Antibacterial type anti-fingerprint agent additive, preparation method and application thereof

Abstract

This invention relates to the field of special polymer coating synthesis, specifically disclosing an antibacterial antifingerprint agent additive, its preparation method, and its application. This invention enhances the antibacterial effect of the antibacterial antifingerprint agent additive by introducing quaternary ammonium cations into its molecular structure and oxygen heteroatoms into the hydrophobic chain of the additive. By employing the synergistic effect of a small-molecule antibacterial antifingerprint agent additive and the macromolecular chain of the antifingerprint agent, it not only overcomes the difficulty in introducing antibacterial functional groups into traditional macromolecular antifingerprint agents, avoiding the cumbersome preparation process and increased costs, but also utilizes the small-molecule antibacterial antifingerprint agent additive to fill the pores of the macromolecular chain of the antifingerprint agent, ensuring that the mixing of the antifingerprint agent and the antibacterial antifingerprint agent additive does not significantly reduce the original performance of the antifingerprint agent.

Description

Technical Field

[0001] This invention relates to the field of special polymer coating synthesis, specifically to an antibacterial anti-fingerprint additive, its preparation method, and its application. Background Technology

[0002] While touchscreens offer convenience, comfort, and speed, frequent finger contact during use easily leaves fingerprints and smudges on the screen. Over time, this not only affects the screen's normal operation but also becomes a breeding ground for bacteria and viruses. Experts have conducted bacterial tests on mobile phones and found over 2,000 types of bacteria on their screens, which can cause colds, gastrointestinal diseases, ear infections, herpes, and even pneumonia and hepatitis B. According to WHO statistics, of the more than 52 million deaths globally each year, over 17 million are due to infectious diseases caused by bacteria and viruses. Research by the foreign media outlet Mashable has indicated that mobile phones contain up to 20 times more bacteria than toilet seats. Frequent hand contact with touchscreens in daily life results in a large number of bacterial fingerprints, seriously threatening human health and viewing experience. Based on these findings, there is a growing demand for anti-fingerprint agents with waterproof, oil-proof, and fingerprint-resistant properties—that is, agents that prevent fingerprints while also possessing antibacterial properties.

[0003] Anti-fingerprint agent is a fluorinated surface treatment agent with a special structure, consisting of a fluorinated main chain and siloxane end groups. The mainstream products on the market use a perfluoropolyether chain as the main chain, which has good waterproof, oil-proof, stain-proof and anti-fingerprint adhesion functions, and is often used in the field of touch screen protection.

[0004] Currently, common antibacterial and anti-fingerprint agents generally involve adding non-toxic metal nanoparticles, such as silver or zinc, with antibacterial properties to the mother liquor. Patent CN116463024A proposes a method for preparing a hydrophobic and oleophobic antibacterial film from a fluorinated silver-loaded nano-silicon dispersion, which simultaneously possesses long-lasting antibacterial efficacy and hydrophobic and oleophobic functions. Patent CN120309184A describes a method for preparing a nano-silver antibacterial hydrophobic solution by adding a high-concentration alcohol-based nano-silver antibacterial solution to a hydrophobic solution composed of low-viscosity hydroxyl silicone oil, polyvinyl acetal, and hydrogen-containing silicone oil; this antibacterial hydrophobic solution combines antibacterial and hydrophobic anti-fingerprint functions. However, the addition of metal nanoparticles in both of these patents affects the adhesion and light transmittance of the anti-fingerprint coating. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by proposing an antibacterial anti-fingerprint additive, its preparation method, and its application. This invention imparts good wear resistance and hydrophobicity to the substrate without affecting the properties of the anti-fingerprint layer, while also possessing good antibacterial properties.

[0006] The technical solution provided by this invention is as follows: An antibacterial anti-fingerprint additive, with the following structural formula:

[0007] The PFPE structure is as follows: CF3(CF2CF2O) p (CF2O) q CF2- or CF3CF2CF2O[CF(CF3)CF2O] a CF (CF3) - or CF3O(CF2CF2CF2O) m (CF2O) n CF2- or CF3CF2CF2O(CF2CF2CF2O) i CF2CF2-; in, p is an integer from 1 to 15, and q is an integer from 1 to 15; a is an integer from 1 to 10; m is an integer from 1 to 15, and n is an integer from 1 to 15; i is an integer from 1 to 10.

[0008] Preferably, the PFPE structure is CF3(CF2CF2O). p (CF2O) q CF2-.

