TW202466B - - Google Patents

Description

202466 Λ 6 η 6 Printed by the Shiyang Standardization Bureau of the Ministry of Economic Affairs, Cooperative Society V. Description of the invention () The present invention is based on an ocular implant and its method of preparation · thereby improving the properties of its material surface. The present invention is the spirit of invention of the Yanmin Mining Application No. 304479, but the content is different; the filing date of the No. 304479 application is February 1, 1989, and the application is the invention of the Yanmei Mining Painting Patent. Soothe. The application date of the No. 037153 application is April 10, 1987, and its US Patent No. 480638 (the image was issued by the US Patent Office on February 21, 1989. According to research, eye implants such as ocular After the endoscopic (I0L) is embedded in the eye concealment during surgery, it will cause a considerable amount of damage to the corneal endothelial tissue, only when there is no contact between the eye concealment implant and the corneal endothelial group iron Causes iron damage to the corneal endothelium. Most of the ocular implants are made of hydrophobic polymethyl methacrylate (PMHA). PMMA polymer has excellent optical properties and can resist biological Degradation. But when the PMMA polymer surface is connected to K endothelial cells, the PHHA polymer surface will adhere to the endothelial tissue and when the PMMA polymer surface is separated from the endothelial tissue, it will cause part of the endothelial tissue to peel off and adhere to the endothelial tissue. On the surface of the PMMA polymer. For the same reason, when the surface of the PMMA polymer is in iridescence with other eye groups, it will also adhere to other eye groups and cause tissue damage. Other hydrophobic polymers such as polypropylene (P P), Polyvinylidene fluoride (PVDF), poly «acid_ (PC), polysilicon« (PSI), etc. can be used as eye implants, but they will stick to the eye group and become the eye group. Even if the PMMA eye lens and the corneal endothelial group make a short and non-invasive connection, it will cause extensive damage to the corneal endothelial tissue (please read back and pay attention to the market item # Item write-up 記-資 _ 線 < 5 good scales of the original paper are used in a B home standard (CNS) T4 specification (2 丨 0> < 297 gong) A 6 η 6 203466 V. Invention description () Harm This kind of lynx can be found in the following documents: Bourne et al, A ·. J. Ophthalmol., Vol. 81, PP.482-485 (1976) 5 Forster et al, Trans. An. Acad. Ophthalaol. Otolaryngol., Vol. 83, OP- 195-OP-203 (1977); Katz et al,

Trans. Ad. Acad. Ophthalaol. Otolaryngol., Vol. 83, OP-204-OP-212 (1977) ί Kaufman et al.

Science, Vol. 198, PP. '525-527 (1977); Sugar et al, Arch. Ophthaleol., Vol. 96, PP.449-450 (1978). The above documents all talk about the implant surface and endothelial group. All kinds of phenomena caused by the problem of contact. However, it is difficult to prevent the surface of the implant from contacting the corneal endothelial tissue or other sensitive eye groups such as iridescent and ciliary sulcus during the operation, so some researchers implanted PMMA eye implants Method to reduce the adhesion and injury of the implant surface to the corneal endothelial group. There are more than one method to modify the surface of the ocular implant. Some methods apply different types of hydrophilic polymer solutions or soluble coatings to the surface of the ocular implant to reduce the surface of the implant to the endothelial group. Adhesion. Some hydrophilic polymer solutions or coatings include methyl methoxine and polyvinyl pyrrolidone (PVP). The above method of modifying the surface of the eye implant can be found in the following literature: Katz et al, supra, and Knight et al, Chen. Abs., Vol, 92: 203547f (1980). Although the above method has a temporary protective effect on endothelial cells, it is still not satisfactory. Because the coating made by the above method cannot be properly adhered to the surface of the implant, the coating will move or change when it is embedded in the eye, or it will dissolve quickly after the operation, and even post-operative complications may occur. Phenomena and other phenomena make this paper use the standard a Η home «Bi (CNS) specifications (210X297 male dragon) (please read 1? Back to the note more matters # 建 写. ^ 〆 装-Ministry of Economic Affairs Industry and Consumers f cooperation Du Printing 202466 A 6 η 6 Ministry of Economic Affairs Central Standards Bureau A Industry and Consumer Cooperation Du printing V. Description of the invention () The operation is more complicated. Furthermore, the above methods can not produce a uniform It is also difficult to control the thickness of the coating. Ye et al. [Please refer to the following documents: Yalon et al, Acta: XXVI, International Congress of Ophthalaologyt ed. Paul Henkind (1983)] IT tried to stimulate ethylene with gamma radiation NVP is polymerized on the surface of the PMMA implant to form a protective coating, but because of the considerable problems of controlling the optical properties of the coating and the protective properties of the component, this type of single waist polymerized PMMA material The superficial method is not successful. The human method cannot specify the conditions and parameters of the reaction process (such as single crocodile concentration, gamma radiation dose and dose rate, etc.). The quality of the coating obtained by the method described by Ye Zi et al. Is extremely poor, and the coating is not good. There are many defects such as unevenness and extremely unstable mechanical properties. The treatment method using PTFE gamma-PVP has been seen in the report, but in severe cases, the gamma JHS is required to be around 1 Mrad. Both sexes are mutated, so it is not recommended to use [Boffa et al, J. Biomed Mater, Res. Vol. 11, P317 (1977)]. The single high-concentration non-hydrophilic solution (50J in this dagger: NVP) The use of it also requires a fairly high dose of "(1-5 Mrad) gamma rays to cause a high degree of grafting, but the volume and surface waitability of PTFE vary more, because PTFE is usually suspended at about 1 Mrad. Under the Mar ray, the quality of shoes changes. The inventor of the present invention has obtained a US patent after completing a surface polymerization method. The US Patent No. 480638 No. 2 image was issued by the US Patent Office on February 21, 1989. The patent uses gamma roller to stimulate the hydrophilic waist to polymerize The surface of the prepared eye implant is grafted and polymerized into a coating (please read the precautions first. Sun fills the standing dress. Order _ line · This paper standard is used in a Η house standard (CHS) 4 specifications ( (210X297 public address) 202466 Λ 6 Η 6 The Ministry of Economic Affairs, the Central Bureau of Industry and Commerce, A Industry and Consumer Goods Cooperation, Du Printing 5. The method of invention (), can successfully overcome the many difficulties and deficiencies of the method described by Ye sleep and others . The inventor found in US Patent No. 4806382 that a thin surface coating can be obtained from certain conditions and parameters of the reaction process to be determined. The single compound used in the above-mentioned compound is vinylpyrrolidone (NVP), methyl hydroxyethyl acrylate (HEMA) or NVP and HEMA copolymer. The above single compound can also be mixed with ionic single snakes as described in the present invention. The method of forming a copolymer on the surface of the material. Materials that can be used as eye implants include polymethyl methacrylate (PMMA), polypropylene (PP), polyvinyl fluoride (PVDF), polysulfonate (PC), and polysilazane (PSi). The above mentioned method is to use gamma radiation to lift the single hungry graft on the surface of the implant to form a thin coating. This coating can increase the hydrophilicity of the implant surface and reduce the adhesion of sturgeon sensitive eye tissues such as iridescent and corneal endothelial group on the surface of the implant, so it can reduce the damage to the tissue when the implant is in contact with the group With the chance of complications after surgery. A thin and uniform coating can be formed by treating the surface of the material with the method used by U.S. Patent No. 480632. Because the coating is chemically bonded to the surface of the eye implant, the coating can be used for a longer period of time, and it is not easy to remove, degrade, and change. This is beyond the reach of conventional technology. Gamma radiation stimulates NVP, HEMA, or a mixture of NVP and HEMA to form a surface coating of PVP, PHEMA, or P (NVP-HEHA) graft polymer on the surface of the two implants. It is carried out in an aqueous solution and meets the following anti-molecular conditions: (A) The monomer concentration is between 0.5 and 50% of the weight of the standard garden; (B) The amount of gamma radiation is between 0.01 and 0.50Mrad Room ί-first * read ih back to the notes, writing and binding

MiUlL scale edge-use medium 8 «home standard (0 昍) Yu 4 specifications (2 丨 0> < 297 male dragon) A 6 Π6 202466 V. Description of invention () (C) The dose rate of gamma radiation Divide table 10 to 250 Qrade in the model nursery; (D) Maintain the polymer molecules in the solution in the 250,000 to 5,000, 00 model garden. The purpose of the present invention is to provide a more advanced method to form a hydrophilic table 1 on the surface of the eye implant material. It is the purpose of the present invention to "maintain" the molecular weight of the polymer in solution between 250, 000 and 5,0G0.G00 according to Meituan Patent No. 4806382, which can produce a hydrophilic surface layer on the surface of the ocular implant The method is to determine the status of the ship's non-compliance. The further improvement of the present invention concludes that the method shown in the above-mentioned US Patent No. 4806382 is effectively implemented, and the gamma setting will exceed its minimum value of 0.001 Mrad. The most successful improvement method of the present invention, "You conclude, if accurate The residue under the conditions described in the above-mentioned Meipu Patent No. 4806382 can be maintained to add a grafted polymer surface layer on the surface of the ocular implant. Figure part: Figures 1-3 Examples of eye implants that you describe according to the present invention: You see a circle of eyeglasses above a piece of man-shaped glasses. Circle two you look at the top of a pair of glasses with fiber touch power, cough mirror can use a different lower polymer other than optics. You see the eyebrows above your corneal prosthesis. Detailed description: As defined by the United States No. 4806382, the standard paper size Λ is used in the B Η home standard (CNS) T4 specification (210X297 male dragon) under the condition of »........ ............. f ·! # · · ·. ^ (please -ΛRead back to the notes) # 幣 写 矣 Ministry of Economics, Central Standards Bureau β 工 消 t cooperation du printing -8-202466 Λ 6 η 6 Printed by the Ministry of Economic Affairs, Bureau of Standards, Bureau of Industry and Commerce Co., Ltd. V. Description of the invention () The method of maintaining the gram molecular weight in the combined solution at a certain value is not practical. The results of the reaction conditions obtained by Xiong engaged in the graft polymerization procedure. Therefore, the present invention is not suitable for detailing the molecular weight of the polymerization solution. The cracking conditions of the monomer underlayer are widely changed due to the influence of different gamma grafts. Assuming that a group such as monosodium, monosodium concentration, total gamma dose, and gamma suspension are placed in a fixed state, the molecular weight of the polymer formed in the solution cannot be changed by itself, but it has become the concentration of the first single, A product of the setting of the gamma coagulant and the setting value of the gamma thinning rate. A large amount of inhibition, if the effective surface graft polymerization I is not broadcast, at the same time, the relative molecular weight of the solution polymer is reduced (as low as 5,000-10,000). Although this invention has been applied for US 4806382 K Degree, but the inventors found that in the mining research, although they believe that 0.01 to 0.20 Mrad is a relatively low amount in the synthesis, the total gamma dose in the synthesis operation is as low as 0.001 Rrad Although the dosage of the prior art mentioned in US No. 4806382 is useful for gamma polymerization grafting is generally higher than 0.5 Mrad, at the same time, it is more surprising to find that surface grafting can be achieved with a low amount of 0.Q1 Mrad, 〃However, the successful successful mining reduced the gamma of the effective grafting to 0.01 Nrad is an unexpected result. In particular, in the US case No. 4806382, the single-gambling soil shrinkage graft was scraped down. 0.5 X, in the same embodiment, the present invention found that after further research, its monomer concentration can be reduced to 0.1 to reset S ;. The following conditions are optional, if there are the following conditions, the reaction conditions are better ： (Please read the notes on the back-l1) -item writing #. 装 · _ 线 · In this paper standard for easy use a Η 家 样 毕 (CNS) T4 specifications (210X297 public) 202466 Ministry of Economic Affairs Printed by the quasi-bureau employee consumer cooperative

