Multifunctional amphiphilic organic silicon coating as well as preparation method and application thereof

Abstract

The invention discloses a multifunctional amphiphilic organic silicon coating as well as a preparation method and application thereof, and relates to an organic silicon coating as well as a preparation method and application thereof. The problems that in the prior art, the hydrophilic modification effect is not lasting, the performance is degraded after multiple times of rubbing or long-time use, the function is single, and multiple properties such as long-acting hydrophilic moisturizing, antifogging, biological pollution resistance and broad-spectrum antibacterial performance are difficult to consider at the same time are solved. The multifunctional amphiphilic organic silicon coating comprises a water-based vinyl organic silicon compound, a water-dispersible sulfydryl organic silicon compound and a photoinitiator, and the mass ratio of the water-based vinyl organic silicon compound to the water-dispersible sulfydryl organic silicon compound is (2: 1)-(1: 2). And the mass of the photoinitiator accounts for 0.1-10% of the total mass of the water-based vinyl organosilicon compound and the water-dispersible sulfydryl organosilicon compound. The invention belongs to the technical field of functional polymer coating materials.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of silicone coating and its preparation method and application, belong to functional polymer coating material technical field. BACKGROUND

[0002] With the wide application of silicon hydrogel materials in the field of contact lenses, its high oxygen permeability significantly improves the wearing safety. However, the inherent hydrophobic surface of silicone materials brings many challenges: first, the lack of surface hydrophilicity leads to uneven tear wetting, easy to produce dry feeling, and the lens surface is easy to fog when the environmental temperature and humidity change, affecting visual clarity; second, the hydrophobic surface is easy to adsorb proteins, lipids and other biomolecules in tear, forming an irreversible biological contamination film, which not only reduces the light transmittance and comfort, but also provides conditions for the adhesion and growth of bacteria (such as Staphylococcus aureus, Escherichia coli, etc.), increasing the risk of eye infection.

[0003] To improve the hydrophilicity and biocompatibility of the surface of silicon hydrogel, the prior art usually adopts methods such as surface grafting of hydrophilic polymer, plasma treatment or application of hydrophilic coating. However, these methods often have the following limitations: (1) the hydrophilic modification effect is not durable, and the performance decays after a few rubs or long-term use; (2) when introducing hydrophilic components or antibacterial agents, the high light transmittance and low haze of the material body are often sacrificed, or harmful small molecules that may be dissolved are introduced, affecting the optical performance and biological safety; (3) the function is single, and it is difficult to simultaneously consider long-term hydrophilic moisturizing, anti-fogging, anti-biological contamination and broad-spectrum antibacterial properties.

[0004] Therefore, it is a key requirement in the field to develop a coating technology that can be firmly combined with the substrate through a simple process, and integrally realize long-term high hydrophilicity (anti-fogging), ultra-high light transmittance, anti-biological contamination and inherent antibacterial properties, without introducing harmful substances that can migrate out. SUMMARY

[0005] The present application is to solve the problem of the prior art that the hydrophilic modification effect is not durable, and the performance decays after a few rubs or long-term use, and the function is single, and it is difficult to simultaneously consider long-term hydrophilic moisturizing, anti-fogging, anti-biological contamination and broad-spectrum antibacterial properties, and further proposes a multifunctional amphiphilic silicone coating and its preparation method and application.

[0006] The technical solution adopted by the present invention to solve the above problems is as follows: The multifunctional amphiphilic organosilicon coating of the present invention comprises a water-based vinyl organosilicon compound, a water-dispersible mercapto organosilicon compound, and a photoinitiator, wherein the mass ratio of the water-based vinyl organosilicon compound to the water-dispersible mercapto organosilicon compound is 2:1 to 1:2, and the mass of the photoinitiator accounts for 0.1% to 10% of the total mass of the water-based vinyl organosilicon compound and the water-dispersible mercapto organosilicon compound.

[0007] Furthermore, the mass ratio of the aqueous vinyl organosilicon compound to the water-dispersible mercapto organosilicon compound is 1:1.

[0008] Furthermore, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0009] The steps of the method for preparing a multifunctional amphiphilic organosilicon coating according to the present invention include: Step 1: Mix the water-based vinyl organosilicon compound, the water-dispersible mercapto organosilicon compound, and the photoinitiator, and then perform ultrasonic treatment to form a uniform and transparent coating. Step 2: Apply the coating formed in Step 1 to the surface of the substrate; Step 3: Curing under ultraviolet light to form a coating.

[0010] Furthermore, the ultrasonic treatment time in step 1 is 5 to 30 minutes.

