CN105111479A - Method for modifying fluorinated siloxane acrylate material of rigid gas-permeable corneal contact lens - Google Patents
Method for modifying fluorinated siloxane acrylate material of rigid gas-permeable corneal contact lens Download PDFInfo
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- CN105111479A CN105111479A CN201510551357.3A CN201510551357A CN105111479A CN 105111479 A CN105111479 A CN 105111479A CN 201510551357 A CN201510551357 A CN 201510551357A CN 105111479 A CN105111479 A CN 105111479A
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Abstract
The invention relates to a method for modifying a material of a rigid gas-permeable corneal contact lens and discloses a method for modifying a fluorinated siloxane acrylate material of a rigid gas-permeable corneal contact lens through plasma treatment and grafting. The method comprises the following steps of carrying out plasma treatment on the fluorinated siloxane acrylate material of the rigid gas-permeable corneal contact lens; and soaking the treated material into a bionic macromolecular water solution to obtain the fluorinated siloxane acrylate material of the rigid gas-permeable corneal contact lens. According to the method, the fluorinated siloxane acrylate material of the rigid gas-permeable corneal contact lens is treated by using a plasma surface treatment method, and then, bionic macromolecules with high hydrophilia, good biocompatibility and protein absorption prevention property are grafted on the surface of the material, so that the hydrophilia of the material is improved, tear is relatively easily spread, the problem of poor comfort when the lens is worn for the first time is solved, the problem that proteins are accumulated because the lens is worn for a long term is not easily caused, the wearing time is prolonged, and the wearing comfort is improved.
Description
Technical field
The present invention relates to a kind of method of modification hard air-permeable cornea contact mirror material, particularly a kind of hard air-permeable cornea contact mirror fluorosilicone acrylate material is by Cement Composite Treated by Plasma, the method for modifying of grafting realization to it.The method can improve traditional fluorosilicone acrylate material wetting ability, make the easier drawout of tear, solve the problem that it just wears comfortableness difference, not easily cause the deposition of protein in tear after wearing for a long time, realization extends wear-time and comfort level is worn in improvement.Material modified improved performance, the optimization that can be applicable to hard air-permeable cornea contact mirror of gained.
Background technology
Contact lens is the medical optical utensil that one is mainly used in correcting all kinds of ametropia (comprising myopia, long sight, astigmatism and presbyopia), comes out existing more than hundred year.Because it directly contacts with cornea, academia is by its called after " contact lens ".No matter correct defects of vision, beautify eyes color and luster or be used for the treatment of keratopathy, existing countless people enjoy the benefit that wearing of contact lens is brought at present.According to statistics, China wearing of contact lens person accounts for 3% of total population, and the U.S., Japan and other countries account for 10%.Along with development and the improvement of contact lens production technique and material, the population ratio of wearing of contact lens has the trend constantly risen, and the purposes of contact lens also gets more and more.
The development of hard corneal contact lens material, experienced by the process from the traditional hard corneal contact lens material of the glass, polymethylmethacrylate (PMMA) etc. at initial stage to breathable hard corneal contact lens materials such as N-BUTYL ACETATE Mierocrystalline cellulose (CBA), fluorosilicone acrylate (FSA), fluorocarbons (FC).Hard corneal contact lens has harder, the shortcoming such as water-absorbent is minimum, be not easily spontaneously wet out by water, the comfort level worn is not high.
Surface modification be improve material surface performance the most directly, the most effective approach, the advantages such as compared with other method, plasma technique has that technique is simple, cost is low, pollution-free, efficiency is high, temperature of reaction is low, the good uniformity of process.Direct plasma surface treatment is exposed to by material in the plasma body of inorganic gas generation of non-polymerization, utilize the energy particle in plasma body and active specy bombardment material surface, react with material surface, its surface is made to produce specific functional group, material structure is caused to change, thus surface modification is carried out to material, improve the surface property of material.Plasma surface treatment can make material surface produce etching and roughening.But simple plasma surface treatment can only give material certain surface property at short notice, ageing due to Cement Composite Treated by Plasma effect, the functional group introduced at material surface can gradually to table in-plane moving and upset.For obtaining lasting surface modification effect, mostly also need to do further finishing to material.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the object of the present invention is to provide a kind of method of modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material.
