CN105111479A - Method for modifying fluorinated siloxane acrylate material of rigid gas-permeable corneal contact lens - Google Patents

Abstract

The invention relates to a method for modifying a rigid gas-permeable corneal contact lens material, and discloses a method for modifying a rigid gas-permeable corneal contact lens fluorosiloxane acrylate material through plasma treatment and grafting. The method comprises the following steps: performing plasma treatment on the fluorosilicone acrylate material of the rigid gas-permeable contact lens; immersing the treated material in a bionic macromolecule aqueous solution to obtain the modified rigid gas-permeable contact lens fluorosilicone Alkacrylate material. The invention adopts the plasma surface treatment method to treat the fluorosiloxane acrylate material of the rigid gas-permeable contact lens, and then grafts the bionic macromolecule with high hydrophilicity, good biocompatibility and protein adsorption prevention property to the The surface of the material improves its hydrophilicity, makes it easier for tears to spread out, and solves the problem of poor comfort when wearing it for the first time. Long-term wearing is not easy to cause protein deposition, prolonging the wearing time and improving the wearing comfort.

Description

Modification method of fluorosilicone acrylate material for rigid gas permeable contact lens

technical field

The invention relates to a method for modifying a rigid gas-permeable contact lens material, in particular to a method for modifying a rigid gas-permeable contact lens fluorosiloxane acrylate material through plasma treatment and grafting. This method can improve the hydrophilicity of traditional fluorosilicone acrylate materials, make tears spread out more easily, and solve the problem of poor comfort when wearing them for the first time. It is not easy to cause protein deposition in tears after long-term wearing, and prolongs the wearing time. and improve wearing comfort. The obtained modified material can be applied to the performance improvement and optimization of the rigid gas permeable contact lens.

Background technique

Contact lens is a medical optical device mainly used to correct various refractive errors (including myopia, hyperopia, astigmatism and presbyopia), and has been around for more than 100 years. Because it is in direct contact with the cornea, the academic circles named it "contact lens". Whether it's correcting vision, beautifying eye color, or treating corneal disease, countless people are already enjoying the benefits of wearing contact lenses. According to statistics, people who wear contact lenses in my country account for about 3% of the total population, and countries such as the United States and Japan account for 10%. With the continuous development and improvement of contact lens production technology and materials, the proportion of the population wearing contact lenses has a rising trend, and the use of contact lenses is also increasing.

The development of hard contact lens materials has gone through the process from the initial glass, polymethyl methacrylate (PMMA) and other traditional hard contact lens materials to butyl cellulose acetate (CBA), fluorosilicone acrylate (FSA) ), fluorocarbon (FC) and other gas permeable rigid contact lens materials. Rigid contact lenses have disadvantages such as relatively hard, extremely small water absorption, not easily wetted by water, and low wearing comfort.

Surface modification is the most direct and effective way to improve the surface properties of materials. Compared with other methods, plasma technology has the advantages of simple process, low cost, no pollution, high efficiency, low reaction temperature, and good treatment uniformity. Direct plasma surface treatment is to expose the material to the plasma generated by non-polymerizable inorganic gas, use the energy particles and active species in the plasma to bombard the surface of the material, react with the surface of the material, and generate specific functional groups on the surface , causing changes in the structure of the material, thereby modifying the surface of the material and improving the surface properties of the material. Plasma surface treatment causes etching and roughening of the material surface. However, simple plasma surface treatment can only endow the material with certain surface properties in a short period of time. Due to the timeliness of the plasma treatment effect, the functional groups introduced on the surface of the material will gradually move into the surface and turn over. In order to obtain a lasting surface modification effect, most of the materials need further surface modification.

Contents of the invention

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a method for modifying the fluorosilicone acrylate material of a rigid gas-permeable contact lens.

The object of the present invention is achieved through the following solutions:

A method for modifying a rigid gas-permeable contact lens fluorosilicone acrylate material, comprising the following specific steps:

(1) Plasma treatment of fluorosilicone acrylate material (FSARGPCL) for rigid gas permeable contact lenses;

(2) Soak the processed material in the bionic macromolecule aqueous solution to obtain the modified rigid gas permeable contact lens fluorosilicone acrylate material.

