TWI786836B - Anti-blue light contact lens and material and method for manufacturing the same - Google Patents

Anti-blue light contact lens and material and method for manufacturing the same Download PDF

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TWI786836B
TWI786836B TW110134835A TW110134835A TWI786836B TW I786836 B TWI786836 B TW I786836B TW 110134835 A TW110134835 A TW 110134835A TW 110134835 A TW110134835 A TW 110134835A TW I786836 B TWI786836 B TW I786836B
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blue light
silver
silicon
monomer
silver ion
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TW202313747A (en
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林文卿
李靜芳
陳季晴
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望隼科技股份有限公司
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The present invention provides an anti-blue light and anti-UV contact lens and its manufacturing material and process. The copolymerized mixture is composed of linear silicon-containing prepolymer monomers, hydrophilic monomers, UV absorbers and silver ion-containing solvents. By starting and completing the free radical chain polymerization and cross-linking reaction by blue light, a lens body can be formed after the material curing process. The present invention does not need to add additional reducing agent and dispersant, and may reduce silver ions into nano-metal silver particles through redox reaction in-situ. In this way, the silver/silicon composite nano-particles in the silicon-containing spectacle lens material can be uniformly distributed without affecting the photopolymerization process, and a very small amount of silver ion concentration may achieve the effect of anti-blue light. The copolymerization of anti-UV reactive monomers may make contact lenses with anti-blue light and anti-UV high oxygen permeable silicone hydrogel at one time.

Description

抗藍光隱形眼鏡及其製造材料和方法Anti-blue light contact lens and manufacturing material and method thereof

本發明係關於矽水膠鏡片,特別是關於可抗藍光的隱形眼鏡的製造方法、材料及成品。The present invention relates to silicone hydrogel lenses, in particular to a manufacturing method, material and finished product of contact lenses capable of resisting blue light.

隱形眼鏡自1950年初發明後,經商品化至今已有70年久,最初之隱形眼鏡係採用硬材(如:PMMA聚甲基丙烯酸甲酯)所製成,由於其材質較硬,加上其本體之透氧能力與親水性均不佳,致使該隱形眼鏡可配戴之時間較短,且會產生有明顯之異物不適感。於70年代中的軟式隱形眼鏡之發明,可謂一進步之改革,其是以一種HEMA(2-羥乙基丙烯酸甲脂)為主之水膠材質所製成。由於該材質吸水性高,水化後形成軟式、高含水性之特性,大幅的增進了配戴之舒適性,但其透氧力仍低,每日僅能配戴8至12小時,久戴後常有發生角膜缺氧性水腫及新生血管增生之病變。於80年代初,雖有了具高透氧性硬式隱形眼鏡之產品,其透氧力超高,但因屬硬性材質,配戴於眼球所產生之異物不適感仍無法突破改善,以致無法普遍化為消費者接受。經由前述可知,隱形眼鏡一直有著高透氧性、高舒適性與可長時間配戴之需求,經由隱形眼鏡業界不斷的改進,最終即以高透氧性軟式之矽水膠為一發展主流。Contact lenses have been commercialized for 70 years since they were invented in early 1950. The initial contact lenses were made of hard materials (such as: PMMA polymethyl methacrylate). The oxygen permeability and hydrophilicity of the main body are not good, so that the wearable time of the contact lens is short, and there will be obvious foreign body discomfort. The invention of soft contact lenses in the mid-1970s can be described as a progressive reform, which is made of a HEMA (2-hydroxyethyl methyl acrylate)-based water-gel material. Due to the high water absorption of this material, after hydration, it becomes soft and highly water-containing, which greatly improves the wearing comfort. However, its oxygen permeability is still low, and it can only be worn for 8 to 12 hours a day. Later, corneal hypoxic edema and neovascularization often occur. In the early 1980s, although there was a product with high oxygen permeability hard contact lens, which had a super high oxygen permeability, but because of the hard material, the foreign body discomfort caused by wearing it on the eyeball still could not be improved, so that it could not be widely used into consumer acceptance. It can be seen from the above that contact lenses have always had the requirements of high oxygen permeability, high comfort and long-term wearability. After continuous improvement in the contact lens industry, the development of soft silicone hydrogel with high oxygen permeability has finally become the mainstream.

隨著液晶螢幕電視、平板電腦與智慧型手機等3C多種產品的普及率及使用時間亦愈來愈多的情況下,藍光危害的問題逐漸為人們所重視,一般認為藍光會提高黃斑部病變和視網膜病變風險,雙眼可見光波長為380-780nm,而增加用眼眩光與疲勞的光波長為為381-460nm之短波藍光。過量的藍光會造成眼睛傷害,藍光會穿透水晶體、玻璃體直達黃斑部與視網膜,對眼睛造成光線傷害。此外,當藍光進入眼睛會產生大量的自由基,侵害視網膜的不飽和脂肪酸,過量藍光傷害的初期,眼睛對光線較敏感,有刺痛、畏光等徵兆;此時若未即時改善過量藍光傷害,使黃斑部發炎、水腫,黃斑區一旦形成隱結,當隱結破裂時,會產生出血現象,將造成中央視力缺損。簡言之,過量藍光可能引起白內障,甚至造成黃斑部病變。藍光會阻礙睡眠,其會延後或停止大腦製造褪黑色素的分泌,進而令人更難進入睡眠狀態。一般而言,人的水晶體即能過濾光線中30%~50%的藍光,且人體還是需要適量的藍光維持視覺與心理的運作。適度的藍光使物體顏色及視野變得更明亮,使人心情較為愉悅;反之,倘若過濾太多藍光,容易令人心情變得低落、焦慮,甚至有憂鬱的情緒產生。濾光值30%就可達到濾藍光效果。鑑於前述問題,有越來越多人開始配戴抗藍光眼鏡,藉此減少藍光(藍紫光)對眼睛的危害,目前抗藍光框架眼鏡大多是在鏡片中添加黃色染劑或表面鍍膜方式,改變鏡片顏色,進而使鏡片能夠濾除藍光,但是,大多數隱形眼鏡無法使用前述製法,尤其運用在矽水膠隱形眼鏡更存在許多障礙與複雜度。因此如何提供使用者更為良好的抗藍光隱形眼鏡產品,即成為本發明在此欲探討之一重要課題。With the increasing penetration rate and usage time of various 3C products such as LCD TVs, tablet computers and smart phones, the problem of blue light hazards has gradually attracted people's attention. It is generally believed that blue light can increase macular degeneration and For the risk of retinopathy, the wavelength of visible light in both eyes is 380-780nm, and the wavelength of light that increases eye glare and fatigue is short-wave blue light in the range of 381-460nm. Excessive blue light will cause eye damage. Blue light will penetrate the lens, vitreous body and reach the macula and retina, causing light damage to the eyes. In addition, when blue light enters the eyes, a large number of free radicals will be generated, which will damage the unsaturated fatty acids in the retina. In the initial stage of excessive blue light damage, the eyes will be more sensitive to light, with symptoms such as tingling and photophobia; if the excessive blue light damage is not immediately improved at this time , Inflammation and edema of the macula. Once a hidden node is formed in the macular area, when the hidden node ruptures, hemorrhage will occur, which will cause central vision loss. In short, excess blue light can cause cataracts and even macular degeneration. Blue light hinders sleep by delaying or stopping the brain's production of melatonin, making it more difficult to fall asleep. Generally speaking, the human crystal can filter 30% to 50% of the blue light in the light, and the human body still needs an appropriate amount of blue light to maintain visual and psychological functions. Moderate blue light makes the color of objects and vision brighter, making people feel more happy; on the contrary, if too much blue light is filtered, it is easy to make people feel depressed, anxious, and even melancholy. A filter value of 30% can achieve the effect of filtering blue light. In view of the aforementioned problems, more and more people are beginning to wear anti-blue light glasses to reduce the harm of blue light (blue-violet light) to the eyes. At present, most of the anti-blue light frame glasses add yellow dye or surface coating to the lenses to change the The color of the lens, and then the lens can filter out blue light. However, most contact lenses cannot use the above-mentioned manufacturing method, especially for silicone hydrogel contact lenses, there are many obstacles and complexities. Therefore, how to provide users with better anti-blue light contact lens products has become an important topic to be discussed in the present invention.