It 6_ V. Description of the invention () (E) Remove the gas from the solution of the graft polymerization reaction to maintain the thickness of PVP or P (NVP-HEMA) grafted on the surface of the material from 100 angstroms to 150 angstroms In the rice garden; (G) Add free radical scavenger to the solution of graft polymerization; (Sin) Add swellable material of PMMA or other polymers to the solution of graft polymerization. The invention uses gamma radiation to stimulate NVP, HEMA, or HVP or HEMA mixed single mole to form PVP, PHEMA or P (HVP-HEMA) on the surface of an eye implant made of PP, PVDF, PC or PSi The surface graft polymer, the reverse conditions can be the same as the reaction conditions of the above-mentioned single brewing graft polymerization on PMMA, if the gas can be degassed from the solution, the result of the graft polymerization reaction will be better, and the The effect of repairing plutonium on the surface of the object is better. In the invention, in the Pujing part, the gun is mentioned as "Yalon" and Knight (Knight) try to use gamma radiation-to lift the coating formed by NVP and HEKA polymerization on the surface of PMMA The properties of the layer are not good, and the coating formed may have a detrimental effect on the endothelial group. Knight coated the surface of the eyes with polyvinyl yeast (PVA), but the results of clinical trials confirmed that it was not conceivable and therefore not practical. Yalon and KnUht cannot confirm the anti-bite conditions such as monomer concentration, solvent, gamma radiation dose and agent ft rate, and the poor quality of their coatings will wear out. Yalon, Knight, or the literature over the past three decades cannot produce a practical and durable PVP or PHEMA coating on the lens surface of glasses made of PUMA. In order to make a useful coating on the surface of the plastic lutetium material, the following complex requirements must be met: The paper is used on the 5 gram scale side with a Η home sample standard (CNS) 4 specifications (210 > < 297 gong) -10- -10 -Λ 6 Β 6 202466 V. Description of the invention () (A) The coating formed by the graft polymerization reaction must be very thin, durable, transparent and transparent, and can be permanently applied to the surface of the eyes that looks like invisible eyes. The literature often uses high radiation doses (greater than IMrad) of gamma radiation and non-aqueous solvents, but the resulting coatings are thick and streaky and uneven. High dose gamma radiation is sufficient to deform or degrade the material. This phenomenon is also recorded in the following documents: Chapiro, Radiation Cheaistry of Polyneric Systens, John ^ Wiley and Sons, Inc., New York (1 962) and Henglein et al, Aiigeii. Che., Vol. 15, P46K1958 ) (B) The coating obtained by the present invention should have long-term biocompatibility in living mussels. (C) When air bubbles are placed on the coating obtained by the present invention, the connection angle of air bubbles in water must be less than 30 ° (low contact angle indicates high wetting effect). (D) The coating obtained by the present invention has no adhesion to tissues (adhesion to the inner skin group is less than 150 / ca). (E) The coating obtained by the present invention has little male injury to the endothelial group (the rate of injury to the group is less than 20%). (X) ESCA or FTIR analysis can detect the graft polymerized coating. (G) During the sliding friction test, the abrasion resistance of the coating is extremely high (its contact angle hardly changes before the sliding friction test. (Xin) The coating obtained by the present invention can be quickly hydrated. The coating obtained by the present invention After the layer was immersed in water, it changed from a dry state to a tarnished state. The time was only 5 minutes, and the hydration speed was quite fast. Yalon showed a kind of in vitro measurement of male injury in the endothelial group. Standard (CNS) Τ4 specification (210X297mm) (Please read the notes on the back of the book to read Sun Xiang. LINE-Ministry of Economic Affairs, Bureau of Standards, A Gongxiaot, Cooperative Duinu 11- 11- A 6 It 6 202466 V. Description of the invention () '' (Please read back to note the technology of the degree of Sun Xiangwo's first degree. Although Yalon pointed out that at a high concentration of monads, the PVP coating of the graft polymerization The level of damage to the cells is low, but the reaction conditions such as gamma radiation and the dose rate cannot be confirmed, and the image between the reaction conditions and the product cannot be specified. Member of the Bureau of Standards, Ministry of Economic Affairs H Xiaojun Cooperative Print the reaction bar used in the present invention And # number must be within a certain range, in order to use Gamma radiation to form an effective graft polymerization reaction to form a Du layer to modify the surface of the material. The coating obtained by the present invention includes PVP, PHEMA or P (NVP-HEMA) The conditions and parameters used in the present invention include the weight percentage of the single unit, the gamma radiation dose and the dose rate, single. The penetration time or expansion time of the material, and the removal of oxygen, etc. Other preferred reaction conditions of the present invention Including catalyst, free radical scavenger, polymer swelling solution and temperature, etc. However, the molecular weight and molecular distribution of the polymer in the solution, the conversion rate of the single compound and the remaining unreacted single myelin compound, grafted polymer The thickness and surface properties of the coating are the results of the graft polymerization reaction. The results of the above reaction vary with the change of the reaction conditions. For example, irradiating the surface of the material with the amount of O.IHrad gamma radiation will make the graft The speed of the polymerization reaction is slowed down so that the polymer molecules in the solution are set higher. If oxygen is removed in the above reaction, the graft polymerization reaction can be made at a lower gamma radiation Carry out under high temperature. Add a free radical scavenger to the solution with high single concentration, such as copper salt, male salt or organic progenitor such as ascorbic acid, which can reduce the polymer molecules in the solution * and avoid solution condensation Gelation. The reaction process conditions and parameters used in the present invention can be changed within a certain range to produce a special combination that is beneficial to the surface repair of the polymer surface. Baht. The reverse process conditions and parameters used in the present invention are as follows: (A) Concentration of single pith: increase the degree of monomer, then graft polymerization, dissolve the paper, and use it as a standard (CNS) Τ4 specification (210x297 mm) 202466 A 6 Π 6-12- 5. Invention Explanation (The molecular weight of the polymer of the Duo Printing Liquid of the Central Standards Bureau of the Ministry of Economic Affairs and Industry will increase and the contact angle will decrease, so the hydrophilicity of the surface of the material will increase. . For example, use 0.1Mrad_quantity and 309rads / Bin.Gamma radiation rate to lift NVP graft polymerization on PMMA surface to form a PVP coating, measured when the concentration of HVP increases from 3% to 15% The molecular weight (Pv) molecular weight (Mv) of PVP will be increased from 560,000 to 2,700,000. And it is connected to "I Angle by 29. Reduced to 21 °. However, the above results will be affected by the dose rate of gamma radiation and the total dose. For example, when the dose rate of gamma radiation is as low as 64rads / nin., And the concentration of NVP increases from 1% to 10%, the molecular weight of PVP increases from 400,000 to 4,590,000 and the contact angle decreases from 49 ° to 18 °. Generally speaking, the unit of the present invention is between 0.1 and 50%, and it is combined with other reaction conditions. When the degree of collapse of the monomer is as low as 0.1 to 0.5% and the gamma radiation is maintained at a low dose rate, the contact angle of the resulting hydrophilic graft polymerization surface can be reduced to between 30 ° and 40 °. When the temperature is within the range of 20% and 30%, free radical scavenger and low gamma dose must be used to produce effective graft polymer and avoid gelation of the solution plate. When the concentration of "Phu Shan" is close to 50%, the conversion rate of monomers will be significantly reduced. When the concentration of HEMA is maintained in the range of 0.5 to 10%, a good PHEMA coating can be produced. (B) The dose of gamma radiation: Generally speaking, if the total amount of gamma radiation is increased, the molecular weight of the polymer in the solution can be increased and the contact angle of the surface of small materials can be extinguished. However, if the dosage of the male single brewer is too high, and the low gamma radiation dose rate and the concentration of Li K are maintained, the solution becomes very viscous or has a condensing effect, so it is difficult to wash or remove it (eg, gamma roller When the shooting director is Q.25Mrad and the dose rate is 3 09 rads / Bin, and the NVP degree is 10J!). Τη 先 -W] Contrary to the note item Α %% of the original paper with 5 gram scale side in the use of a National Completion (CNS) T4 specifications (210 father 297 male dragon) -13-202466 V. Description of invention () (please Read first, pay attention to the market, and then know how to use the invention. The invention can also use the beam radiation and the graft polymerization reaction. * If the energy of the electron beam radiation and the energy of the gamma radiation are the same, the electron beam can be used. Radiation replaces the gamma radiation used in the present invention. The electron beam radiation is maintained at a pressure range of 50Kev to 10 Mev, and its current is between 5 · A and 100bA. The dose rate of the 霣 子 束 of the present invention is generally higher than The dose rate of the gamma roller is usually between 10 and 10 radS / Bin. (C) The dose rate of gamma radiation or beam radiation: reducing the dose rate of gamma radiation will increase The molecular weight of PVP is set in the solution. If the single-element irrigation of NVP is maintained at 10% and the dose of the gamma roller is maintained at 0.1 Mrad, the gamma radiation dose rate is reduced from 1 2 35 to 49 rads / Bin. Then the contact angle of the surface of the material will be reduced from 31 ° to 15 °. The dosage rate can be as low as if rads / * in. Ο (D) The molecular weight of the polymer in the reaction solution: the small amount of the polymer in the reaction solution will change with the reaction process conditions, such as single β concentration or whether to use free radicals It can be changed after being removed. When the molecular weight of the polymer in the reaction solution is as low as 5000 or 1000, it can still produce effective graft polymerization. If the polymer has a degree of greater than 5,000,000, the liquid will be too viscous or have a coagulation effect that is difficult to wash, so it is not practical.

