Antibacterial paper coating film and method for preparing the same

Abstract

The present application provides an antibacterial paper coating and a preparation method thereof. The antibacterial paper coating is composed of the following raw materials in parts by weight: acrylic resin 60-70 parts, TiO2 sol 10-14 parts, silicon dioxide 4-8 parts, surfactant 2-6 parts, humectant 8-12 parts, leveling agent 1-3 parts, and deionized water 80-100 parts. The present application uses TiO2 sol and alkyl acid modified nano-TiO2 as antibacterial components of the ceramic coating, and the composite antibacterial effect is better than that of a single antibacterial component. At the same time, the composite antibacterial component can effectively reduce the dosage of silver agent, thereby meeting the safe use requirements of edible tipping paper. TiO2 sol is also used as an anti-curling component, thereby reducing the addition of other additives.

Description

Technical Field

[0001] This invention relates to the field of ceramic coatings, and more particularly to an antibacterial coated ceramic coating for paper and its preparation method. Background Technology

[0002] Nano silver utilizes nanotechnology to nanoscale silver, resulting in a significant leap in its bactericidal capabilities. Nano silver particles can be manufactured and controlled to around 25 nanometers in size, exhibiting strong inhibitory and bactericidal effects against dozens of pathogenic bacteria, including Escherichia coli, Neisseria gonorrhoeae, and Chlamydia trachomatis. It provides broad-spectrum bactericidal activity without any drug resistance, promotes wound healing, cell growth, and the repair of damaged cells, and has not shown any skin irritation. The application of non-liquid nano silver products is already widespread. However, nano silver should not be used in large quantities, as this can easily lead to the accumulation of heavy metals, which is detrimental to human health.

[0003] Nano TiO2 is an inorganic antibacterial agent that is non-toxic, odorless, non-irritating, has good thermal stability, is non-flammable, and is white in color. Furthermore, nano TiO2 possesses the following characteristics: (1) broad-spectrum, long-lasting, safe, and stable antibacterial activity; (2) rapid and strong bactericidal effect, suitable for long-term use and recyclable; (3) wash-resistant and wear-resistant; (4) harmless to humans, odorless, and light in color; (5) good thermal stability, remaining unchanged, non-decomposing, non-volatile, and non-deteriorating at high temperatures; and (6) inexpensive and readily available. Therefore, in recent years, nano TiO2 has been increasingly used as an antibacterial agent in various industries.

[0004] Based on the above, this invention proposes an antibacterial paper-coated ceramic coating and its preparation method, which can effectively solve the above problems. Summary of the Invention

[0005] The purpose of this invention is to provide an antibacterial paper-coated ceramic coating and its preparation method.

[0006] To achieve the above objectives, the present invention provides an antibacterial ceramic coating for paper, wherein the antibacterial ceramic coating for paper is composed of the following raw materials in parts by weight: 60-70 parts acrylic resin, 10-14 parts TiO2 sol, 4-8 parts silica, 2-6 parts surfactant, 8-12 parts humectant, 1-3 parts leveling agent, and 80-100 parts deionized water.

[0007] Preferably, the TiO2 sol is prepared by the following method: 50 mL of tetrabutyl titanate is added dropwise at a rate of 0.5 mL / s to anhydrous ethanol with a volume of 3 times that of tetrabutyl titanate. After the addition is completed, the mixture is stirred at 50-55°C for 25-30 min to obtain the sol.

[0008] Preferably, the antibacterial paper coating ceramic coating further includes 6 to 12 parts of alkyl acid modified nano-TiO2.

[0009] Preferably, the alkyl acid-modified nano-TiO2 is dodecyl salicylic acid-modified TiO2.