The plasma described in step (1) can be ammonia plasma or oxygen plasma.

The plasma treatment time in step (1) is preferably 30-300s, and the discharge power is preferably 50-200W.

More preferably, the plasma treatment time in step (1) is 120s, and the discharge power is 100W.

In order to better realize the present invention, the rigid gas-permeable contact lens fluorosilicone acrylate material described in step (1) can be a cut sheet of about 1 mm.

Preferably, the rigid gas-permeable contact lens fluorosilicone acrylate material in step (1) can be polished after cutting, ultrasonically cleaned, washed with deionized water, and then dried at room temperature.

More preferably, the above-mentioned ultrasonic cleaning refers to cleaning with an ultrasonic cleaner for 10-20 minutes, most preferably 15 minutes.

The biomimetic macromolecule aqueous solution described in step (2) is preferably 2-methacryloyloxyethyl phosphorylcholine (MPC) aqueous solution, polyethylene glycol diacrylate (PEGDA) aqueous solution or polyethylene glycol (PEG) One of the aqueous solutions.

Preferably, the biomimetic macromolecule aqueous solution described in step (2) is 2-methacryloyloxyethyl phosphorylcholine (MPC) aqueous solution or polyethylene glycol diacrylate (PEGDA) aqueous solution. 2-Methacryloyloxyethylphosphorylcholine and polyethylene glycol diacrylate are biomimetic macromolecules with high hydrophilicity and good biocompatibility. Their structures are similar to those of biological membranes. They are used in Surface modification of biomaterials can significantly improve the hydrophilicity and biocompatibility of materials, and reduce the adsorption of proteins on the surface of materials.

More preferably, the polyethylene glycol diacrylate (PEGDA) described in step (2) has a molecular weight of 4000-10000.

The concentration of the biomimetic macromolecule aqueous solution described in step (2) is preferably 0.01-0.1 wt%.

The soaking described in step (2) is preferably soaking for 2-4 hours.

The soaking described in step (2) is preferably stirred while soaking.

The modified rigid gas permeable contact lens fluorosilicone acrylate material obtained in step (2) can be rinsed with deionized water and dried at room temperature for post-treatment.

Mechanism of the present invention is:

The present invention adopts plasma surface treatment method to carry out surface treatment to rigid gas permeable contact lens (RGPCL) fluorosilicone acrylate (FSA) material, improves the hydrophilic property of contact lens surface, because the aging of plasma treatment effect The functional groups introduced on the surface of the material will gradually move and turn over on the surface. In order to obtain a lasting surface modification effect, the present invention will have bionic macromolecules with high hydrophilicity, good biocompatibility and protein adsorption prevention The molecule 2-methacryloyloxyethylphosphorylcholine (MPC) or polyethylene glycol diacrylate (PEGDA) is grafted onto the surface of FSARGPCL contact lens material to further improve the hydrophilicity of the contact lens surface and reduce the Adsorption of protein on the contact lens surface achieves ideal surface properties.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The surface modification method proposed by the present invention can improve the hydrophilicity of the traditional FSA material, make the tears easier to spread, and solve the problem of poor comfort when wearing it at the beginning, and it is not easy to cause protein deposition in the tears after wearing for a long time. Achieve extended wearing time and improve wearing comfort.

(2) The surface modification method proposed by the present invention does not change the bulk performance of the contact lens, and the refractive index of the contact lens does not change significantly before and after modification.

(3) The processing technology adopted in the present invention is simple, and the cost is relatively low, which is conducive to large-scale production.

Description of drawings

Figure 1 is the SEM photographs of the surface of FSARGPCL contact lens before and after ammonia plasma treatment.

Figure 2 is the SEM photographs of the surface of the FSARGPCL contact lens before and after oxygen plasma treatment.

Fig. 3 is the SEM photograph of the surface of FSARGPCL contact lens before and after ammonia plasma grafting MPC.

Fig. 4 is the SEM photograph of the surface of FSARGPCL contact lens before and after oxygen plasma grafting MPC.