(E) Removal of gas: When the gas is removed from the solution of graft polymerization by vacuum or unique gas snake such as argon, the total dose of gamma radiation can be reduced (in fact, the total dose can be as low as 0.1Mrad) Can stimulate effective graft polymerization. The conversion rate of degassing gas is comparable to the molecular weight of single PVP polymer. For example, the gamma radiation dose is 0.05Mrad and NVP. The paper is used as the home standard iMCNS) T4 specification (210x297 g *) 202466 A 6 It 6 14 Central Printing and Quarantine Bureau of the Ministry of Economic Affairs. V. Description of the invention () When the monomer irrigation is 10%, if the gas is removed, NVP can be grafted and polymerized on PP to form a good PVP surface coating with a contact angle of 15 °. If oxygen is not removed, it is difficult to carry out graft polymerization under the above conditions. Therefore, the removal of gas is very important to produce a good PVP surface coating. When the material is PP, PVDF or PSi, the graft polymerization on the surface must first remove the gas, otherwise a good PVP surface coating cannot be produced. Degassing also helps to produce a good surface coating on the surface of PMMA or PC, that is, using very low gamma radiation (0.01 to 0.15 Mrad) can form an effective graft on the surface of PKMA or PC polymer. Under the above reaction conditions, if the gas is not removed first, the effect of graft polymerization is not good. 0 (H) Thickness of the graft polymer: when the thickness of the coating layer formed by the graft polymer is extremely thin (100 to 200 A) Although it is hydrophilic and has no adhesion to the group, but its mechanical properties are too soft, it may also produce a gel-like coating, so it is easy to cause trauma when it comes into contact with the group. When the thickness of the graft polymer coating is between 300-500 Angstroms to 50 nanometers, it is more suitable for many different applications. The thicker surface coating has the properties of light, uniformity, optical clarity and rapid hydration. If no swelling solvent is used and the bonding time between the monomer and the material surface is not prolonged, the thickness of the grafted polymer coating is relatively thin, with a thickness of about 0.1 to 5 microns. If a swelling solvent such as ethyl acetate is used, the thickness of the grafted polymer coating on the PMMA surface is about 100 meters or more. In some special applications, the thickness of the surface coating must be increased to 20 to 100 meters to form a thick sponge-like coating. (Geng) free radical scavengers: commonly used reducing agents such as Cu · Fe, (please read the notes on the back first # 难 写 太 | This paper is used in a standard ah family quasi (CNS) T4 specifications (210X297 : ":) 202466 V. Description of invention () Anti-phlegm blood acid and other trapped free radicals can effectively inhibit the polymerization reaction of free radicals in the solution. (To be distinguished in high single irradiance and high gamma radiation dose and dose rate Time), which can slow down the coagulation of the solution. However, the use of free radicals to remove rain also has the following lack of viscosity, which results in a lower polymer molecular scene, more unreacted single marrow and a wider molecular weight distribution. If used The gold salts are not good for biocompatibility. In most of the grafts, the amount of moles avoids the use of free radical scavengers. However, when forming PVP, PHEMA or P (HVP-HEMA) coatings Ascorbic acid helps to reduce the solution & supportability and gelation. Under the above conditions, add ethyl acetate (0.5 to 5%) as a solvent to the single-phase solution. Even if the concentration of the single-phase is as high as 5 〇χ can also get a thicker surface coating and can avoid the viscosity and coagulation of the solution. Liquid: Adding an effective swelling solvent of the material to the solution in the single sheet is beneficial to the expansion of the material eye and helps the dispersion of the single mole on the surface of the material eye. The above phenomenon will occur before and at the time of gamma radiation. Single full penetration of the material can increase the thickness of the surface coating and lift off the degree of bonding of the surface coating on the surface of the material. Ethyl acetate can be used as an effective swelling solution for materials such as PMMA. Gong Xiaot cooperation Du Yin 3i The method of (A) to (Xin) can be used to obtain a good surface graft polymer in this invention, this method is inferior to the conventional method. Because the combination of parameters and conditions of the above methods can be made different The results are different. If NVP and HEHΑ are copolymerized on the surface of the material to form a P (NVP-HEMA) surface coating, then the succession of HEMA in the mixture of NVP and HEMA can be as high as 50 Percentage. However, HEME and the original size of the 5G standard of the original paper are used in a S home standard (CNS) > f 4 specifications (2) 0X297 public; «:) 202466 Ministry of Economic Affairs, Bureau of Standards, the page work consumer price cooperative, Indian slaves. Description of the invention ) If the infusion of NVP and HEMA single-hybrid mixture is 20 to 30 seconds apart, then a free radical scavenger must be used in the single-waist mixture and the single haze stress must be lowered to avoid the solution's sleep effect, because HEMA will Promote the coagulation effect of the main solution. Although the above method represents a major improvement to the prior art, the most suitable result for each case depends on the combination of the execution parameter lanthanum number and the choice of on-site conditions. The present invention not only NVP, HEMA or NVP and HEMA single «can be used to form? 卩?,? 〇> ^ or? (》 ^?-1 ^ 1 (/ 0 surface coating, and different caries can be added to the above single acid Single sweet wine. And non-ionic single "and ionic single B can form a copolymer. The ionic monomers used in the present invention include ethylene «acid, styrene sulfonic acid, methyl thioethyl acrylate, methyl thiopropyl acrylate or other vinyl sulfonic acid, or ethylene methyl carboxylate, crotonic acid or isobutylene Acids, etc. can be used as anionic monochelic. If the ionic monomer used in the present invention contains a functional group such as a vinyl group or an amine group, such as vinylidine, a styrene-based urethane acrylate, or a methyl cyanoacrylate such as dimethyl ethyl methacrylate Or dimethylaminostyrene can be used as ion-limiting single B. In the present invention, ionic monosodium salts and nonionic monomers can also be mixed to form a copolymer. Considering the above phenomena and the reaction process, different reaction conditions must be applied to the articles split by different materials. The following examples will detail the conditions required by the present invention. Here are some highlights of the anti-plaque conditions: The determination of the range of reaction conditions is very useful for cracking good products. The choice of S for the best reaction process depends on the molecular structure of the material and the thickness of the graft polymer coating. The present invention should avoid the conditions that make the solution viscous or produce a sleeping effect, and at the same time avoid the reaction conditions that cause the material to crack or crack. (E.g. Li (please read the back and attention notes # 项 写 官 _ 丨 This paper is used in a national standard (CNS) τ 4 specifications (210X297; «：) 202466 Λ 6 Η 6 Ministry of Economic Affairs Printed by the Cooperative Society of the Provincial Bureau of Management. V. Description of the invention () Ethyl acetate at 203! Is used as the swelling solution of PMMA I). The following four conditions of the anti-mole process are very practical for improving the properties of the material surface: 1) The concentration of singe in aqueous solution is maintained within a range of 5 to 20% (the optimal degree is 10%). The dose of gamma radiation is maintained within a range of 0.05 to 0.20 Mrad (the optimal dose O.lOMrad). The dose rate of gamma radiation is maintained in the range of 20 to 1500 rads / nin (the optimal dose rate is 50 to 2000 rads / atin). The contact angle is less than 30 °. (2) Except for the conditions for purging the gas, other conditions are similar to (1). The gas can be purged with an inert gas such as vacuum or argon, and the dose of gamma radiation is maintained within the range of 0.01 to 0.15 Mrad (the optimal agent is 0.05Mrad). The weight percentage of NVP monomer is maintained in the range of 1 to 15% (the optimal weight percentage is 5 to 10%). The conditions should be better than (1). (3) Except for the condition with extra swelling solvent, the other conditions are similar to (1) and (2). For example, using ethyl acetate as the swelling solvent for PUMA material can make more The body penetrates to the surface of the material and increases the thickness of the grafted polymer coating. (4) Use a high concentration of ethyl acetate (25 to 50%), less than 5% of ethyl acetate swelling solution, and free radicals such as anti-blood Acid (concentration: 0.1 to 1.0 ObM). The dose of the gamma roller is maintained within the range of 0.10 to 0.20 Mrad, and the dose rate is maintained within the range of 20 to 50000 rads / Bin. Special instructions are weight percentages. Unless otherwise stated, all measurements of angles and surface properties are first subjected to the following treatment process • The coating obtained by the gamma radiation graft polymerization reaction is at room temperature or above the room temperature Wash the remaining monomers and ungrafted polymer in warm water or a solution mixed with water and alcohol to improve the properties of the surface of the material. The grafted polymer coating has stable properties and can be used regularly without being soluble In aqueous solution. The size of this paper is in accordance with China National Standard (CNS) 4 (210X297) PCT) 202466 Λ 6 Η6 18 · Printed by the Ministry of Economic Affairs, Central Bureau of Industry and Commerce, Co., Ltd. V. Description of the invention () The present invention can be prepared on the following materials including PHMA, PP, PVDF, PC and PSi surface graft polymer coating The present invention can perform partial graft polymerization or full graft polymerization on the surface of the above material to improve the properties of the material surface of the device or appliance. The surface modification method of the hydrophilic graft polymer used in the present invention is suitable for embedding into various parts of the eye (Such as anterior chamber, posterior chamber, crystalline ") is particularly advantageous for eye penetration. At the same time, the protection of the muscle group and the biocompatibility of other ocular implants, such as corneal inlays, corneal fillings, external corneal surgical instruments, shunts for tarsal eyes, retinal locks and solid buckles The improvements are of great value. * Example 1: This example indicates that the polymerization parameters of the PVP graft polymerization on the surface of PMMA due to the change of the above-mentioned reaction process and gamma-ray irradiation will have an important effect on the results of the reaction. First wash the sample of PMMA plate with soap solution twice, and then wash it with ultrasonic water in the ultrasonic processor. When the PMMA plate is completely dry, place the sample in the glassware containing NVP solution. Then irradiate the product with gamma radiation of different conditions. After irradiating with gamma radiation, the surface of PMMA was washed several times with rubbing water. After being grafted and polymerized with NVP on the surface of the PHUA sample, the sample was freeze-dried in the air. The PVP product in the solution can be measured with a viscometer for molecular weight (Oiv) or with a gel permeation chromatograph for molecular weight (Mw). When you have Mv, you can dissolve PVP in distilled water, and then use a capillary viscometer to measure its characteristic viscosity. The coating of PVP graft polymerization on the surface of PMHA can be used for water droplets or water vapor (please pay attention to the matter first # 项 舄 木 < Binding · Binding-line. This paper is used in 5 gram size side a B Jiayu standard (CNS)肀 4 specifications (210X297 public address) 202466 -19- Λ 6 Π 6 V. Description of the invention () Bubble measuring its contact angle. On extremely hydrophilic coatings, the bubble measurement method is more accurate than the water drop measurement method. The invention The method for measuring the angle of the bubble joint is as follows: first place the PMMA after graft polymerization horizontally in distilled water, and place bubbles with a volume of about 0.8 μl on the bottom surface of PMMA. Both opposite sides of PMMA are measured. A sample is measured five times. Tables 1 to 9 are the measurement results. Table 1: The effect of gamma radiation on the intrinsic viscosity of gamma radiation induced by NVP graft polymerization on the surface of PMMA: Concentration: 10% NVP The total dose of gamma radiation in water: O.lMrads dose rate time 2m 1235rads / nin thorn 21 pass 1.48 1.15X10 'surface 309rads / nin 5 / J t 24 fiber 2.21 2.27X104 _ 137rads / nin 12 / j 0m 0 2.61 3.04X106 sm 77rads / ain 2_3 phen 2.85 3.49X10 * 1 side 49rads / min 3.56 5.09X106 Printed in Table 1 of the Central Standards Bureau of the Ministry of Economic Affairs, Mgong Consumer Cooperatives 1. Estimate the effect of the dose rate of gamma radiation on the molecular weight and viscosity of PVP in the solution by viscometry. When the rate of the gamma radiation agent decreases and the exposure time is increased Even if the gamma radiation agent absorbed by the sample is the same, the molecular weight of PVP in the solution will increase. When the lowest agent is 49rads / Bin, this paper is used in the 81HS home standard (CNS) T4 specification (210X297 ; ":) -20-202466 Λ 6 It 6 V. Description of the invention () The highest molecular weight of PVP available. Mv = 5.09X 106 0 Table 2: Gamma radiation is used to lift the HVP graft polymerized on the surface of the gamma gamma Total Radiation_Measurement of the color viscosity of the color broadcast: R: 10% NVP in water gamma radiation agent ft rate: 309rads / nin. (Distance from the gamma radiation source is 4 inches) Gamma radiation total "set time Characteristics Cobalt molecular weight (Mv) 0. OSMrads 2 hours 42 minutes 0. lONrads 5 small selection. 24 minutes 0.25Mrads 13 hours 30 minutes sickle 0.50Mrads 27 hours 6 1 8 2 1 2 ο ο 11 1 * XX 9 7 6 2 (please read the note section first, fill in the wood / install-* polymer condensed in the mash . -An undetermined molecular home (Mv). Table 2 shows the effect of using the viscosity measurement method to estimate the total dose of gamma radiation on the suspension and viscosity of PVP molecules in solution ». When the gamma radiation rate in Table 2 is maintained at 309 rads / nin, the molecular weight of PVP can be increased if the total gamma radiation agent JK is increased. When the gamma radiation junction dose is higher than 0.25Mrads, the polymer will gel in solution. Table 2 indicates that too high a gamma radiation dose will cause the condensation effect of PVP solution and the polymerization reaction. Printed by the Ministry of Economic Affairs, the Central Bureau of Industry and Commerce, A Industrial and Consumer Cooperatives, ft'14 paper, 5 good-size side-use Chinese S national standards (〇 奶), 4 specifications (210X297 male dragons) 5. Description of invention () Table 3: Gamma radiation The effect of NVP concentration on the surface of PKMA induced by NVP graft polymerization on the molecular weight of PVP in the solution ί Ρ: Total gamma dose: 0.1Mrads Gamma radiation dose rate: 309 rads / aiin. Gamma radiation exposure time: 5 hours 24 minutes NVP concentration to be determined viscosity molecular weight (Mv) 3% 0.97 0.5, 6Χ 1〇 '6% 1.58 1.2 9 X 10 * 1096 1,94 1.82Χ 1〇6 1596 2.45 2 .7 0 X 1 〇4 Table 3 Shown at a fixed gamma radiation dose and dose rate, between the concentration of NVP monomer and the molecular weight of PVP. The higher the NVP concentration, the higher the molecular weight of the PVP polymer in the solution. The influence of the gamma radiation dose rate on the molecular weight of PVP can also be known from the following facts. When the concentration is maintained at 15%, gamma radiation at a dose rate of 309rads / ain can produce PVP of 2,7 X 10 molecular weight, while gamma radiation at a dose rate of 49rads / Bin can produce PVP of 5.0 X 10 molecular weight. Table 4: What is the ratio of gamma radiation to pvp graft polymerization? } () ^ The shadow of the contact angle on the surface: Printed by the Ministry of Economic Affairs

