 10; R2, R3, R4, R5are each independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or C3-C7 cycloalkyl; And / or, the epoxy resin curing agent comprises an amine curing agent and / or an acid anhydride curing agent; And / or, the curing accelerator comprises any one or a combination of two or more of Lewis acid, imidazole compound, organic phosphine compound; And / or, the auxiliary agent comprises a leveling agent, pigment and filler.

5. The intrinsically antimicrobial powder coating composition of claim 1, wherein: The intrinsic antibacterial powder coating composition comprises the following components by weight parts: 30-60 parts of intrinsic antibacterial modified epoxy resin precursor, 6-30 parts of second epoxy resin precursor, 12-50 parts of epoxy resin curing agent, 1-2 parts of curing accelerator and 7-36 parts of auxiliary agent; And / or, the mass ratio of the intrinsic antibacterial modified epoxy resin precursor and the second epoxy resin precursor is 10-90:90-10; And / or, the ratio of the sum of the epoxy equivalent values of the intrinsic antibacterial modified epoxy resin precursor and the second epoxy resin precursor to the equivalent value of the active hydrogen or anhydride group of the epoxy curing agent is 100:(10-100).

6. A method for the production of the intrinsically antimicrobial powder coating composition according to any one of claims 1 to 5, characterized in that, Comprising: The intrinsic antibacterial powder coating composition is obtained by fully mixing the intrinsic antibacterial modified epoxy resin precursor, the second epoxy resin precursor, the epoxy resin curing agent, the curing accelerator and the auxiliary agent, and then melt-mixing extrusion and fine pulverization.

7. An intrinsic antibacterial powder paint cured product, characterized by: The intrinsic antibacterial powder coating cured product is obtained by curing treatment of the intrinsic antibacterial powder coating composition according to any one of claims 1-5.

8. The intrinsic antimicrobial powder paint-cured product according to claim 7, characterized by: The intrinsic antibacterial powder coating cured product has a glass transition temperature of 70-200℃, a tensile strength of 60-180MPa, and an antibacterial rate of >91%.

9. A method for producing an intrinsically antibacterial coating, characterized by, Comprising: The intrinsic antibacterial coating is prepared by applying the intrinsic antibacterial powder coating composition according to any one of claims 1-5 to a substrate and curing treatment.

10. The method of claim 9, wherein: The intrinsic antibacterial powder coating composition is applied to the substrate by dry powder spraying.

11. The method of claim 9, wherein: The curing treatment is performed at a temperature of 100-200℃ for 0.5-10h.

12. The intrinsically antimicrobial coating produced by the method of any one of claims 9-11, characterized by: The intrinsic antibacterial coating has an antibacterial rate of >91%.

13. The intrinsic antimicrobial coating of claim 12, wherein: The intrinsic antibacterial coating has a killing rate of 100% for gram-positive bacteria and a killing rate of >91% for gram-negative bacteria.

14. Use of the intrinsic antibacterial powder coating composition according to any one of claims 1-5, the intrinsic antibacterial powder coating cured product according to any one of claims 7-8, or the intrinsic antibacterial coating according to any one of claims 12-13 in household electronic appliances, architectural coatings, home furnishing coatings, or coatings for decorative surfaces of rail transit.

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