[0010] Preferably, the dodecyl salicylic acid modified TiO2 is prepared by the following method: 1 mL of titanium tetrachloride is added to a 1 mol / L hydrochloric acid solution with a volume of 50 times that of titanium tetrachloride, and stirred at room temperature for 5 min. Then, an ethanol solution of dodecyl salicylic acid with a volume of 5 times that of titanium tetrachloride is added. The ethanol solution of dodecyl salicylic acid is prepared by mixing dodecyl salicylic acid and anhydrous ethanol at a volume ratio of 1:4. The temperature is raised to 80 °C, and the reaction is refluxed for 24 h. After centrifugation, the mixture is washed 2-3 times with anhydrous ethanol and deionized water, and dried at 75-80 °C to constant weight to obtain the TiO2.

[0011] Preferably, the acrylic resin is a water-based acrylic resin, and in one embodiment, the acrylic resin is a styrene-acrylic resin.

[0012] Preferably, the surfactant is a Tween or Span surfactant. In one embodiment, the surfactant is Tween 80.

[0013] Preferably, the humectant comprises one or a combination of two or more of polyethylene glycol, glycerol, and dodecyl alcohol ester. In one embodiment, the humectant is polyethylene glycol.

[0014] Preferably, the leveling agent comprises one or a combination of two or more of polydimethylsiloxane, dimethyl silicone oil, and epoxy hydrocarbon-based polysiloxane. In one embodiment, the leveling agent is polydimethylsiloxane.

[0015] This invention also provides a method for preparing an antibacterial paper-coated ceramic coating, the method comprising the following steps:

[0016] Acrylic resin, silica, and surfactant are added to deionized water and stirred at 500-550 rpm for 50-60 minutes at 40-45°C. Then, TiO2 sol is added and stirred at 750-800 rpm for 60 minutes. Alkyl acid-modified nano-TiO2 is then added and stirring is continued for 110-120 minutes. Subsequently, humectant and leveling agent are added and stirring is continued for 50-60 minutes to obtain the final product.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. This invention utilizes TiO2 sol and alkyl acid-modified nano-TiO2 as antibacterial components in ceramic coatings, achieving a combined antibacterial effect superior to that of a single component. Simultaneously, the combined antibacterial components effectively reduce the dosage of silver additives, thus meeting the safety requirements for edible tipping paper. The TiO2 sol also functions as an anti-curling component, further reducing the need for other additives.

[0019] 2. The preparation method of the present invention is convenient to operate, easy to mass-produce, and has stable quality.

[0020] 3. The raw materials for this invention are abundant and reasonably priced in China, which means that there are no high cost restrictions on its large-scale production. Detailed Implementation

[0021] Example 1

[0022] Weigh the specific raw materials according to Table 1. The preparation steps are as follows:

[0023] (1) Add 50 mL of tetrabutyl titanate to anhydrous ethanol at a rate of 0.5 mL / s, which is 3 times the volume of tetrabutyl titanate. After the addition is complete, stir at 55°C for 25 min to obtain TiO2 sol.

[0024] (2) Add 1 mL of titanium tetrachloride to a 1 mol / L hydrochloric acid solution with a volume of 50 times that of titanium tetrachloride and a concentration of 1 mol / L. Stir at room temperature for 5 min. Then add an ethanol solution of dodecyl salicylic acid with a volume of 5 times that of titanium tetrachloride. The ethanol solution of dodecyl salicylic acid is prepared by mixing dodecyl salicylic acid and anhydrous ethanol at a volume ratio of 1:4. Heat to 80 °C and reflux for 24 h. After centrifugation, wash twice with anhydrous ethanol and deionized water, and dry at 80 °C to constant weight to obtain dodecyl salicylic acid modified TiO2.

[0025] (3) Add acrylic resin, silica, and surfactant to deionized water and stir at 550 r / min for 50 min at 40°C. Then add TiO2 sol and stir at 750 r / min for 60 min. Then add dodecyl salicylic acid modified TiO2 and continue stirring for 110 min. Then add humectant and leveling agent and continue stirring for 60 min to obtain the final product.

