TW201518344A - Silicon-containing prepolymer containing three-dimensional network structure and its preparation method - Google Patents
Silicon-containing prepolymer containing three-dimensional network structure and its preparation method Download PDFInfo
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本發明係有關於一種含矽預聚物，特別是具有三維網狀結構，其末端基為親水鏈段，內部為含矽鏈段，外部為親水鏈段，可應用於製備矽水膠隱形眼鏡之含矽預聚物。 The invention relates to a cerium-containing prepolymer, in particular to a three-dimensional network structure, the terminal group is a hydrophilic segment, the inner part is a bismuth-containing segment, and the outer part is a hydrophilic segment, which can be used for preparing a hydrophobic gel contact lens. a cerium-containing prepolymer.
按，聚甲基丙烯酸甲酯(Polymethyl methacrylate，PMMA)由於具有優良的光學性質與製程簡單、來源充足、價格低廉等優點，結合較佳的穩定性、低毒性與抗沉澱物的形成，因此係為市面上第一個用來製作隱形眼鏡的塑膠，不過PMMA的問題在於，其親水性跟透氧性都不佳，造成其日後在隱形眼鏡的應用上仍具有相當大之瓶頸。 According to polymethyl methacrylate (PMMA), it has excellent optical properties, simple process, sufficient source and low price, combined with better stability, low toxicity and anti-precipitate formation. It is the first plastic on the market to make contact lenses, but the problem with PMMA is that its hydrophilicity and oxygen permeability are not good, which will still have a considerable bottleneck in the future application of contact lenses.
之後，最早成功將水膠應用在生醫高分子材料上的是Wichterle和Lim所提出的聚甲基丙烯酸-2-羥基乙酯poly(2-hydroxyethyl methacrylate)(PHEMA)水膠。此種水膠是一種三維的網狀結構高分子材料，具有在水中膨潤但不會溶解的特性，在眾多水膠當中，Poly(hydroxyethyl-methacrylate，PHEMA)毫無疑問地是一種廣泛應用的生物材料，特別是在隱形眼鏡應用上，更可看到PHEMA的極大功用。然而，PHEMA仍具有其缺失，在於其低平衡含水率及低氧穿透度上，一直是限制PHEMA廣泛應用的因素。因此，有鑑於此，迄今仍有許多研究學者發展出結合親水性單體的共聚合PHMEA水膠來改善此缺點。 After that, the earliest successful application of water gel to biomedical polymers was the poly(2-hydroxyethyl methacrylate) (PHEMA) water gel proposed by Wichterle and Lim. This kind of water gel is a three-dimensional network structure polymer material, which has the characteristics of swelling in water but does not dissolve. Among many water glues, Poly(hydroxyethyl-methacrylate, PHEMA) is undoubtedly a widely used organism. Materials, especially in contact lens applications, can be seen in the great use of PHEMA. However, PHEMA still has its lack, because its low equilibrium moisture content and low oxygen permeability have been the factors limiting the wide application of PHEMA. Therefore, in view of this, many research scholars have developed a copolymerized PHMEA water gel combined with a hydrophilic monomer to improve this disadvantage.
其中，為了提高水膠隱形眼鏡的配戴舒適性，業界不斷的研究其改進之道，於是，習知技術遂研發出一種利用電漿表面改質，並結合親水性物質來增進鏡片表面親水性，並保有矽水膠高透氧的性質。但值得注意的是，此種方法的設備成本高、製程繁瑣，在製作鏡片時，親水性物質與矽水膠表面結合不穩定，因此品質參差不一，導致良率不穩定，無法降低生產成本。 Among them, in order to improve the wearing comfort of water-based contact lenses, the industry has continuously studied its improvement. Therefore, the conventional technology has developed a use of plasma surface modification, combined with hydrophilic substances to enhance the hydrophilicity of the lens surface. And retains the high oxygen permeability of hydrophobic glue. However, it is worth noting that this method has high equipment cost and complicated process. When the lens is made, the hydrophilic substance and the surface of the hydrophobic glue are unstable, so the quality is uneven, resulting in unstable yield and low production cost. .
