Antibacterial mildew-proof material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of antibiosis and mildew prevention, and particularly relates to an antibiosis and mildew prevention material and a preparation method and application thereof. The antibacterial and mildew-proof material comprises the following components in percentage by mass: 0.01%-1% of a mildew-proof agent, 0.1%-5% of sustained-release micelles, 0.03%-1.5% of a cross-linking agent, 10%-20% of acrylic acid slurry and 75%-85% of water, wherein the mildewproof agent is iodopropynyl n-butylamine formic ester; the mixed monomer of the sustained-release micelle is an acrylate compound and quaternary ammonium salt; and the cross-linking agent is polyhydroxy melamine. According to the antibacterial and mildew-proof material and the preparation method thereof, the problem that the antibacterial and mildew-proof performance of a filter element fabric is obviously reduced in the using process is solved, and the filter element fabric has lasting and efficient antibacterial and mildew-proof performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial and mildew proofing, and in particular relates to an antibacterial and mildew proofing material and a preparation method and application thereof. Background Art

[0002] Air conditioners, air purifiers, humidifiers, and other devices provide optimal temperature and humidity, creating a comfortable environment. The internal components of these appliances all involve the use of filter elements. Filter elements are made of fabric, rich in cellulose, and have a porous structure that absorbs various substances from the air. However, during use, these elements can easily breed microorganisms such as bacteria and mold, affecting their performance and even endangering human health. For example, humidifiers can relieve dryness and increase air humidity. However, they require long-term water storage. Water in a closed environment is prone to breeding microorganisms such as bacteria and mold. The filter element fabric provides favorable conditions for the proliferation of bacteria and mold. During humidification operation, these microorganisms can spread and cause cross-infection, affecting human health. Therefore, antibacterial and antifungal finishing of filter element fabrics is necessary to address these issues, and antibacterial and antifungal fabric materials have garnered extensive attention and research.

[0003] Traditional inorganic antibacterial and mildew-proofing materials commonly used in textiles have weak binding forces with fabrics, poor durability of their antibacterial and mildew-proofing properties, and contain heavy metal ions, posing certain environmental pollution hazards. Organic antibacterial and mildew-proofing materials have a stronger affinity for textile fibers and can improve the long-term effectiveness of fabric antibacterial and mildew-proofing properties. Iodopropynyl n-butylamine formate is a new, environmentally friendly bactericidal and mildew-proofing agent with broad-spectrum antimicrobial activity and strong inhibitory and killing effects on bacteria, molds, and yeasts. It is low in toxicity and relatively mild, but its water solubility is poor, resulting in poor durability of fabric antibacterial and mildew-proofing properties. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide an antibacterial and mildew-proof material and its preparation method and application, so as to solve the problem that the antibacterial and mildew-proof performance of filter element fabric is significantly reduced during use, so that the filter element fabric has long-lasting and efficient antibacterial and mildew-proof performance.

[0005] The present invention provides an antibacterial and mildew-proof material, which comprises the following components in percentage by mass:

[0006] Antifungal agent: 0.01% to 1%, sustained-release micelles: 0.1% to 5%, cross-linking agent: 0.03% to 1.5%, acrylic acid slurry: 10% to 20%, water: 75% to 85%;

[0007] The mildew inhibitor is iodopropynyl n-butylamine formate; the mixed monomers of the sustained-release micelles are acrylic acid ester compounds and quaternary ammonium salts; and the cross-linking agent is polyhydroxy melamine.

[0008] Iodopropynyl n-butylcarbamate is a new, environmentally friendly bactericidal and mildew-proof agent. Its mechanism of action is through the interaction of iodine on the molecule with the sulfhydryl or hydroxyl groups in the active enzyme sites of microbial cells, causing the enzyme to lose activity and leading to the death of the microorganisms. However, its poor water solubility results in weak binding between the two when used in fabric finishing, resulting in poor durability of the fabric's antibacterial and mildew-proof properties.

[0009] Therefore, by adding polymethylol melamine and acrylic sizing agent, the present invention improves the bonding strength between the antibacterial and mildew-proof material and the fabric, providing long-lasting and effective antibacterial and mildew-proof properties. Acrylic sizing agent has a large number of polar groups or charged groups. When interacting with fiber molecules, in addition to van der Waals forces, there are also hydrogen bonding forces, resulting in strong adhesion.