A 6 Π 6 V. Description of the invention () Concentration: 10% NVP total gamma radiation ft: O.lMrad Time mn — — 65. 1 2 Si 1235 rads / nin Thorn 21 award 31. Outline 309rads / oin 5 / J secluded 24 minutes 24. Face 137rads / niin 12 < J secluded. Pink Clock 21. Face 77rads / nin 2 touch 36 Jian 19. 1 side 49rads / min 33 / jM ^ 45 ^ «15. The Ministry of Economic Affairs, Ministry of Economic Affairs, Bureau of Employee Consumption, Du Yin, Table 4 shows that when the dose rate of gamma radiation decreases, the angle of contact angle also decreases. This is due to the higher degree of hydrophilic PVP graft polymerization on the surface of PMMA. Table 5: The shadow of the total dose of different gamma radiation on the contact angle of PVP graft polymerization on the surface of PUMA W: 鼸 度: 10% NVP in water Dose rate: 3 0 9 rads / nin. The paper scale uses the country of China Standard (CNS) TM specifications (210X297 g; ":") -23 * 202466 Λ 6 It 6 V. Description of the invention () Total dose is connected to the control group 65 ° PVP grafted and polymerized in PMMA at the angle not exposed to gamma radiation ♦ · 0.05Mrads 27 ° 0.lOHrads, 25 ° 0.05 »Mrads 24. 0.50 * Mrads 24. »Gelation of polymer-containing solutions. Table 5 shows the total dose of gamma radiation on the contact angle of PVP graft polymerization on the surface of PMMA. It can be seen from Table 5 that when the gamma radiation dose rate is 309 rads / nin, the change of its total value above 0.05 Mrads has little effect on the contact angle fee. Table 6: Effect of different single-sleep concentrations on the contact angle of PVP graft polymerization on the surface of PMMA: Gamma radiation total agent suspension: Q.lMrad Gamma radiation dose rate: 309rads / Bin NVP »degree contact angle (please read the back And the matters needing attention written by Sun Xiang— / Cooperative Du Printing of PMMA 65. 3% (NVP graft polymerization on PMMA) 29. 6% (NVP connection) Branch polymerization in PMMA) 27. 10% (NVP graft polymerization in PMMA) 25. 15% (NVP graft polymerization in PMJiA) 21. The size of this paper is used in the BB home kneading 1MCNS) T4 specification (210 > < 297 Gonglong) 202466 Λ 6 Π6 -24- V. Description of the invention () Table 6 shows the colorful sound of different NVP single concentrations on the contact angle of PVP graft polymerization on the surface of PMMA. When the concentration of NVP is as low as 3%, the gamma radiation dose is maintained at 0.1Mrad, which can also produce a small contact angle, which greatly improves the hydrophilicity. When the concentration of NVP monomer is greater than 3%, the influence of the contact angle is very small. Table 7: The effect of different monomers on the molecular weight of PVP in the solution of PVP graft polymerization on the surface of PMMA «: Gamma radiation total agent ft: O.lMrad Gamma radiation is thin! Quantity rate: 64rads / nin NVPift Viscosity molecular weight (Hv)% ¾¾% 13 5 0 9 5 3 5 7 6 2 3 • · · 0 12 3 1 * 1X 1 * XXXX 0 8 0 9 4 3 3 5 Please. Note t- The matter is again%. The Ministry of Economic Affairs, Ministry of Economic Affairs, Bureau of Industry and Fisheries cooperates with Du Yin, and Table 7 shows the concentration of the UVP unit and the molecular weight of the PVP in the solution. When the gamma rate of the gamma propellant is maintained at 64 rads / Bin, and increasing the single NVP degree, the molecular weight of PVP in the solution will also increase. Table 8: Contact angle shadow forging of PVP graft polymerization on the surface of PHMA with different monomer intensities: Gamma radiation total agent Ji: O.IHrad Gamma radiation agent setting rate: 64rads / Bin This paper is for standard use. Zhongwei S home standard (CNS) T4 specification (2 丨 0X297 male; «:) -25-202466 Λ 6 Ii6 V. Description of invention () NVP« degree PMMA 0% without gamma radiation exposure (NVP graft polymerized in PMMA ) 1% (NVP graft polymerization on PMMA) 3% (HVP graft polymerization on PMHA) 5% (NVP graft polymerization on PHKA) 15% (NVP graft polymerization on PKMA) Contact angle 65 ° 62 ° 49 ° 43 ° 31 ° 18 ° The Ministry of Economic Affairs, Central Bureau of Standards, A Industrial Consumer Affairs Cooperative Printed Table 8 shows the contact angle of different NVP single pus concentrations for PVP graft polymerization on the surface of PMMA when the rate of gamma radiation is maintained at 64rads / iin Shadow ». When the HVP concentration increases, the angle of the contact angle will decrease. The results in Table 8 are similar to Table 6. The difference is that the gamma radiation dose rate in Table 8 is 64 rads / nin and the gamma radiation dose rate in Table 6 is 3 0 9 rads / Bin. Comparing Table 8 and Table 6, it can be seen that when the NVP degree is 10%, the lower gamma radiation dose rate will slightly increase the hydrophilicity of the grafted polymer coating (combine 18 ° in Table 8 and 25 ° in Table 6). Take Meijiao for comparison). The mixture of polar organic solvent or its aqueous solution is quite beneficial to the graft polymerization of hydrophilic armour. Typical polar organic solvents include enzymes and ethers such as formazan, ethylene glycol, glyphosate, and dioxane, etc. can be used. When the above organic solvent is used as a free radical chain transfer agent, its concentration must be less than 50%, and the degree of single mollusc can be very high (for example, greater than 25%). For example, formazan has the property of scavenging free radicals, and the concentration of methanol in water can be as high as 50% to 60%. If the concentration of NVP is «α1, please read the note on the first W1 / H m% wooden π line Κpaper 5 good-scale reuse iMCHS) Τ4 specifications (210X297 g; Jt) 202466 Λ 6 It 6 -26- V. Description of invention (), then use 0.1Mrad dose of gamma radiation to convert PVP Graft polymerization on the surface of PMMA. Refer to Table 9 for the above conditions. Formazan can promote free radical chain transfer, but the reaction conditions must be limited to low gamma radiation rate and 10% NVP single eel. In general, the above-mentioned reaction solution has a very low degree of catfish, which means that the molecular weight of the polymer in the solution where the free radical inhibitor is present will be very low. Table 9: Effect of different gamma radiation dose rates on the contact angle of PVP grafted and dissolved in formazan on the surface of PMMA: Irrigation: 10% NVP in 50% of the total gamma radiation in formazan: O. lMrad Gamma radiation agent contact angle PMMA without gamma radiation 65 ° 1065rads / oin 36 ° 326rads / nin 28 ° 157rads / nin 27. 64 rads / n in 20 ° Example 2: (Please ^ ^ 而 而 之 念 亊 项 # 项 艿 木 ^ The Ministry of Economic Affairs, Central Bureau of Standards and Quarantine only printed by the cooperative cooperative 51 This example illustrates the expansion of the solvent for surface modification The sound of the process. The monomers stimulated by gamma radiation are grafted and polymerized on the anti-plaque solution on the surface of PMMA. If a swelling solution such as ethyl acetate is added to the solution of single alcohol, the paper scale can be used as a trapped house in China. Standard (CNS) 4 specifications (210X297 male dragon) 27.202466 Printed by the Ministry of Economic Affairs of the People's Republic of China, the standard is printed by the Beigong Xiaozhong Cooperative Society. 5. Description of the invention () The monomer diffuses more effectively to the surface of PKMA. Although the solubility of ethyl acetate in water It is not high, but if there is NVP monomer in the solution, it can still be made into a uniform reaction solution. When the concentration of ethyl acetate increases and the time of monomer diffusion increases, a thicker grafted polymerization surface can be obtained. The time of encounter can be called the prepreg time. Generally speaking, if the oxygen radiation is not removed and the gamma radiation dose is maintained in the range of 0.10 to 0.15 Mrad, a good graft polymer can be obtained. 、 HVP · ethyl acetate -The solvent system of water is also a good solvent for PVP, and The polymer in the solution remains in a uniform state. The invention can also embed PVP grafting polymerization on the surface of PMHA. PMMA is immersed in the mixture of single-expansion solvent-water first, and then the grafting is stimulated by gamma radiation After polymerization, PVP can be buried and grafted on the surface of PMMA. In the experiment, the following technique can be used to wash the sample with an ultrasonic processor containing 10% soapy water, and then wash the sample with distilled water. Before surface treatment, dry the sample in a vacuum dryer for 18 hours and then weigh it. Purify the NVP monocylinder in 4 1C vacuum distillation. In the graft polymerization reaction of gamma radiation, the PKMA material is first Dip into a single fishy solution, and then irradiate it with gamma radiation. The typical method is to immerse the PMMA material in NVP-ethyl acetate-water mixture, and then induce the grafting with a 600 Curie cobalt sixty gamma radiation source Polymerization. Exposure of the sample to the monomer solution at different times can result in grafted polymer coatings of different thicknesses. The gamma radiation dose is between 0.01 and Q.1SMrad, and Fricke is used. Agent * Holder Hold | Give it. Gamma The rate of the thin I can also be changed within a certain range. The sample is in the photo (please read the back-end notes first) # 项 写 务 装-order_ line · This paper scale uses the Chinese standard (CNS) T4 Specification (210X297g *) -28-202466 Λ 6 It 6

5. Description of the invention () After emitting gamma radiation, it can be removed from the solution and washed several times with distilled water, then placed in deionized water and agitated in deionized water. Some samples will combine with water, so use filter paper to absorb and remove the water on the surface of the material and place the sample in a vacuum dryer to dry for 24 hours. The state of the polymerizable solution varies from a clear viscous solution to a solidified solution. The following parameters can be obtained from the volume. The degree of graft polymerization can be measured by the increase in material reset and calculated by the following formula: W -W Percentage of graft polymerization -X 100 W0 is the original weight of PHMA. W1 is the weight of PMKA polymerized on the surface by single graft grafting. In the same way, the percentage of hydration can be calculated according to the following formula: Ww-Wd The percentage of hydration -X 100. Read first in the back and pay attention to the item% wood

Wd, Ministry of Economic Affairs, Central Standards Bureau, A Industrial and Consumer Cooperative, printed 5i

Wd is the weight of PMHA after drying. h is the weight of PMMA obtained after the filter paper is dried with PMMA. Gamma radiation was used to evaluate the degree of hydrophilicity of the modified surface of the material after the "I graft polymerization on the PMMA surface, and then the bubble connection angle or octane connection" angle measurement method. The angle of "Static Connection" can be set by Lan Ming-Hart (Ra «e-Hart) connecting temple angle protractor. Take at least 5 different surfaces for each sample to measure the joint angle. The IR / ATR surface analysis can be used in the form of perkin-yeschi (perkin-private paper scale side using the Chinese S home standard (CNS) A 4 specifications (210X297 male dragon) 202466 V. Invention description () Read in advance Contrary considerations%

Elmer) Model 283B Infrared Light Entry Meter measures the surface of ungrafted polymer material and the surface of grafted polymer material with a diminishing total reflectance. The PMMA lemon products of ungrafted polymerization and grafted polymerization, each lc · was placed in Kraros ES3 00 type ESCA optical detector to analyze its surface. The spectrometer uses magnesium as the source of X-rays. The analysis of the graft polymerization results can be judged by the ratio of nitrogen / master. The molecular placement of the PVP polymer in the solution is determined by the intrinsic viscosity. The pseudo-viscosity is determined by the Ubbelhode viscometer. In this embodiment, the dose of gamma gamma is maintained within the range of 0.01 to 0.15Mrad, while the range of the concentration of single snake is maintained at 5 to 15%. Printed by the Co-operative Society of the Ministry of Economic Affairs, Central Standards Bureau. Table 10 shows the results of PVP graft polymerization on the surface of PMMA, using ethyl acetate as the swelling surface. Although the effect of pre-immersing PMMA in the swelling solution before gamma irradiation is better, Table 10 shows that PMMA was not pre-immersed in the swelling solution before gamma irradiation, but when PMMA was immersed in the swelling solution It is irradiated with gamma radiation. Table 10 can be used as a typical behavior of the reaction system to control the monomer diffusion. The swelling solvent containing ethyl acetate is very helpful for the diffusion of NVP monomer to the hydrophobic PMHA surface.

