Curable antibacterial material, preparation method thereof, antibacterial ink and application

Abstract

The invention discloses a curable antibacterial material, a preparation method thereof, antibacterial ink and application, and relates to the technical field of ink-jet printing. Wherein the amino-modified erythrosine is wide in light absorption range, does not need a light source with a specific wave band, can generate ROS (reactive oxygen species) under the driving of visible light, has broad-spectrum and lasting bactericidal characteristics, and is not easy to cause drug resistance of bacteria; the structural unit derived from the monomer as shown in the formula I has a plurality of double bonds, so that the polymer has higher crosslinking density, and the prepared antibacterial coating has better hardness and durability; besides, the polymer has unsaturated carbon-carbon double bonds, so that the polymer can quickly form a firm coating through ultraviolet light or other curing modes, the treatment time is shortened, and the obtained antibacterial coating is not easy to fall off and can be used for a long time.

Description

Technical Field

[0001] The invention relates to the technical field of inkjet printing, and in particular to a curable antibacterial material and a preparation method thereof, antibacterial ink and application thereof. Background Art

[0002] At present, public trash cans are important facilities for urban garbage disposal, and their surfaces are often exposed to various garbage and microorganisms. These microorganisms will multiply rapidly in a suitable environment, not only causing the garbage to rot and stink, but also becoming a source of bacteria and viruses, posing a threat to public health.

[0003] Although there are some antibacterial coating products on the market, their antibacterial properties are limited by factors such as materials and preparation processes, and it is difficult for them to remain effective for a long time under complex and changing environmental conditions. In particular, the performance of antibacterial coatings may be seriously affected in high temperature, high humidity, acid and alkali environments. Public trash cans need to frequently come into contact with various types of garbage, which requires high durability of the coating. In addition, existing antibacterial coatings have problems such as easy wear and easy shedding, which makes it impossible to maintain effective antibacterial effects for a long time during use. Summary of the invention

[0004] The main purpose of the present invention is to propose a negative electrode material and a preparation method and application thereof, aiming to solve the problems in the prior art that the antibacterial coating material has poor acid and alkali resistance, unstable antibacterial performance, and is easy to fall off and wear.

[0005] To achieve the above object, the present invention provides a curable antibacterial material, comprising a polymer and an amino-modified erythrosine connected to the polymer, wherein the polymer comprises a structural unit derived from a monomer represented by formula I, a structural unit derived from a monomer represented by formula II, and a structural unit derived from a monomer represented by formula III;

[0006]

[0007] Among them, the average value of n is 10;

[0008] The polymer includes unsaturated carbon-carbon double bonds.

[0009] In one embodiment, the amino-modified erythrosine and the structural unit derived from the monomer represented by formula II in the polymer are connected via an amide bond;

[0010] The mass percentage of amino-modified erythrosine in the curable antibacterial material is 8-9%;

[0011] The average molecular weight of the polymer is 1100;

[0012] The structure of the amino-modified erythrosine is shown in Formula IV:

[0013]

[0014] The present invention provides a method for preparing a curable antibacterial material, comprising the following steps:

[0015] S10, mixing the erythrosine derivative and the amino organic bromide, and performing a substitution reaction to obtain amino-modified erythrosine;

[0016] S20, mixing the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III, and performing copolymerization reaction to obtain a branched polymer having a carboxylic acid group;

[0017] S30, mixing the amino-modified erythrosine derivative and the polymer having a branched carboxylic acid group, and performing an amide reaction to connect the amino-modified erythrosine with the polymer to obtain a curable antibacterial material.