[0010] The presence of active groups such as hydroxyl and carboxyl groups in polymethylol melamine and acrylic acid slurries can form strong hydrogen bonds with active groups such as hydroxyl or amino groups on fabric fibers, and can also undergo dehydration condensation reactions to form covalent bonds, which helps the mildew inhibitor to firmly bind to the fabric surface, thereby providing long-lasting and efficient antibacterial and mildew-proof properties.

[0011] In some embodiments, the structural formula of the quaternary ammonium salt is:

[0012]

[0013] Wherein, X is fluorine, chlorine, bromine or iodine; R is H, C 1-6 Straight chain alkyl or C 1-6 Branched chain alkyl.

[0014] Furthermore, the quaternary ammonium salt is acryloyloxyethyltrimethylammonium chloride or methacryloyloxyethyltrimethylammonium chloride.

[0015] In some embodiments, the acrylic ester compound is methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate; the polyhydroxy melamine is trimethylol melamine or hexamethylol melamine; the component monomer of the acrylic syrup is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

[0016] A method for preparing an antibacterial and mildew-proof material comprises the following steps:

[0017] Step 1: polymerizing an acrylate compound with a quaternary ammonium salt to obtain a sustained-release micelle solution;

[0018] Step 2: dispersing the iodopropynyl n-butylamine formate mildew inhibitor and polyhydroxy melamine in the sustained-release micelle solution to form a stable mildew inhibitor emulsion;

[0019] Step three: mixing the mildew-proof agent emulsion with the acrylic slurry to obtain the filter element fabric antibacterial and mildew-proof material.

[0020] The invention disperses iodopropynyl n-butylcarbamate mildew preventer in a slow-release micelle solution to obtain a mildew preventer emulsion. The positively charged groups in the quaternary ammonium salt molecules have good surface activity, thereby improving the water solubility of the mildew preventer. Meanwhile, the quaternary ammonium salt in the micelles can play an antibacterial role.

[0021] Furthermore, the step 1 is: dissolving the acrylic acid ester compound in a mixed solution of isopropyl alcohol and water, adding the quaternary ammonium salt, heating and stirring, and then adding ammonium persulfate to react to obtain the sustained-release micelle solution.

[0022] In some embodiments, the molar ratio of the acrylic acid ester compound to the quaternary ammonium salt is 1:1-5; the volume ratio of isopropyl alcohol to water is 1:1-10; the amount of ammonium persulfate used is 0.1%-1.5% by mass of the mixed monomers; the reaction temperature ranges from 60° C. to 90° C., and the reaction time is 1-8 hours.

[0023] Furthermore, the step 2 is: diluting the sustained-release micelle solution obtained in the step 1, adding the iodopropynyl n-butylamine formate mildew inhibitor and the polymethylol melamine under stirring conditions, and dispersing them at room temperature to obtain a mildew inhibitor emulsion; wherein the stirring rate is 500 to 2000 rpm, and the stirring time is 6 to 24 hours.

[0024] In some embodiments, in step 2, the mass concentration of the sustained-release micelle solution is 10% to 30%; the mass concentration of iodine propargyl n-butylamine formate is 1% to 20%; and the mass concentration of polymethylol melamine is 3% to 15%.

[0025] Furthermore, the step three is: adding the mildew-proof agent emulsion in the step two to the acrylic slurry, stirring, and reacting at room temperature to obtain the filter element fabric antibacterial and mildew-proof material; wherein the stirring rate is 300 to 1000 rpm, and the stirring time is 2 to 12 hours.

[0026] In some embodiments, the mass concentration of the acrylic slurry is 10% to 20%; the mass concentration of the antifungal active ingredient in the antifungal emulsion is 0.01% to 1%.

[0027] The invention discloses an application of an antibacterial and mildew-proof material, including application of the antibacterial and mildew-proof material in antibacterial and mildew-proofing of fabrics.

[0028] Furthermore, the fabric is a filter element material.