緣是，鑑於上述之缺失亟待改進，故本發明人有感上述缺失之可改善，且依據多年來從事此方面之相關經驗，悉心觀察且研究之，並配合學理之運用，而提出一種設計合理且有效改善上述缺失之本發明，其係揭露一種具有三維網狀結構之含矽預聚物及其製備方法，其具體架構及實施方式將詳述於下。 Therefore, in view of the above-mentioned lack of improvement, the inventors felt that the above-mentioned deficiencies could be improved, and based on years of experience in this field, carefully observed and studied, and with the use of academics, a reasonable design was proposed. The present invention, which effectively improves the above-mentioned deficiency, discloses a cerium-containing prepolymer having a three-dimensional network structure and a preparation method thereof, and the specific structure and embodiment thereof will be described in detail below.
為解決習知技術存在的問題，本發明之主要目的係在於提供一種具有三維網狀結構之含矽預聚物及其製備方法，其主要成分為具高透氧之疏水矽膠，且末端基為親水鏈段，形成內部為含矽鏈段，外部為親水鏈段之含矽預聚物，結合親水性生醫材料，以增進隱形眼鏡之保水性與配戴舒適性，並解決了習知技術因親疏水物質不相容而引起的相分離之問題。 In order to solve the problems of the prior art, the main object of the present invention is to provide a cerium-containing prepolymer having a three-dimensional network structure and a preparation method thereof, the main component of which is a hydrophobic silicone having high oxygen permeability, and the terminal group is The hydrophilic segment forms a cerium-containing prepolymer having a ruthenium-containing segment inside and a hydrophilic segment on the outside, and is combined with a hydrophilic biomedical material to enhance the water repellency and wearing comfort of the contact lens, and solves the conventional technology. The problem of phase separation due to incompatible hydrophilic and hydrophobic materials.
本發明之另一目的在於提供一種具有三維網狀結構之含矽預聚物及其製備方法，其係利用簡單的水解縮合聚合反應即可得到含矽預聚物，並呈現出三度空間的網狀結構，使得其機械強度良好。 Another object of the present invention is to provide a cerium-containing prepolymer having a three-dimensional network structure and a preparation method thereof, which can obtain a cerium-containing prepolymer by a simple hydrolysis condensation polymerization reaction and exhibit a three-dimensional space. The mesh structure makes it mechanically strong.
本發明之再一目的在於提供一種具有三維網狀結構之含矽預聚物及其製備方法，其係可更進一步藉由與親水性單體及含矽疏水性單 體進行自由基鏈鎖共聚合反應而形成一兼具有良好透氣性、親水性、機械性質的矽水膠，不僅沒有伸長率過低及硬脆的缺點，更可製成一兼具有良好透氧性且配戴舒適性的隱形眼鏡。 A further object of the present invention is to provide a ruthenium-containing prepolymer having a three-dimensional network structure and a preparation method thereof, which can be further processed by a hydrophilic monomer and a hydrazine-containing hydrophobic single The body undergoes free radical chain-locking copolymerization to form a hydrophobic rubber which has good gas permeability, hydrophilicity and mechanical properties, and has the advantages of low elongation and hard brittleness, and can be made into a good one. A contact lens that is oxygen permeable and comfortable to wear.
為達到上述之目的，本發明係揭露一種具有三維網狀結構之含矽預聚物，其結構式(I)係為：
另一方面而言，本發明另揭露一種具有三維網狀結構之含矽預聚物的製備方法，其係包括以下步驟：將莫耳數含量比為1~50：1之六 烷氧基矽醚(TEOS)與反應型矽聚合物混合，以形成一矽氧烷前驅物；以及將莫耳數含量比為1：1~40之矽氧烷前驅物與親水反應性單體混合，以形成一含矽預聚物，其具有結構式如上式(I)所示。 In another aspect, the present invention further discloses a method for preparing a cerium-containing prepolymer having a three-dimensional network structure, which comprises the steps of: a molar ratio of 1 to 50:1; Alkoxy oxime ether (TEOS) is mixed with a reactive ruthenium polymer to form a oxane precursor; and a oxane precursor and a hydrophilic reactive monomer having a molar ratio of 1:1 to 40 Mixing to form a cerium-containing prepolymer having the structural formula shown in the above formula (I).
