TWI407980B - Crystalline lens material with nano titanium dioxide particles and the method thereof - Google Patents
Crystalline lens material with nano titanium dioxide particles and the method thereof Download PDFInfo
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本發明係關於一種人工水晶體材料及其形成方法，特別是關於一種包含泊洛沙姆(poloxamer)交聯高分子與奈米二氧化鈦粒子之人工水晶體材料。The present invention relates to an artificial crystal material and a method of forming the same, and more particularly to an artificial crystal material comprising a poloxamer crosslinked polymer and nano titanium dioxide particles.
一般而言，傳統人工水晶體主要是以壓克力系高分子作為材料製備而成，此材料折射率佳，硬度高。因此人工水晶體植入過程中，需造成7至8 mm之傷口。In general, the conventional artificial crystal crystal is mainly prepared by using an acrylic polymer as a material, and the material has a good refractive index and a high hardness. Therefore, a 7 to 8 mm wound is required during the implantation of the artificial crystal.
為了嘗試解決此問題，柔軟性較佳之軟性水晶體水膠材料成為人工水晶體之發展重點。但是，由於水膠本身含有大量水分，所以折射率通常較低，限制了其在光學上面的運用。In order to try to solve this problem, the softer water soft gel material with better softness has become the focus of the development of artificial crystals. However, since the water gel itself contains a large amount of water, the refractive index is usually low, which limits its use in optics.
另外，泊洛沙姆(poloxamer)是一種聚氧乙烯-聚氧丙烯共聚而成之生物可相容性高分子，對皮膚黏膜無刺激性亦無過敏性，常用於肌肉、皮下注射。其具有溶膠-凝膠(sol-gel)相變化之特性，在較低溫時為液體，在接近人體溫度時呈凝膠狀，在肌肉或皮下可儲存藥物，有助於藥物緩慢釋放(Y K Han,etc."In vitro and in vivo study of lens refilling with poloxamer hydrogel." Br J Ophthalmol,2003,1399-1402)。此外，海容等人揭示，泊洛沙姆尾端官能基改質後，可藉由光起始互相交聯(HaeYong Kweon,etc."Preparation of a Novel Poloxamer Hydroge." Journal of Applied Polymer Science,2003.2670-2676.)。In addition, poloxamer is a biocompatible polymer made of polyoxyethylene-polyoxypropylene. It is non-irritating and non-allergenic to the skin mucosa. It is often used for muscle and subcutaneous injection. It has a sol-gel phase change characteristic, is a liquid at a lower temperature, is gelatinous when it is close to human body temperature, and can store drugs under muscle or subcutaneous, contributing to slow drug release (YK Han) , etc. "In vitro and in vivo study of lens refilling with poloxamer hydrogel." Br J Ophthalmol, 2003, 1399-1402). In addition, Hairong et al. revealed that after the poloxamer tail functional group is modified, it can be cross-linked by light (HaeYong Kweon, etc. "Preparation of a Novel Poloxamer Hydroge." Journal of Applied Polymer Science, 2003.2670-2676.).
目前人工水晶體材料正在發展當中，但其含水量、折射率與手術傷口大小表現上仍未滿意。有鑑於此，新的人工水晶體材料及其製備方式係亟欲發展技術。At present, artificial crystal materials are under development, but their water content, refractive index and surgical wound size are still not satisfactory. In view of this, new artificial crystal materials and their preparation methods are in the hope of developing technology.
鑒於上述之發明背景中，為了符合產業上之要求，本發明提供一種新的具有奈米二氧化鈦粒子之光起始高分子水晶體材料及其形成方法。藉由光起始水溶液材料，以得到水晶體水膠材料。並且，水晶體材料之折射率隨著奈米二氧化鈦粒子含量提高而提高。In view of the above-described background of the invention, in order to meet the industrial requirements, the present invention provides a novel photo-initiated polymer hydrocrystal material having nano-titanium dioxide particles and a method of forming the same. The aqueous solution material is obtained by light to obtain a hydrogel water-repellent material. Further, the refractive index of the crystal material increases as the content of the nano titanium dioxide particles increases.
本發明之一目的為揭露了一種具有奈米二氧化鈦粒子之光起始高分子水晶體水溶液材料，包含：泊洛沙姆(poloxamer)尾端改質高分子與奈米二氧化鈦粒子。其中，上述之水晶體水溶液材料可經由光起始作用，使高分子尾端官能基相互交聯，以得到一水膠材料。An object of the present invention is to disclose a light-initiating polymer aqueous solution aqueous material having nano titanium dioxide particles, comprising: a poloxamer tail modified polymer and a nano titanium dioxide particle. Wherein, the above aqueous crystal aqueous material material can crosslink the polymer tail end functional groups via photoinitiation to obtain a hydrocolloid material.