[0009] The weight-average molecular weight of the antibacterial antifingerprint additive is 850~2500 g / mol.

[0010] The preparation method of the above-mentioned antibacterial anti-fingerprint additive includes the following steps: (1) Under an inert gas atmosphere, perfluoropolyether carboxylic acid and 6-dimethylamino-1-hexanol react in a reaction solvent under the action of a catalyst to produce substance a; (2) Under an inert gas atmosphere, substance a reacts with (3-chloropropyl)trimethoxysilane in a mixed solvent, and after post-treatment, an antibacterial anti-fingerprint additive is obtained.

[0011] The synthetic route for the above reaction process is as follows: Step (1): ; Step (2): .

[0012] In step (1), the molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol is 1:(1.2-1.5). The catalyst is one of dicyclohexyldiimide, azobisisobutyronitrile, and p-toluenesulfonic acid, preferably dicyclohexyldiimide; the weight ratio of the catalyst to perfluoropolyether carboxylic acid is 1‰-3‰.

[0013] The reaction temperature is 60-65℃, and the reaction time is 4-6 hours; The reaction solvent is a mixture of trifluorotrichloroethane and nonafluorobutyl ethyl ether, in a weight ratio of 1:(1-1.5).

[0014] In step (2), the mixed solvent is a mixed solution of trichlorotrifluoroethane and 1,3-bistrifluoromethylbenzene, with a weight ratio of 2:(1-1.5). The molar ratio of substance a to (3-chloropropyl)trimethoxysilane is 1:(2-2.2). The reaction temperature is 45-55℃, and the reaction time is 3.5-5h.

[0015] The above-mentioned antibacterial antifingerprint additive is used in antifingerprint agents, wherein the antifingerprint agent includes a diluent, an antifingerprint main agent, and an antibacterial antifingerprint additive; The anti-fingerprint agent has a mass concentration of 0.5‰-1.5‰, and the antibacterial anti-fingerprint additive has a mass concentration of 0.5‰~1.5‰. The anti-fingerprint agent is a perfluoropolyether siloxane compound.

[0016] The diluent is hydrofluoroether or hexafluoropropylene trimer.

[0017] Beneficial effects of the present invention Compared with the prior art, the present invention has the following beneficial effects: 1. This invention utilizes the synergistic effect of small-molecule antibacterial antifingerprint additives and the macromolecular chains of antifingerprint main agents. This not only overcomes the problem of traditional macromolecular antifingerprint main agents having difficulty in introducing antibacterial functional groups, avoiding the cumbersome preparation process and increased costs, but also utilizes small-molecule antibacterial antifingerprint additives to fill the pores of the macromolecular chains of antifingerprint main agents. This ensures that the mixing of antifingerprint agents and antibacterial antifingerprint additives does not significantly reduce the original performance of the antifingerprint agent.

[0018] 2. This invention introduces quaternary ammonium cations into the molecular structure, endowing the antibacterial antifingerprint additive with antibacterial properties. Simultaneously, it introduces oxygen heteroatoms into the hydrophobic chain of the antibacterial antifingerprint additive to enhance its antibacterial effect. The ester group is a polar group; introducing it into the long hydrophobic chain of the quaternary ammonium salt improves the hydrophilic-lipophilic balance of the molecule, allowing the antibacterial molecular chain to adsorb more efficiently onto the bacterial surface and insert into the membrane. Furthermore, the introduction of the ester group alters the rigidity and rotational freedom of the carbon chain. The planar structure and electronic effects of the ester group enable the molecule to bind in a more favorable conformation when approaching the negatively charged bacterial cell membrane. This conformational adaptability helps the positively charged center of the quaternary ammonium cation form a tighter electrostatic interaction with the phosphate groups on the cell membrane surface, thereby enhancing antibacterial activity.

[0019] 3. When the antibacterial antifingerprint additive provided by this invention is used in combination with the antifingerprint main agent, it can not only give the glass substrate excellent antibacterial properties (antibacterial rate can reach 99.9%), but also have excellent hydrophobicity (initial water contact angle reaches more than 110°). On this basis, it will not cause a significant decrease in the wear resistance of the antifingerprint coating. Attached Figure Description

[0020] Figure 1 The hydrogen spectrum of the antibacterial antifingerprint additive prepared in Example 2 ( 1 HNMR spectrum. Detailed Implementation

[0021] To better understand the present invention, the antibacterial antifingerprint additive, synthesis method, and testing method of the present invention are further illustrated by the following embodiments, but the present invention is not limited to these embodiments.