[0029] Beneficial effects:

[0030] The present invention provides an antibacterial and mildew-proof material, a preparation method, and an application thereof. By adding polymethylol melamine and acrylic acid slurry, the bonding strength between the antibacterial and mildew-proof material and fabric is enhanced, providing long-lasting and efficient antibacterial and mildew-proof properties. The polymethylol melamine and acrylic acid slurry can form strong hydrogen bonds with active groups such as hydroxyl groups or amino groups on fabric fibers, helping the mildew inhibitor to firmly bind to the fabric surface, thereby providing long-lasting and efficient antibacterial and mildew-proof properties. Fabrics treated with the antibacterial and mildew-proof material of the present invention have an antibacterial rate of over 99% against Staphylococcus aureus and Escherichia coli, and a mildew-proof grade of 0 against molds (Aspergillus niger, Aspergillus terreus, Chaetomium globosum, Paecilomyces variotii, and Penicillium funiculosum). After the fabrics are processed into humidification filter elements and operated on a machine for 14 days, the antibacterial rate reaches 92%, and the mildew-proof grade reaches 1. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings required for use in the embodiments. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0032] Figure 1 This is the anti-mildew effect of the anti-mildew material of Example 1 applied to fabric;

[0033] Figure 2 This is the anti-mildew effect of the anti-mildew material of Example 2 applied to fabric;

[0034] Figure 3 This is the anti-mildew effect of the anti-mildew material of Example 3 applied to fabric;

[0035] Figure 4 This is the anti-mildew effect of the anti-mildew material of Comparative Example 1 after being applied to fabric;

[0036] Figure 5 This is the anti-mildew effect of the anti-mildew material of Comparative Example 2 after being applied to the fabric;

[0037] Figure 6 This is the anti-mildew effect of the anti-mildew material of Comparative Example 3 after being applied to the fabric;

[0038] Figure 7 This is the anti-mildew effect on fabric after 14 days of long-term testing in Example 1;

[0039] Figure 8 This is the anti-mildew effect on fabric after 14 days of the long-term test of Example 2;

[0040] Figure 9 This is the anti-mildew effect on fabric after 14 days of long-term testing in Example 3. DETAILED DESCRIPTION

[0041] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0042] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0043] Herein, all features such as values, amounts, amounts, and concentrations defined in numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0044] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0045] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0046] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and ratios are expressed by weight.

[0047] The following is a further description of an antibacterial and mildew-proof material provided by the present application, and its preparation method and application in conjunction with specific embodiments.

[0048] Example 1

[0049] (1) Dissolve 1 g of methyl methacrylate and 1.9 g of acryloyloxyethyltrimethylammonium chloride in a mixture of 4 mL of water and 4 mL of isopropanol. Stir and heat to 80°C. Add 15 mg of ammonium persulfate and react for 4 h. After the reaction is complete, cool to room temperature to obtain a sustained-release micelle solution.

[0050] (2) The above-obtained sustained-release micelle solution was diluted with 9 mL of water, and 2 g of iodopropynyl n-butylamine formate mildew inhibitor and 1.5 g of hexahydroxymethylmelamine were added under stirring at 800 rpm, and stirred at room temperature for 12 h to obtain a mildew inhibitor emulsion.

[0051] (3) The acrylic acid slurry was prepared into 50 mL of a 10% aqueous solution, 3 g of the antifungal agent emulsion was added, and the mixture was stirred at a rate of 500 rpm and reacted at room temperature for 6 h to obtain an antibacterial and antifungal material for a filter element fabric.

[0052] Example 2

[0053] (1) Dissolve 1 g of methyl methacrylate and 2 g of methacryloyloxyethyltrimethylammonium chloride in a mixture of 5 mL of water and 3 mL of isopropanol. Stir and heat to 60°C. Add 30 mg of ammonium persulfate and react for 1 h. After the reaction is complete, cool to room temperature to obtain a sustained-release micelle solution.

[0054] (2) The above-obtained sustained-release micelle solution was diluted with 9 mL of water, and 1 g of iodopropynyl n-butylamine formate mildew inhibitor and 2 g of trimethylolmelamine were added under stirring at 500 rpm, and stirred at room temperature for 6 h to obtain a mildew inhibitor emulsion.

[0055] (3) The acrylic acid slurry was prepared into 50 mL of an aqueous solution with a concentration of 15%, 3 g of an antifungal agent emulsion was added, and the mixture was reacted at room temperature for 2 h at a stirring rate of 300 rpm to obtain an antibacterial and antifungal material for a filter element fabric.

[0056] Example 3

[0057] (1) Dissolve 1 g of methyl methacrylate and 2.8 g of acryloyloxyethyltrimethylammonium chloride in a mixture of 4 mL of water and 4 mL of isopropanol. Stir and heat to 90°C. Add 20 mg of ammonium persulfate and react for 8 h. After the reaction is complete, cool to room temperature to obtain a sustained-release micelle solution.