[0011] Furthermore, in step 3, the wavelength of the ultraviolet light irradiation is 300~400nm, and the irradiation time is 10~120 seconds.

[0012] Furthermore, the water contact angle of the coating surface is less than 40°, the average transmittance in the visible light area is greater than 92%, and the haze is less than 2%.

[0013] Furthermore, the coating exhibits an antibacterial rate of over 97.5% against both Staphylococcus aureus and Escherichia coli.

[0014] The multifunctional amphiphilic organosilicon coating described in this invention is applied in the preparation of contact lenses.

[0015] The beneficial effects of this invention are: 1. This invention features multifunctional integration: Through molecular design, hydrophilic polyether segments are grafted onto the Si-O-Si backbone via photocurable vinyl and thiol groups, forming a stable amphiphilic network structure after curing. This structure imparts in one step a coating with durable surface hydrophilicity (achieving anti-fogging / anti-drying), excellent anti-protein adsorption capability, and broad-spectrum contact antibacterial function.

[0016] 2. This invention possesses excellent optical properties: the coating itself is an organosilicon system, exhibiting good compatibility with substrates such as silicone hydrogels, and forms a uniform, transparent film after curing. Actual measured light transmittance reaches over 92%, while haze is as low as below 2%, fully meeting the stringent requirements for clear vision in high-end optical products such as contact lenses.

[0017] 3. This invention features high biocompatibility and durability: the coating forms a covalently cross-linked network through a photoclick chemical reaction, eliminating the risk of small molecule migration or leaching. Simultaneously, the reactive organosilicon structure forms a strong bond with the substrate surface, providing resistance to rubbing and washing, and ensuring long-lasting performance.

[0018] 4. The process of the present invention is simple and environmentally friendly: the composition uses water as the dispersion medium, has extremely low VOC content, the coating process is simple (such as wire rod coating), and the curing speed is fast (second level), making it very suitable for large-scale continuous production. Attached Figure Description

[0019] Figure 1 This is a photograph of the coating mixture solution from Example 1; Figure 2 This is a diagram illustrating the synthesis mechanism in a comparative manner; Figure 3 This is a water contact angle test diagram of the coating; Figure 4 This is a bar chart comparing the transmittance and haze test data before and after the anti-fog test of the coating; Figure 5 This is a schematic diagram of the antibacterial test results of the coating against Escherichia coli; Figure 6 This is a schematic diagram showing the results of the anti-fogging and anti-freezing tests on the coating.

[0020] Example Example 1: Coating preparation and standard coating formation Step 1: Weigh 1.0 g of PGPC-V10 (a water-based vinyl organosilicon compound in a specific ratio) and 1.0 g of PGPC-S1 (a water-dispersible thiol organosilicon compound in a specific ratio) into a vial, and add 0.2 g of photoinitiator 1173 (accounting for 10% of the total mass). Step 2: After manually shaking to mix initially, place it in an ultrasonic cleaner and ultrasonically vibrate for 10 minutes to obtain a colorless, transparent and homogeneous prepolymer liquid. Step 3: Using a 50 μm wire bar coater, evenly coat the coating onto a clean PET film and glass slide. Step 4: Place in a UV curing machine (main wavelength 365 nm, light intensity 80). Irradiate for 30 seconds to obtain a fully cured transparent coating PGPC-V10S1.

[0021] Example 2: Description of precursor variants The aqueous vinyl organosilicon compounds involved in this invention include, but are not limited to, specific compounds PGPC-V10, PGPC-V20, and PGPC-V30 synthesized through different polyether / siloxane ratios; similarly, water-dispersible thiol organosilicon compounds include, but are not limited to, PGPC-S1, PGPC-S2, PGPC-S3, PGPC-S4, and PGPC-S5. These specific compounds may use solvents during their synthesis, but all organic solvents have been removed through post-treatment, and the final products are solvent-free functional pure substances. They can all be combined with photoinitiators to form target coatings using the method described in this invention.

[0022] Examples 2-15: By changing the types of waterborne vinyl organosilicon compounds and water-dispersible mercapto organosilicon compounds, a series of coatings PGPC-V10S2, PGPC-V10S3, PGPC-V10S4, PGPC-V10S5, PGPC-V20S1, PGPC-V20S2, PGPC-V20S3, PGPC-V20S4, PGPC-V20S5, PGPC-V30S1, PGPC-V30S2, PGPC-V30S3, PGPC-V30S4, and PGPC-V30S5 were synthesized according to the method of Example 1.