Object of the present invention is realized by following proposal:
A method of modifying for hard air-permeable cornea contact mirror fluorosilicone acrylate material, comprises following concrete steps:
(1) Cement Composite Treated by Plasma is carried out to hard air-permeable cornea contact mirror fluorosilicone acrylate material (FSARGPCL);
(2) material after process is immersed in bionical macromolecular aqueous solution, obtains modification hard air-permeable cornea contact mirror fluorosilicone acrylate material.
Plasma body described in step (1) can be ammonia plasma treatment or oxygen plasma.
The time of the Cement Composite Treated by Plasma described in step (1) is preferably 30 ~ 300s, and discharge power is preferably 50 ~ 200W.
Preferred, the time of the Cement Composite Treated by Plasma described in step (1) is 120s, and discharge power is 100W.
In order to realize the present invention better, the hard air-permeable cornea contact mirror fluorosilicone acrylate material described in step (1) can be the thin slice of about the 1mm of cutting.
Preferably, the described hard air-permeable cornea contact mirror fluorosilicone acrylate material in step (1) can carry out polishing, ultrasonic cleaning after dicing, Air drying after deionization washing.
Preferred, above-mentioned ultrasonic cleaning refers to ultrasonic cleaner cleaning 10 ~ 20min, most preferably is 15min.
Bionical macromolecular aqueous solution described in step (2) is preferably the one in 2-methylacryoyloxyethyl phosphorylcholine (MPC) aqueous solution, polyethyleneglycol diacrylate (PEGDA) aqueous solution or polyoxyethylene glycol (PEG) aqueous solution.
Preferably, the bionical macromolecular aqueous solution described in step (2) is 2-methylacryoyloxyethyl phosphorylcholine (MPC) aqueous solution or polyethyleneglycol diacrylate (PEGDA) aqueous solution.2-methylacryoyloxyethyl phosphorylcholine and polyethyleneglycol diacrylate are all the bionical macromole with high-hydrophilic and good biocompatibility, their similar is in biomembranous structure, modify wetting ability and the biocompatibility that significantly can improve material for biomaterial surface, reduce material surface to the absorption of protein.
Preferred, the molecular weight of the polyethyleneglycol diacrylate (PEGDA) described in step (2) is 4000 ~ 10000.
The concentration of the bionical macromolecular aqueous solution described in step (2) is preferably 0.01 ~ 0.1wt%.
Immersion described in step (2) is preferably immersion 2 ~ 4h.
Immersion described in step (2) is preferably immersion limit, limit and stirs.
The modification hard air-permeable cornea contact mirror fluorosilicone acrylate material obtained described in step (2) can utilize deionized water rinsing and Air drying carries out aftertreatment.
Mechanism of the present invention is:
Using plasma surface treatment method of the present invention carries out surface treatment to hard air-permeable cornea contact mirror (RGPCL) fluorosilicone acrylate (FSA) material, improve the wetting ability on contact lens surface, ageing due to Cement Composite Treated by Plasma effect, the functional group introduced at material surface can gradually to table in-plane moving and upset, for obtaining lasting surface modification effect, the present invention will have high-hydrophilic, good biocompatibility and prevent bionical macromole 2-methylacryoyloxyethyl phosphorylcholine (MPC) of protein adsorption character or polyethyleneglycol diacrylate (PEGDA) be grafted to FSARGPCL Contact Lens surface, the wetting ability on further raising contact lens surface, decrease the absorption of contact lense surface to protein, reach desirable surface property.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) surface modifying method of the present invention's proposition, the wetting ability of traditional F SA material can be improved, make the easier drawout of tear, solve the problem that it just wears comfortableness difference, not easily cause the deposition of protein in tear after wearing for a long time, realization extends wear-time and comfort level is worn in improvement.
(2) surface modifying method of the present invention's proposition, does not change the bulk properties of contact lens, and before modified, the specific refractory power of contact lense does not have considerable change.
(3) complete processing of the present invention is simple, and cost is lower, is conducive to scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photo on FSARGPCL contact lens surface before and after ammonia plasma treatment process.
Fig. 2 is the SEM photo on FSARGPCL contact lens surface before and after oxygen plasma treatment.
Fig. 3 is the SEM photo on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting MPC.
Fig. 4 is the SEM photo on FSARGPCL contact lens surface before and after oxygen plasma grafting MPC.
Fig. 5 is the specific refractory power comparison curves of FSARGPCL contact lens before and after ammonia plasma treatment grafting MPC.
Fig. 6 is the protein adsorption amount on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting MPC.