[0022] In the following examples and comparative examples, antibacterial agent ZY was purchased from Baicaobian Biotechnology (Qingdao) Co., Ltd., model: Da Biofunctional Agent - Oil-based Transparent Type; antibacterial agent BB was purchased from Shandong Aipute New Material Technology Co., Ltd., model: EP-DC5700; and anti-fingerprint agent was purchased from PTFE New Material (Suzhou) Co., Ltd., model: OPTOOL UD509.

[0023] Example 1 In a four-necked flask equipped with a stirrer, thermometer, and condenser, 30 g of perfluoropolyether carboxylic acid (Mw = 1074 g / mol) and 5.2 g of 6-dimethylamino-1-hexanol (molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol was 1:1.28) were added. The catalyst was 0.03 g of p-toluenesulfonic acid, and the reaction solvent was a mixture of 50 g of trifluorotrichloroethane and 50 g of nonafluorobutyl ethyl ether (weight ratio of trifluorotrichloroethane to nonafluorobutyl ethyl ether was 1:1). The reaction was carried out at 60 °C for 5 h. After extraction and vacuum distillation, 28 g of substance a was obtained.

[0024] The structural formula of the perfluoropolyether carboxylic acid is: CF3(CF2CF2O) p (CF2O) q CF2COOH, where p is 5 and q is 5.

[0025] Substance a (Mw=1201.24 g / mol) was dissolved in a mixed solution of 40 g of trichlorotrifluoroethane and 20 g of 1,3-bis(trifluoromethylbenzene) (the weight ratio of trichlorotrifluoroethane to 1,3-bis(trifluoromethylbenzene) was 2:1), and reacted with 9.26 g of (3-chloropropyl)trimethoxysilane (Mw=198.72 g / mol) (the molar ratio of substance a to (3-chloropropyl)trimethoxysilane was 1:2) at 55 °C for 3.5 h. After filtration and vacuum distillation, an antibacterial anti-fingerprint additive was obtained.

[0026] Example 2 In a four-necked flask equipped with a stirrer, thermometer, and condenser, 30 g of perfluoropolyether carboxylic acid (Mw = 1074 g / mol) and 6 g of 6-dimethylamino-1-hexanol (molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol is 1:1.49) were added. The catalyst was 0.03 g of dicyclohexyldiimide. The reaction solvent was a mixture of 50 g of trifluorotrichloroethane and 75 g of nonafluorobutyl ethyl ether (weight ratio of trifluorotrichloroethane to nonafluorobutyl ethyl ether is 1:1.5). The reaction was carried out at 60 °C for 6 h. After extraction and vacuum distillation, 30 g of substance a was obtained.

[0027] The structural formula of the perfluoropolyether carboxylic acid is: CF3(CF2CF2O) p (CF2O) q CF2COOH, where p is 5 and q is 5.

[0028] Substance a (Mw=1201.24 g / mol) was dissolved in a mixed solution of 40 g trichlorotrifluoroethane and 30 g 1,3-bistrifluoromethylbenzene (weight ratio 2:1.5), and reacted with 10.42 g (3-chloropropyl)trimethoxysilane (Mw=198.72 g / mol) (molar ratio of substance a to (3-chloropropyl)trimethoxysilane 1:2.1) at 50 °C for 4 h. After filtration and vacuum distillation, an antibacterial anti-fingerprint additive was obtained.

[0029] Figure 1The 1H NMR spectrum of the antibacterial antifingerprint additive prepared in this embodiment shows the following: The peak at 4.18-4.20 ppm is the methylene peak directly bonded to the ester group; the peaks at 3.63-3.66 ppm and 3.51-3.54 ppm are the two methylene peaks directly bonded to the quaternary ammonium group, respectively; the peak at 3.33 ppm is the methoxy peak bonded to silicon; the peak at 3.23 ppm is the two methyl peaks bonded to the quaternary ammonium group; and six smaller peaks appear in the 1.48-1.97 ppm range, corresponding to the remaining six methylene peaks on the carbon chain of the product. This indicates that the product was successfully prepared in this embodiment.

[0030] Example 3 In a four-necked flask equipped with a stirrer, thermometer, and condenser, 30 g of perfluoropolyether carboxylic acid (Mw = 528 g / mol) and 10.5 g of 6-dimethylamino-1-hexanol (molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol was 1:1.27) were added. The catalyst was 0.03 g of p-toluenesulfonic acid, and the reaction solvent was a mixture of 50 g of trifluorotrichloroethane and 50 g of nonafluorobutyl ethyl ether (weight ratio 1:1). The reaction was carried out at 65 °C for 4 h. After extraction and vacuum distillation, 32 g of substance a was obtained.