本發明之另一目的為揭露了一種具有奈米二氧化鈦粒子之光起始高分子水晶體水膠材料，包含：一水膠材料以及一奈米二氧化鈦粒子。其中，水膠材料係由泊洛沙姆尾端改質高分子交聯而成，且該奈米二氧化鈦粒子均勻固定分佈在水膠材料中，以提高該水晶體材料折射率。Another object of the present invention is to disclose a photoinitiator polymer hydrogel material having nano titanium dioxide particles, comprising: a hydrocolloid material and a nano titanium dioxide particle. Wherein, the water-adhesive material is formed by crosslinking the poloxamer end-modified polymer, and the nano-titanium dioxide particles are uniformly and uniformly distributed in the water-gel material to increase the refractive index of the crystal material.
本發明之另一目的為揭露了一種具有奈米二氧化鈦粒子之光起始高分子水晶體材料的形成方法包含：光起始一水溶液，以得到一具有奈米二氧化鈦粒子之光起始高分子水晶體材料水膠材料。其中，上述之水溶液包含奈米二氧化鈦粒子與泊洛沙姆尾端改質高分子。其中，該泊洛沙姆
尾端改質高分子經由光起始產生交聯，使該奈米二氧化鈦粒子均勻固定分佈在水膠材料中，以提高該水晶體材料折射率；其中，上述之該泊洛沙姆尾端改質高分子一般式如下：
因此，本發明所揭露之具有奈米二氧化鈦粒子之光起始高分子水晶體材料及其形成方法，以光起始作用將水溶液交聯成水膠溶液，同時混摻奈米二氧化鈦粒子於水膠中，以提高折射率。解決傳統高分子溶液流動性過高或過低不易處理的問題，並且同時解決傳統水膠折射率不高的問題。Therefore, the photo-initiated polymer water crystal material having the nano titanium dioxide particles and the method for forming the same disclosed in the present invention cross-link the aqueous solution into a water gel solution by photoinitiation, and simultaneously mix the nano titanium dioxide particles in the water gel. To increase the refractive index. It solves the problem that the traditional polymer solution is too fluid or too low to be easily handled, and at the same time solves the problem that the conventional water gel has a low refractive index.
本發明在此揭示一種具有奈米二氧化鈦粒子之光起始高分子水晶體材料及其形成方法。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡的步驟及其組成。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的組成或步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的較佳實施例會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的實施例中，且本發明的範圍不受限定，其以之後的專利範圍為準。The present invention discloses a photoinitiating polymer hydrocrystal material having nano titanium dioxide particles and a method of forming the same. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention are described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the scope of the following patents. .
本發明之第一實施例揭露一種具有奈米二氧化鈦粒子之光起始高分子水晶體水溶液材料，包含：泊洛沙姆(poloxamer)尾端改質高分子與奈米二氧化鈦粒子。上述之水溶液材料具有溶膠-凝膠(sol-gel)相變化特性，且上述之泊洛沙姆尾端改質高分子一般式如下：
較宜者，奈米二氧化鈦粒子粒徑小於等於50奈米。更佳者，奈米二氧化鈦粒子粒徑約為20奈米。上述之水晶體材料中，奈米二氧化鈦粒子含量提高則該折射率提高。Preferably, the nano titanium dioxide particles have a particle size of 50 nm or less. More preferably, the nano titanium dioxide particles have a particle size of about 20 nm. In the above-mentioned crystal material, when the content of the nano titanium dioxide particles is increased, the refractive index is increased.
於本實施例之一較佳範例中，上述之水晶體材料可經由光起始作用，使泊洛沙姆尾端改質高分子尾端官能基相互交聯，以得到一水膠材料。較宜者，光起始作用光源包含下列之一者及其任意組合：藍光、紫外光。較佳者，光起始時間小於等於5分鐘。In a preferred embodiment of the present embodiment, the above-mentioned crystal material can crosslink the functional end groups of the poloxamer end-modifying polymer via a light-initiating action to obtain a hydrocolloid material. Preferably, the light-initiating light source comprises one of the following and any combination thereof: blue light, ultraviolet light. Preferably, the light start time is less than or equal to 5 minutes.