坊間所通稱的抗藍光隱形眼鏡有如中華民國專利第M487455號「具有濾藍光及抗UV功能之彩色隱形眼鏡」揭露的一種抗藍光及抗UV之隱形眼鏡,其由上、中間及下層鏡片所組成,且使用該上層鏡片內之濾藍光鍍膜劑來達成減低藍光穿透隱形眼鏡直射眼睛之功效,其中濾藍光鍍膜劑目前尚無合法添加於隱形眼鏡的美國FDA之安全許可範圍,而將有傷害眼睛之疑慮,且除了耗時、耗工及耗成本外無大量生產之效率。The anti-blue light contact lens commonly known in the market is like the anti-blue light and anti-UV contact lens disclosed in the Republic of China Patent No. M487455 "Colored Contact Lens with Blue Light Filter and Anti-UV Function", which consists of upper, middle and lower lenses. , and use the blue light filter coating agent in the upper lens to achieve the effect of reducing the blue light penetrating contact lenses and direct eyes. Among them, the blue light filter coating agent is currently not legally added to the US FDA safety approval scope of contact lenses, and will cause harm Eyes are worried, and there is no efficiency in mass production except time-consuming, labor-consuming and cost-consuming.

中華民國專利第I554803號揭露了一種可簡化製程並一貫化生產具抗藍光及抗紫外線的抗藍光隱形眼鏡製法。其係將一種或多種黃色、橘色、紅色、綠色等染料依染料顏色及添加比例作調整、或將藍光吸收劑加入隱形眼鏡水凝膠或矽水膠單體裡,然後進行模鑄成型或旋模成型等製程,待乾片固化成型後將其丟入水化槽裡進行顏色固色與水化萃取完成抗藍光隱形眼鏡成品。但此發明並不適用於高濃度染料,因為如此也阻隔UV-可見光起始反應(波長380~400nm)而無法聚合形成鏡片。Patent No. I554803 of the Republic of China discloses a manufacturing method that can simplify the manufacturing process and consistently produce anti-blue light contact lenses with anti-blue light and anti-ultraviolet rays. It is to adjust one or more yellow, orange, red, green and other dyes according to the color of the dye and the addition ratio, or add the blue light absorber to the contact lens hydrogel or silicon hydrogel monomer, and then carry out molding or Rotary molding and other processes, after the dry film is cured and formed, throw it into the hydration tank for color fixation and hydration extraction to complete the finished anti-blue light contact lens. However, this invention is not suitable for high-concentration dyes, because it also blocks the initial reaction of UV-visible light (wavelength 380-400nm) and cannot be polymerized to form lenses.

中華民國專利第I725719號揭露另一種用以抗藍光之眼鏡鏡片材料、眼鏡鏡片及其製程,其中,該眼鏡鏡片材料能用以製作出所需的眼鏡鏡片,其至少包括由銀/氧化矽複合奈米顆粒與至少一種高分子單體所組成之混合物,各該高分子單體經一材料固化程序後能形成一本體,分析其發明最前端即添加還原劑溶液使其先還原成奈米銀後,經離心再濃縮後回溶於反應單體中,最後以紫外光(UV)照射該混合物,使得高分子單體與光起始劑經紫外光(UV)交聯後,能固化(或聚合)形成該本體混合含有該銀/氧化矽複合奈米顆粒。以上製程極為繁瑣而且已形成奈米銀之複合物經離心濃縮後無法避免再聚集影響其分散性,因此在某程度上會影響光聚合反應性,進而造成鏡片本體結構或規格上變化。Patent No. I725719 of the Republic of China discloses another spectacle lens material for anti-blue light, spectacle lens and its manufacturing process, wherein the spectacle lens material can be used to produce the required spectacle lens, which at least includes silver/silicon oxide composite A mixture of nanoparticles and at least one kind of macromolecular monomer, each of which can form a body after a material solidification process. The most advanced analysis of the invention is to add a reducing agent solution to reduce it to nano silver Afterwards, after being centrifuged and concentrated, it is redissolved in the reaction monomer, and finally the mixture is irradiated with ultraviolet light (UV), so that the polymer monomer and the photoinitiator are crosslinked by ultraviolet light (UV), and can be cured (or polymerization) to form the bulk mixture containing the silver/silicon oxide composite nanoparticles. The above process is extremely cumbersome, and the nano-silver complex cannot avoid re-aggregation after centrifugation and concentration, which affects its dispersion. Therefore, to a certain extent, it will affect the photopolymerization reactivity, which will cause changes in the structure or specifications of the lens body.

目前大眾對於奈米銀的認識不深,因為不了解,容易產生一些不實的謠言或是誤會,其中奈米銀被歐盟、美國禁用為最容易被以訛傳訛的誤會之一,奈米銀在歐盟及美國沒有禁止奈米銀的使用及販售,而美國及歐盟市場上也有許多添加奈米銀的化妝及日用產品。再則,奈米銀水溶液在正常使用下,不會滲透皮膚真皮層,也不會穿透鼻腔黏膜上皮細胞層。奈米銀水溶液不但經過認證,不會對皮膚及眼睛造成刺激及過敏反應。由於奈米銀具有相當好的抗菌活性,因此常被作為工業上製成的原料並應用,在日常生活用品與醫療照護產品上,包括洗衣機表面塗抹的抗汙層、純水淨化、玩具、外科手術用具等。另外其特殊光學性質也逐漸被光學材料廣泛應用,原理為利用銀奈米粒子對於光波(紫外線、可見光、近紅外線範圍)具有表面電漿子共振 ( Surface Plasmon Resonance;SPR ) 效應。由於銀具有許多自由電子,這些電子容易隨外在電磁場而運動,並由外往內逐漸形成障避作用 ( shielding effect ),使得內部電子無法感受到外在電磁場的變化;但是當金或銀粒子直徑夠小(約小於 200 nm 以下),整顆金屬粒子內的所有自由電子做集體式運動時,這會對於入射光波造成極大的吸收及散射,此種現象稱為表面電漿子共振效應。合成的含銀奈米粒子的溶液為黃色是因為表面電漿子共振造成銀奈米粒子吸收及散射 420 nm的藍光,使得白光透射過溶液時,僅主要的光波(紅光與綠光)穿透,故人的視覺呈現黃色的效果。因此可利用其濾藍光特性發展出抗藍光隱形眼鏡。At present, the general public does not have a deep understanding of nano-silver. Because they do not understand, it is easy to generate some false rumors or misunderstandings. Among them, nano-silver is banned by the European Union and the United States, which is one of the most misunderstandings. Nano-silver is in the EU. And the United States has not banned the use and sale of nano-silver, and there are many cosmetics and daily products that add nano-silver in the US and EU markets. Furthermore, under normal use, the nano-silver aqueous solution will not penetrate the dermis of the skin, nor will it penetrate the epithelial cell layer of the nasal mucosa. The nano-silver aqueous solution has been certified and will not cause irritation and allergic reactions to the skin and eyes. Because nano silver has quite good antibacterial activity, it is often used as a raw material and applied in industry. It is used in daily necessities and medical care products, including anti-fouling layer applied on the surface of washing machine, pure water purification, toys, surgery, etc. Surgical tools, etc. In addition, its special optical properties are gradually being widely used in optical materials. The principle is that silver nanoparticles have Surface Plasmon Resonance (SPR) effect on light waves (ultraviolet, visible, and near-infrared ranges). Since silver has many free electrons, these electrons are easy to move with the external electromagnetic field, and gradually form a shielding effect from the outside to the inside, so that the internal electrons cannot feel the change of the external electromagnetic field; but when gold or silver particles When the diameter is small enough (less than 200 nm), all the free electrons in the entire metal particle move collectively, which will cause great absorption and scattering of incident light waves. This phenomenon is called the surface plasmon resonance effect. The synthesized solution containing silver nanoparticles is yellow because surface plasmon resonance causes silver nanoparticles to absorb and scatter blue light at 420 nm, so that when white light is transmitted through the solution, only the main light waves (red and green) pass through. Transparent, the old man's vision presents a yellow effect. Therefore, anti-blue light contact lenses can be developed by utilizing its blue light filtering properties.