[0018] In one embodiment, the erythrosine derivative comprises erythrosine B sodium salt or tetraiodofluorescein sodium salt;

[0019] The amino organic bromide includes 3-bromopropylamine hydrobromide, p-bromoaniline, 3-bromoaniline or 2-amino-5-bromoindan hydrobromide;

[0020] The monomer represented by formula I includes trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate or tris(2-hydroxyethyl)isocyanuric acid triacrylate;

[0021] The monomer represented by formula II includes acrylic acid, methacrylic acid, hexadienedioic acid or maleic acid;

[0022] The monomer represented by formula III includes polyethylene glycol methacrylate, methacrylic acid, hexadienedioic acid or maleic acid;

[0023] In step S20, the molar ratio of the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III is (3-5):1:(4-5);

[0024] The molar ratio of erythrosine in the erythrosine derivative to the carboxylic acid group in the copolymer is 1:(1-2).

[0025] The present invention provides an antibacterial ink, which comprises a solvent, a photoinitiator and the aforementioned curable antibacterial material or a curable antibacterial material prepared by the aforementioned method for preparing the curable antibacterial material.

[0026] In one embodiment, the mass ratio of the curable antibacterial material, the solvent and the photoinitiator is (35-45): (50-60): (3-6).

[0027] In one embodiment, the solvent comprises tetrahydrofuran, 2-methyltetrahydrofuran or diethoxymethane;

[0028] The photoinitiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide;

[0029] The viscosity of the antibacterial ink at 50° C. is 9 to 10.5 mPa·s;

[0030] The surface tension of the antibacterial ink is 34-36 mN / m.

[0031] The present invention also provides an application, wherein an antibacterial coating is prepared by using the antibacterial ink as described above, comprising the following steps:

[0032] A curable antibacterial material is obtained, and the curable antibacterial material is mixed with a solvent and a photoinitiator, and light-cured to obtain an antibacterial coating.

[0033] In one embodiment, the step of obtaining a curable antibacterial material, mixing the curable antibacterial material with a solvent and a photoinitiator, and photocuring the curable antibacterial material to obtain an antibacterial coating comprises:

[0034] A curable antibacterial material is obtained, the curable antibacterial material is mixed with a solvent and a photoinitiator, and the antibacterial coating is obtained by inkjet printing and photocuring.

[0035] In one embodiment, the nozzle temperature of the inkjet printing is 50-55°C;

[0036] The light curing includes ultraviolet light curing, and the power of the ultraviolet light curing is 400-500W;

[0037] The light curing includes ultraviolet light curing, and the time of the ultraviolet light curing is 10 to 15 seconds.

[0038] The present invention proposes a curable antibacterial material and its preparation method, antibacterial ink and application, wherein the amino-modified erythrosine has a wide light absorption range, does not require a specific band light source, can generate ROS under visible light drive, has a broad spectrum, lasting bactericidal properties, and is not easy to make bacteria resistant; the structural unit derived from the monomer shown in formula I has multiple double bonds, so that the polymer has a higher cross-linking density, ensuring that the prepared antibacterial coating has good hardness and durability; in addition, due to the unsaturated carbon-carbon double bonds in the polymer, the polymer can be quickly formed into a solid coating by ultraviolet light or other curing methods, reducing the processing time, and the obtained antibacterial coating is not easy to fall off and can be used for a long time. The antibacterial ink configured by the curable antibacterial material of the present invention has the characteristics of good acid and alkali resistance, high adhesion, strong antibacterial property and good bacterial adhesion resistance, and the coating surface energy prepared by the ink through the inkjet printing method is low, the ink layer has high bonding strength, and is suitable for the field of public health, especially for public trash cans. The excellent anti-bacterial adhesion properties of the antibacterial coating can prevent bacteria, mold, etc. from adhering to the surface and forming plaque, making public trash cans less likely to get dirty, which is helpful in improving the appearance of the city. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0040] Figure 1 This is a schematic diagram of the preparation principle of the curable antibacterial material in Example 1 provided by the present invention;

[0041] Figure 2 This is an X-ray photoelectron spectroscopy (XPS) graph of the curable antibacterial material in Example 1 provided by the present invention;

[0042] Figure 3 The antibacterial effect diagram of the antibacterial coating under different illumination times in Comparative Example 1 and Example 6 provided by the present invention.