本發明之第二實施例揭露一種具有奈米二氧化鈦粒子之光起始高分子水晶體水膠材料，包含：水膠材料以及奈米二氧化鈦粒子。其中，水膠材料係由泊洛沙姆尾端改質高分子交聯而成，使該奈米二氧化鈦粒子均勻固定分佈在水膠材料中，以提高該水晶體材料折射率。上述之泊洛沙姆尾端改質高分子一般式如下：
較宜者，上述之具有奈米二氧化鈦粒子之光起始高分子水晶體水膠材料折射率範圍為1.35至1.42，而上述之奈米二氧化鈦粒子含量提高則水晶體材料折射率提高。較佳者，奈米二氧化鈦粒子粒徑小於等於20奈米。Preferably, the above-mentioned light-initiating polymer hydrogel material having nano titanium dioxide particles has a refractive index ranging from 1.35 to 1.42, and the above-mentioned nano titanium dioxide particle content is increased to increase the refractive index of the crystal material. Preferably, the nano titanium dioxide particles have a particle size of 20 nm or less.
本發明之第三實施例揭露一種具有奈米二氧化鈦粒子之光起始高分子水晶體材料的形成方法，包含：光起始一水溶液，以得到一具有奈米二氧化鈦粒子之光起始高分子水晶體水膠材料。上述之水溶液包含奈米二氧化鈦粒子與泊洛沙姆尾端改質高分子；上述之泊洛沙姆尾端改質高分子經由光起始產生交聯，使該奈米二氧化鈦粒子均勻固定分佈在水膠材料中，以提高該水晶體材料折射率；
上述之該泊洛沙姆尾端改質高分子一般式如下：
其中，該奈米二氧化鈦粒子含量提高則該水晶體材料折射率提高。較宜者，該奈米二氧化鈦粒子粒徑小於等於20 奈米。較佳者，具有奈米二氧化鈦粒子之光起始高分子水晶體材料之折射率範圍為1.35至1.42。Wherein, the content of the nano titanium dioxide particles is increased to increase the refractive index of the crystal material. Preferably, the nano titanium dioxide particle size is less than or equal to 20 Nano. Preferably, the light-initiating polymer hydrocrystal material having nano titanium dioxide particles has a refractive index ranging from 1.35 to 1.42.
其中，上述之光起始光源較宜者包含下列之一者及其任意組合：藍光、紫外光。較佳者，光起始時間小於等於5分鐘。Wherein, the above light starting light source preferably comprises one of the following and any combination thereof: blue light, ultraviolet light. Preferably, the light start time is less than or equal to 5 minutes.
於本實施例之一較佳範例中，水溶液可先注入眼部，接著，進行該光起始反應，以得到人工水晶體於眼部中。相對於傳統人工水晶體，本發明有效減少傷口大小及反應時間。In a preferred embodiment of the present embodiment, the aqueous solution may be injected into the eye first, and then the photoinitiation reaction is performed to obtain an artificial crystal in the eye. The present invention effectively reduces wound size and reaction time relative to conventional artificial crystals.
將15 g泊洛沙姆(poloxamer407)溶於80ml四氫呋喃(THF)中，攪拌至完全溶解。接著，加入0.67ml三乙胺(Triethylamine)與0.39ml丙烯酰氯(Acryloyl chloride)，於60℃下反應24hr。以重力過濾溶液去除白色鹽類沉澱，得透明含有尾端改質高分子之四氫呋喃(THF)溶液。15 g of poloxamer 407 was dissolved in 80 ml of tetrahydrofuran (THF) and stirred until completely dissolved. Next, 0.67 ml of Triethylamine and 0.39 ml of Acryloyl chloride were added and reacted at 60 ° C for 24 hr. The white salt precipitate was removed by gravity filtration to obtain a tetrahydrofuran (THF) solution containing a modified polymer at the end.
其次，將含有尾端改質高分子之四氫呋喃溶液以緩慢之速度滴入240ml正己烷(Hexane)中，並利用攪拌子攪拌使尾端改質高分子析出。接著，利用重力過濾去除正己烷，得到尾端改質高分子之白色沉澱物。Next, a tetrahydrofuran solution containing a modified polymer at a tail end was dropped into 240 ml of n-hexane (Hexane) at a slow rate, and stirred at a stirring point to precipitate a modified polymer at the tail end. Next, n-hexane was removed by gravity filtration to obtain a white precipitate of the modified polymer at the tail end.
最後，以50℃烘箱乾燥24hr，得到尾端改質高分子之白色蓬鬆粉末泊洛沙姆尾端改質高分子(poloxamer 407A)。Finally, it was dried in an oven at 50 ° C for 24 hr to obtain a white fluffy powder poloxamer tail modified polymer (poloxamer 407A) which was modified at the end.