本發明提供一種抗藍光隱形眼鏡的製造方法,其步驟包括合成聚矽氧烷預聚物, 其中聚矽氧預聚物中含有聚乙二醇;將銀離子化合物溶於非水溶劑中, 以製備一銀離子溶液;將該銀離子溶液與該聚矽氧烷預聚物混合, 以使該銀離子溶液中之銀離子均勻分佈於該聚矽氧烷預聚物中;將親水性單體 及感光起始劑加入該聚矽氧烷預聚物中混合,以形成一矽水膠組成物;以及以藍光照射該矽水膠組成物,以同時進行交聯固化反應及銀離子還原反應,而形成具有抗藍光奈米銀的矽水膠鏡片。The invention provides a method for manufacturing an anti-blue light contact lens. The steps include synthesizing a polysiloxane prepolymer, wherein the polysiloxane prepolymer contains polyethylene glycol; dissolving the silver ion compound in a non-aqueous solvent, and Prepare a silver ion solution; mix the silver ion solution with the polysiloxane prepolymer, so that the silver ions in the silver ion solution are uniformly distributed in the polysiloxane prepolymer; the hydrophilic monomer and a photosensitive initiator is added to the polysiloxane prepolymer and mixed to form a silicone hydrogel composition; and the silicone hydrogel composition is irradiated with blue light to simultaneously perform a cross-linking curing reaction and a silver ion reduction reaction, A silicone hydrogel lens with anti-blue light nano-silver is formed.

上述矽水膠組成物中, 更可同時加入含矽單體與聚矽氧烷預聚物混合, 其中聚矽氧烷預聚物加上含矽單體之含量為30~80wt%,親水性單體的重複單元之含量為10~50wt%,感光起始劑之含量為0.1~2wt %,銀離子化合物的含量為10~200ppm。In the above silicone hydrogel composition, silicon-containing monomers and polysiloxane prepolymers can be added to mix at the same time. The content of polysiloxane prepolymers plus silicon-containing monomers is 30~80wt%, and the hydrophilicity The content of the repeating unit of the monomer is 10-50wt%, the content of the photosensitive initiator is 0.1-2wt%, and the content of the silver ion compound is 10-200ppm.

可用下列方法,合成雙性含矽預聚物:以一雙羥型聚二甲基矽氧烷化合物和一異氰酸化合物為原料,再添加一稀釋劑下於一中溫環境進行反應,以獲得一第一生成物;將第一生成物加入一親水擴鏈劑,依次進行末端羥基化反應、進而擴鏈反應以獲得一第二生成物;將第二生成物和一丙烯酸酯類化合物在常溫繼續反應至少12小時,以獲得一雙性含矽預聚物;其中親水擴鏈劑主要為多元醇系列,可以包含乙二醇、丙二醇、1,4丁二醇、聚乙二醇、聚丙二醇、聚丙二醇二縮水甘油醚等。The following method can be used to synthesize the amphoteric silicon-containing prepolymer: a bishydroxy polydimethylsiloxane compound and an isocyanate compound are used as raw materials, and then a diluent is added to react in a medium-temperature environment to Obtain a first product; add the first product to a hydrophilic chain extender, sequentially carry out terminal hydroxylation reaction, and then chain extension reaction to obtain a second product; combine the second product and an acrylate compound in Continue to react at room temperature for at least 12 hours to obtain an amphoteric silicon-containing prepolymer; the hydrophilic chain extender is mainly polyol series, which can include ethylene glycol, propylene glycol, 1,4 butanediol, polyethylene glycol, polyol Propylene glycol, polypropylene glycol diglycidyl ether, etc.

上述矽水膠組成物中更可以包括10~20wt%的稀釋劑。The above silicon hydrogel composition may further include 10-20wt% diluent.

上述含矽單體可為3-甲基丙烯醯氧丙基三(三甲基矽氧基)矽烷(3-methacryloxypropyl tris(tirmethylsiloxy)silane,TRIS)、3-丙烯醯氧丙基三(三甲基矽氧基)矽烷 (3-acryloxypropyl tri(trimethylsiloxy)silane)、3-丙烯醯胺丙基三(三甲基矽氧基)矽烷(3-acrylamidopropyl tris(trimethylsiloxy)silane)、3-甲基丙烯醯胺丙基三(三甲基矽氧基)矽烷、(3-甲基丙烯醯氧基-2-羥基丙氧基)丙基雙(三甲基矽氧基)甲基矽烷,SiGMA)、數量平均分子量為657至1500的單官能基聚二甲基矽氧烷高聚物 (monofunctional Polydimethylsiloxane,mPDMS)或其組合。The aforementioned silicon-containing monomers can be 3-methacryloxypropyl tris(trimethylsiloxy)silane (TRIS), 3-acryloxypropyl tris(trimethylsiloxy)silane, TRIS, 3-acryloxypropyl tri(trimethylsiloxy)silane), 3-acrylamidopropyl tris(trimethylsiloxy)silane, 3-methacrylamide Amidopropyltris(trimethylsiloxy)silane, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, SiGMA), A monofunctional polydimethylsiloxane polymer (monofunctional Polydimethylsiloxane, mPDMS) or a combination thereof with a number average molecular weight of 657 to 1500.

親水性單體可以是2-羥基乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate,HEMA);N,N-二甲基丙烯醯胺(N,N-dimethyl acrylamide,DMA)、N,N-二乙基丙烯醯胺(N,N-diethyl acrylamide,DEA)、N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)、、甲基丙烯酸甘油酯(glycerol methacrylate,GMA)、分子量400的聚乙二醇甲基丙烯酸甲醚(polyethylene glycol methacrylate mono methyl ether)或其組合。The hydrophilic monomer can be 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA); N, N-dimethyl acrylamide (N, N-dimethyl acrylamide, DMA), N, N-dimethacrylate Ethyl acrylamide (N, N-diethyl acrylamide, DEA), N-vinyl pyrrolidone (N-vinyl pyrrolidone, NVP), glycerol methacrylate (glycerol methacrylate, GMA), polyethylene glycol with a molecular weight of 400 Polyethylene glycol methacrylate mono methyl ether or combinations thereof.