根據本發明之實施例，在得到此種含矽預聚物後，更可進一步將其與一親水性單體與含矽疏水性單體反應成一矽水膠混合物，以進一步製成一兼具有良好透氧性且配戴舒適性的矽水膠隱形眼鏡。 According to the embodiment of the present invention, after the cerium-containing prepolymer is obtained, it can be further reacted with a hydrophilic monomer and a hydrazine-containing hydrophobic monomer to form a water-hybrid mixture, thereby further forming a mixture. Hydrophobic contact lenses with good oxygen permeability and comfortable wearing.
底下藉由具體實施例配合所附的圖式詳加說明，當更容易瞭解本發明之目的、技術內容、特點及其所達成之功效。 The purpose, technical contents, features and effects achieved by the present invention will be more readily understood by the detailed description of the embodiments and the accompanying drawings.
第1圖係為根據本發明實施例之含矽預聚物之製備方法的步驟流程圖。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing the steps of a method for preparing a ruthenium-containing prepolymer according to an embodiment of the present invention.
第2圖係為根據本發明實施例之矽水膠混合物之製備方法的步驟流程圖。 Figure 2 is a flow chart showing the steps of a method for preparing a hydrophobic glue mixture according to an embodiment of the present invention.
以上有關於本發明的內容說明，與以下的實施方式係用以示範與解釋本發明的精神與原理，並且提供本發明的專利申請範圍更進一步的解釋。有關本發明的特徵、實作與功效，茲配合圖式作較佳實施例詳細說明如下。 The above description of the present invention is intended to be illustrative and illustrative of the spirit and principles of the invention, and to provide further explanation of the scope of the invention. The features, implementations, and utilities of the present invention are described in detail with reference to the preferred embodiments.
有鑑於HEMA軟式隱形眼鏡的製備，主要都係以親水性單體的合成為主，因此高含水率係為HEMA隱形眼鏡的主要特色，但是，低透氧率則是它的缺點，在長時間配戴下會使眼睛乾澀，而限制了使用者的配 戴時間。因此，本發明所製備出的含矽預聚物，為了提高透氧量，乃是利用矽單體(疏水單體)與親水性單體進行合成，並解決了親疏水單體不相容的問題，成功製備出具有高透氧、親水性佳、且色澤透明的矽水膠隱形眼鏡，進一步地延長其配戴的時間。 In view of the preparation of HEMA soft contact lenses, mainly based on the synthesis of hydrophilic monomers, high water content is the main feature of HEMA contact lenses, but low oxygen permeability is its shortcomings, Wearing it will dry your eyes and limit the user's Wear time. Therefore, the cerium-containing prepolymer prepared by the present invention is synthesized by using a hydrazine monomer (hydrophobic monomer) and a hydrophilic monomer in order to increase the oxygen permeability, and solves the incompatibility of the hydrophilic and hydrophobic monomer. The problem is that the hydrophobic contact lens with high oxygen permeability, good hydrophilicity and transparent color is successfully prepared, and the wearing time is further extended.
根據本發明之實施例，請參閱第1圖所示，其係為根據本發明實施例之含矽預聚物之製備方法的步驟流程圖。以下關於本發明揭示之含矽預聚物及其製備方法的說明，請一併參照第1圖所示，茲詳細說明如下。 In accordance with an embodiment of the present invention, reference is made to Figure 1 which is a flow diagram of the steps of a method for preparing a ruthenium-containing prepolymer according to an embodiment of the present invention. Hereinafter, the description of the cerium-containing prepolymer disclosed in the present invention and a method for producing the same will be described below with reference to Fig. 1, which will be described in detail below.