If a swelling solvent of material such as ethyl acetate is used, the NVP-ethyl acetate-water solution system will swell the surface layer of PMMA, so that the NVP striker adjacent to the surface layer of PMMA will quickly graft and polymerize on the surface of PMMA. Under the above conditions, the effect of graft polymerization is very good. On the one hand, it can use a lower gamma radiation dose. On the other hand, HVP can be grafted and polymerized in PMMA. (210X297 male dragon) 202466

The Ministry of Economic Affairs has approved the cooperation of the β-worker and the consumer in Duin fr, A V. Description of invention () Deeper layers under the surface layer. In the present invention, the swelling concentrate of NVP-ethyl acetate monohydrate (1: 1: 8) was used to observe the colorful response of the swelling percentage of the PMA sample to the length of swelling time. PMMA can be swollen by 6% when immersed in PMMA for 12 hours. If the length of the single skull diffusion time is controlled, the thickness of NVP graft polymerization on the surface of PMMA can be controlled. Table 11 shows the results of pre-immersing PMMA in a 1: 9 ethyl acetate: water swelling solution containing 15% NVP. Table 10 The PMHA was not pre-immersed in the swelling solution before the irradiation of gamma radiation, but the graft polymerization was stimulated by gamma radiation immediately after the PHMA was placed in the swelling solution. Comparing Table 11 and Table 10, it can be seen that the PMMA was pre-immersed in The results in the swelling solution are better. When the degree of ethyl acetate is fixed. Is the difference between PMMA pre-immersed in the swelling solution and the low NVP single concentration (eg 5%) more pronounced than the higher single concentration (eg 15%)? In the swelling solution The addition of NVP is important because NVP is both a simple ingredient and a part of the swelling solution. If no NVP is present, the swelling solution such as ethyl acetate and water will form a miscible solvent. Therefore, HVP can maintain the swelling solution in a homogeneous phase. When the concentration of the NVP sheet is fixed (for example, maintained at 10%), the concentration of ethyl acetate must be maintained below 10¾ to avoid phase separation and generation of emulsion. When the concentration of ethyl acetate changes, it will affect the yield of graft polymerization. Table 12 shows that when other factors remain unchanged, if the concentration of ethyl acetate increases, the production percentage of graft polymer also increases. Under the low dose of gamma radiation, the effect of the expansion of the volume of the liquid on the graft polymer can be seen from the increase in the yield of the graft polymer and the decrease in the graft angle. For example, when the gamma radiation dose is 0.05Mrad, please use the single one (please read the back-end precautions #fill in the Cistanche · order-the Chinese standard B (CNS) T4 specification (210X297 %) -31-202466 Λ 6 Π 6 V. Description of the invention () First read in Contrary to note / Bu pot% Λ There are very few graft polymers produced in a simple aqueous solution. However, even as low as O.OlMrad dose Gamma radiation, in 9 · .1 water: ethyl acetate expansion solution can reduce the contact angle to 35 °, and in 9: 1 water: ethyl acetate expansion solution using 0.03Mrad dose of gamma radiation , The contact angle can be reduced to 23 ° (see table 11 for the postmortem, the prepreg expansion time is 24 hours). Some chemical analysis techniques can be used for polymer analysis but not for polymer surface Analysis. Because the structure of the plaque domain on the polymer surface is different from the chemical properties and the properties of other parts of the polymer. The plaque domain on the polymer surface only occupies a small part of the polymer. Therefore, Fu Tong ’s chemical analysis technology k The analysis of the polymer surface area is not appropriate, so it must be used Special surface analysis technology is necessary to analyze the polymer surface area and the coating polymer grafted on the polymer surface area. Because the polymer surface tooth area is pseudo-generated by the material, graft polymer, base garden and bond transfer products The formed heterogeneous mixture, so the present invention uses two very useful surface # analysis technology Di ATR-IR spectroscopic analysis and ESCA spectroscopic analysis to determine the material after graft polymerization of the surface of the Ministry of Economic Affairs #quasi bureau only work elimination t Cooperative Duprinting Table 13 shows the results of ATR-IR light analysis. After the PVP graft polymerization on the surface of PMMA, the ratio of C = 0 radicals of amides in the ATR-IR spectroscopic analysis with the gamma radiation dose Increase and decrease. When the gamma radiation dose is increased from 0.01Mrad to 0.1OMrad, the ratio is reduced from 7.67 to 1.68. When the ratio of emirates gamma radiation agent Li is higher than 0.1Mrad, the ratio is almost unchanged. (Table 14 The results of ESCA spectroscopic analysis are shown. When the amount of gamma radiation is increased, the nitrogen / sulfur (N / C) ratio is increased, and the increase in deuterium is equivalent to the standard of the paper standard (CNS) T4 specification. (210x297 male; ":) 32202466 Λ 6 Π6 V. Description of the invention ( The effect of PVP graft polymerization on the surface of PMHA is alternated. Scanning electronic display mirror can be used to observe the surface morphology of PVP graft polymerization on the surface of PMMA. All the graft polymerization coatings are still very smooth when viewed at 10,000 times magnification. Therefore, the coating of graft polymerization is very uniformly coated on the surface of PMHA. The above characteristics are very important for maintaining the best optical properties. When PMMA and its coating are used as optical implants such as eye lenses, the best Optical properties. T The following conclusions can be drawn from this example: The solvent system of NVP-ethyl acetate monohydrate can not only produce a uniform hydrophilic polymer coating, but also control the penetration of NVP on the surface of PMA and the degree of graft polymerization. If you change the "degree" and prepreg expansion time of the bulging solvent, you can control the degree of penetration of the single lysate dissolved in a single feed of ethyl acetate-water solvent on the surface of the material. From the results of heavy ft analysis, contact angle change, ATR-IR spectroscopy analysis and ESCA spectroscopy analysis, the fact that PVP grafted on the surface of the material can be determined. The extremely low gamma radiation agent Λ is a necessary condition for effective graft polymerization. The extremely low gamma radiation agent ft can destroy the radiation on the surface of the material. Read the notes of vfTj first lTh Item% The Ministry of Economic Affairs Central Bureau of Precision Industry β-Work Digest Cooperation Du Yin 51 Table 10: NVP graft polymerization on the surface of PMMA Swell time: 0 hours Swell solvent: ethyl acetate: water ( 1: 9) This paper is good for 5 good-size edges. "Sleepy home-like 1MCNS" < IM specifications (2 丨 0X297 public address) -33-202466 Λ 6 η 6 V. Description of the invention (1111 $ KfPlIt fe «« 10.01Xra < i Q.05Kraij O.lOIrad O.lSKrad m & m% ira μϊη mm nm 309rads / iin 77r8ds / iia ην Αν r5 rhv Λν Γο οο AD Λυ Λν CV οο 14 · n 4 — —4 MJ Λίυ