[0043] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0044] To make the purpose, technical scheme and advantages of the embodiment of the present invention clearer, the technical scheme in the embodiment of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiment, it is carried out according to the normal conditions or the conditions recommended by the manufacturer. If the reagents or instruments used do not specify the manufacturer, they are all conventional products that can be purchased commercially. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes, taking "A and / or B" as an example, including scheme A, or scheme B, or schemes that A and B meet at the same time. In addition, the technical schemes between the various embodiments can be combined with each other, but must be based on the ability of ordinary technicians in the field to achieve. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that the combination of such technical solutions does not exist, and is not within the scope of protection required by the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present invention.

[0045] At present, public trash cans are important facilities for urban garbage disposal, and their surfaces are often exposed to various garbage and microorganisms. These microorganisms will multiply rapidly in a suitable environment, not only causing the garbage to rot and stink, but also becoming a source of bacteria and viruses, posing a threat to public health.

[0046] Although there are some antibacterial coating products on the market, their antibacterial properties are limited by factors such as materials and preparation processes, and it is difficult for them to remain effective for a long time under complex and changing environmental conditions. In particular, the performance of antibacterial coatings may be seriously affected in high temperature, high humidity, acid and alkali environments. Public trash cans need to frequently come into contact with various types of garbage, which requires high durability of the coating. In addition, existing antibacterial coatings have problems such as easy wear and easy shedding, which makes it impossible to maintain effective antibacterial effects for a long time during use.

[0047] In view of this, the present invention provides a curable antibacterial material, comprising a polymer and an amino-modified erythrosine connected to the polymer, wherein the polymer comprises a structural unit derived from a monomer represented by formula I, a structural unit derived from a monomer represented by formula II, and a structural unit derived from a monomer represented by formula III;

[0048]

[0049] Among them, the average value of n is 10;

[0050] The polymer includes unsaturated carbon-carbon double bonds.

[0051] In the technical scheme of the present invention, the amino-modified erythrosine has a wide light absorption range, does not require a light source of a specific wavelength band, can generate ROS under the drive of visible light, has a broad-spectrum and lasting bactericidal property, and is not easy to cause bacteria to develop drug resistance; the structural unit derived from the monomer shown in formula I has a plurality of double bonds, so that the polymer has a higher cross-linking density, ensuring that the prepared antibacterial coating has good hardness and durability; in addition, since the number of double bonds of the structural unit derived from the monomer shown in formula I in the polymer is excessive, the polymer still has additional unsaturated carbon-carbon double bonds after formation, and the curable antibacterial material can be cross-linked with each other through the carbon-carbon double bonds by ultraviolet light or other curing methods to quickly form a strong coating, thereby reducing the processing time, and the obtained antibacterial coating is not easy to fall off and can be used for a long time.

[0052] In some embodiments of the present invention, the amino-modified erythrosine and the structural unit derived from the monomer represented by Formula II in the polymer are connected via an amide bond.

[0053] In the technical scheme of the present invention, the amino-modified erythrosine has an amino group, and the structural unit derived from the monomer shown in Formula II in the polymer has a carboxylic acid group. The amide bond formed by the amino group and the carboxyl group connects the amino-modified erythrosine and the polymer. The amide bond has high chemical stability and is not easily hydrolyzed under mild conditions. The chemical stability of the amide bond ensures that the antibacterial agent is not easy to fall off under complex environmental conditions and can continuously release antibacterial activity, thereby improving the long-term durability of the antibacterial material and having a positive impact on the persistence of the antibacterial effect.

[0054] In some embodiments of the present invention, the mass percentage of amino-modified erythrosine in the curable antibacterial material is 8-9%. The mass percentage of amino-modified erythrosine within a suitable range can ensure that the curable antibacterial material has a strong antibacterial effect.

[0055] In some embodiments of the present invention, the average molecular weight of the polymer is 1100. The average molecular weight of the polymer within a suitable range can ensure that the polymer has a good antibacterial effect and a suitable cross-linking density, thereby ensuring that the antibacterial coating prepared therefrom has good stability, adhesion and durability.