首先，在步驟S102中，混合一六烷氧基矽醚與一反應型矽聚合物，以形成一矽氧烷前驅物。在本實施例中，此六烷氧基矽醚係具有化學式(II)為：
根據本發明之實施例，以莫爾數計，該六烷氧基矽醚與反應型矽聚合物於該矽氧烷前驅物的含量比，較佳地可為5~30：1。更佳地，該六烷氧基矽醚與反應型矽聚合物於該矽氧烷前驅物的含量比可為7~20：1，其反應式(a)係如下所示：
其中，R22、R23、R24、R25、R26、R27係為C1~C12之烷基；R30、R32、R33、R35、R36、R37係為C1~C10之烷基；R31、R34係為C1~C8之烷基；以及a係為1~100之間的整數。較佳地，該六烷氧基矽醚中的R22、R23、R24、R25、R26、R27各自分別表示：一C1~C10之烷基。更佳地，該六烷氧基矽醚中的R22、R23、R24、R25、R26、R27各自分別表示：一C1~C8之烷基，在本發明具體例中即是使用六烷氧基矽醚(TEOS)作為反應物。 Wherein R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are alkyl groups of C1 to C12; and R 30 , R 32 , R 33 , R 35 , R 36 and R 37 are C1 to C10. The alkyl group; R 31 and R 34 are C1 to C8 alkyl groups; and a is an integer between 1 and 100. Preferably, R 22 , R 23 , R 24 , R 25 , R 26 and R 27 in the hexaalkyloxyanthracene each represent a C1 to C10 alkyl group. More preferably, each of R 22 , R 23 , R 24 , R 25 , R 26 and R 27 in the hexadecanoxy oxime ether represents a C1-C8 alkyl group, which is a specific example in the present invention. Hexaalkyloxy oxime ether (TEOS) was used as a reactant.
其次，該反應型矽聚合物中的R30、R32、R33、R35、R36、R37較佳地可為C1~C10之烷基；R31、R34係為C1~C8之烷基。更佳地，該反應型矽聚合物中的R30、R32、R33、R35、R36、R37各自分別表示：一C1~C8之烷基；R31、R34各自分別表示：一C1~C6之烷基，在本發明具體例中即是 使用分子量為2000~8000的反應型矽聚合物(PDMS-diol)作為反應物。 Next, R 30 , R 32 , R 33 , R 35 , R 36 and R 37 in the reaction-type ruthenium polymer may preferably be a C1 to C10 alkyl group; R 31 and R 34 are C1 to C8. alkyl. More preferably, each of R 30 , R 32 , R 33 , R 35 , R 36 , and R 37 in the reactive ruthenium polymer represents: a C1 to C8 alkyl group; and R 31 and R 34 each represent: A C1-C6 alkyl group, in the specific example of the present invention, uses a reactive ruthenium polymer (PDMS-diol) having a molecular weight of 2000 to 8000 as a reactant.
之後，在步驟S104中，將上式(a)所得的矽氧烷前驅物混合一親水反應性單體，以形成一含矽預聚物。在此步驟中，矽氧烷前驅物與親水反應性單體之莫耳數含量比為1：1~40，以藉此形成本發明之含矽預聚物。根據本發明之實施例，以莫爾數計，該矽氧烷前驅物與親水反應性單體於含矽預聚物的含量比，較佳地可為1：2~30。更佳地，該矽氧烷前驅物與親水反應性單體於含矽預聚物的含量比可為1：3~20，其反應式(b)係如下所示：
根據本發明之實施例，該親水反應性單體係具有化學式(IV)係為：
是以，本發明乃是透過將上述三種反應物(六烷氧基矽醚、反應型矽聚合物、以及親水反應性單體)依序混合，並在弱酸性條件下進行水解縮合聚合反應，以製成如上式(b)具有三維結構之含矽預聚物，其結構式(I)係為：
詳細而言，根據本發明之實施例，此一水解縮合聚合反應是在一介於10℃至70℃之間的溫度下；pH值介於2至6或8至11之間的環境下；以及反應時間介於6至72小時之間進行。更佳地，該水解縮合聚合反應可在一介於20℃至40℃之間的溫度下；pH值介於3至5或9至10之間的環境下；以 及反應時間介於10至48小時之間進行。 In detail, according to an embodiment of the present invention, the hydrolytic condensation polymerization reaction is carried out at a temperature between 10 ° C and 70 ° C; and the pH is between 2 and 6 or 8 to 11; The reaction time is between 6 and 72 hours. More preferably, the hydrolysis condensation polymerization reaction can be carried out at a temperature between 20 ° C and 40 ° C; at a pH between 3 and 5 or 9 to 10; And the reaction time is between 10 and 48 hours.