混合上述矽水膠組成物時更可同時加入阻隔紫外光單體,其中阻隔紫外光單體之含量為0.1~1.5wt%。阻隔紫外光單體可為具有苯並三唑(benzotriazole)的單體。When mixing the above silicon hydrogel composition, UV-blocking monomers can be added at the same time, wherein the content of UV-blocking monomers is 0.1-1.5wt%. The UV-blocking monomer may be a monomer having benzotriazole.

本發明也提供一種製造抗藍光眼鏡鏡片的材料,包含了上述矽水膠組成物。The present invention also provides a material for manufacturing anti-blue light spectacle lenses, which includes the above silicon hydrogel composition.

本發明還提供了一種以前述方法製成的抗藍光眼鏡鏡片。The present invention also provides an anti-blue light spectacle lens made by the aforementioned method.

本發明之目的,係提供一種用以抗藍光之眼鏡鏡片材料,其能用以製作眼鏡鏡片,其中,該眼鏡鏡片材料至少包括由聚矽氧烷預聚物、銀離子溶液與至少一種親水性高分子單體所組成之混合物,該混合物經一材料固化程序後能形成一本體,且該本體內混合含有該銀/矽複合奈米顆粒,當銀的顆粒尺寸為1奈米(nm)至100奈米時,其能夠吸收波長400奈米至500奈米的藍光,因此,藉由銀/矽複合奈米顆粒,便能夠使穿透眼鏡鏡片的可見光中,具有較大能量的藍光被吸收,以達到抗藍光之目的,如此,聚矽氧烷預聚物可視為奈米銀保護劑或分散劑,也可當作本體聚合之交鏈劑。其中聚矽氧烷預聚物內之聚乙二醇(Polyethylene Glycols, PEG)透過結構方式來穩定奈米微粒,與中心的鍵結能力較強而不容易解離成離子。透過藍光還原銀離子不須額外加入任何還原劑即能形成在本體分布均勻之奈米銀粒子,最重要,此流程為原位形成(in-situ)不致影響光聚合程度,所以能保持鏡片強度與完整性,從而達到隱形眼鏡舒適配戴規格。這有別於其他抗藍光隱形眼鏡製作原理,其做法先行還原成金屬奈米粒子再添加於反應單體中,如此利用光聚合反應會受到極大困擾。因其紫外光作用之光起始波長即在360~420nm之間,如此金屬奈米粒子會吸收或散射其波段造成起始能量不足及均勻度,大大影響鏡片本體完整性與強度,亦即會使鏡片扭曲變形影響視力矯正有效性以及配戴舒適性與安全性。The purpose of the present invention is to provide a spectacle lens material for anti-blue light, which can be used to make spectacle lenses, wherein the spectacle lens material at least includes polysiloxane prepolymer, silver ion solution and at least one hydrophilic A mixture composed of high molecular monomers, the mixture can form a body after a material solidification process, and the silver/silicon composite nanoparticles are mixed in the body, when the particle size of silver is 1 nanometer (nm) to At 100nm, it can absorb blue light with a wavelength of 400nm to 500nm. Therefore, silver/silicon composite nanoparticles can absorb blue light with greater energy in the visible light that penetrates the lens of the glasses. , in order to achieve the purpose of anti-blue light, so the polysiloxane prepolymer can be regarded as a nano-silver protective agent or dispersant, and can also be used as a cross-linking agent for bulk polymerization. Among them, the polyethylene glycol (Polyethylene Glycols, PEG) in the polysiloxane prepolymer stabilizes the nanoparticles through the structural method, and has a strong bonding ability with the center and is not easy to dissociate into ions. Reduction of silver ions through blue light can form uniformly distributed nano-silver particles in the body without adding any additional reducing agent. Most importantly, this process is in-situ formation (in-situ) without affecting the degree of photopolymerization, so the strength of the lens can be maintained and integrity to meet contact lens comfort-wearing specifications. This is different from other production principles of anti-blue light contact lenses, which are first reduced to metal nanoparticles and then added to the reaction monomer, so the use of photopolymerization will be greatly troubled. Because the initial wavelength of ultraviolet light is between 360 and 420nm, the metal nanoparticles will absorb or scatter the wavelength band, resulting in insufficient initial energy and uniformity, which will greatly affect the integrity and strength of the lens body, that is, it will Distorting and deforming the lens affects the effectiveness of vision correction as well as wearing comfort and safety.

<聚矽氧烷預聚物的合成><Synthesis of polysiloxane prepolymer>

在於提供一種雙性含矽預聚物之製備方法,其係以聚二甲基矽氧烷化合物為原料進行異氰酸反應後,再以羥類單體進行封端後所得,其包括有下列步驟:異氰酸反應:係以一雙羥型聚二甲基矽氧烷化合物和一異氰酸化合物為原料,再添加一稀釋劑下於一中溫環境進行反應,以獲得一第一生成物;將第一生成物加入親水擴鏈劑(鏈延長劑),依次進行末端羥基化反應、進而擴鏈反應以獲得一第二生成物:係將該第二生成物和一丙烯酸酯類化合物在常溫繼續反應至少12小時以獲得一雙性含矽預聚物為第三生成物。其中親水擴鏈劑主要為多元醇系列包括有乙二醇、丙二醇、1,4丁二醇、聚乙二醇、聚丙二醇、聚丙二醇二縮水甘油醚等。To provide a method for preparing an amphoteric silicon-containing prepolymer, which is obtained by reacting isocyanic acid with polydimethylsiloxane compound as a raw material, and then capping with a hydroxyl monomer, which includes the following Steps: Isocyanic acid reaction: use a bishydroxy polydimethylsiloxane compound and an isocyanic acid compound as raw materials, and then add a diluent to react in a medium temperature environment to obtain a first formation product; the first product is added to a hydrophilic chain extender (chain extender), and the terminal hydroxylation reaction is carried out in turn, and then the chain extension reaction is obtained to obtain a second product: the second product and an acrylate compound Continue the reaction at room temperature for at least 12 hours to obtain an amphoteric silicon-containing prepolymer as the third product. Among them, the hydrophilic chain extenders are mainly polyol series, including ethylene glycol, propylene glycol, 1,4 butanediol, polyethylene glycol, polypropylene glycol, polypropylene glycol diglycidyl ether, etc.