[0023] Example 16: Coating Performance Test Anti-fogging performance test: A beaker containing 85 ℃ hot water was used to test the anti-fogging performance of the coating. The bottom of the beaker was lined with background paper with the words "anti-fogging" written on it. The coated slide and the blank slide were placed parallel to each other above the beaker, with the distance between the slide and the water surface being 2~3 cm. After waiting for 30 seconds, the fogging of the slide was observed.

[0024] Freeze-thaw resistance test: The coated samples were tested for freeze-thaw resistance in an ultra-low temperature freezer. Coated slides and blank slides were fixed on a slide holder and placed in an ultra-low temperature freezer at -50 ℃ for 4 hours to reach thermal equilibrium. After the freezing time was reached, the slides were removed and the frost formation on the slide surface was observed at room temperature.

[0025] Antimicrobial performance test: The PGPC-VS coating was applied to a clean glass slide and cured for later use. *Escherichia coli* and *Staphylococcus aureus* were selected as representative Gram-negative and Gram-positive strains, respectively. The antimicrobial performance of the coating was evaluated using the plate count method. Sterilized glass slides were immersed in 40 mL of a suspension of *E. coli* or *Staphylococcus aureus* (10... 6 After 1 hour, gently rinse three times with PBS, then treat with an ultrasonic cleaner (40 kHz) for 5-10 minutes to disperse the bacteria adhering to the modified glass slide surface into 40 mL of PBS. Take 10 μL of each sample. Bacterial dispersions were coated onto beef protein agar and incubated at 37 °C for 16 h. Bacterial adhesion was then assessed by counting the number of Escherichia coli or Staphylococcus aureus colonies, with each experiment repeated three times.

[0026] Common contaminant antifouling test: Soy sauce, vinegar, and sesame oil were selected as common contaminants to test the PGPC-VS coating. Coated and blank glass slides were placed at a 45° angle on a horizontal platform. A suitable amount of the test liquid was dripped onto the same position on both slides, and the flow and residue of the test liquid on the slide surface were observed.

[0027] Table 1 PET and PGPC - / PET light transmittance and haze

[0028] Comparative Example Trimethyl-terminated vinyl polysiloxane and trimethyl-terminated mercapto polysiloxane (PSTC) were synthesized without introducing polyether linkages. Then, a coating polysiloxane-sulfide block copolymer was synthesized as a coating PGPC-, following the method described in Example 1. control group The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent substitutions, and improvements made to the above embodiments without departing from the scope of the present invention, based on the technical essence of the present invention and within the spirit and principles of the present invention, shall still fall within the protection scope of the present invention.

Claims

1. A multifunctional amphiphilic silicone coating, characterized in that, The multifunctional amphiphilic silicone coating comprises a waterborne vinyl silicone compound, a water-dispersible mercapto silicone compound and a photoinitiator, wherein the mass ratio of the waterborne vinyl silicone compound to the water-dispersible mercapto silicone compound is 2:1-1:2, and the mass of the photoinitiator accounts for 0.1%-10% of the total mass of the waterborne vinyl silicone compound and the water-dispersible mercapto silicone compound.

2. The multifunctional amphiphilic silicone coating according to claim 1, characterized in that, The mass ratio of the waterborne vinyl silicone compound to the water-dispersible mercapto silicone compound is 1:

1.

3. The multifunctional amphiphilic silicone coating of claim 1, wherein, The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

4. A process for the production of the silicone coating as claimed in any one of claims 1 to 3, characterized in that The specific steps include: Step 1, mixing the waterborne vinyl silicone compound, the water-dispersible mercapto silicone compound and the photoinitiator, and performing ultrasonic treatment to form a uniform transparent coating; Step 2, coating the coating formed in Step 1 on the surface of a substrate; Step 3, performing curing under ultraviolet light irradiation to form a coating layer.

5. The method of claim 4, wherein the method further comprises the step of adding a second amphiphilic organosilica coating to the surface of the substrate. 5 The ultrasonic treatment time in Step 1 is 5-30 minutes.

6. The method of claim 4, wherein the method is characterized by, The wavelength of the ultraviolet light irradiation in Step 3 is 300-400 nm, and the irradiation time is 10-120 seconds.

7. The method of claim 4, wherein the method is characterized by, The water contact angle of the surface of the coating layer is less than 40°, the average visible light transmittance is greater than 92%, and the haze is less than 2%.

8. The method for preparing a multifunctional amphiphilic organosilicon coating according to claim 4, characterized in that, The average antibacterial rate of the coating layer against Staphylococcus aureus is greater than 97.5%.

9. Use of the silicone coating according to any one of claims 1 to 3, characterized in that The multifunctional amphiphilic silicone coating is applied to the preparation of contact lenses.

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