是以，本發明所揭露之含矽預聚物係為具有3D的網狀結構，此與市面上所使用的直鏈型含矽預聚物的結構是不相同的，該3D網狀結構可使得矽預聚物具有良好的機械強度。其次，本發明利用不同莫爾比例的反應物來合成矽預聚物，可以修飾矽預聚物不同比例的不飽和官能基，使得本發明所揭示之矽預聚物亦具有較佳之反應性。 Therefore, the cerium-containing prepolymer disclosed in the present invention has a network structure of 3D, which is different from the structure of a linear cerium-containing prepolymer used in the market, and the 3D network structure can be The cerium prepolymer has good mechanical strength. Secondly, the present invention utilizes reactants of different Mohr ratios to synthesize the ruthenium prepolymer, and can modify the unsaturated functional groups of the ruthenium prepolymer in different proportions, so that the ruthenium prepolymer disclosed in the present invention also has better reactivity.
之後，根據本發明所揭示之含矽預聚物，更可進一步與一親水性單體與一含矽疏水性單體反應而成一矽水膠混合物，其步驟流程請一併參照第2圖所示，更包含有步驟S106~S110。 Thereafter, the ruthenium-containing prepolymer disclosed in the present invention can be further reacted with a hydrophilic monomer and a hydrazine-containing hydrophobic monomer to form a water-hybrid mixture. For the procedure of the step, please refer to FIG. 2 together. Further, steps S106 to S110 are included.
其中，如步驟S106所示，本發明在步驟S102、S104之後係接著混合該含矽預聚物、一親水性單體與一含矽疏水性單體，並添加一起始劑以進行自由基連鎖共聚合反應；然後，再如步驟S108所示，以比例為5：5的酒精：水混合液進行膨潤萃取；最後，如步驟S110所示，將該混合液於生理食鹽水中進行回復反應，以獲得矽水膠混合物。 Wherein, as shown in step S106, the present invention is followed by mixing the cerium-containing prepolymer, a hydrophilic monomer and a hydrazine-containing hydrophobic monomer after steps S102 and S104, and adding a starter for radical linkage. Co-polymerization; then, as shown in step S108, performing a swelling extraction with an alcohol:water mixture at a ratio of 5:5; finally, as shown in step S110, the mixture is subjected to a reaction in physiological saline to A hydrophobic glue mixture is obtained.
根據本發明之實施例，該混合物之總重量計，其中含矽預聚物的含量係介於1~65wt%之間；更佳地，該含矽預聚物的含量係介於10~60wt%之間；最佳地，該含矽預聚物的含量係介15~50wt%之間。另一方面而言，該混合物之總重量計，其中親水性單體的含量係介於1~65wt%之間；更佳地，該親水性單體的含量係介於10~55wt%之間；最佳地，該親水性單體的含量係介於15~45wt%之間。再一方面而言，該混合物之總重量計，其中含矽疏水性單體的含量係介於1~70wt%之間；更佳地，該含矽疏水性單體的含量係介於10~55wt%之間；最佳地，該含矽疏水性單體的含量係介於15~40wt%之間。其中，該含矽疏水性單體係選自由三(三甲基矽氧烷)-2-甲基丙烯酸丙氧基矽烷(tris(trimethylsiloxy)silypropyl methacrylate，TRIS)、 雙三甲基矽氧烷-甲基丙烯酸丙甲基矽烷(bis(trimethylsiloxy)methylsilylpropyl methacrylate)、五甲基二矽氧烷-甲基丙烯酸丙甲基矽烷(pentamethyldisiloxanyl methylmethacrylate、三(三甲基矽氧烷)-甲基氨基甲酸乙酯丙基矽烷(tris(trimethylsiloxy)silylpropyl methacryloxyethylcarbamate，TSMC)、三(三甲基矽氧烷)-甲基丙烯酸丙三醇丙基矽烷(tris(trimethylsiloxy)silypropyl glycerol methacrylate，SIGMA)、三(聚二甲基矽氧烷)丙烯酸丙基矽烷(tris(polydimethylsiloxy)silylpropyl methacrylate)及其混合物所組成之群組；該親水性單體係選自由羥乙基甲基丙烯酸酯(hydroxyethyl methacrylate，HEMA)、甘油丙烯酸甲酯(glycerol methacrylate)、甲基丙烯酸(methacrylic acid，MAA)、N-乙烯基咯烷酮(N-vinyl prrrrolidone，NVP)、N-異丙烯醯胺(N-isopropylacrylamide)、2-羥乙基丙烯酸(2-hydroxyethyl acrylate)、N,N’-二乙基丙烯醯酸(N,N’-diethylacrylamide)、N,N’-二甲基苯胺(N,N’-dimethylacrylamide，DMA)、乙酸乙烯(vinyl acetate)、N-丙烯醯基嗎碄(N-acryloymorpholine)、2-二甲基氨乙基丙烯酸(2-dimethylaminoethyl acrylate)及其混合物所組成之群組。在本發明具體之實施例中，本發明所使用之含矽疏水性單體係可為三(三甲基矽氧烷)-2-甲基丙烯酸丙氧基矽烷(TRIS)，而親水性單體則為羥乙基甲基丙烯酸酯(HEMA)、甲基丙烯酸(MAA)、甘油丙烯酸甲酯(GMA)。 