其詳細實施例為以下說明:取50g含雙末端羥基的二甲基聚矽氧烷(商品名為KF-6001,購買自信越化學工業株式會社),於室溫氮氣條件下,加入10g異氟爾酮二異氰酸酯及0.02g二月桂酸二丁基錫,反應12小時後,再加入30g聚乙二醇(重量平均分子量為600)、100g四氫呋喃及0.02g二月桂酸二丁基錫,再反應24小時,以 紅外線吸收光譜確認2250cm-1左右之-NCO特徵峰消失即完成反應。再次於室溫氮氣環境下,加入10g異氟爾酮二異氰酸酯及0.02g二月桂酸二丁基錫,反應24小時後,再加入12g的2-甲基-2-丙烯酸-2,3-二羥基丙酯、0.02g二月桂酸二丁基錫,60℃反應24小時,以紅外線吸收光譜確認2250cm-1左右之-NCO特徵峰消失即完成反應,獲得以二甲基聚矽氧烷為主架構之聚矽氧烷預聚物,其重量平均分子量為11,000~13,000(經GPC鑑定)。Its detailed example is as follows: take 50g of dimethyl polysiloxane containing double-terminal hydroxyl groups (trade name KF-6001, purchased from Zixinyue Chemical Industry Co., Ltd.), add 10g of isofluorine under nitrogen at room temperature ketone diisocyanate and 0.02g dibutyltin dilaurate, after reacting for 12 hours, add 30g polyethylene glycol (weight average molecular weight is 600), 100g tetrahydrofuran and 0.02g dibutyltin dilaurate, react for 24 hours again, with Infrared absorption spectrum confirms that the characteristic peak of -NCO at around 2250 cm-1 disappears and the reaction is completed. Add 10g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate at room temperature under nitrogen again, and after 24 hours of reaction, add 12g of 2-methyl-2-acrylic acid-2,3-dihydroxypropyl Esters, 0.02g of dibutyltin dilaurate, reacted at 60°C for 24 hours, confirmed by infrared absorption spectrum that the -NCO characteristic peak at around 2250cm-1 disappeared and the reaction was completed, and polysiloxane with dimethylpolysiloxane as the main structure was obtained. The oxane prepolymer has a weight average molecular weight of 11,000~13,000 (identified by GPC).

<親水性共聚物組成物><Hydrophilic copolymer composition>

本發明提供一種親水性共聚物組成物,其包含聚矽氧烷預聚物 、單端壓克力矽烷 與親水性單體。親水性單體可為但不限於N,N-二甲基丙烯醯胺(簡稱DMA,可購買自TCI公司)、N-乙烯吡喀酮(簡稱NVP,可購買自ALDRICH公司)、甲基丙烯酸-2-羥乙酯(簡稱HEMA,可購買自TCI公司)或二甲基丙烯酸乙二醇酯(簡稱EGDMA,可購買自BASF公司)。此外,親水性單體可單獨使用或同時使用兩種以上(含兩種)。The invention provides a hydrophilic copolymer composition, which comprises polysiloxane prepolymer, single-end acrylic silane and hydrophilic monomer. The hydrophilic monomer can be but not limited to N,N-dimethylacrylamide (referred to as DMA, available from TCI Company), N-vinylpyrrolidone (abbreviated as NVP, available from ALDRICH Company), methacrylic acid -2-hydroxyethyl ester (abbreviated as HEMA, available from TCI Company) or ethylene glycol dimethacrylate (abbreviated as EGDMA, available from BASF Company). In addition, the hydrophilic monomers may be used alone or in combination of two or more.

前述親水性共聚物組成物可更包含稀釋劑及感光起始劑。稀釋劑可增加互溶性,稀釋劑的含量可為0至25 重量百分比。稀釋劑可為但不限於異丙醇(簡稱IPA )。此外,稀釋劑可單獨使用或同時使用兩種以上(含兩種)。感光起始劑有利於進行UV光固化,感光起始劑的含量可為0.1重量百分比至2重量百分比。感光起始劑可為但不限於商品名Ciba®IRGACURE®1173,簡稱I-1173,以及商品名Ciba®IRGACURE®819),簡稱I-819。此外,感光起始劑可單獨使用或同時使用兩種以上(含兩種)。前述親水性共聚物組成物可選擇性地更包含其他添加劑,以滿足實際需求,可使用的添加劑包含但不限於抗UV吸收劑以及流平劑等。The aforementioned hydrophilic copolymer composition may further include a diluent and a photoinitiator. The diluent can increase the miscibility, and the content of the diluent can be 0 to 25 weight percent. The diluent can be but not limited to isopropanol (IPA for short). In addition, diluents may be used alone or in combination of two or more. The photosensitive initiator is beneficial to UV light curing, and the content of the photosensitive initiator may be 0.1 weight percent to 2 weight percent. The photoinitiator can be but not limited to the trade name Ciba®IRGACURE®1173, referred to as I-1173, and the trade name Ciba®IRGACURE®819), referred to as I-819. In addition, photoinitiators may be used alone or in combination of two or more (including two). The aforementioned hydrophilic copolymer composition may optionally further include other additives to meet actual needs, and the additives that may be used include but are not limited to anti-UV absorbers and leveling agents.

<銀離子溶液><Silver ion solution>

無機銀鹽是最常見的銀離子化合物,比較常見的有硝酸銀,醋酸銀和硫代硫酸銀。將銀離子化合物溶於非水溶劑中,常為甲醇(Methanol)、乙醇(Ethanol)、丙醇(Propanol,分子式為C 3H 7OH)、異丙醇(isopropanol,分子式為C 3H 8O)、丁醇(Butanol,分子式為C 4H 9OH)或乙二醇(ethylene glycol)等 Inorganic silver salts are the most common silver ion compounds, and the more common ones are silver nitrate, silver acetate and silver thiosulfate. Dissolve the silver ion compound in a non-aqueous solvent, usually methanol (Methanol), ethanol (Ethanol), propanol (Propanol, molecular formula is C 3 H 7 OH), isopropanol (molecular formula is C 3 H 8 O ), butanol (Butanol, molecular formula C 4 H 9 OH) or ethylene glycol (ethylene glycol), etc.

本發明係一種用以抗藍光之眼鏡鏡片材料、眼鏡鏡片及其製程,在一實施例中,該眼鏡鏡片能作為隱形眼鏡或一般外戴式眼鏡的鏡片。The present invention is a spectacle lens material for anti-blue light, spectacle lens and its manufacturing process. In one embodiment, the spectacle lens can be used as a lens of contact lenses or general external glasses.

在本發明之實施例中,上述除聚矽氧烷預聚物外可再自由選擇含矽單體包括3-甲基丙烯醯氧丙基三(三甲基矽氧基)矽烷(3-methacryloxypropyl tris(tirmethylsiloxy)silane,TRIS)、3-丙烯醯氧丙基三(三甲基矽氧基)矽烷 (3-acryloxypropyl tri(trimethylsiloxy)silane)、3-丙烯醯胺丙基三(三甲基矽氧基)矽烷(3-acrylamidopropyl tris(trimethylsiloxy)silane)、3-甲基丙烯醯胺丙基三(三甲基矽氧基)矽烷、(3-甲基丙烯醯氧基-2-羥基丙氧基)丙基雙(三甲基矽氧基)甲基矽烷,SiGMA)、數量平均分子量為657至1500的單官能基聚二甲基矽氧烷高聚物 (monofunctional Polydimethylsiloxane,mPDMS)及其組合所組成之群組;In an embodiment of the present invention, the silicon-containing monomer that can be freely selected in addition to the polysiloxane prepolymer includes 3-methacryloxypropyl tris(trimethylsiloxy)silane (3-methacryloxypropyl tris(tirmethylsiloxy)silane, TRIS), 3-acryloxypropyl tri(trimethylsiloxy)silane (3-acryloxypropyl tri(trimethylsiloxy)silane), 3-acrylamidopropyl tri(trimethylsilane) Oxy)silane (3-acrylamidopropyl tris(trimethylsiloxy)silane), 3-methacrylamidopropyl tris(trimethylsiloxy)silane, (3-methacrylamideoxy-2-hydroxypropoxy base) propylbis(trimethylsiloxy)methylsilane, SiGMA), monofunctional polydimethylsiloxane polymer (monofunctional Polydimethylsiloxane, mPDMS) with a number average molecular weight of 657 to 1500, and combinations thereof the group formed;

