TW200813102A - Wettable silicone hydrogel contact lenses and related compositions and methods - Google Patents
Wettable silicone hydrogel contact lenses and related compositions and methods Download PDFInfo
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200813102 九、發明說明: 【發明所屬之技術領域】 本發明尤其係針對矽氧水凝膠眼科裝置及相關組合物及 方法。更特定言之,本發明係關於經模製之可濕性矽氧水 凝膠隱形眼鏡及相關組合物及方法。 【先前技術】 〇200813102 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention is particularly directed to helium oxygenated hydrogel ophthalmic devices and related compositions and methods. More particularly, the present invention relates to molded wettable hydrogel hydrogel contact lenses and related compositions and methods. [Prior Art] 〇
石夕氧水凝膠隱形眼鏡已普及,此係由於與非石夕氧水凝膠 隱形眼鏡相比,隱形眼鏡配戴者在其眼睛上配戴該等眼鏡 持續更長時間的能力。舉例而言,視特定眼鏡而定,矽氧 水凝膠隱形眼鏡可經每天配戴、每週配戴、雙週配戴或每 月配戴而磨損或規定為每天配戴、每週配戴、雙週配戴或 每月配戴。與矽氧水凝膠隱形眼鏡相關之對眼鏡配戴者之 盈處可至少部分歸因於隱形眼鏡之親水性組份與含矽聚合 物質疏水特性的組合。 非矽氧水凝膠隱形眼鏡(諸如基於甲基丙烯酸2_羥乙酯 (HEMA)之水凝膠隱形眼鏡)常在非極性樹脂隱形眼鏡模具 (例如自聚烯烴基樹脂產生之隱形眼鏡模具)中產生。換言 之用於非石夕氧水凝膠隱形眼鏡之眼鏡前驅體組合物在非 極性樹脂隱形眼鏡模具中聚合以產生基於取财之聚合眼 鏡產物。由於基於HEMA之隱形眼鏡之聚合組份的親水性 質’即使儘管使用非極性樹脂模具產生,但基於hema之 眼鏡在眼睛上仍相容且具有眼用可接受之表面可濕性。 相比之下’自非極性樹脂模具所獲得之現切氧水凝膠 隱形眼鏡具有疏水性眼鏡表面。換言之,該㈠氧水凝膠 121841.doc 200813102 隱形眼鏡之表面具有低可濕性,纟因此在眼睛上不相容或 為眼睛所不可接受。舉例而言,該等石夕氧水凝膠隱形眼鏡 可與增加之脂質沈積、蛋白質沈積、眼鏡與眼睛表面之結 合及對眼鏡配戴者之普遍刺激相關。 • 在努力克服此等問題中,已嘗試採用對該等矽氧水凝膠 ; 11形眼鏡或眼鏡產物進行表面處理或表面改質以增加眼鏡 表面之親水性及可濕性。矽氧水凝膠眼鏡之表面處理的實 例包括塗佈眼鏡表面,將化學物質吸附至眼鏡表面上,且 表面處理,其包括使用電漿氣體塗佈聚合眼鏡表面,或在 隱形眼鏡模具表面上使用電漿氣體以在形成聚合眼鏡之前 處理模具。不幸的是,若干缺點與此方法相關。與不使用 表面處理或改質之製造方法相比,隱形眼鏡之表面處理需 要更多機械及時間來產生隱形眼鏡。此外,當眼鏡由眼鏡 配戴者配戴及/或觸摸時,經表面處理之矽氧水凝膠隱形 目艮鏡可展示減少之表面可濕性。舉例而言,增加對^面 U 處理之眼鏡的觸摸可導致親水性表面降解或磨損。 另一種增加矽氧水凝膠眼鏡之可濕性及眼睛相容性的方 :法為在包含聚合濕潤劑(諸如聚乙烯吡咯啶酮(pvp))之第一 :組合物存在下聚合矽氧水凝膠隱形眼鏡前驅體組合物。該 等類型之眼鏡在本文中稱為具有聚合内部濕潤劑之石夕氧水 凝膠隱形眼鏡,且通常包含包括高分子量聚合物(諸如 pvp)之互穿聚合物網路(IPN)。