[0026] Example 2

[0027] (1) Add 50 mL of tetrabutyl titanate to anhydrous ethanol at a rate of 0.5 mL / s, which is 3 times the volume of tetrabutyl titanate. After the addition is complete, stir at 50°C for 30 min to obtain TiO2 sol.

[0028] (2) Add 1 mL of titanium tetrachloride to a 1 mol / L hydrochloric acid solution with a volume of 50 times that of titanium tetrachloride and a concentration of 1 mol / L. Stir at room temperature for 5 min. Then add an ethanol solution of dodecyl salicylic acid with a volume of 5 times that of titanium tetrachloride. The ethanol solution of dodecyl salicylic acid is prepared by mixing dodecyl salicylic acid and anhydrous ethanol at a volume ratio of 1:4. Heat to 80 °C and reflux for 24 h. After centrifugation, wash with anhydrous ethanol and deionized water three times in sequence. Dry at 75 °C to constant weight to obtain dodecyl salicylic acid modified TiO2.

[0029] (3) Add acrylic resin, silica, and surfactant to deionized water and stir at 500 r / min for 60 min at 45°C. Then add TiO2 sol and stir at 800 r / min for 60 min. Then add dodecyl salicylic acid modified TiO2 and continue stirring for 120 min. Then add humectant and leveling agent and continue stirring for 50 min to obtain the final product.

[0030] Example 3

[0031] (1) Add 50 mL of tetrabutyl titanate to anhydrous ethanol at a rate of 0.5 mL / s, which is 3 times the volume of tetrabutyl titanate. After the addition is complete, stir at 55°C for 30 min to obtain TiO2 sol.

[0032] (2) Add 1 mL of titanium tetrachloride to a 1 mol / L hydrochloric acid solution with a volume of 50 times that of titanium tetrachloride and a concentration of 1 mol / L. Stir at room temperature for 5 min. Then add an ethanol solution of dodecyl salicylic acid with a volume of 5 times that of titanium tetrachloride. The ethanol solution of dodecyl salicylic acid is prepared by mixing dodecyl salicylic acid and anhydrous ethanol at a volume ratio of 1:4. Heat to 80 °C and reflux for 24 h. After centrifugation, wash with anhydrous ethanol and deionized water three times in sequence. Dry at 80 °C to constant weight to obtain dodecyl salicylic acid modified TiO2.

[0033] (3) Add acrylic resin, silica, and surfactant to deionized water and stir at 550 r / min for 60 min at 45°C. Then add TiO2 sol and stir at 800 r / min for 60 min. Then add dodecyl salicylic acid modified TiO2 and continue stirring for 120 min. Then add humectant and leveling agent and continue stirring for 60 min to obtain the final product.

[0034] Comparative Example 1

[0035] Unlike Example 3, dodecyl salicylic acid-modified TiO2 was not prepared. The rest is the same as in Example 3. The amounts of each raw material are shown in Table 1.

[0036] Comparative Example 2

[0037] Unlike Example 3, TiO2 sol was not prepared. The rest is the same as in Example 3. The amounts of each raw material are shown in Table 1.

[0038] Comparative Example 3

[0039] Unlike Example 3, nano-silver was used instead of dodecyl salicylic acid to modify TiO2. The rest is the same as in Example 3. The amounts of each raw material are shown in Table 1.

[0040] Comparative Example 4

[0041] Unlike Example 3, nano-silver was used instead of dodecyl salicylic acid to modify TiO2. The rest is the same as in Example 3. The amounts of each raw material are shown in Table 1.