在本發明之實施例中,上述第一親水性單體選用2-羥基乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate,HEMA);N,N-二甲基丙烯醯胺(N,N-dimethyl acrylamide,DMA)、N,N-二乙基丙烯醯胺(N,N-diethyl acrylamide,DEA)、N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)、、甲基丙烯酸甘油酯(glycerol methacrylate,GMA)、分子量400的聚乙二醇甲基丙烯酸甲醚(polyethylene glycol methacrylate mono methyl ether)及其組合所組成之群組。In an embodiment of the present invention, the above-mentioned first hydrophilic monomer is selected from 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA); N,N-dimethylacrylamide (N,N-dimethyl acrylamide, DMA), N, N-diethyl acrylamide (N, N-diethyl acrylamide, DEA), N-vinyl pyrrolidone (N-vinyl pyrrolidone, NVP), glycerol methacrylate (glycerol methacrylate, GMA), polyethylene glycol methacrylate monomethyl ether with a molecular weight of 400 (polyethylene glycol methacrylate mono methyl ether) and a group consisting of combinations thereof.

根據本發明之實施例,上述衍生含矽單體包含聚矽氧烷預聚物佔全部總重量之含量為30~80wt%,親水性單體的重複單元佔重量之含量為10~50wt%,稀釋劑占整體重量10~20wt%,阻隔紫外光單體為具有苯並三唑(benzotriazole)的單體。根據本發明之實施例,阻隔紫外光單體佔矽水膠組成物總重量之含量為0.1~1.5wt%;另外光起始劑占整體重量0.1~2wt%,銀離子化合物占整體重量10~200 ppm。According to an embodiment of the present invention, the above-mentioned derivatized silicon-containing monomers include polysiloxane prepolymers in an amount of 30-80 wt%, and the repeating units of hydrophilic monomers in an amount of 10-50 wt%, The diluent accounts for 10-20 wt% of the whole weight, and the UV-blocking monomer is a monomer containing benzotriazole. According to the embodiment of the present invention, the content of UV-blocking monomer accounts for 0.1~1.5wt% of the total weight of the silicon hydrogel composition; in addition, the photoinitiator accounts for 0.1~2wt% of the overall weight, and the silver ion compound accounts for 10~10wt% of the overall weight. 200 ppm.

根據本發明其中之一實施例,提供一種抗藍光含奈米銀矽水膠隱形眼鏡的製備方法。According to one of the embodiments of the present invention, there is provided a method for preparing an anti-blue light silicon hydrogel contact lens containing nano-silver.

首先,在稀釋液中,加入銀離子化合物進行攪拌約0.5小時~1.5小時左右,且使該銀離子溶液的溫度保持於常溫(攝氏20~40度使其完全溶解,先加入聚矽氧烷預聚物攪拌0.5小時~1.5小時左右後,可一起加入含矽單體/親水性單體/起始劑與阻隔紫外光單體持續攪拌0.5小時~1.5小時左右後,即可成為本發明之矽水膠組成物。本發明之一態樣,提供一種上述矽水膠鏡片的製造方法。將上述任一實施方式或實施例之矽水膠組成物注入製備鏡片之模具內;對模具內之矽水膠組成物進行光固化處理30~60分鐘,使其進行交聯固化反應,以形成矽水膠鏡片;以含有水的液體萃取上述矽水膠鏡片,以移除未進行交聯固化反應的矽高聚物;將上述矽水膠鏡片置於pH值為7.1~7.5的磷酸或硼酸食鹽水緩衝溶液中進行高溫高壓滅菌。First, in the diluent, add the silver ion compound and stir for about 0.5 hours to 1.5 hours, and keep the temperature of the silver ion solution at room temperature (20-40 degrees Celsius to completely dissolve it, first add polysiloxane to pre- After the polymer is stirred for about 0.5 hours to 1.5 hours, the silicon-containing monomer/hydrophilic monomer/initiator and the UV-blocking monomer can be added together. After stirring for about 0.5 hours to 1.5 hours, the silicon of the present invention can be formed. Hydrogel composition. One aspect of the present invention provides a method for manufacturing the above-mentioned silicon hydrogel lens. The silicon hydrogel composition of any of the above-mentioned embodiments or examples is injected into the mold for preparing the lens; The hydrogel composition is subjected to photocuring treatment for 30 to 60 minutes to allow it to undergo a cross-linking and curing reaction to form a silicone hydrogel lens; the above-mentioned silicone hydrogel lens is extracted with a liquid containing water to remove the parts that have not undergone a cross-linking and curing reaction. Silicon high polymer; put the above silicon hydrogel lens into phosphoric acid or boric acid saline buffer solution with a pH value of 7.1~7.5 for high temperature and high pressure sterilization.

在下述的實施例中,以上述製造方法製造的矽水膠鏡片進行各項參數,依據國際標準ISO 18369作檢測,包括水含量、光折射率、可見光穿透率、抗藍光穿透率及透氧率檢測,另外包括鏡片強度與彈性係數等。所有市售矽水膠鏡片規格皆具如下特質:可見光穿透率需大於89%、含水量為24至74%,透氧率為45至140DK,抗張強度大於1MPa,彈性係數在0.4~1.2之間;延伸率(%)為50%以上。In the following examples, various parameters of the silicon hydrogel lenses manufactured by the above manufacturing method were tested according to the international standard ISO 18369, including water content, light refractive index, visible light transmittance, anti-blue light transmittance and transmittance Oxygen rate detection, including lens strength and elastic coefficient, etc. All commercially available silicon hydrogel lens specifications have the following characteristics: visible light transmittance must be greater than 89%, water content must be 24 to 74%, oxygen transmission rate is 45 to 140DK, tensile strength is greater than 1MPa, and elastic coefficient is between 0.4 and 1.2 Between; the elongation (%) is more than 50%.

依據上述實施方式有以下實施例According to above-mentioned implementation mode, following embodiment is arranged

實施例1Example 1

將0.001、0.005,0.01及0.02g(代號為SHy、SAg10、SAg50、SAg100及SAg200硝酸銀分別溶於20g IPA中常溫攪拌1小時,加入50g 矽氧烷預聚物常溫攪拌1小時,再加入10g TRIS/30g DMA)/1g 2-(2’-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, HMEPB/0.8g I819在常溫攪拌1小時完成銀/矽水膠組合溶液。此溶液注入模具進行藍光固化處理60分鐘形成矽水膠乾片。經過常溫酒精與水溶液膨潤清洗後置於磷酸鹽緩衝液,進行121℃高溫滅菌30分鐘。如此完成抗藍光/抗UV矽水膠隱形眼鏡。以下表列實施例結果Dissolve 0.001, 0.005, 0.01 and 0.02g (codenamed SHy, SAg10, SAg50, SAg100 and SAg200) of silver nitrate in 20g of IPA and stir for 1 hour at room temperature, add 50g of siloxane prepolymer and stir for 1 hour at room temperature, then add 10g of TRIS /30g DMA)/1g 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, HMEPB/0.8g I819 and stirred at room temperature for 1 hour to complete the silver/silicon hydrocolloid combined solution. This solution is injected into the mold for blue light curing for 60 minutes to form a silicon hydrogel dry film. After swelling and washing with alcohol and aqueous solution at room temperature, it was placed in phosphate buffer solution and sterilized at 121°C for 30 minutes. This completes the anti-blue light/anti-UV silicone hydrogel contact lenses. The results of the examples are listed in the following table