n nyw ot AO 11 t Λν Λπν Λν Αυ. H 7— —4 Λί ΛΛν 9W Γ5 4J 7U Λ / m Ρ3 J7 Γ3 9 «» 4 CJ Λν * Μν Λν Λν ΛΜν Λν f · οβ Αο 7- οη ν Λν Λν Απν Λο 71 οο οο eD &lt; 3 1-1 11 ΛίιΜ 3-71 »ΓΊν r9 u cv« ο Αν Λν ΛΜν Λν ο Table 11: NVP graft polymerization on PMMA surface • Expansion time: 24 hours swelling solvent ： 9: 1 water with ethyl acetate and 15% NVP ^ M ^! IAfi309rads / iDin M ^ Phl ^ ft77rads / nin 'Area-to-Percentage O.OlMrads 38 1.0 35 1.3 0.03Mrads 27 2.3 23 2.8 0.05Mrads 17 2.5 17 2.4 O. OMrads 16 3.0 16 3.2 0.15Mrads 10 3.0 16 3.4 Please • iL Read the contrary notes% This table is printed by the Employee Consumer Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs 12: NVI graft polymerization on the surface of PHMA : 12 / J Sai Laifu: 10 »Rate: 309rads / ain The standard size of this paper is used in the national standard (CNS) ΊΜ specification (210X29 / male dragon) 202466 Λ 6 156 -34- V. Description of the invention mmmmm mzmzm Percentage ϊ O. OlMrads 43 0.2 44 0.4 48 0.6 0.03Mrads 38 0.3 26 0.5 25 1.7 0.05Mrads 23 0.3 21 0.5 22 1.9 O.lOHrads 18 OS 17 0.5 18 2.2 0.15Mrads 15 0.5 17 0.6 18 2.2 mzrnm: l starve ae ^ · percentage · I Contrary / i matter m. Jie Table 13: ATR-IR light Clamp analysis of samples of PVP graft polymerized on the surface of PMMA ": Gamma radiation total dose Vc = 0 (esters) The Ministry of Economic Affairs, Ministry of Economic Affairs, Central Bureau of Labor and Welfare Cooperative Printing Co., Ltd. ft, l4 O. OlMrad Vc = C (enzymes ) 7.67 0.03Mrad 6.51 0.07Mrad 4.61 0.lOMrad 1,68 0.15Mrad 1.66 &gt;: &lt; Mix 5% NVP in 9: 1 water: ethyl acetate solvent expansion time: 17 hours gamma radiation dose Feng: lQ65rads / min Table 14: Analysis of the sample gamma-radiation total agent ft Ot of PVP graft polymerized on the surface of PMMA by ESCA: N / C ratio 0.03Mrad 2 .2 X 1 〇'Z 0 · 05Mrad 3.1 X 1 〇'2 0 .07Mrad 4.5X 10'4 0 .lOMrad 4.7 x 1 * Mixing 5% NVP in 9: 1 water: ethyl acetate solvent Expansion time: 17 hours Gamma Ihi dose rate : L〇65rads / nin This paper scale is used in China 漣 戣 Bi (CNS) T4 specification (210x297 g; ¢) ο 2 The Ministry of Economic Affairs ’Bureau of Standards only works with the Consumers and Consumers to set up a cooperation du ft'14 -35 &quot; Λ 6 Η 6466 five DESCRIPTION OF THE INVENTION () Example 3: The following experiments show that the oxygen of gamma Shan "Movies exit roller from the graft polymerization of the reaction is extremely significant depression, run flat state so that graft polymerization is very important to excite gamma radiation. The state of gamma-radiation-induced graft polymerization of 10% HVP aqueous solution is as follows: (A) In the presence of gas, the graft polymerization is reversed. (B) In the absence of gas, the graft polymerization reaction is initiated, and argon is added to facilitate the removal of oxygen. (C) Initiate graft polymerization under anoxic conditions, and evacuate the gas to a vacuum state. In condition (A), if the rate of gamma radiation is maintained at 213rads / nin, and different doses such as 0.01, 0.05, 0.20 and 0.25Mrad of gamma radiation induce 10% HVP to produce graft polymerization. In condition (B), add argon for 1Q minutes to remove the gas. In condition (C), extract the gas by vacuum freezing and thawing method. The monomer solution was first frozen in liquid nitrogen, and then evacuated to a vacuum (0.3BB Hg) to remove the gas. Before irradiating gamma radiation, the above-mentioned frozen solution is melted to room temperature. Some products must be frozen and thawed three times in vacuum. Each experiment was repeated twice to ensure its reproducibility. In order to determine the effect of the degassing effect on the gamma-radiation-induced graft polymerization reaction. The present invention measures different concentrations of the single dose when the gamma radiation dose rate is 2 13rads / nin and the cut amount is 0.01Mrad and 0.25Mrad respectively Conversion rate and molecular weight. In order to determine the amount of NVP single carbohydrates that did not participate in the reaction, the present invention is used (please note first -wift Sun Xiang writes wood ar. (Public) 202466 Λ 6 II 6 -36 ** Printed by the Mongong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 51 V. Description of invention () The method is as follows: firstly irradiate 5 «1NVP with gamma radiation, then 50ml Take NVP solution. Unreacted NVP is soluble in acetonitrile, but NVP is insoluble in acetonitrile after it is polymerized into PVP. Separate PVP sludge and supernatant with a centrifuge. The supernatant contains NVP. The invention uses 10% NVP solution, and the NVP analysis result is as follows: 10% NVP aqueous solution is diluted with ethyl acetate to the range of 0.5g / Bl to 5.0mg / ml. The absorption rate is measured with ultraviolet light of 3 2 3nni wavelength, and the NVP concentration is plotted against the absorption rate to obtain the same quasi-curve. The regression coefficient of this curve is 0.99. Its molecular weight and molecular weight distribution can be determined by a condensate permeation analyzer. The NVP conversion rate (the number of NVP monomers participating in the reaction) is strongly influenced by methods such as injecting argon to remove oxygen or vacuum freezing and thawing to remove gas. If the gas is not removed, gamma radiation with a dose as low as 1Hrad cannot initiate any graft polymerization reaction. However, after removing oxygen * with argon, the conversion rate of NVP to PVP was 46%, and the gas was removed by vacuum freezing and thawing once and three times. The conversion rates of NVP to PVP were 61% and 63%. The gamma radiation dose is as high as 0.1 OMrad, and the conversion rate of the graft polymerization induced in the air is only 90% (that is, there are 10 nm NVP monomers not participating in the reaction); however, the conversion rate of the oxygen removal graft polymerization is As high as 99%. Because the NVP single marrow that is not involved in the reaction will produce a serious poisoning reaction when the surface of the implant comes into contact with the biological mule, the result of the near-finish metal reaction (99%) is very important for the biological implant. The present invention has proved that after removing oxygen, low dose of gamma radiation can be used to stimulate PVP graft polymerization on the surface of PMMA. The present invention uses 0.05Mrad dose and 157 rads / nin dose of gamma radiation to stimulate radon removal (please Read the notes beforehand. Sun fills in this one! This paper is used in the standard SB Family Standard (CNS) T4 specification (210X297 ;;: :) -37-202466 Λ 6 Η 6 The Ministry of Economic Affairs Standard Standard Η Cooperated with the Consumers and Consumers Co., Ltd. Du Printed 5. Description of the invention () 10% NVP graft polymerized on PMMA coatings. The contact angle of the surface of the hydrophilic graft polymer is 20 °. And it is stable against mechanical friction (ie. 》 The angle remains unchanged. As mentioned above, the hydrophilic PVP that is stable to mechanical abrasion is grafted and polymerized on the surface of PMMA, the conversion rate of KVP monomer is quite high (98%) and the molecular egg of the polymer in solution Very high (the molecule is set to 1.65 X 106). If there is gas in the solution, you can use high gamma radiation agent (greater than 0.11 ^ 3 (1) or high monoether concentration (more than 15%) to get Low connection angle, high monomer conversion rate and high molecular weight results. When the hydrophilic monomer is stimulated by gamma radiation When polymerized on the surface of other polymer materials such as polypropylene, fluoropolymer (such as PTFE or PVDF) or siloxane, the effect of degassing is more significant. Degassing can be combined with swelling solvent and free radical scavenging The use of the agent enhances the effect of gamma radiation on grafting polymerization. The free radical scavengers used in the present invention include vaporizable metal compounds or organic compounds such as ascorbic acid. The advantage of using free radical scavengers is that It can produce effective graft polymerization and reduce the molecular egg of the polymer in the solution. The effect of removing oxygen on the molecular weight of pvp is quite large. Isi; after removing the gas or removing the gas plaque by vacuum freezing and thawing, use it as low as O. OlMrad dose of gamma radiation can produce PVP with a molecular weight of 1.6 × 106. Conversely, the molecular weight of PVP without degassing gas is extremely low. When the dose of flute gamma radiation is 0.05Krad, the PVP of atmosphere is not cleared The molecular setting is only 0.35 X 106, and the PVP molecule for degassing is between 1.65 X 106 and 1.8 X 106. When the dose of Emirates gamma radiation is 0.1 Mrad, all samples can be degassed or not Get The molecular weight of PVP is between 1.8 X 10 * and 2.0 X 104. First • W read back and forth> idea term η-m writing η line κ paper 5 Gen scale side use a Β 家 样 iMWS) Ψ 4 Specifications (210 &gt; &lt; 297 public address) 202466 V. Description of the invention () Example 4: The following experimental examples are used to prove that free radical scavengers can inhibit the solution polymerization reaction and the solution condensation, which is a high order. The concentration of the graft polymerization process. According to the conditions described in Example 1, the PVP graft was polymerized on the surface of the PMMA sample by gamma radiation. In this example, ascorbic acid was used as a free radical scavenger. Gamma radiation-induced graft polymerization anti-incubation conditions are listed in Table 15. (A) 30! I! NVP / 0.5bM ascorbic acid / 2.53; ethyl acetate / 0.21 ^ 8 (1 gamma radiation <(B) 3 (^ 1 ^? / 0.51111 &lt; ascorbic acid / 2.5 * Ethyl acetate / 0.151 ^ 3 (1 Gamma Radiation ((C) 4 0% NVP / 1. OmM Ascorbic Acid / 0 · IMrad Gamma Radiation (D) 50! KNVP / 1. ObM Ascorbic Acid / 0. IMrad gamma radiation (E) 5 0! £ HVP / 1.0iiiM ascorbic acid / 0.2Mrad gamma radiation * * The starting dose is O.IHrad, the single waist in the solution that does not participate in the reaction is polymerized with the solution The objects are washed from the surface of the sample, and then the sample is irradiated with gamma radiation at a dose of 0.1 Mrad. The Ministry of Economic Affairs + Central Standards Bureau staff eliminates crimes and cooperates with Du printed (please read the back and pay attention to the item # item write wood in Table 15 The contact angle of all PMMA samples is between 18 ° and 24 °, so the graft polymer is very hydrophilic. Gamma radiation agent in (A) (B) (C) (D) (E) * The rate is 33 rads / iin, and the gamma radiation rate of 667rads / Bin is used only in (B). When the monomer concentration is 30% to 50%, the use of free radical scavenger will cause solution polymer Coagulation effect. If free radical scavenger is used in the solution such as anti-corruption Blood acid will inhibit the coagulation effect of the solution polymer. It will reduce the molecular weight of the solution polymer but will not affect the yield of the graft polymer. This paper is used in the middle of the 8 standard (CNS) «P4 specification (210侂 297 公 龙) -39-20: 466 Λ 6 It 6 The Ministry of Economic Affairs, Jiyang, Bureau of Industry and Engineering only Gongxiao # Cooperation Du Yin ^. V. Description of the invention (). Proof of PVP graft polymerization on the surface of PMMA except for available contacts In addition to the angle measurement method, ESCA and FTIR-ATR analysis can also be used to prove the presence of nitrogen on the surface of the material. The source of nitrogen is PVP grafted polymerized imide-based garden. Good mechanical properties can be changed by contact angle after the wear test It is proved by the presence of very small or nitrogen on the surface of the material. Experimental Example 5: This example demonstrates that the surface-modified material of the present invention has a reduced tissue adhesion effect on the endothelial group and a reduced cell adhesion effect on the susceptible mother cells of the Jiwei group. Hydrophilic graft polymers can improve the effectiveness of the surface of the material. This effect is very important for improving the biocompatibility of the material and reducing the irritability or damage of the surface of the material. table The adhesion force (unit is mg / cin) during surface contact can measure the cobalt adhesion force of the corneal endothelial group of rabbit eyes after contact with the surface of the material. Materials such as PMA, silicon, polypropylene and polypropylene come into contact with the corneal endothelial tissue of rabbit eyes The adhesion force is between 250 and 400 BU / CIB. The surface of the above materials exhibits a small adhesion force after graft polymerization, and the adhesion force is less than 15〇Bg / cn and usually less than 100mg / cm. The reduction in adhesion is also accompanied by a reduction in the damage rate of the material to the group. When observing the injury rate of endothelial group with electron microscope, the injury rate of PKMA or polysilazane without treatment of the present invention is 50 to 80%, but the injury rate of PHMA or silazane treated by the present invention is reduced to less than 20% 〇The damage rate of the material to living cells can also be known from the adhesion effect of the material to the difficult-to-embryo follow-up tissue mother cells (CEF) or rabbit eye lens endothelial cells (LE). The experiment proves that the material that is not treated by the present invention is more processed by the present invention