According to an embodiment of the present invention, the total weight of the mixture, wherein the content of the cerium-containing prepolymer is between 1 and 65 wt%; more preferably, the content of the cerium-containing prepolymer is between 10 and 60 wt. Between %; optimally, the content of the cerium-containing prepolymer is between 15 and 50% by weight. In another aspect, the total weight of the mixture is such that the content of the hydrophilic monomer is between 1 and 65 wt%; more preferably, the content of the hydrophilic monomer is between 10 and 55 wt%. Preferably, the hydrophilic monomer is present in an amount between 15 and 45 wt%. In a further aspect, the total weight of the mixture, wherein the content of the hydrophobic monomer is between 1 and 70% by weight; more preferably, the content of the hydrophobic monomer is between 10 and Between 55 wt%; optimally, the content of the rhodium-containing hydrophobic monomer is between 15 and 40 wt%. Wherein the hydrophobic monolithic system is selected from the group consisting of tris(trimethylsiloxy)silypropyl methacrylate (TRIS), Bis (trimethylsiloxymethylsilylpropyl methacrylate), pentamethyldisiloxanyl methylmethacrylate, tris(trimethylhydrazine) Tris(trimethylsiloxy)silylpropyl methacryloxyethylcarbamate (TSMC), tris(trimethylsiloxane)-trisyltrifluoropropane (tris(trimethylsiloxy)silypropyl glycerol methacrylate) , SIGMA), tris(polydimethylsiloxy)silylpropyl methacrylate, and a mixture thereof; the hydrophilic single system is selected from the group consisting of hydroxyethyl methacrylate (hydroxyethyl methacrylate, HEMA), glycerol methacrylate, methacrylic acid (MAA), N-vinyl rolrrolidone (NVP), N-isopropenylamine (N -isopropylacrylamide), 2-hydroxyethyl acrylate, N,N'-diethylacrylamide, N,N'-dimethylaniline (N , N'-dimethylacrylamide, DMA), vinyl acetate, N-acryloymorpholine, 2-dimethylaminoethyl acrylate, and mixtures thereof In a specific embodiment of the present invention, the hydrazine-containing hydrophobic single system used in the present invention may be tris(trimethyldecane)-2-methyl acrylate propoxy decane (TRIS), and The hydrophilic monomer is hydroxyethyl methacrylate (HEMA), methacrylic acid (MAA), glycerol methyl acrylate (GMA).
此外，在步驟S106中所添加之起始劑係可為一光起始劑或一熱起始劑，其中該光起始劑及熱起始劑可以是任何現有已知的起始劑。在本發明具體實施例中乃是使用一例如為：2-羥基-2-甲基-1-戊基-1-丙酮(2-Hydroxy-2-methyl-1-pentyl-1-propanone)之光起始劑。當所添加之起始劑為一熱起始劑(AIBN)時，則該熱起始劑例如可為一學名為：2,2'-二氰 基-2,2'-偶氮丙烷之熱起始劑。根據本發明之實施例，當使用光起始劑時，則步驟S106中的自由基連鎖聚合反應較佳地係在一介於2mW/cm2至12mW/cm2之間的光照條件下進行反應。更佳地，該自由基連鎖聚合反應可在一介於4mW/cm2至10mW/cm2之間的光照條件下進行反應。 Further, the initiator added in step S106 may be a photoinitiator or a thermal initiator, wherein the photoinitiator and the thermal initiator may be any of the currently known initiators. In a particular embodiment of the invention, a light such as 2-Hydroxy-2-methyl-1-pentyl-1-propanone is used. Starting agent. When the initiator to be added is a thermal initiator (AIBN), the hot initiator may be, for example, a scientific name: 2,2'-dicyano-2,2'-azopropane. Hot starter. According to an embodiment of the present invention, when a photoinitiator, radical chain polymerization, step S106 in the reaction system is preferably in a range from at 2mW / cm 2 to 12mW / light conditions between 2 cm. More preferably, the radical chain polymerization can be carried out under a light condition of between 4 mW/cm 2 and 10 mW/cm 2 .