Fig. 7 is the specific refractory power comparison curves of FSARGPCL contact lens before and after oxygen plasma grafting MPC.
Fig. 8 is the protein adsorption amount on FSARGPCL contact lens surface before and after oxygen plasma grafting MPC.
Fig. 9 is the specific refractory power comparison curves of FSARGPCL contact lens before and after ammonia plasma treatment grafting PEGDA.
Figure 10 is the protein adsorption amount on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting PEGDA.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In the following example, agents useful for same is all commercially available.
Embodiment 1
Be treated to surface treatment method with ammonia plasma treatment, 2-methylacryoyloxyethyl phosphorylcholine (MPC) is grafting molecules, and step is as follows:
(1) FSARGPCL Contact Lens (BostonXO, Wenzhou Medical College) is cut into the thin slice of about 1mm, and carry out polishing, 15min is cleaned with numerical control ultrasonic cleaner, deionized water rinsing is clean, dry under normal temperature, saves backup.
(2) at ammonia plasma treatment process 120s, discharge power is under 100W, carries out Cement Composite Treated by Plasma to FSARGPCL Contact Lens.
(3) material after process being immersed in concentration is 3h in 2-methylacryoyloxyethyl phosphorylcholine (MPC) aqueous solution of 0.02wt%, and period ceaselessly stirs with magnetic stirring apparatus.
(4) deionized water rinsing contact glass material surface 3 times are used, dry under normal temperature, preserve.
Fig. 1 is the SEM photo on FSARGPCL contact lens surface before and after ammonia plasma treatment process, Fig. 3 is the SEM photo on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting MPC, before modified, contact lense surface opposed flattened, illustrates that ammonia plasma treatment process can not produce a very large impact contact lense configuration of surface under certain modified condition.
Fig. 5 is the specific refractory power comparison curves of FSARGPCL contact lens before and after ammonia plasma treatment grafting MPC.Before and after grafting, the specific refractory power of FSARGPCL contact lens does not have considerable change, does not change the bulk properties of contact lens, illustrates that the most basic visual function of method of modifying corneal contact lense does not have disadvantageous effect.
Fig. 6 is the protein adsorption amount on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting MPC, reduces the deposition of protein on eyeglass through modified contact lens.
Embodiment 2
Take oxygen plasma treatment as surface treatment method, 2-methylacryoyloxyethyl phosphorylcholine (MPC) is grafting molecules, and step is as follows:
(1) FSARGPCL Contact Lens (BostonXO, Wenzhou Medical College) is cut into the thin slice of about 1mm, and carry out polishing, 15min is cleaned with numerical control ultrasonic cleaner, deionized water rinsing is clean, dry under normal temperature, saves backup.
(2) at oxygen plasma treatment 120s, discharge power is under 100W, carries out Cement Composite Treated by Plasma to FSARGPCL Contact Lens.
(3) material after process being immersed in concentration is 2h in 2-methylacryoyloxyethyl phosphorylcholine (MPC) aqueous solution of 0.05wt%, and period ceaselessly stirs with magnetic stirring apparatus.
(4) deionized water rinsing contact glass material surface 3 times are used, dry under normal temperature, preserve.
Fig. 2 is the SEM photo on FSARGPCL contact lens surface before and after oxygen plasma treatment, Fig. 4 is the SEM photo on FSARGPCL contact lens surface before and after oxygen plasma grafting MPC, before modified, contact lense surface opposed flattened, illustrates that oxygen plasma treatment can not produce a very large impact contact lense configuration of surface under certain modified condition.
Fig. 7 is the specific refractory power comparison curves of FSARGPCL contact lens before and after oxygen plasma grafting MPC, and before and after grafting, the specific refractory power of FSARGPCL contact lens does not have considerable change, does not change the bulk properties of contact lens.Illustrate that the most basic visual function of this method of modifying corneal contact lense does not have disadvantageous effect.
Fig. 8 is the protein adsorption amount on FSARGPCL contact lens surface before and after oxygen plasma grafting MPC, reduces the deposition of protein on eyeglass through modified contact lens.
Embodiment 3
Be treated to surface treatment method with ammonia plasma treatment, polyethyleneglycol diacrylate (PEGDA) is grafting molecules, and step is as follows:
(1) FSARGPCL Contact Lens (BostonXO, Wenzhou Medical College) is cut into the thin slice of about 1mm, and carry out polishing, 15min is cleaned with numerical control ultrasonic cleaner, deionized water rinsing is clean, dry under normal temperature, saves backup.