表1   SHy SAg10 SAg50 SAg100 SAg200 折射率/水含量% 1.400/52.6 1.398/56.3 1.395/58.6 1.393/62.6 1.390/62.4 透氧率(DK, barrers) 75.0 78.6 82.5 82.4 83.3 抗張強度(MPa) 1.6 1.2 1.2 1.0 0.7 彈性係數 (Mpa) 0.65 0.61 0.51 0.48 0.47 延伸率(%) 85.2 86.3 88.5 75.3 57.1 Table 1 SHy SAg10 SAg50 SAg100 SAg200 Refractive index/water content% 1.400/52.6 1.398/56.3 1.395/58.6 1.393/62.6 1.390/62.4 Oxygen transmission rate (DK, barrers) 75.0 78.6 82.5 82.4 83.3 Tensile strength (MPa) 1.6 1.2 1.2 1.0 0.7 Elastic coefficient (Mpa) 0.65 0.61 0.51 0.48 0.47 Elongation (%) 85.2 86.3 88.5 75.3 57.1

由表1可見,各實施例中所生成的鏡片的物理性質差異並不大,足見利用本發明之方法所製得之鏡片,其物理性質符合隱形眼鏡之標準要求。It can be seen from Table 1 that the physical properties of the lenses produced in each embodiment are not very different, which shows that the physical properties of the lenses produced by the method of the present invention meet the standard requirements for contact lenses.

表2   SHy SAg10ppm SAg50 SAg100 SAg200 可見光透過率 a% 96.2 93.5 92.7 90.5 88.2 藍光透過率/阻隔率 b% 94.2/5.8 81.6/18.4 74.8/25.2 57.9/42.1 45.8/55.2 UVA透過率/阻隔率 c% 92.3/7.7 5.2/94.2 3.2/96.8 2.0/98.0 1.2/98.8 UVB透過率/阻隔率 d% 78.8/21.2 0.1/99.9 0.1/99.9 0.1/99.9 0.1/99.9 a 表示波長在380~780 nm b 表示波長在380~460 nm c  表示波長在316~380 nm d 表示波長在281~315 nm Table 2 SHy SAg10ppm SAg50 SAg100 SAg200 Visible light transmittance a % 96.2 93.5 92.7 90.5 88.2 Blue light transmittance/blocking rate b % 94.2/5.8 81.6/18.4 74.8/25.2 57.9/42.1 45.8/55.2 UVA transmittance/blocking ratec % 92.3/7.7 5.2/94.2 3.2/96.8 2.0/98.0 1.2/98.8 UVB transmittance/blocking rate d % 78.8/21.2 0.1/99.9 0.1/99.9 0.1/99.9 0.1/99.9 a means the wavelength is 380~780 nm b means the wavelength is 380~460 nm c means the wavelength is 316~380 nm d means the wavelength is 281~315 nm

以下進一步分析實施例結果。The results of the examples are further analyzed below.

本實施例產出之隱形眼鏡隨著銀離子增加顏色由微黃漸變至淡黃,但在200ppm下顏色仍不會形成深黃色以致於影響外觀配戴性,由SPR效應也證明本體上為奈米銀均勻分布。The color of the contact lenses produced in this example gradually changes from light yellow to light yellow with the increase of silver ions, but the color still does not become dark yellow at 200ppm so as to affect the appearance and wearability. The SPR effect also proves that the body is Nai The rice silver is evenly distributed.

由表1銀離子濃度增加由10ppm-200ppm時其折射率逐漸下降,含水量逐漸上升, 惟其變化量並不明顯,這說明奈米銀仍然會阻隔光起始能量,影響光聚合程度,使本體結構較為鬆散,這造成含水量上升,強度與延伸率都因而下降,但在最大量200ppm銀離子存在下,僅約比對照品(SAg)下降10%左右而且鏡片外觀形狀並無扭曲或變形。其幾何性質如鏡片直徑、曲率半徑與中心厚度與比對品皆無明顯差異。另外不同銀離子濃度對透氧率並無明顯差異皆可達到80Dk左右再配合含水量50%以上,說明其為擁有優越矽水膠隱形眼鏡特性。From Table 1, when the concentration of silver ions increases from 10ppm to 200ppm, the refractive index gradually decreases and the water content gradually increases, but the change is not obvious, which shows that nano-silver will still block the initial energy of light, affect the degree of photopolymerization, and make the bulk The structure is relatively loose, which leads to the increase of water content, which reduces the strength and elongation. However, in the presence of the maximum amount of 200ppm silver ions, it is only about 10% lower than that of the reference substance (SAg) and the appearance of the lens is not distorted or deformed. Its geometric properties such as lens diameter, radius of curvature and center thickness are not significantly different from those of the comparison product. In addition, different silver ion concentrations have no significant difference in the oxygen transmission rate, and can reach about 80Dk, combined with a water content of more than 50%, which shows that it has superior characteristics of silicon hydrogel contact lenses.

由表2及圖1顯示實施例產出鏡片光學性質的變化,當UV吸收劑加入會非常明顯增加抗UV能力,皆可達Class I等級(UVA >90%、UVB >99%),當銀離子濃度在10ppm下即有約20%抗藍光能力,說明本製程對銀離子有極佳之還原能力,由其可見光透過率皆可在90%以上,這說明並不影響視力矯正,在奈米銀200ppm存在能達到50%左右抗藍光能力,這說明奈米銀與藍光阻隔率有非常高相關性。Table 2 and Figure 1 show the changes in the optical properties of the lenses produced in the examples. When the UV absorber is added, the anti-UV ability will be significantly increased, and both can reach Class I (UVA > 90%, UVB > 99%). When silver When the ion concentration is 10ppm, it has about 20% anti-blue light ability, which shows that this process has an excellent reduction ability to silver ions, and its visible light transmittance can be above 90%, which shows that it does not affect vision correction. The presence of silver at 200ppm can achieve about 50% anti-blue light ability, which shows that nano-silver has a very high correlation with the blue light blocking rate.

圖1是本發明實施例產出鏡片的光學性質的變化比較圖。FIG. 1 is a comparison chart of the changes in the optical properties of the lenses produced in the examples of the present invention.