[0056] In some embodiments of the present invention, the structure of the amino-modified erythrosine is shown in Formula IV:

[0057]

[0058] In the technical solution of the present invention, the amino-modified erythrosine can be obtained by chemically modifying erythrosine or its derivatives, and the introduction of amino groups can significantly enhance the antibacterial activity of erythrosine (ER).

[0059] The present invention provides a method for preparing a curable antibacterial material, comprising the following steps:

[0060] S10, mixing the erythrosine derivative and the amino organic bromide, and performing a substitution reaction to obtain amino-modified erythrosine;

[0061] S20, mixing the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III, and performing copolymerization reaction to obtain a branched polymer having a carboxylic acid group;

[0062] S30, mixing the amino-modified erythrosine derivative and the branched polymer having a carboxylic acid group, and performing an amide reaction to connect the amino-modified erythrosine with the polymer to obtain a curable antibacterial material.

[0063] like Figure 1 As shown, in the technical scheme of the present invention, the prepared polymer has the monomer shown in formula I as the main chain, the monomer shown in formula II and the monomer shown in formula III as the side chain, the monomer shown in formula II is grafted on the side chain, providing more carboxylic acid groups, and the amino group on the amino-modified erythrosine is combined with the carboxylic acid of the monomer shown in formula II in the polymer through an amide bond to obtain a curable antibacterial material. The above preparation method can quickly obtain a curable antibacterial material with relatively stable performance, and the curable antibacterial material has all the above-mentioned beneficial effects, which will not be repeated here one by one.

[0064] In some embodiments of the present invention, the erythrosine derivative includes erythrosine B sodium salt or tetraiodofluorescein sodium salt; the amino organic bromide includes 3-bromopropylamine hydrobromide, p-bromoaniline, 3-bromoaniline or 2-amino-5-bromoindan hydrobromide; the monomer shown in formula I includes trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate or tris(2-hydroxyethyl)isocyanuric acid triacrylate; the monomer shown in formula II includes acrylic acid, methacrylic acid, hexanedioic acid or maleic acid; the monomer shown in formula III includes polyethylene glycol methacrylate or polyethylene glycol acrylate. Selecting the above compounds can obtain a curable antibacterial material with good antibacterial properties, stability and environmental adaptability.

[0065] In some embodiments of the present invention, in step S20, the molar ratio of the monomer represented by formula I, the monomer represented by formula II and the third monomer is (3-5):1:(4-5). The molar ratio of the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III can be 3:1:5, 4:1:4, 3:1:4 or 5:1:4, preferably 3:1:4. The molar ratio within a suitable range can ensure that the formed polymer still has unsaturated carbon-carbon double bonds, which are provided by the monomer represented by formula I. Under light conditions, the presence of carbon-carbon double bonds can cause the polymers to cross-link and solidify.

[0066] In some embodiments of the present invention, the molar ratio of erythrosine in the erythrosine derivative to the carboxylic acid group in the copolymer is 1:(1-2). The molar ratio of erythrosine in the erythrosine derivative to the carboxylic acid group in the copolymer can be 1:1, 1:1.5 or 1:2. The molar ratio within a suitable range can ensure that more amino-modified erythrosine is connected to the curable antibacterial material to form a sufficient number of amide bonds, which not only enhances the fixation of the antibacterial agent, but also ensures the antibacterial performance of the material.

[0067] The present invention provides an antibacterial ink, which includes a solvent, a photoinitiator, and the aforementioned curable antibacterial material or a curable antibacterial material prepared by the aforementioned method for preparing the curable antibacterial material. The antibacterial ink includes the curable antibacterial material, and thus has all the beneficial effects of the aforementioned curable antibacterial material, which will not be described one by one here.

[0068] The antibacterial ink has the characteristics of good acid and alkali resistance, high adhesion, strong antibacterial property and good resistance to bacterial adhesion.