Read the first $ and pay attention to Ψ items% Wood JI Threading paper size in the use of BI8 standard (CNS) T4 specifications (210X297 public) 202466 Λ 6 Μ 6 -40-Ministry of Economic Affairs + Central Standards Bureau Price-cutting cooperation Du Yin 51 V. Invention description () The damage rate of the material to living cells is 2 to 4 times higher. The adhesion of O.IHrad and 15% NVP graft polymerization on the surface of PMMA to CEF cells is only 35% of the original PMMA adhesion. The cobalt adhesion of PHEMA grafted on the surface of PMMA to CEF cells is only 38% of the original adhesion of PMMA. 15: 1 NVP: The adhesion of HEMA grafted polymerized on the surface of PMMA to CEF cells is only 20% of the original adhesion of PMMA. Under preferred conditions, the adhesion of the PVP treated by the present invention to the surface of PMMA, PC or PSi to LE is only 1 to 2 LE per square millimeter, and the surface of PMMA, PC or PSi not treated by the present invention is The adhesion of LE is 1 per square millimeter (more than 3 LEs. Example 6: This example illustrates the results of graft polymerization of HEMA or NVP and HEMA mixture on the surface of PMMA. In this example, 16% NVP / HEMA ( 15: 1) Single-medullary mixture, O.lOMrad agent and 1 300 rads / oin dose rate gamma radiation, other conditions are the same as Example 1. The contact angle of PMMA surface modified with PVP-PHEMA is 17 °. Under similar conditions, the contact angle of 7% NVP / HEMA (5: 2) graft polymerization on the surface of PMMA is 23 °, and the contact angle of 2.5% HEMA graft polymerization on the surface of PM HA is 18 °. Example 7: This example illustrates the effect of mixing anionic mono-cary or cationic mono-lep and hydrophilic mono-hybrid. In the present invention, ionic mono-cary or NVP single-sleep can be used in combination. A, 15% NVP is added to 1 to 5 weight M Percentage of full-line dicarboxylic acid (AA) or crotonic acid (CA) as a mixed monomer, and as in the method of Example 1 with 0. IMrad dose and 12 35rads / min rate of gamma radiation induces graft polymerization reaction paper 5 good scales for easy use a Η Family tree (CNS) &gt; F4 specifications (210X297 public address) -41-2〇24aa Λ 6 Π 6 5 Description of the invention (), the contact angle of the resulting coating is between 18 ° and 22 °, and its adhesion to the endothelial group is only less than one-half of the original PMMA. Good hydrophilicity. A similar effect can be obtained by a coating of cationic one-touch dimethylaminoethyl acrylic acid methylester graft polymerization. Styrene sulfonic acid (SSA) can be used as an anionic single plaque and NVP as a mixed single-dye graft It is polymerized on the surface of PMMA. Use 1: 2 SSA: HVP (containing 33% SSA) to mix the mixture, the degree is 30%, the gamma radiation dose is 0.15Mrad and the dose rate is 70 0rads / Bin, can get hydrophilic Polymerized coating with a k contact angle of 30 ° to 40 °. Na, sodium salt of styrene sulfonic acid (NaSSA) can be used as a highly hydrophilic anionic monosodium, and copolymerized with NVP in polydimethylsilicone Oxidane (PDMS) surface. In this example, the PDMS sample was washed with an ultrasonic treatment machine containing ethyl yeast, then dried in vacuum, and then placed in the monomer-containing The aqueous solution was irradiated with gamma radiation. Table 16 lists the conditions of graft polymerization, such as single-bone irrigation, gamma radiation agent, and keep the gamma radiation dose rate at 70 0rads / Bin, and list the graft The contact angle of the polymerized surface. Table 16: Gamma radiation dose NaSSA percentage NVP percentage contact angle (please read the notes beforehand Sun Xiangshu Mumu j _ line-0.05Mrad Ο.lOMrad 0.15Mrad ο ο 2 2 2 ο ο ο 2 2 2

7 5 3 1A 1X The Ministry of Economic Affairs is approved by the Ministry of Economic Affairs and the only consumer cooperation is Du Yin. 4 As shown in Table 16, even if the amount of gamma radiation used is as low as 0.05 Mrad, the concentration of the monomers is 40% of which NaSSA and NVP account for half of each, can get extremely hydrophilic surface graft polymer (the contact angle is 17 °) The paper size is easy to use in the middle of the S sleepy home sample (CNS) T4 specifications (210X297 public; it) -42-202466 Λ 6 Η6 Ministry of Economic Affairs, Bureau of Economics and Trade, A industrial price-cutting cooperation Du Yin 51 V. Description of invention () Example 8: This example illustrates the removal of oxygen for hydrophilic The importance of the effect of branch polymerization on the surface of polypropylene (PP). In the presence of gas, the effect of grafting polymerization of hydrophilic monomers on the surface of PP with gamma radiation is not good. Under the same conditions as in Example 1, even if the dose of gamma radiation is higher than Q.lMrad and the concentration of single radiation is higher than 10%. If there is «qi, the hydrophilicity of the material surface is poor and the contact angle is reduced. Small is not obvious. However, under the condition of removing oxygen, the dose of gamma radiation is as low as 0.C1 to 0.05Mrad, and the dose rate is maintained at 157rads / min, the single concentration is 10% MP, the contact angle of the resulting coating is about 15 °. The change in the surface properties of PP can also be measured by a small change in the contact angle of the mechanical abrasion test, and it can be seen that the coating of NVP graft polymerized on PP has excellent hydrophilicity. This hydrophilicity is very important for the repair of the surface of the eye lens split with PMMA and the contact surface made of PP. Example 9: Polyethylesterate (PC) is a useful engineering plastic® that can be used as an eye implant. Under degassing conditions, the NVP grafting is induced by gamma radiation to polymerize on the PC surface, which can make excellent surface modification on the PC surface. For example, gamma radiation with a dose of 0.05 Hrad and a dose rate of 93 rads / Bin stimulates 10% NVP of the degassed gas to be grafted and polymerized on the surface of the PC. The joint angle of the resulting product is 19 °. Example 10: The rate of NVP graft polymerization on the surface of polyoxyalkylene (PSi) by gamma radiation is not as good as the rate of NVP graft polymerization on PMMA, but its (please read the back side and note the general matters # Code 艿 木 亘 装-Order * Line _ This paper size 4 is used in the BH home sample standard (CNS) T4 specifications (210x297 public; «:) -43- 202466 Μ 5. Invention description () The contact angle of the product will also be reduced Gamma radiation at a dose of 0.05 Mrad and a rate of 93 rads / min M stimulates the degassed 10 96 NVP graft polymerization on the surface of the PSi, the contact angle of the product is about 45 °, which shows that the graft polymerization The surface of PSi has a considerable degree of hydrophilicity. If the dose of gamma radiation is increased, and the use of eye-expansion solvent and a relatively single, single-sleep concentration, the hydrophilicity of the product can be improved. The gamma radiation of the setting rate lifts the NVP / HEMA (10: 1) mixed monomer graft polymerization on the surface of PSi. In the presence of gas, the contact angle of the product is reduced to 30 °. Example 11: Printed ft, l4 by the Ministry of the People ’s Republic of China Central People ’s Government Staff Cooperative Association (please read the back-to-back notes of the general city item Wood sheet- · In this embodiment, polyvinyl fluoride (PVDF) is used as an example of fluorosulfon polymer material. The solution for graft polymerization can be NVP aqueous solution, KVP-containing water and methanol solution, or NVP-containing ethyl acetate solution. Then, the NVP graft polymerized with 0.20Hrad and 3 2 6 rads / min of GPR on the PVDF surface, the contact angle of the product is about 30 °. If the gas is removed, the effect of the graft polymerization on the PVDF surface Very good. After degassing, the PVP coating formed by NVP graft polymerization on the PVDF surface with 0.05Mrad and 157rads / in. Gamma radiation is excited, and its contact angle is only 17 °. HVP is also applicable to PVDP. It is a good swelling solvent, so a relatively long swelling time is of great help to the efficiency of NVP single graft polymerization on the surface of PVDF. For example, after pre-soaking PVDF with 7¾ HVP monomer for 5 hours, O.lOMrad and Radiated by 94rads / ^ in of gamma radiation, the joint angle of the resulting product is only 14 °. Example 12: Grafting conditions of the composition: the contact of different polymers Under the conditions, there is a medium-scale B (CNS) T4 specification (210X297; a :) 202466 Λ 6 Η 6 _ 4 4 V. Description of invention () The feasibility of using the decorated surface as a lens «« group in an eye implant. Composed of different materials The eye lens can be grafted and polymerized on its surface at one time to produce a biocompatible coating. It can be seen that the lens materials such as PMMA, PC and PSi and the contact materials such as PVDF or PP can obtain good graft polymerization products under the special conditions of the present invention. Table 16 lists the conditions for mutual grafting of PVP to polymerize PVP onto the surface of the lens and whisker composition. t

PMM / PP and PMMA / PVDF were deoxygenated at 0.05 Mrad and 157 rads / ain gamma radiation and 10% NVP was grafted and polymerized on the surface of PMHA and PP compositions. The contact angles of the products were 20 ° (PMMA) and 15 0 (PP), and has mechanical ear qualitative. If the gas is not removed, the effect of graft polymerization on the surface of PP is worse than that on the surface of PMMA. The removal of oxygen is very important for the effect of graft polymerization on the PVDF surface. Under the condition of degassing gas, the effect of stimulating 10% NVP graft polymerization on the surface of PMHA and PVDF compositions with 0.05 Mrad and 157 rads / nin gamma radiation is excellent. See Table 16.

PC / PP and PC / PVDF Central Ministry of Economic Development, Printed by ^ Work Consumers' Cooperative (please read the back-to-back notes first # 建 写 木 1 under degassing conditions, with 0.05Mrad and 157rads / Bin gamma Radiation induced 10% NVP graft polymerization on the surface of PC and PP compositions, the contact angles of the products were 19 ° (PC) and 15 ° (PP). Under degassing conditions, with 0.05Mrad and 157rads / Bin gamma radiation inspires 10 nm NVP graft polymerization on the surface of PVDF and PC composition, the result is similar to PC / PP or PMMA / PP composition. Because PVDF will expand in NVP, the pre-expansion time helps PVP Printed on the side of this paper for standard a Η 家 榣 iMCNS) Τ4 specifications (210X297 g; it) -45-203466 Λ 6 Η 6 Ministry of Economic Affairs, Biyang Liangzhunpao A industrial consumer cooperation cooperative

5. Description of the invention () The combination of PVDF. Good hydrophilic graft polymers can also be obtained on the surface of ocular implants split by other compositions composed of two or more polymers. See Table 16. Example 13: Several conditions for surface modification of embedded lenses (IOLs) inside the eyeball have been described in the previous examples, and they were implanted into the rabbit eye for about one year under the cracking conditions determined according to the present invention, to prove Good bio-acceptance of eye implants (IOLS) modified with hydrophilic gamma polymerized surface. For example, the Sinskey-03 7 Ding Chen-shaped lens (PMMA optics / PP contact type) was surface-modified with PVP and sterilized by ethylene vaporization, and then implanted into the anterior chamber of the New Zealand white rabbit eye. PM elastic IOLs with Η elasticity are implanted in the posterior chamber of the eye. The conditions for the surface modification of IOLs are as follows: (A) 15% NVP, O. l OMrad, 30 and 12 rads / ain, connection angle CA 20 °-25 ° (B) According to Example 4 and Table 15, a, b, c and d conditions, regular inspection of eyes with slit lamp, one year later, and visual inspection of implanted lens (compared with non-grafted PMMA control IOLs), showing good biocompatibility And the normal behavior of the hydrophilic polymer surface graft modification of the present invention. Table 17: Modified Gamma Radiation Grafting Polymerization Conditions with PVP Modified Lens / Touch Surface Lens / Thumb X PMMA / PP A, degassed 10% NVP, low dose rate * ※, 0.05 Mrad B, 2.5% Ethyl acetate, 6 hours swelling time, deoxygenated 10% NVP, low volume rate * ※ .0.05Mrad PMHA / PVDF A, dehydrated 10% NVP, low dose rate ※※, 0.05 Mrad B, deoxygenated 10% NVP, 5 hours swelling time, low dose rate Mimi, 0.15Mrad C, 2.5% ethyl acetate, S hour swelling time, degassing 10% HVP, low dose rate ※ Come, 0.05Mrad the paper size side Use Chinese National Standard (CNS) f 4 specifications (210x297 g; ft) * 4 6 A 6 It 6 V. Description of invention () PC / PP A, deoxygenated 10% NVP, low dose rate meter ※, 0.05 Mrad please .First read &quot; ift back to the note section and then m% wood B, 2.5% ethyl acetate, 6 hours expansion time, deoxygenated 10% NVP, low dose rate ※ ※, 0.05Mrad PC / PVDF A, go Oxygen 10% NVP, low dose rate *, 0. 05 Hrad B, go to "10% NVP, 5 hours film expansion time, low dose rate come, 0.05 Mrad C, 2.5% ethyl acetate, 6 Expansion time in hours 10% NVP, low dose rate ※※, 0.05Mrad * The contact angle of the product is less than 25 °. Rice ※ The low volume rate is 30 to 300 rads / nino. Example 14: This example illustrates that at very low concentration (below 0.5 reset percentage) monomers, very low dose (below 〇.Q〇5Mrad) gamma can be used The shot stimulates effective graft polymerization.