[0042] Table 1

[0043]

[0044]

[0045] Performance testing

[0046] Antibacterial test: The sterilized instruments and samples were placed in a sterile workbench and irradiated with UV light for 30 minutes. Then, approximately 30 mL of LB solution was poured into each petri dish, and allowed to stand for 15 minutes until the agar solidified. The coatings from Examples 1-3 and Comparative Examples 1-4 were applied to each dish, and allowed to stand for approximately 15 minutes. 200 μL of diluted *E. coli* bacterial suspension was then added to each petri dish, and the dish was rotated to distribute the bacterial suspension evenly on the surface. The petri dishes were then capped, sealed with sealing film, and placed in an incubator at 37.5°C. After 7 hours, the diameter and number of inhibition zones around the filter paper were observed and measured, the area of ​​the bacterial zones was calculated, and the results were recorded. The test results are shown in Table 2.

[0047] A second layer of the tipping paper from Examples 1-3 and Comparative Examples 1-4 was printed on top of the graphic printing layer using gravure printing. Ten professionals visually inspected the curling and tackiness of the cigarette tipping paper, and the average result was taken. The test results are shown in Table 2.

[0048] Table 2 Test Results

[0049] Example 1 13.1 Not curled No sticking Example 2 12.6 Not curled No sticking Example 3 10.9 Not curled No sticking Comparative Example 1 34.5 Not curled Slight re-adhesion Comparative Example 2 32.8 Severe curl No sticking Comparative Example 3 41.6 Not curled No sticking Comparative Example 4 22.5 Not curled No sticking

[0050] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. An antibacterial ceramic coating for paper, characterized in that, The antibacterial ceramic coating for paper is composed of the following raw materials in parts by weight: 60-70 parts acrylic resin, 10-14 parts TiO2 sol, 4-8 parts silica, 2-6 parts surfactant, 8-12 parts humectant, 1-3 parts leveling agent, and 80-100 parts deionized water. The TiO2 sol was prepared by the following method: 50 mL of tetrabutyl titanate was added dropwise at a rate of 0.5 mL / s to anhydrous ethanol with a volume of 3 times that of tetrabutyl titanate. After the addition was completed, the mixture was stirred at 50-55°C for 25-30 min to obtain the sol. Antibacterial paper-coated ceramic coatings also include 6-12 parts of dodecyl salicylic acid-modified nano-TiO2; The dodecyl salicylic acid modified nano-TiO2 was prepared by the following method: 1 mL of titanium tetrachloride was added to a 1 mol / L hydrochloric acid solution with a volume of 50 times that of titanium tetrachloride, and stirred at room temperature for 5 min. Then, an ethanol solution of dodecyl salicylic acid with a volume of 5 times that of titanium tetrachloride was added. The ethanol solution of dodecyl salicylic acid was prepared by mixing dodecyl salicylic acid and anhydrous ethanol at a volume ratio of 1:

4. The temperature was raised to 80 °C, and the reaction was refluxed for 24 h. After centrifugation, the nano-TiO2 was washed 2-3 times with anhydrous ethanol and deionized water, and dried at 75-80 °C to constant weight to obtain the final product.

2. The antibacterial paper coating ceramic coating according to claim 1, characterized in that, The acrylic resin is a water-based acrylic resin.

3. The antibacterial paper coating ceramic coating according to claim 1, characterized in that, The surfactants are from the Tween and Span series.

4. The antibacterial paper coating ceramic coating according to claim 1, characterized in that, The humectant includes one or both of polyethylene glycol and glycerol.

5. The antibacterial ceramic coating for paper according to claim 1, characterized in that, The leveling agent includes one or both of polydimethylsiloxane and epoxy hydrocarbon-based polysiloxane.

6. A method for preparing the antibacterial paper coating according to any one of claims 1-5, characterized in that, The method includes the following steps: Acrylic resin, silica, and surfactant are added to deionized water and stirred at 500-550 rpm for 50-60 minutes at 40-45°C. Then, TiO2 sol is added and stirred at 750-800 rpm for 60 minutes. Dodecyl salicylic acid-modified nano-TiO2 is added and stirring is continued for 110-120 minutes. Subsequently, humectant and leveling agent are added and stirring is continued for 50-60 minutes to obtain the final product.

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