[0069] In some embodiments of the present invention, the mass ratio of the curable antibacterial material, the solvent and the photoinitiator is (35-45): (50-60): (3-6). The photoinitiator stimulates a polymerization reaction between the curable antibacterial material under ultraviolet or visible light irradiation to solidify the material; the solvent is used to dissolve the antibacterial material and the photoinitiator to make them into a sprayable or printable liquid. The mass ratio of the curable antibacterial material, the solvent and the photoinitiator can be 35:60:6, 40:55:4 or 45:50:3. The mass ratio within a suitable range can ensure that the antibacterial ink is easy to handle before curing, has good mechanical strength and lasting antibacterial effect after curing, and ensures that the entire curing process is efficient and controllable.

[0070] In some embodiments of the present invention, the solvent includes tetrahydrofuran, 2-methyltetrahydrofuran or diethoxymethane; the photoinitiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide or bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. The above solvent and photoinitiator are selected to ensure that the antibacterial ink has good fluidity and stability during preparation, and can quickly form a more stable and harder coating during curing.

[0071] In some embodiments of the present invention, the viscosity of the antibacterial ink is 9-10.5 mPa·s at 50° C. The viscosity within the above range can ensure that the antibacterial ink has good rheological properties, so as to facilitate the application of inkjet printing technology.

[0072] In some embodiments of the present invention, the surface tension of the antibacterial ink is 34-36 mN / m. The surface tension within a suitable range can ensure that the antibacterial ink has good droplet formation, print head compatibility, printing quality and storage stability during inkjet printing, thereby achieving a more efficient and high-quality printing effect.

[0073] The present invention also provides an application, wherein an antibacterial coating is prepared by using the antibacterial ink as described above, comprising the following steps:

[0074] A curable antibacterial material is obtained, and the curable antibacterial material is mixed with a solvent and a photoinitiator, and light-cured to obtain an antibacterial coating.

[0075] In the technical solution of the present invention, the curable antibacterial material has unsaturated carbon-carbon double bonds. Under light conditions, the photoinitiator will excite the curable antibacterial material to cross-link and cure through the carbon-carbon double bonds.

[0076] In some embodiments of the present invention, the step of obtaining a curable antibacterial material, mixing the curable antibacterial material with a solvent and a photoinitiator, and photocuring to obtain an antibacterial coating includes: obtaining a curable antibacterial material, mixing the curable antibacterial material with a solvent and a photoinitiator, and performing inkjet printing and photocuring to obtain an antibacterial coating.

[0077] As an advanced manufacturing technology, inkjet printing technology has the advantages of high precision, high efficiency and low cost. Applying inkjet printing technology to the preparation of antibacterial coatings can achieve uniform spraying and precise control of antibacterial coatings, thereby improving the antibacterial effect and durability of antibacterial coatings.

[0078] The coating prepared by inkjet printing has low surface energy and high ink layer bonding strength, which is suitable for the public health field, especially for public trash cans. The excellent antibacterial adhesion performance of the antibacterial coating can prevent bacteria, mold, etc. from adhering to the surface and forming plaque, making public trash cans less likely to get dirty, which is helpful to improve the appearance of the city.

[0079] In some embodiments of the present invention, the nozzle temperature of the inkjet printing is 50-55° C. The nozzle temperature of the inkjet printing can be 50° C., 3° ​​C. or 55° C. The nozzle temperature within a suitable range can ensure good stability of the antibacterial ink during jetting and good consistency of printing quality.

[0080] In some embodiments of the present invention, the light curing includes ultraviolet light curing, and the power of the ultraviolet light curing is 400-500 W. The power of the ultraviolet light curing can be 400 W, 450 W or 500 W, preferably 450 W. The power within a suitable range can ensure that the antibacterial ink can be cured more quickly and more fully, while avoiding material damage or performance degradation caused by excessive power.

[0081] In some embodiments of the present invention, the light curing includes ultraviolet light curing, and the ultraviolet light curing time is 10 to 15 seconds. The ultraviolet light curing time can be 10 seconds, 13 seconds or 15 seconds. The ultraviolet light curing time within a suitable range can ensure the formation of a relatively stable, tough and durable antibacterial coating.