The Ministry of Economic Affairs, Ministry of Economic Affairs, Bureau of Employee's Explosive Cooperation Cooperative M. This example stimulates low-degree (0.5 to 2.0%) methyl hydroxyethyl acrylate with gamma radiation from very low dose Dong (0.01 and 0.0 05Mrad) (HEMA) graft polymerization on a clean PVDF surface, and other reaction conditions are similar to the above examples, the results are shown in Table 18. First, wipe the PVDF sample clean, then immerse it in the HEMA aqueous solution, and then use gamma radiation to stimulate the HEMA graft polymerization on the PVDF surface, and then wash it by the method of Example 1. From the low contact angle shown in Table 18, it can be seen that the surface of the graft polymerization has high hydrophilicity. The results of XPS analysis in Table 19 show that the surface of the graft polymerization contains a very small amount of fluorine but a large amount of aluminum. Its composition is PHEMA. It can be seen that PHEMA is grafted and polymerized on the surface of PVDF (PHEMA-g-PVDF). Gamma radiation with a very low dose and a single concentration can effectively graft and polymerize PHEHA on the surface of PVDF. The size of the paper is used in the standard B Mingjia sample standard (CNS) (210x297mm; ¢) 202466 Λ 6 li 6 -47- V. Description of the invention () Table 18: HEMA graft polymerization induced by 88rads / nin gamma radiation On the surface of PVDF, use argon gas to remove other gas anions. Gamma radiant radiation volume HEKA percentage Contact angle 0.005Nrad 0.5 24 ° 1.0 24. 2.0 12. 0.01 Nrad 0.5 21. 1.0 19 ° 2.0 16. Even at very low gamma radiation levels below 0.005 Mrad, and at a concentration of 0.5 weight percent, the hydrophilic PHEMA can still be effectively graft polymerized on the PVDF surface. Conversely, PVDF that has not been treated by the present invention is inherently hydrophobic, and its contact angle is greater than 85 °. Even at very low gamma radiation doses, such as 0.005 Mrad or less, and at 0.5 reset percentage of very low monomer irrigation, the hydrophilic PHEMA can still be effectively graft polymerized on the PVDF surface. Conversely, PVDF that has not been treated by the present invention is inherently hydrophobic, and its contact angle is greater than 85 °. Table 19: Analysis of PVDF and PHEKA-g-PVDF by XPS. Fluoride PVDF not treated by the present invention 50.5 45.3 PHEHA-g-PVDF 69.0 0.9 (Conditions for Luo held at 2% HEMA and 0.005 Mrad) PVDF (theoretical value) 50.0 50.0 PHEMA (theoretical value) 66.7 One, (please read the back first and note the item # 项 写 木 &amp;;-outfit-order-by the quasi-bureau of the quasi-bureau, the quasi-bureau of the monthly work, the cooperation, the Duinu XPS pair Analysis of the surface shows that the gamma radiation of 〇.〇〇5Mi: ad can induce PHEMA to effectively graft and polymerize on the PVDF surface. Table 19 The analysis of the material surface concentration and PHEMA graft polymerization on the PVDF surface is the same, only a very small amount of Fluorine can be detected. It means that there is only a small amount of PVDF on the surface of PHEMA-g-PVDF. The paper is used in the "B Jia Biao Bi (CNS) T4 specification (2 丨 0x297 public;« :)

Claims (1)

202466 B7 C7 D7 -48- VI. Patent application Fanyuan 1. A method for surface modification of eye implant material, the surface mainly contains polymethyl methacrylate (PMMA), which uses N-vinyl pyrrolidone ( NVP), a mixture of methyl 2-hydroxyethylmalonate (HEMA) or (NVP) and (HEMA), and a chemically grafted coating that induces polymerization by gamma irradiation once, and then forms a polyvinyl-containing Pyrrolidone (PVP), polyhydroxyethyl methacrylate (PHEMA) or (NVP) and (HEMA) copolymers with a thin hydrophilic outer layer on the surface, the improvement is mainly based on the following conditions: In essence, a gamma-ray-induced graft polymerization is carried out in the water solution: (A) The single warm concentration should be maintained at 0.U to 503; between the weight ratio; (B) The total gamma agent is set from 0.001 to Below 0.50Mrad; and (C) The gamma dose rate is between 10 and 2500 rqds / ninute. 2. According to the method for surface modification of the eye implant material described in item 1 of the patent application scope, which still contains one or more of the following conditions: (D) degassing from the graft polymerization solution; (E) The thickness of the polymerized outer layer is maintained between 100 angstroms and 100 micrometers (the) the water-soluble graft polymer solution still includes a free radical scavenger; and (h) the water-soluble graft polymer solution also includes the PMMA Swelling solvent on the surface. 3. According to the method for surface modification of the eye implant material as described in paragraphs 1 and 2 of the patent application, the eye implant material is like an intraocular transflective lens. 4. According to the method for surface modification of the eye implant material described in items 1 and 2 of the patent application scope, wherein the eye is implanted with a material keratoconus implant. 5. According to the method for surface modification of the eye implant material as described in items 1 and 2 of the patent application scope, wherein the eye implant material pseudo-corneal filler. (Please read the precautions on the back before filling in this page) • Installed • • Played •. Line • A 4 (210X 297 public) 78. 8. 3,000 203466 AB c D Printed by the Central Bureau of Standards of the Ministry of Economy Fan Yuan 6. According to the surface modification method of the eye implant material according to the first and second items of the patent application scope, wherein the eye implant material is pseudo-glaucoma shunt. 7. — A method for surface modification of the eye implant material, the surface mainly contains polypropylene (PP), polyvinyl fluoride (PVDF), — a kind of polyacrylic acid ester (PC) or a kind of polymethan L (Psi), 傜Using N-vinyl pfct pyrrolidine (NVP), 2-hydroxyethyl methacrylate (HEMA) or both (NVP) and (HEMA) mixed by a single irradiation of gamma rays to induce polymerization of chemically grafted coating, and then formed A thin hydrophilic outer layer containing polyvinyl &amp; pyrrolidone (PVP), polyhydroxyethyl methacrylate (PHEMA) or (NVP) and (HEMA) copolymer on the surface; the main basis for its improvement The following conditions are to implement a gamma ray-induced graft polymerization in an aqueous solution: (A) The total monomer content should be maintained between 0.1% and 50% by weight; (B) The total gamma dose is from 0.001 to Below 0.50Mrad; (C) The gamma dose rate is between 10 and 2500 rads / minute. (D) Degassing is carried out from the water-soluble graft polymerization solution. 8. According to the method for surface modification of the eye implant material described in item 7 of the patent application, which includes one or more of the following conditions: (E) Maintain the thickness of the polymeric outer layer at 100 Angstroms to 100 meters. Between I (he) the water-soluble graft polymerization solution still includes free radical scavenging and (h) the water-soluble graft polymerization solution includes surface swelling solvent. 9. According to the surface modification method of the eye implant material described in item 1 of the patent application scope, the mixed sleep of NVP, HEMA, or NVP and ITEMA is an ionic monomer or copolymerized by gamma-ray-induced copolymerization under the above conditions Mixed fishy, the total infusion of the monomer in this solution is between 0.1% and 50% by weight. (Please read the precautions on the back before filling in this page) Yung 4 (210X 297 public) 78. 8, 3,000 20 246b 7 7 7 7 A B c D 6. Applying for a patent fan garden 10. According to the surface modification method of the eye implant material as described in item 9 of the patent application country, the ion monobloc is pseudoethylene sulfonic acid or ethylene carboxylic acid. Π. According to the surface modification method of the eye implant material described in item 10 of the patent application park, in which ethylene sulfonic acid methyl sulfoethyl acrylate, methyl thiopropyl acrylate, styrene sulfonic acid or vinyl sulfonic acid . 12. According to the surface modification method of the eye implant material described in item 10 of the patent application, the ethylene carboxylic acid pseudo-acrylic acid, methacrylic acid or crotonic acid. 13. According to the surface modification method of the eye implant material described in item 9 of the patent scope, where the ion is single, you have an amine-functional single joy. 14. According to the surface modification method of the eye implant material as described in item 13 of the patent application park, wherein the amine-functional monohydrazine is vinyl pkL pyridine, aminostyrene, aminoacrylic acid or aminomethacrylate. 15. An eye implant material made according to the surface modification method of the eye implant material described in item 1 of the patent scope. 16. According to the surface modification method of the eye implant material described in item 15 of the patent application scope, in which the eye implant material pseudo-eye internal lens, corneal inlay, corneal filling, corneal surgical tool, glaucoma shunt, Retinal lock ring or solid buckle. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs 17. A method of surface modification of eye implant materials, the surface mainly contains polymethyl methacrylate (PMMA), like the use of N-vinyl vinylpyrrolidone (NVP), 2-Hydroxyethyl Methyl Acrylate (HEMA) or (NVP) and (HEHA) are mixed together and are irradiated by electron beam once to form a thin hydrophilic outer layer of the following substances on the surface: (1) Polyethylene Pyrrolidone (PVP), 78. 8. 3,000 (Please read the precautions on the back before filling in this page) A4 (210X297 Public Broadcasting) 202466 B7 C7 D7 • 51 · Printed by the Central Bureau of Standards of the Ministry of Economy ¾ 6. Apply for a patent The surface (2) polyhydroxyethyl methacrylate (PHEKA), or (3) a copolymer of (PVP) and (PHEMA) on the surface, wherein the primary beam of light is irradiated in a substantially aqueous solution according to the following conditions Implementers: (A) The single susceptibility is between 0.1 and 50¾ weight ratio ... (B) The total dose of electron beam irradiation is the same as that of gamma rays and is between 0.001 and 0.50 Mrad; and (C) The electron beam The irradiation dose is between 110 and 10 * rads / ninute. 18. According to the «surface modification method for ocular implants described in item 17 of the application scope, which includes one or more of the following conditions: (D) degassing from the graft polymerization solution; (E ) &Amp; The thickness of the polymerized outer layer is maintained between 100 Angstroms and 100 Angstroms; (he) the water-soluble graft polymer solution still includes a free radical scavenger; and (h) the water-soluble graft polymer solution And includes the swelling solvent on the surface of the PMMA. 19. A method for modifying the surface of an eye implant material. The surface mainly contains polypropylene (PP), polyvinyl fluoride (PVDF), polysulfonate (PC) or polysilicon (PSi). Ketone (NVP), 2-Hydroxyethyl Methyl Acrylate (HEMA) or a mixture of (NVP) and (HEMA) is irradiated with electron beam once to induce polymerization of chemically grafted coating to form a thin hydrophilic outer layer of the following substances, and then Becomes a thin hydrophilic outer layer of polyvinyl / pyrrolidone (PVP), polyhydroxyethyl methacrylate (PHEMA) or (PVP) and (PHEMA) q copolymer on the surface; wherein the electron beam is once Irradiation-induced graft polymerization is carried out in a substantially aqueous solution according to the following conditions: (Please read the precautions on the back before filling in this page). Installation · Line. A 4 (210X297 Public Radio) 78. 8. 3,000 -52 --m4B £ _ VI. Patent application B7 C7 D7 and (A) monomer concentration between 0.1% and 50% by weight; (B) electron beam irradiation total agent between 0.001 and 〇 . Below 50Mrad; (C) The electron beam irradiation dose is between 10 and 10f rads / ainute. 20. According to the method for surface modification of eye implant material described in item 19 of Shen_Patent Fanyi, which also includes one or more of the following conditions: t (D) Deoxygenation is carried out from the graft polymerization solution (E) Maintain the thickness of the outer layer of the polymer between 100 Angstroms and 100 nm; (H) The water-soluble graft polymer solution still includes free radical scavenger; and (G) The water-soluble graft polymer solution And includes the surface swelling solvent. (Please read the precautions on the back before filling out this page) • Install *. Line · Printed by the Central Standards Bureau of the Ministry of Economic Affairs f 4 (210X 297 public) 78. 8. 3,000