[0058] (2) The above-obtained sustained-release micelle solution was diluted with 9 mL of water, and 0.4 g of iodopropynyl n-butylamine formate mildew inhibitor and 1 g of hexahydroxymethylmelamine were added under stirring at 2000 rpm, and stirred at room temperature for 24 h to obtain a mildew inhibitor emulsion.

[0059] (3) The acrylic acid slurry was prepared into 50 mL of a 20% aqueous solution, 3 g of the antifungal agent emulsion was added, and the mixture was reacted at room temperature for 12 h at a stirring rate of 1000 rpm to obtain an antibacterial and antifungal material for a filter element fabric.

[0060] Comparative Example 1

[0061] (1) Dissolve 2 g of iodopropynyl n-butylamine formate mildew inhibitor and 1.5 g of hexahydroxymethyl melamine in a mixture of 4 mL of water and 4 mL of isopropyl alcohol, and stir at 800 rpm at room temperature for 12 h to obtain a mildew inhibitor emulsion.

[0062] (2) The acrylic acid slurry was prepared into 50 mL of a 10% aqueous solution, 3 g of the antifungal agent emulsion was added, and the mixture was stirred at a rate of 500 rpm and reacted at room temperature for 6 h to obtain an antibacterial and antifungal material for a filter element fabric.

[0063] Comparative Example 2

[0064] (1) 1.5 g of dodecylphenol polyoxyethylene ether was diluted with 9 mL of water, and 1 g of iodopropynyl n-butylamine formate mildew inhibitor and 2 g of polymethylol melamine were added under stirring at 1000 rpm. The mixture was stirred at room temperature for 12 h to obtain a mildew inhibitor emulsion.

[0065] (2) The acrylic acid slurry was prepared into 50 mL of an aqueous solution with a concentration of 15%, 3 g of an antifungal agent emulsion was added, and the mixture was reacted at room temperature for 8 h at a stirring rate of 300 rpm to obtain an antibacterial and antifungal material for a filter element fabric.

[0066] Comparative Example 3

[0067] (1) Dissolve 1 g of methyl methacrylate and 2.8 g of acryloyloxyethyltrimethylammonium chloride in a mixture of 4 mL of water and 4 mL of isopropyl alcohol. Stir and heat to 85°C. Add 20 mg of ammonium persulfate and react for 2 h. After the reaction is complete, cool to room temperature to obtain a sustained-release micelle solution.

[0068] (2) The above-obtained sustained-release micelle solution was diluted with 9 mL of water, and 0.4 g of iodopropynyl n-butylamine formate antifungal agent was added under stirring at 500 rpm. The mixture was stirred at room temperature for 18 h to obtain an antifungal agent emulsion.

[0069] (3) The acrylic acid slurry was prepared into 50 mL of a 10% aqueous solution, 3 g of the antifungal agent emulsion was added, and the mixture was stirred at a rate of 500 rpm and reacted at room temperature for 4 h to obtain an antibacterial and antifungal material for a filter element fabric.

[0070] Performance Testing

[0071] 1. Antibacterial performance testing

[0072] The antibacterial and mildew-proof materials prepared in the above examples and comparative examples were applied to fabric finishing. The antibacterial properties of the finished fabrics were tested according to Appendix B of GB21551.2-2010. The results are as follows: Figures 1 to 6As shown in Table 1, the antibacterial rates of the fabrics finished in the examples against Staphylococcus aureus and Escherichia coli were both above 99%, while the antibacterial rates of the fabrics finished in the comparative examples against Staphylococcus aureus and Escherichia coli were both below 90%. Antifungal performance testing was conducted in accordance with Appendix C of GB 21551.2-2010. The results showed that the fabrics finished in the examples achieved an antifungal rating of Grade 1 or higher against mold fungi (Aspergillus niger, Aspergillus terreus, Chaetomium globosum, Paecilomyces variotii, and Penicillium funiculosum), while the fabrics finished in the comparative examples achieved an antifungal rating of Grade 4 against mold fungi (Aspergillus niger, Aspergillus terreus, Chaetomium globosum, Paecilomyces variotii, and Penicillium funiculosum).