如第二圖所示，末端改質後高分子的溶膠-凝膠(sol-gel)溫度會比未改質的提升。以18wt%為例，改質 前在25℃會從溶液狀態變成膠狀，而改質後相同濃度會提升至32℃。(如第一圖所示)As shown in the second figure, the sol-gel temperature of the polymer after end modification is higher than that of the unmodified one. Take 18wt% as an example, upgrade The former will change from a solution state to a gel at 25 ° C, and the same concentration will increase to 32 ° C after the modification. (as shown in the first figure)
將20ml四氯化鈦(titanium tetrachloride)，於冰浴下加入20ml冰塊，得一淡黃微稠液體。冰浴下，將10M氫氧化鈉(NaOH)溶液緩慢滴入上述溶液中，至pH到7為止，此時會有大量白色固體析出。將上述溶液以8000 rpm離心10min，去掉溶液部分後再加入去離子水(dH2 O)攪拌，並重複離心步驟共3次，以去掉固體中之離子，最後可得白色黏土狀之氫氧化鈦(Ti(OH)4 )。20 ml of titanium tetrachloride was added to 20 ml of ice in an ice bath to obtain a pale yellow slightly thick liquid. Under ice bath, a 10 M sodium hydroxide (NaOH) solution was slowly dropped into the above solution until the pH reached 7, at which time a large amount of white solid precipitated. The above solution was centrifuged at 8000 rpm for 10 min, the solution portion was removed, and then deionized water (dH 2 O) was added to stir, and the centrifugation step was repeated 3 times to remove ions in the solid, and finally a white clay-like titanium hydroxide was obtained. (Ti(OH) 4 ).
其次，將1g氫氧化鈦(Ti(OH)4 )加入0.3ml 37%鹽酸(HCl)，攪拌30min後便可得到奈米二氧化鈦粒子水溶液。分別加入5.26/1.98/0.89/0.34 ml之去離子水(dH2 O)，攪拌均勻。再加入含有0.005 wt%光起始劑(photoinitiator)之尾端改質高分子(poloxamer 407A)，冰浴下攪拌至溶解，即可得到含有二氧化鈦(TiO2 )2.5/5/7.5/10 wt%之高分子溶液。最後，以紫外光起始，使尾端官能基反應交聯，便可固定其組成。Next, 1 g of titanium hydroxide (Ti(OH) 4 ) was added to 0.3 ml of 37% hydrochloric acid (HCl), and after stirring for 30 minutes, an aqueous solution of nano titanium dioxide particles was obtained. Add 5.26/1.98/0.89/0.34 ml of deionized water (dH 2 O) and mix well. Further, a modified end polymer (poloxamer 407A) containing 0.005 wt% of a photoinitiator was added, and the mixture was stirred to dissolve in an ice bath to obtain titanium oxide (TiO 2 ) 2.5/5/7.5/10 wt%. Polymer solution. Finally, starting with ultraviolet light, the tail functional group is cross-linked to fix its composition.
如第三圖所示，高分子溶液中加入奈米二氧化鈦粒子後，可提升高分子溶液折射率，從原本的1.355提升至1.405。其中，高分子重量百分比為18，橫軸0/2.5/5/7.5/10為奈米二氧化鈦粒子之重量百分比。As shown in the third figure, the addition of nano titanium dioxide particles to the polymer solution can increase the refractive index of the polymer solution from the original 1.355 to 1.405. Wherein, the weight percentage of the polymer is 18, and the horizontal axis is 0/2.5/5/7.5/10, which is the weight percentage of the nano titanium dioxide particles.
顯然地，依照上面實施例中的描述，本發明可能有許多的修正與差異。因此需要在其附加的權利要求項之範圍 內加以理解，除了上述詳細的描述外，本發明還可以廣泛地在其他的實施例中施行。上述僅為本發明之較佳實施例而已，並非用以限定本發明之申請專利範圍；凡其它未脫離本發明所揭示之精神下所完成的等效改變或修飾，均應包含在下述申請專利範圍內。Obviously, many modifications and differences may be made to the invention in light of the above description. Therefore, it is necessary to be within the scope of its appended claims. It is to be understood that the invention may be embodied in other embodiments in addition to the detailed description above. The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following claims. Within the scope.
第一圖係本發明之泊洛沙姆尾端改質高分子製備方式。The first figure is a preparation method of the poloxamer tail modified polymer of the present invention.
第二圖係本發明之泊洛沙姆尾端改質前/後高分子濃度與溶膠-凝膠相變化溫度。The second graph is the pre-/post-polymer concentration and sol-gel phase change temperature of the poloxamer tail end of the present invention.
第三圖係本發明之水晶體材料中二氧化鈦重量百分濃度與折射率關係圖。The third graph is a graph showing the relationship between the weight percent concentration of titanium dioxide and the refractive index in the crystal material of the present invention.
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| TW200848833A (en) * | 2006-12-13 | 2008-12-16 | Novartis Ag | Production of ophthalmic devices based on photo-induced step growth polymerization |
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| TW200848833A (en) * | 2006-12-13 | 2008-12-16 | Novartis Ag | Production of ophthalmic devices based on photo-induced step growth polymerization |
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