[0031] The structural formula of the perfluoropolyether carboxylic acid is: CF3(CF2CF2O) p (CF2O) q CF2COOH, where p is 2 and q is 2.

[0032] Substance a (Mw=655.24g / mol) was dissolved in a mixed solution of 40g trichlorotrifluoroethane and 30g 1,3-bis(trifluoromethylbenzene) (weight ratio 2:1.5), and reacted with 19.4g (3-chloropropyl)trimethoxysilane (molar ratio of substance a to (3-chloropropyl)trimethoxysilane 1:2) at 45℃ for 3.5 h. After filtration and vacuum distillation, an antibacterial anti-fingerprint additive was obtained.

[0033] Example 4 In a four-necked flask equipped with a stirrer, thermometer, and condenser, 30 g of perfluoropolyether carboxylic acid (Mw = 528 g / mol) and 12.3 g of 6-dimethylamino-1-hexanol (molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol was 1:1.49) were added. The catalyst was 0.03 g of p-toluenesulfonic acid, and the reaction solvent was a mixture of 50 g of trifluorotrichloroethane and 75 g of nonafluorobutyl ethyl ether (weight ratio of 1:1.5). The reaction was carried out at 65 °C for 5 h. After extraction and vacuum distillation, 30 g of substance a was obtained.

[0034] The structural formula of the perfluoropolyether carboxylic acid is: CF3(CF2CF2O)p (CF2O) q CF2COOH, where p is 2 and q is 2.

[0035] Substance a was dissolved in a mixed solution of 40 g of trichlorotrifluoroethane and 30 g of 1,3-bis(trifluoromethylbenzene) (weight ratio 2:1.5), and reacted with 20 g of (3-chloropropyl)trimethoxysilane (molar ratio of substance a to (3-chloropropyl)trimethoxysilane 1:2.2) at 50 °C for 5 h. The resulting solution was filtered and distilled under reduced pressure to obtain an antibacterial anti-fingerprint additive.

[0036] Comparative Example 1 This comparative example uses antibacterial agent ZY as an antibacterial anti-fingerprint agent additive.

[0037] Comparative Example 2 This comparative example uses antibacterial agent BB as an antibacterial anti-fingerprint agent additive.

[0038] Experimental Example I. Experimental Objective: To investigate the performance of the antibacterial and anti-fouling layer formed by the antibacterial anti-fingerprint additives and anti-fingerprint agents described in Examples 1-4 and Comparative Examples 1-2, including hydrophobicity, abrasion resistance and antibacterial properties.

[0039] II. Experimental Methods: (1) Take 0.5g of anti-fingerprint agent (the finished product is 20% mass concentration) and add it to 99.4g of hydrofluoroether to obtain the anti-fingerprint agent working solution. Then take 0.1g of the antibacterial anti-fingerprint agent additives in Examples 1-4 and Comparative Examples 1-2 and add them to the anti-fingerprint agent working solution to obtain 6 anti-fingerprint agents.

[0040] (2) Spray the anti-fingerprint agent prepared in step (1) onto the glass slide, with a spraying amount of 60 g / m. 2 Cured at 130℃ for 30 minutes.

[0041] (3) Test the contact angle, abrasion resistance, and antibacterial properties of the coated glass slide. The specific methods are as follows: Water contact angle test: The measurement is carried out at room temperature. The sample to be tested is laid flat on the horizontal platform of the contact angle measuring instrument. The water droplet size is 2μl. Three points are measured for the same sample and the average value is taken.

[0042] Abrasion resistance test: A coated glass slide was placed horizontally, and steel wool (Bonstar #0000, size 5mm) was subjected to abrasion. 10mm A 10mm steel wool pad is placed in contact with the side of a glass slide coated with an anti-fingerprint agent, and a 1 kg load is applied on it. The steel wool pad is then moved back and forth at a speed of 50 times / min. The static contact angle of the water is measured at regular intervals (1000 times) until the measured value of the water contact angle is less than 100°.

[0043] Antimicrobial activity test: The antimicrobial activity of the coated glass slide against Escherichia coli and Staphylococcus aureus was determined according to the test standards in JIS Z 2801:2010 (COR 1:2011, AMD 1:2012).

[0044] III. Experimental Results: Table 1. Performance test results of glass slides after coating.