[0073] Table 1 Antibacterial and anti-mildew properties of materials

[0074] Material Type Antibacterial rate - Escherichia coli Mildew resistance level Example 1 ＞99％ Level 0 Example 2 ＞99％ Level 0 Example 3 ＞99％ Level 0 Comparative Example 1 75％ Level 4 Comparative Example 2 83％ Level 4 Comparative Example 3 88％ Level 4

[0075] 2. Long-term effectiveness test

[0076] After the above-mentioned example materials were applied to fabric and processed into humidification filter elements, they were put into operation on the machine for 14 days, and then the antibacterial and anti-mildew properties of the materials were tested according to Appendix B and Appendix C of GB 21551.2-2010. The results are as follows: Figures 7-9 As shown in Table 2, the humidification filter element made of the fabric containing the antibacterial and mildew-proof material of the present invention maintained excellent antibacterial and mildew-proof properties even after 14 days of use, with an antibacterial rate of 92% and a mildew-proof rating of Class 1. However, due to unsatisfactory initial antibacterial and mildew-proof effects, long-term efficacy testing was not performed on Comparative Examples 1-3.

[0077] Table 2 Antibacterial and anti-mildew performance of materials after 14 days of use

[0078] Material Type Antibacterial rate - Escherichia coli Mildew resistance level Example 1 93％ Level 1 Example 2 95％ Level 1 Example 3 92％ Level 1

[0079] Although the present invention has been disclosed above in terms of preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. An antibacterial and mildew-proof material, characterized in that: The antibacterial and mildew-proof material includes the following components in percentage by mass: Antifungal agent: 0.01% to 1%, sustained-release micelles: 0.1% to 5%, cross-linking agent: 0.03% to 1.5%, acrylic acid slurry: 10% to 20%, water: 75% to 85%; The mildew inhibitor is iodopropynyl n-butylamine formate; the mixed monomers of the sustained-release micelles are acrylic acid ester compounds and quaternary ammonium salts; and the cross-linking agent is polyhydroxy melamine.

2. The antibacterial and mildew-proof material according to claim 1, characterized in that: The structural formula of the quaternary ammonium salt is: Wherein, X is fluorine, chlorine, bromine or iodine; R is H, C 1-6 Straight chain alkyl or C 1-6 Branched chain alkyl.

3. The antibacterial and mildew-proof material according to claim 2, characterized in that: The quaternary ammonium salt is acryloyloxyethyl trimethyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride.

4. The antibacterial and mildew-proof material according to claim 1, characterized in that: The acrylic acid ester compound is methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate; the polyhydroxy melamine is trimethylol melamine or hexamethylol melamine; the component monomer of the acrylic acid slurry is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

5. A method for preparing the antibacterial and mildew-proof material according to claim 1, characterized in that: The steps include: Step 1: polymerizing an acrylate compound with a quaternary ammonium salt to obtain a sustained-release micelle solution; Step 2: dispersing the iodopropynyl n-butylamine formate mildew inhibitor and polyhydroxy melamine in the sustained-release micelle solution to form a stable mildew inhibitor emulsion; Step three: mixing the mildew-proof agent emulsion with the acrylic slurry to obtain the filter element fabric antibacterial and mildew-proof material.

6. The method for preparing the antibacterial and mildew-proof material according to claim 5, characterized in that: The step 1 is: dissolving the acrylic acid ester compound in a mixed solution of isopropyl alcohol and water, adding the quaternary ammonium salt, heating and stirring, and then adding ammonium persulfate to react to obtain the slow-release micelle solution.

7. The method for preparing the antibacterial and mildew-proof material according to claim 6, characterized in that: The molar ratio of the acrylic acid ester compound to the quaternary ammonium salt is 1:1-5; the volume ratio of the isopropyl alcohol to water is 1:1-10; the amount of the ammonium persulfate is 0.1%-1.5% of the mass of the mixed monomers; the reaction temperature range is 60-90°C, and the reaction time is 1-8 hours.

8. The method for preparing the antibacterial and mildew-proof material according to claim 5, characterized in that: In the step 2, the mass concentration of the sustained-release micelle solution is 10% to 30%; the mass concentration of iodine propargyl n-butylamine formate is 1% to 20%; and the mass concentration of polymethylol melamine is 3% to 15%.

9. The method for preparing the antibacterial and mildew-proof material according to claim 5, characterized in that: In the step 3, the mass concentration of the acrylic acid slurry is 10% to 20%; the mass concentration of the antifungal active ingredient in the antifungal emulsion is 0.01% to 1%.

10. An application of the antibacterial and mildew proof material according to any one of claims 1 to 4, characterized in that: Including the application of antibacterial and mildew-proof materials in the antibacterial and mildew-proofing of fabrics.

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