[0082] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments and drawings. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0083] Example 1

[0084] A method for preparing a curable antibacterial material comprises the following steps:

[0085] (1) Preparation of amino-modified erythrosine: Under N2 protection, erythrosine B sodium salt (1 mmol), dimethylformamide (DMF) (5 mL) and 3-bromopropylamine hydrobromide (1.5 mmol) were added to a round-bottom flask. The device was placed in an 80°C water bath and kept away from light. The reaction was stirred for 7 hours. After the reaction stopped, a mixed solution containing ER and ER-NH2 was obtained. It was then added to a mixed solution of ether and deionized water and precipitated at 5°C. ER-NH2 was obtained after filtration, washing and vacuum drying.

[0086] (2) Preparation of polymer: The polymer is prepared by polymerization initiated by azobisisobutyronitrile. 200 mg of acrylic acid (AA), 600 mg of trimethylolpropane triacrylate (TMPTA), 800 mg of polyethylene glycol methacrylate (PEG), and 20 mg of thermal initiator azobisisobutyronitrile were dissolved in anhydrous ethanol and added to a 50 mL eggplant-shaped bottle. Under the protection of N2, the mixture was slowly heated to 60°C, stirred and refluxed for 12 hours, and the reaction was terminated. After the reaction system was cooled, part of the solvent was removed by rotary evaporation. Subsequently, a large amount of n-hexane was added to the system to obtain a white precipitate. The precipitate was collected and vacuum dried overnight to obtain a polymer. The average molecular weight of the polymer is 1100.

[0087] (3) Preparation of curable antibacterial material: ER-NH2 was grafted onto the polymer backbone by amide reaction. 1.5 g of polymer was added to 40 mL of dimethyl sulfoxide and stirred vigorously until completely dissolved. Then, under an atmosphere of N2, 0.1 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and 0.2 mmol of N-hydroxysuccinimide (NHS) were added to the system, and the pH value of the reaction solution was adjusted to 5.5 with 2M hydrochloric acid solution and 2M sodium hydroxide solution, and the reaction was stirred for 1 hour. Finally, 1 g of ER-NH2 was added, and the pH value of the reaction solution was adjusted to 7.5. After reacting for 12 hours, the pH was adjusted to around 7.0 to terminate the reaction. Finally, dimethyl sulfoxide was removed by dialyzing with a dialysis membrane. After the dialysis was completed, the mixed solution was centrifuged to collect the precipitate, and the impurities were washed with deionized water several times. The precipitate was dissolved with a small amount of dichloromethane, and the insoluble impurities were removed after high-speed centrifugation. The solution was rotary evaporated to remove the solvent to obtain a curable antibacterial material.

[0088] Example 2

[0089] A curable antibacterial material is obtained by the preparation method of Example 1. The grafting rate of erythrosine in the curable antibacterial material is 8.67%.

[0090] Example 3

[0091] An antibacterial ink comprises 35 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0092] Example 4

[0093] An antibacterial ink comprises 37 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0094] Example 5

[0095] An antibacterial ink comprises 39 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0096] Example 6

[0097] An antibacterial ink comprises 41 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0098] Example 7

[0099] An antibacterial ink comprises 43 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0100] Example 8

[0101] An antibacterial ink comprises 45 parts of the curable antibacterial material described in Example 2, 53 parts of tetrahydrofuran solvent, and 4 parts of TPO photoinitiator.

[0102] Comparative Example 1

[0103] An antibacterial ink comprises 53 parts of tetrahydrofuran solvent and 4 parts of TPO photoinitiator.

[0104] Performance Testing

[0105] The curable antibacterial material prepared in Example 1 was subjected to X-ray photoelectron spectroscopy (XPS) analysis, and the results were as follows: Figure 2 shown.