[0045] The blank sample refers to the sample using only the anti-fingerprint agent. Compared to the blank sample, Examples 1-4 showed a significant antibacterial effect, and their water contact angle and abrasion resistance did not decrease significantly.

[0046] The data above shows that the antibacterial anti-fingerprint additive of the present invention, when used in combination with the anti-fingerprint agent, exhibits good hydrophobicity, abrasion resistance, and antibacterial properties, with Example 2 showing the best performance in all aspects. Therefore, applying the antibacterial anti-fingerprint additive of the present invention to the surface of a touchscreen can impart good hydrophobicity, abrasion resistance, and antibacterial properties.

[0047] Compared to Examples 1-4, Comparative Examples 1 and 2 showed a small amount of white substance precipitated on the surface of the glass sheet after spraying, indicating that it did not bond well with the substrate and was not suitable for direct spraying after mixing with the anti-fingerprint agent; in addition, its antibacterial properties were poor, because during the antibacterial test, the two antibacterial agents peeled off the substrate surface due to poor bonding with the substrate.

Claims

1. An antibacterial anti-fingerprint additive, characterized in that, The structural formula is: The PFPE structure is as follows: CF3(CF2CF2O) p (CF2O) q CF2- or CF3CF2CF2O[CF(CF3)CF2O] a CF(CF3)- or CF3O(CF2CF2CF2O) m (CF2O) n CF2- or CF3CF2CF2O(CF2CF2CF2O) i CF2CF2-; in, p is an integer from 1 to 15, and q is an integer from 1 to 15; a is an integer from 1 to 10; m is an integer from 1 to 15, and n is an integer from 1 to 15; i is an integer from 1 to 10.

2. The antibacterial anti-fingerprint additive according to claim 1, characterized in that, The PFPE structure is CF3(CF2CF2O). p (CF2O) q CF2-.

3. The antibacterial anti-fingerprint additive according to claim 1, characterized in that, The weight-average molecular weight of the antibacterial anti-fingerprint additive is 850~2500 g / mol.

4. A method for preparing an antibacterial antifingerprint additive as described in any one of claims 1 to 3, characterized in that, Includes the following steps: (1) Under an inert gas atmosphere, perfluoropolyether carboxylic acid and 6-dimethylamino-1-hexanol react in a reaction solvent under the action of a catalyst to produce substance a; (2) Under an inert gas atmosphere, substance a reacts with (3-chloropropyl)trimethoxysilane in a mixed solvent, and after post-treatment, an antibacterial anti-fingerprint additive is obtained.

5. The preparation method according to claim 4, characterized in that, In step (1), the molar ratio of perfluoropolyether carboxylic acid to 6-dimethylamino-1-hexanol is 1:(1.2-1.5).

6. The method for preparing the antibacterial antifingerprint additive according to claim 4, characterized in that, The catalyst is one of dicyclohexyldiimide, azobisisobutyronitrile, and p-toluenesulfonic acid; The weight ratio of the catalyst to the perfluoropolyether carboxylic acid is 1‰-3‰.

7. The method for preparing the antibacterial antifingerprint additive according to claim 4, characterized in that, In step (1), the reaction temperature is 60-65℃ and the reaction time is 4-6 hours; The reaction solvent is a mixture of trifluorotrichloroethane and nonafluorobutyl ethyl ether, with a weight ratio of 1:(1-1.5).

8. The method for preparing the antibacterial antifingerprint additive according to claim 4, characterized in that, In step (2), the mixed solvent is a mixed solution of trichlorotrifluoroethane and 1,3-bis(trifluoromethylbenzene) in a weight ratio of 2:(1-1.5). The molar ratio of substance a to (3-chloropropyl)trimethoxysilane is 1:(2-2.2). The reaction temperature is 45-55℃, and the reaction time is 3.5-5h.

9. The application of an antibacterial antifingerprint additive as described in any one of claims 1 to 3, or an antibacterial antifingerprint additive prepared by the preparation method described in any one of claims 4 to 8, in an antifingerprint agent, characterized in that, The anti-fingerprint agent includes a diluent, an anti-fingerprint main agent, and an antibacterial anti-fingerprint additive; The mass concentration of the anti-fingerprint agent is 0.5‰-1.5‰, and the mass concentration of the antibacterial anti-fingerprint additive is 0.5‰~1.5‰.

10. The application according to claim 9, characterized in that, The diluent is hydrofluoroether or hexafluoropropylene trimer.

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