Claims (10)

一種抗藍光隱形眼鏡的製造方法,包括下列步驟:a.合成一聚矽氧烷預聚物,其中該聚矽氧烷預聚物中含有聚乙二醇;b.將銀離子化合物溶於非水溶劑中,以製備一銀離子溶液;c.將該銀離子溶液與該聚矽氧烷預聚物混合,以使該銀離子溶液中之銀離子均勻分佈於該聚矽氧烷預聚物中;d.將親水性單體及感光起始劑加入該聚矽氧烷預聚物中混合,以形成一矽水膠組成物;以及e.以藍光照射該矽水膠組成物,以同時進行交聯固化反應及銀離子還原反應,而形成具有抗藍光奈米銀的矽水膠鏡片。 A method for manufacturing an anti-blue light contact lens, comprising the following steps: a. synthesizing a polysiloxane prepolymer, wherein the polysiloxane prepolymer contains polyethylene glycol; b. dissolving the silver ion compound in non- In an aqueous solvent, to prepare a silver ion solution; c. mix the silver ion solution with the polysiloxane prepolymer, so that the silver ions in the silver ion solution are evenly distributed in the polysiloxane prepolymer middle; d. adding hydrophilic monomers and photoinitiators to the polysiloxane prepolymer and mixing to form a silicone hydrogel composition; and e. irradiating the silicone hydrogel composition with blue light to simultaneously Carry out cross-linking curing reaction and silver ion reduction reaction to form silicon hydrogel lenses with anti-blue light nano-silver. 如請求項1所述之方法,其中於該步驟d的該矽水膠組成物中,更可同時加入含矽單體與該聚矽氧烷預聚物混合,該聚矽氧烷預聚物加上該含矽單體之含量為30~80wt%,該親水性單體的重複單元之含量為10~50wt%,該感光起始劑之含量為0.1~2wt%,銀離子化合物的含量為10~200ppm。 The method as described in claim 1, wherein in the silicone hydrogel composition in the step d, a silicon-containing monomer can be added to mix with the polysiloxane prepolymer at the same time, and the polysiloxane prepolymer In addition, the content of the silicon-containing monomer is 30-80wt%, the content of the repeating unit of the hydrophilic monomer is 10-50wt%, the content of the photosensitive initiator is 0.1-2wt%, and the content of the silver ion compound is 10~200ppm. 如請求項1所述之方法,其中於該步驟的該聚矽氧烷預聚物的合成包括下列步驟:以一雙羥型聚二甲基矽氧烷化合物和一異氰酸化合物為原料,再添加一稀釋劑下於一中溫環境進行反應,以獲得一第一生成物;將該第一生成物加入一親水擴鏈劑,依次進行末端羥基化反應、進而擴鏈反應以獲得一第二生成物;將該第二生成物和一丙烯酸酯類化合物在常溫繼續反應至少12小時,以獲得一雙性含矽預聚物;其中該親水擴鏈劑選自由乙二醇、丙二醇、1,4丁二醇、聚乙二醇、聚丙二醇、聚丙二醇二縮水甘油醚及其組合所組成之群組。 The method as described in claim 1, wherein the synthesis of the polysiloxane prepolymer in this step includes the following steps: using a bishydroxy polydimethylsiloxane compound and an isocyanate compound as raw materials, Then add a diluent and react in a medium temperature environment to obtain a first product; add a hydrophilic chain extender to the first product, carry out terminal hydroxylation reaction in turn, and then chain extension reaction to obtain a first product The second product; continue to react the second product with an acrylate compound at room temperature for at least 12 hours to obtain an amphoteric silicon-containing prepolymer; wherein the hydrophilic chain extender is selected from ethylene glycol, propylene glycol, 1 , A group consisting of 4 butanediol, polyethylene glycol, polypropylene glycol, polypropylene glycol diglycidyl ether and combinations thereof. 如請求項1所述之方法,其中該矽水膠組成物更包括10~20wt%的稀釋劑。 The method as described in claim 1, wherein the silicone hydrogel composition further includes 10-20wt% diluent. 如請求項2所述之方法,其中該含矽單體選自由3-甲基丙烯醯氧丙基三(三甲基矽氧基)矽烷(3-methacryloxypropyl tris(tirmethylsiloxy)silane,TRIS)、3-丙烯醯氧丙基三(三甲基矽氧基)矽烷 (3-acryloxypropyl tri(trimethylsiloxy)silane)、3-丙烯醯胺丙基三(三甲基矽氧基)矽烷(3-acrylamidopropyl tris(trimethylsiloxy)silane)、3-甲基丙烯醯胺丙基三(三甲基矽氧基)矽烷、(3-甲基丙烯醯氧基-2-羥基丙氧基)丙基雙(三甲基矽氧基)甲基矽烷,SiGMA)、數量平均分子量為657至1500的單官能基聚二甲基矽氧烷高聚物(monofunctional Polydimethylsiloxane,mPDMS)及其組合所組成之群組。 The method as described in claim 2, wherein the silicon-containing monomer is selected from the group consisting of 3-methacryloxypropyl tris(tirmethylsiloxy)silane (TRIS), 3 -Acryloxypropyltris(trimethylsiloxy)silane (3-acryloxypropyl tri(trimethylsiloxy)silane), 3-acrylamidopropyl tris(trimethylsiloxy)silane (3-acrylamidopropyl tris(trimethylsiloxy)silane), 3-methacrylamidopropyl tri( Trimethylsiloxy)silane, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, SiGMA), number average molecular weight of 657 to A group consisting of 1500 monofunctional polydimethylsiloxane polymers (monofunctional Polydimethylsiloxane, mPDMS) and combinations thereof. 如請求項1所述之方法,其中該親水性單體選自由2-羥基乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate,HEMA);N,N-二甲基丙烯醯胺(N,N-dimethyl acrylamide,DMA)、N,N-二乙基丙烯醯胺(N,N-diethyl acrylamide,DEA)、N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)、、甲基丙烯酸甘油酯(glycerol methacrylate,GMA)、分子量400的聚乙二醇甲基丙烯酸甲醚(polyethylene glycol methacrylate mono methyl ether)及其組合所組成之群組。 The method as described in claim item 1, wherein the hydrophilic monomer is selected from 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA); N,N-dimethylacrylamide (N,N- dimethyl acrylamide, DMA), N, N-diethyl acrylamide (N, N-diethyl acrylamide, DEA), N-vinyl pyrrolidone (N-vinyl pyrrolidone, NVP), glycerol methacrylate , GMA), polyethylene glycol methacrylate monomethyl ether with a molecular weight of 400 (polyethylene glycol methacrylate mono methyl ether) and a group consisting of combinations thereof. 如請求項1所述之方法,於該步驟d中更同時加入一阻隔紫外光單體,其中該阻隔紫外光單體之含量為0.1~1.5wt%。 In the method described in Claim 1, a UV-blocking monomer is added simultaneously in the step d, wherein the content of the UV-blocking monomer is 0.1-1.5 wt%. 如請求項7所述之方法,其中該阻隔紫外光單體為具有苯並三唑(benzotriazole)的單體。 The method according to claim 7, wherein the UV-blocking monomer is a monomer having benzotriazole. 一種製造抗藍光眼鏡鏡片的材料,包含如請求項1至8所述之方法中的該矽水膠組成物。 A material for manufacturing anti-blue light spectacle lenses, comprising the silicon hydrogel composition in the method described in claims 1 to 8. 一種抗藍光眼鏡鏡片,係由如請求項1至8所述之方法製成。 An anti-blue light spectacle lens is made by the method described in claims 1 to 8.
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TW200819819A (en) * 2006-06-30 2008-05-01 Johnson & Johnson Vision Care Antimicrobial lenses, processes to prepare them and methods of their use
US20140171542A1 (en) * 2012-12-14 2014-06-19 Novartis Ag Amphiphilic siloxane-containing vinylic monomers and uses thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200819819A (en) * 2006-06-30 2008-05-01 Johnson & Johnson Vision Care Antimicrobial lenses, processes to prepare them and methods of their use
US20140171542A1 (en) * 2012-12-14 2014-06-19 Novartis Ag Amphiphilic siloxane-containing vinylic monomers and uses thereof

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