是以，由上可知，本發明所揭示之製備方法乃是先均勻混合一定比例的含矽預聚物、含矽疏水性單體(TRIS)與親水性單體(HEMA、MAA、GMA)，並藉由添加作為分散劑的異丙醇，作為光起始劑2-羥基-2-甲基-1-戊基-1-丙酮進行自由基連鎖共聚合反應，並在5至6mW/cm2的光照條件下光照歷時一小時，以形成矽水膠。之後，再將此矽水膠依比例為5：5的酒精：水混合液進行膨潤萃取約3至4小時，再於生理食鹽水中進行2至3小時之回復反應，方可製得一本發明之矽水膠混合物。之後，此矽水膠混合物係可注入一具有凹形表面的模具中，以形成鏡片的前表面，並藉由經旋轉熱化以獲得所需型態的前表面之型態體，或者，可選擇將前述之混合物注入一分別控制鏡片前、後表面的母模與公模中，再經光或熱熟化後獲得型態前表面之型態體，即可製得一如上述的矽水膠所形成之隱形眼鏡。 Therefore, it can be seen from the above that the preparation method disclosed in the present invention is to uniformly mix a certain proportion of the cerium-containing prepolymer, the hydrazine-containing hydrophobic monomer (TRIS) and the hydrophilic monomer (HEMA, MAA, GMA). And by adding isopropanol as a dispersing agent as a photoinitiator 2-hydroxy-2-methyl-1-pentyl-1-propanone for radical chain copolymerization at 5 to 6 mW/cm 2 The illumination lasted for one hour under light conditions to form a hydrophobic gel. After that, the water-repellent gel is subjected to a swell extraction with a ratio of 5:5 alcohol:water mixture for about 3 to 4 hours, and then subjected to a reaction reaction in physiological saline for 2 to 3 hours to obtain an invention. The water gel mixture. Thereafter, the hydrophobic glue mixture can be injected into a mold having a concave surface to form a front surface of the lens, and can be heated by rotation to obtain a shape of the front surface of a desired type, or Optionally, the mixture is injected into a master mold and a male mold which respectively control the front and back surfaces of the lens, and then the shape or the shape of the front surface is obtained by light or heat curing, thereby obtaining a water-repellent gel as described above. The formed contact lens.
以上已完整說明本發明之含矽預聚物及其製備方法。接續，以下係利用實際的範例以及實驗來說明本發明之功效。 The cerium-containing prepolymer of the present invention and its preparation method have been fully described above. Next, the following examples and experiments are used to illustrate the effects of the present invention.
首先，如下表一之實施例1~8所示，本發明係分別採用不同比例的六烷氧基矽醚、反應型矽聚合物、親水反應性單體以及醋酸溶液來製備含矽預聚物。 First, as shown in Examples 1 to 8 of Table 1 below, the present invention prepares a cerium-containing prepolymer by using different ratios of hexadecanoxy oxime ether, reactive ruthenium polymer, hydrophilic reactive monomer and acetic acid solution, respectively. .
之後，本發明接續利用表一所得之含矽預聚物分別混合不同比例之含矽疏水性單體、親水性單體、以及光起始劑來製備矽水膠隱形眼鏡，其重量百分比分別如下表二之應用例1~12所示。 Thereafter, the present invention successively uses the cerium-containing prepolymer obtained in Table 1 to separately mix different proportions of hydrazine-containing hydrophobic monomer, hydrophilic monomer, and photoinitiator to prepare hydrophobic rubber contact lenses, the weight percentages thereof are as follows: Tables 1 to 12 are shown in Application Examples 1 to 12.