[0106] Depend on Figure 2 It can be seen that, since ER contains iodine, its content is tested by XPS, and the grafting rate of erythrosine in the curable antibacterial material is 8.67%.

[0107] The viscosity and surface tension of the antibacterial inks of Examples 3 to 8 were tested. The viscosity at 50° C. was measured by a rheometer, and the surface tension was measured by a surface tension meter. The results are shown in Table 1.

[0108] Table 1 Viscosity and surface tension of the antibacterial ink of Examples 3 to 8

[0109]

[0110]

[0111] The antibacterial inks of Examples 3 to 8 and Comparative Example 1 were coated on a culture dish by inkjet printing (the nozzle temperature was set at 50° C.), and cured under a 450W ultraviolet lamp. The antibacterial properties, acid and alkali resistance, adhesion, and anti-bacterial adhesion were tested. The results are shown in Tables 2 and 3.

[0112] Antibacterial test: Place the sterilized coated culture dishes and bare culture dishes in a 24-well cell culture plate, and add 1 mL of bacterial solution (Escherichia coli, Staphylococcus aureus) to each well. First, place the plate in a 37°C incubator and incubate it in the dark for 1 hour. Then place it under a xenon light source, take 100 μL of bacterial solution when irradiated with visible light for 30 minutes and 60 minutes, and evenly apply it on the solid culture medium. Finally, invert and culture in a 37°C bacterial incubator for 24 hours before counting the colonies.

[0113] Antifouling performance (anti-bacterial adhesion) test: take 1×10 7 CFU / mL of Escherichia coli and Staphylococcus aureus were used. 30μL of bacterial solution was placed on an untreated glass plate and a coated glass plate, covered with a polyethylene film, and cultured at 37°C for 4h. After gently washing with phosphate buffered saline (PBS), the sample was transferred to a 2mL PBS buffer sterilized tube, and after ultrasonication for 2min, 50μL of liquid was applied to the plate. After culture at 37°C for 12h, the anti-bacterial adhesion ability of the coating was observed. The antifouling performance of the coating was tested after 30min and 60min of visible light irradiation.

[0114] Adhesion test: Test according to the method described in the national standard GB / T 9286-1998 "Scratch test for paint and varnish". Test the adhesion performance of the coating after irradiation with visible light for 30 minutes and 60 minutes.

[0115] Acid and alkali resistance test: (1) Acid resistance: Immerse the culture dish in a 10% sulfuric acid solution for 30 minutes, take it out, rinse it with clean water and dry it, stick the coating with 3M tape, tear it off quickly, and observe the shedding of the coating. (2) Alkali resistance: Immerse the culture dish in a 10% sodium hydroxide solution for 30 minutes, take it out, rinse it with clean water and dry it, stick the coating with 3M tape, tear it off quickly, and observe the shedding of the coating. The acid and alkali resistance of the coating was tested after it was exposed to visible light for 30 minutes and 60 minutes.

[0116] Table 2 Performance results of the antibacterial coatings of Examples 3 to 8 and Comparative Example 1 after irradiation with visible light for 30 min

[0117]

[0118]

[0119] Table 3 Performance results of the antibacterial coatings of Examples 3 to 8 and Comparative Example 1 after 60 min of visible light irradiation

[0120]

[0121]

[0122] It can be seen from Tables 2 and 3 that each embodiment has excellent antibacterial performance, acid and alkali resistance, adhesion and anti-bacterial adhesion performance, and the antibacterial rate of the coating against Escherichia coli and Staphylococcus aureus is still maintained above 99.3% after being placed for one month, which shows that the stability of the coating provides excellent long-term antibacterial performance.

[0123] In summary, the ink containing curable antibacterial material provided by the present invention has the characteristics of rapid reaction and simple operation, that is, after casting the mixed solution on the substrate, the double bond reaction is triggered by ultraviolet light to achieve in-situ synthesis of the coating. The coating is applied to public trash cans, and due to sufficient outdoor light, the photocatalytic antibacterial performance of the coating can be well exerted.