(2) at ammonia plasma treatment process 120s, discharge power is under 100W, carries out Cement Composite Treated by Plasma to FSARGPCL Contact Lens.
(3) material after process being immersed in concentration is 3h in polyethyleneglycol diacrylate 10000 (PEGDA10000) aqueous solution of 0.01wt%, and period ceaselessly stirs with magnetic stirring apparatus.
By above-mentioned steps (1) ~ (3) with polyethyleneglycol diacrylate 4000 (PEGDA4000) for grafting molecules carries out modification to FSARGPCL Contact Lens.
(4) deionized water rinsing contact glass material surface 3 times are used, dry under normal temperature, preserve.
Fig. 9 is the specific refractory power comparison curves of FSARGPCL contact lens before and after ammonia plasma treatment grafting PEGDA, and before and after grafting, the specific refractory power of FSARGPCL contact lens does not have considerable change, does not change the bulk properties of contact lens.Illustrate that the most basic visual function of this method of modifying corneal contact lense does not have disadvantageous effect.
Figure 10 is the protein adsorption amount on FSARGPCL contact lens surface before and after ammonia plasma treatment grafting PEGDA, reduces the deposition of protein on eyeglass through modified contact lens.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a method of modifying for hard air-permeable cornea contact mirror fluorosilicone acrylate material, is characterized in that comprising the following steps:
(1) Cement Composite Treated by Plasma is carried out to hard air-permeable cornea contact mirror fluorosilicone acrylate material;
(2) material after process is immersed in bionical macromolecular aqueous solution, obtains modification hard air-permeable cornea contact mirror fluorosilicone acrylate material.
2. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the plasma body described in step (1) is ammonia plasma treatment or oxygen plasma.
3. the method for modifying of the hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the time of the Cement Composite Treated by Plasma described in step (1) is 30 ~ 300s, and discharge power is 50 ~ 200W.
4. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the bionical macromolecular aqueous solution described in step (2) is the one in the 2-methylacryoyloxyethyl phosphorylcholine aqueous solution, the polyethyleneglycol diacrylate aqueous solution or Aqueous Solutions of Polyethylene Glycol.
5. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the bionical macromolecular aqueous solution described in step (2) is the 2-methylacryoyloxyethyl phosphorylcholine aqueous solution or the polyethyleneglycol diacrylate aqueous solution.
6. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 5, is characterized in that: the molecular weight of described polyethyleneglycol diacrylate is 4000 ~ 10000.
7. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the concentration of the bionical macromolecular aqueous solution described in step (2) is 0.01 ~ 0.1wt%.
8. the method for modifying of hard air-permeable cornea contact mirror fluorosilicone acrylate material according to claim 1, is characterized in that: the immersion described in step (2) refers to immersion 2 ~ 4h.
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Cited By (3)
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CN110194846A (en) * | 2019-06-26 | 2019-09-03 | 江苏彩康隐形眼镜有限公司 | The preparation method of the modified and its colored Ortho-K in Ortho-K surface |
CN112375247A (en) * | 2020-12-02 | 2021-02-19 | 中国科学院合肥物质科学研究院 | Corneal contact lens treatment method based on amphiphilic composite gradient functional membrane |
CN115197522A (en) * | 2022-06-10 | 2022-10-18 | 甘肃康视丽隐形眼镜有限公司 | High-water-content high-oxygen-permeability silicon hydrogel, corneal contact lens and preparation method of corneal contact lens |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110194846A (en) * | 2019-06-26 | 2019-09-03 | 江苏彩康隐形眼镜有限公司 | The preparation method of the modified and its colored Ortho-K in Ortho-K surface |
CN112375247A (en) * | 2020-12-02 | 2021-02-19 | 中国科学院合肥物质科学研究院 | Corneal contact lens treatment method based on amphiphilic composite gradient functional membrane |
CN115197522A (en) * | 2022-06-10 | 2022-10-18 | 甘肃康视丽隐形眼镜有限公司 | High-water-content high-oxygen-permeability silicon hydrogel, corneal contact lens and preparation method of corneal contact lens |
CN115197522B (en) * | 2022-06-10 | 2024-02-23 | 甘肃康视丽隐形眼镜有限公司 | High-water-content high-oxygen-permeability silicon hydrogel, cornea contact lens and preparation method of cornea contact lens |
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