Figure 5 is a comparison curve of the refractive index of the FSARGPCL contact lens before and after ammonia plasma grafting MPC.

Figure 6 shows the amount of protein adsorption on the surface of FSARGPCL contact lens before and after ammonia plasma grafting MPC.

Figure 7 is a comparison curve of the refractive index of the FSARGPCL contact lens before and after oxygen plasma grafting MPC.

Figure 8 shows the amount of protein adsorption on the surface of FSARGPCL contact lens before and after oxygen plasma grafting MPC.

Fig. 9 is a comparison curve of the refractive index of the FSARGPCL contact lens before and after ammonia plasma grafting PEGDA.

Figure 10 shows the amount of protein adsorption on the surface of FSARGPCL contact lens before and after ammonia plasma grafting PEGDA.

Detailed ways

The present invention will be further described in detail below with reference to the examples and drawings, but the implementation of the present invention is not limited thereto.

All reagents used in the following examples can be purchased from the market.

Example 1

Ammonia plasma treatment is used as the surface treatment method, and 2-methacryloyloxyethyl phosphorylcholine (MPC) is used as the grafted molecule. The steps are as follows:

(1) The FSARGPCL contact lens material (BostonXO, Wenzhou Medical College) was cut into thin slices of about 1 mm, polished, cleaned with a digitally controlled ultrasonic cleaner for 15 minutes, rinsed with deionized water, dried at room temperature, and stored for later use.

(2) Under the ammonia plasma treatment for 120s and the discharge power of 100W, plasma treatment was performed on the FSARGPCL contact lens material.

(3) Soak the treated material in a 0.02wt% 2-methacryloyloxyethylphosphorylcholine (MPC) aqueous solution for 3 hours, during which time a magnetic stirrer is used to continuously stir.

(4) Rinse the surface of the contact lens material 3 times with deionized water, dry at room temperature, and store.

Figure 1 is the SEM photograph of the surface of FSARGPCL contact lens before and after ammonia plasma treatment, and Figure 3 is the SEM photograph of the surface of FSARGPCL contact lens before and after ammonia plasma grafting with MPC. Ammonia plasma treatment under neutral conditions does not have a great effect on the surface morphology of contact lenses.

Figure 5 is a comparison curve of the refractive index of the FSARGPCL contact lens before and after ammonia plasma grafting MPC. The refractive index of FSARGPCL contact lenses did not change significantly before and after grafting, and the bulk performance of contact lenses did not change, which indicated that the modification method had no adverse effect on the most basic visual function of contact lenses.

Figure 6 shows the amount of protein adsorption on the surface of FSARGPCL contact lens before and after ammonia plasma grafting MPC, the modified contact lens reduces the deposition of protein on the lens.

Example 2

Oxygen plasma treatment is used as the surface treatment method, and 2-methacryloyloxyethyl phosphorylcholine (MPC) is used as the graft molecule, and the steps are as follows:

(1) The FSARGPCL contact lens material (BostonXO, Wenzhou Medical College) was cut into thin slices of about 1 mm, polished, cleaned with a digitally controlled ultrasonic cleaner for 15 min, rinsed with deionized water, dried at room temperature, and stored for later use.

(2) Under oxygen plasma treatment for 120s and discharge power of 100W, plasma treatment was performed on FSARGPCL contact lens material.

(3) Soak the treated material in an aqueous solution of 2-methacryloyloxyethylphosphorylcholine (MPC) with a concentration of 0.05wt% for 2 hours, and stir continuously with a magnetic stirrer during this period.

(4) Rinse the surface of the contact lens material 3 times with deionized water, dry at room temperature, and store.

Figure 2 is the SEM photograph of the surface of the FSARGPCL contact lens before and after oxygen plasma treatment, and Figure 4 is the SEM photograph of the surface of the FSARGPCL contact lens before and after oxygen plasma grafted with MPC. Oxygen plasma treatment under neutral conditions does not significantly affect the surface morphology of contact lenses.