最後，將應用例1~12所製得的試片分別進行接觸角、含水 率、透氧率及機械強度的測試，其中接觸角是依據一般液滴法(sessile drop method)進行測量；含水率是依據ISO standard 10399進行測量；透氧率是依據ISO9931-1進行測量；機械性質(伸長量與彈性模數)則是依據ASTM D1780進行測量。由下表三得知，本發明所製備出的矽水膠，其表面接觸角都介於40°到60°之間，因此表面潤濕性佳，適用於隱形眼鏡之應用。而含水率部分，其數值介於40%到70%之間，透氧率(Dk)則是介於40barrers到100barrers之間，與目前市場最大宗的HEMA隱形眼鏡相比，顯見其透氧率已大幅的提升。除此之外，由表三亦可看出，本發明所製得之矽水膠試片，其伸長率皆位在80~200%之間，不具有習見伸長率過低的問題，表示矽水膠在受到外力拉伸時較不易斷裂，且其彈性模數皆維持在1MPa以下，因此在配戴上亦能具有相當良好的舒適性。 Finally, the test pieces prepared in Application Examples 1 to 12 were respectively subjected to contact angles and containing water. Rate, oxygen permeability and mechanical strength test, wherein the contact angle is measured according to the sessile drop method; the water content is measured according to ISO standard 10399; the oxygen permeability is measured according to ISO 9931-1; The properties (elongation and modulus of elasticity) are measured in accordance with ASTM D1780. It is known from the following Table 3 that the hydrophobic adhesive prepared by the invention has a surface contact angle of between 40° and 60°, so that the surface wettability is good and is suitable for the application of contact lenses. The moisture content is between 40% and 70%, and the oxygen permeability (Dk) is between 40barrers and 100barrers. Compared with the largest HEMA contact lenses in the market, the oxygen permeability is obvious. Has been greatly improved. In addition, as can be seen from Table 3, the elongate gel test pieces prepared by the present invention all have an elongation of between 80% and 200%, and have no problem of low elongation. Water gel is less likely to break when stretched by external force, and its elastic modulus is maintained below 1 MPa, so it can also have quite good comfort in wearing.
是以，綜上所述，本發明係可利用簡易的水解縮合聚合反 應，形成呈現出三度空間網狀結構之含矽預聚物，其具備有機械強度良好之優勢。之後，更可進一步利用此種含矽預聚物混合親水性單體與含矽疏水性單體進行共聚合反應，以製備出兼具有良好透氧性、親水性、以及配戴性舒適的矽水膠隱形眼鏡。本發明所揭示之矽預聚物，不僅將親疏水鏈段結合，形成內部為矽疏水鏈段及外部為親水鏈段之結構，更進一步地解決了習知技術油水不相容的問題，使得本發明所揭示之隱形眼鏡鏡片可呈現出透明之狀態，具有極高的市場競爭力。 Therefore, in summary, the present invention can utilize a simple hydrolysis condensation polymerization reaction It is desirable to form a cerium-containing prepolymer exhibiting a three-dimensional network structure, which has the advantage of having good mechanical strength. Thereafter, the cerium-containing prepolymer-mixed hydrophilic monomer and the hydrazine-containing hydrophobic monomer may be further copolymerized to prepare a mixture having good oxygen permeability, hydrophilicity, and wearing comfort. Water-repellent contact lenses. The ruthenium prepolymer disclosed by the invention not only combines the hydrophilic and hydrophobic segments, but also forms a structure in which the inner hydrophobic group and the outer portion are hydrophilic segments, which further solves the problem of oil-water incompatibility of the prior art. The contact lens disclosed by the invention can exhibit a transparent state and has high market competitiveness.
以上所述之實施例僅係為說明本發明之技術思想及特點，其目的在使熟習此項技藝之人士能夠瞭解本發明之內容並據以實施，當不能以之限定本發明之專利範圍，即大凡依本發明所揭示之精神所作之均等變化或修飾，仍應涵蓋在本發明之專利範圍內。 The embodiments described above are merely illustrative of the technical spirit and the features of the present invention, and the objects of the present invention can be understood by those skilled in the art, and the scope of the present invention cannot be limited thereto. That is, the equivalent variations or modifications made by the spirit of the present invention should still be included in the scope of the present invention.
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