[0124] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A curable antibacterial material, characterized in that: The invention comprises a polymer and an amino-modified erythrosine connected to the polymer, wherein the polymer comprises a structural unit derived from a monomer represented by formula I, a structural unit derived from a monomer represented by formula II, and a structural unit derived from a monomer represented by formula III; Among them, the average value of n is 10; The polymer includes unsaturated carbon-carbon double bonds.

2. The curable antibacterial material according to claim 1, characterized in that: The amino-modified erythrosine and the structural unit derived from the monomer represented by formula II in the polymer are connected via an amide bond; The mass percentage of amino-modified erythrosine in the curable antibacterial material is 8-9%; The average molecular weight of the polymer is 1100; The structure of the amino-modified erythrosine is shown in Formula IV:

3. A method for preparing a curable antibacterial material according to any one of claims 1 to 2, characterized in that: The following steps are involved: S10, mixing the erythrosine derivative and the amino organic bromide, and performing a substitution reaction to obtain amino-modified erythrosine; S20, mixing the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III, and performing copolymerization reaction to obtain a branched polymer having a carboxylic acid group; S30, mixing the amino-modified erythrosine derivative and the branched polymer having a carboxylic acid group, and performing an amide reaction to connect the amino-modified erythrosine with the polymer to obtain a curable antibacterial material.

4. The method for preparing a curable antibacterial material according to claim 3, characterized in that: The erythrosine derivatives include erythrosine B sodium salt or tetraiodofluorescein sodium salt; The amino organic bromide includes 3-bromopropylamine hydrobromide, p-bromoaniline, 3-bromoaniline or 2-amino-5-bromoindan hydrobromide; The monomer represented by formula I includes trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate or tris(2-hydroxyethyl)isocyanuric acid triacrylate; The monomer represented by formula II includes acrylic acid, methacrylic acid, hexadienedioic acid or maleic acid; The monomer represented by formula III includes polyethylene glycol methacrylate or polyethylene glycol acrylate; In step S20, the molar ratio of the monomer represented by formula I, the monomer represented by formula II and the monomer represented by formula III is (3-5):1:(4-5); The molar ratio of erythrosine in the erythrosine derivative to the carboxylic acid group in the copolymer is 1:(1-2). 5.An antibacterial ink, characterized in that: The antibacterial ink comprises a solvent, a photoinitiator and the curable antibacterial material according to any one of claims 1 to 2 or the curable antibacterial material prepared by the method for preparing the curable antibacterial material according to any one of claims 3 to 4.

6. The antibacterial ink according to claim 5, characterized in that: The mass ratio of the curable antibacterial material, the solvent and the photoinitiator is (35-45): (50-60): (3-6).

7. The antibacterial ink according to claim 5, characterized in that: The solvent includes tetrahydrofuran, 2-methyltetrahydrofuran or diethoxymethane; The photoinitiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; The viscosity of the antibacterial ink at 50° C. is 9 to 10.5 mPa·s; The surface tension of the antibacterial ink is 34-36 mN / m.

8. An application, characterized in that, The antibacterial coating is prepared by the antibacterial ink according to any one of claims 5 to 7, comprising the following steps: A curable antibacterial material is obtained, and the curable antibacterial material is mixed with a solvent and a photoinitiator, and light-cured to obtain an antibacterial coating.

9. The use according to claim 8, characterized in that The steps of obtaining a curable antibacterial material, mixing the curable antibacterial material with a solvent and a photoinitiator, and photocuring the material to obtain an antibacterial coating include: A curable antibacterial material is obtained, the curable antibacterial material is mixed with a solvent and a photoinitiator, and the antibacterial coating is obtained by inkjet printing and photocuring.

10. The use according to claim 9, characterized in that The nozzle temperature of the inkjet printing is 50-55°C; The light curing includes ultraviolet light curing, and the power of the ultraviolet light curing is 400-500W; The light curing includes ultraviolet light curing, and the time of the ultraviolet light curing is 10 to 15 seconds.

Images