Figure 7 is the comparison curve of the refractive index of the FSARGPCL contact lens before and after oxygen plasma grafting MPC, the refractive index of the FSARGPCL contact lens did not change significantly before and after grafting, and did not change the bulk performance of the contact lens. It shows that this modification method has no adverse effect on the most basic visual function of contact lenses.

Figure 8 shows the amount of protein adsorption on the surface of the FSARGPCL contact lens before and after oxygen plasma grafting MPC, the modified contact lens reduces the deposition of protein on the lens.

Example 3

Ammonia plasma treatment is used as the surface treatment method, polyethylene glycol diacrylate (PEGDA) is used as the graft molecule, and the steps are as follows:

(1) The FSARGPCL contact lens material (BostonXO, Wenzhou Medical College) was cut into thin slices of about 1 mm, polished, cleaned with a digitally controlled ultrasonic cleaner for 15 minutes, rinsed with deionized water, dried at room temperature, and stored for later use.

(2) Under the ammonia plasma treatment for 120s and the discharge power of 100W, plasma treatment was performed on the FSARGPCL contact lens material.

(3) Soak the treated material in a polyethylene glycol diacrylate 10000 (PEGDA10000) aqueous solution with a concentration of 0.01 wt% for 3 hours, and stir continuously with a magnetic stirrer during this period.

According to the above steps (1)-(3), polyethylene glycol diacrylate 4000 (PEGDA4000) was used as the graft molecule to modify the FSARGPCL contact lens material.

(4) Rinse the surface of the contact lens material 3 times with deionized water, dry at room temperature, and store.

Figure 9 is a comparison curve of the refractive index of the FSARGPCL contact lens before and after ammonia plasma grafting with PEGDA. The refractive index of the FSARGPCL contact lens did not change significantly before and after grafting, and the bulk performance of the contact lens did not change. It shows that this modification method has no adverse effect on the most basic visual function of contact lenses.

Figure 10 shows the amount of protein adsorption on the surface of the FSARGPCL contact lens before and after ammonia plasma grafting with PEGDA. The modified contact lens reduces the deposition of protein on the lens.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (8)

1. A method for modifying a rigid gas-permeable contact lens fluorosilicone acrylate material, characterized in that it comprises the following steps: (1) Plasma treatment of the fluorosilicone acrylate material of the rigid gas-permeable contact lens; (2) Soak the processed material in the bionic macromolecule aqueous solution to obtain the modified rigid gas permeable contact lens fluorosilicone acrylate material. 2. The method for modifying the fluorosilicone acrylate material of rigid gas-permeable contact lenses according to claim 1, wherein the plasma described in step (1) is ammonia plasma or oxygen plasma. 3. The modification method of the rigid gas permeable contact lens fluorosilicone acrylate material according to claim 1, characterized in that: the plasma treatment time described in step (1) is 30 to 300s, and the discharge The power is 50-200W. 4. the modification method of rigid gas permeable contact lens fluorosilicone acrylate material according to claim 1, is characterized in that: the bionic macromolecule aqueous solution described in step (2) is 2-methacryloyl One of oxyethyl phosphorylcholine aqueous solution, polyethylene glycol diacrylate aqueous solution or polyethylene glycol aqueous solution. 5. the modification method of rigid gas permeable contact lens fluorosilicone acrylate material according to claim 1, is characterized in that: the bionic macromolecule aqueous solution described in step (2) is 2-methacryloyl Oxyethyl phosphorylcholine aqueous solution or polyethylene glycol diacrylate aqueous solution. 6 . The method for modifying the fluorosilicone acrylate material of rigid gas-permeable contact lenses according to claim 5 , wherein the polyethylene glycol diacrylate has a molecular weight of 4,000-10,000. 7. The method for modifying the fluorosilicone acrylate material of rigid gas-permeable contact lenses according to claim 1, characterized in that: the concentration of the bionic macromolecular aqueous solution described in step (2) is 0.01 to 0.1wt %. 8. The method for modifying the fluorosilicone acrylate material of rigid gas permeable contact lenses according to claim 1, characterized in that: the soaking in step (2) refers to soaking for 2-4 hours.