如一般熟習此項技術者所 瞭解,IPN係指兩種或兩種以上不同聚合物以網路形式之 121841.doc 200813102 :、中至少-種聚合物在另-種聚合物存在下合成及/ ’兩者之間無任何共價鍵。聰可由兩種形成兩個 毗鄰或互穿之網路的鏈組成。㈣之實例包括分步 —同步1PN、半㈣及均1PN。雖然包括聚合濕潤劑IPN ,石夕氧水凝膠隱形眼鏡避免與表面處理相關之問題,但該 等眼鏡歷時延長之時間可能無法保留其眼睛相容性,包括 (、 可‘〖生舉例而言,由於内部濕潤劑未共價結合形成 =合眼鏡之其他組份’因此當由眼鏡配戴者配戴時,其可 自艮鏡/又出,且藉此隨時間推移導致表面可濕性降低及 眼鏡配戴者之不適感增加。 作為如上所述之表面處理或使用聚合濕潤劑IPN之替代 方式,已發現可使用極性樹脂模具代替非極性樹脂模具來 產生具有眼用可接受之表面可濕性的矽氧水凝膠隱形眼 鏡。舉例而言,在乙烯_乙烯醇基或聚乙烯醇基模具中形 成之矽氧水凝膠隱形眼鏡具有所需之表面可濕性。適用於 製造用於產生無聚合濕潤劑IPN之未經表面處理的矽氧水 /旋膠fe:形眼鏡之隱形眼鏡模具的極性樹脂之一種實例為乙 烯-乙烯醇共聚物之樹脂,諸如由Nipp〇n G〇hsei,Ltd以商 標名稱soarlite™出售之乙烯·乙烯醇共聚物樹脂。除其 極性之外,SOARLITETM描述為具有以下特徵··極高機械 強度、抗靜電性、當用於模製過程時的低收縮性、優良抗 油性及抗溶劑性、小的熱膨脹係數及良好耐磨性。 雖然基於SOARLITE™之模具對於在不使用表面處理或 聚合濕潤劑IPN下產生眼睛上相容之矽氧水凝膠隱形眼鏡 121841.doc 200813102 提供有利之替代方式,但S0ARLITETM模具與非極性樹脂 模具(諸如聚丙烯模具)相比之可變形性或可撓性較小,且 與非極性樹脂模具相比相對較難以工作。 根據上文,可見需要眼睛上相容之矽氧水凝膠隱形眼 鏡Y其與自s〇ARLITE™隱形眼鏡模具獲得之矽氧水凝膠 隱形眼鏡相比更易於產生,且無需表面處理或使用聚合濕 潤劑IPN(包括PVP IPN)來達成眼睛相容性。此外,極為需 要提供-種自非極性樹脂或料烴基隱形眼鏡模具構件產 ^眼睛上相容之矽氧水凝膠隱形眼鏡(諸如具有眼睛上相 容之表面可濕性的矽氧水凝膠隱形眼鏡)的方法,該方法 克服現有方法之缺點。亦即,需要一種用於製備眼睛上相 容^夕氧水凝«形眼鏡之改良方法,其既無需表面處理 所得隱形眼鏡產物’亦無需使用聚合濕潤劑㈣作為可聚 合石夕氧水凝膠隱形眼鏡前驅體組合物之部分。本發明滿足 该等需要。 【發明内容】 本發明之隱形眼鏡、眼鏡產物、組合物及方法解決與現 有石夕氧水凝膠隱形眼鏡及其目前之生產方法相關的需要及 問題。已驚人地發現’眼睛上相容之石夕氧水凝膠隱形眼鏡 可心在預萃取之聚合石夕氧水凝膠隱形眼鏡產物中提供相 里之可移除物質,接著將該產物萃取以移除該等可移 除物質且水合以產生石夕氧水凝膠隱形眼鏡而獲得。具有可 移除組份(亦即一或多種可移除物質,包括可萃取物質及 其類似物)之預萃取聚合石夕氧水凝膠眼鏡產物通常含有至 121841.doc 200813102 少約10重量〇/〇之可移除組份。 s ^ Λ u 177 鞍者將預卒取之聚合矽氧水 凝膠眼鏡產物萃取(以藉此孩W γ — 1猎此移除可萃取組份)且水合以形成 士本文所述具有眼用可接f之表面可濕性的砍氧水凝膠隱 形眼鏡。本發明之石夕董:絲_晚/ 7乳水/旋膠形眼鏡具有允許患者眼睛 上舒適配戴該眼鏡歷時延長之時間,諸如至少一天、至少 週至V兩週或約一個月而無需自眼睛移除眼鏡之透氧 性、表面可濕性、模數、水含量、離子流及設計。Shixi oxygen hydrogel contact lenses have become popular because of the ability of contact lens wearers to wear these glasses for longer periods of time than non-shixi oxygen hydrogel contact lenses. For example, depending on the particular lens, the oxygenated hydrogel contact lens can be worn daily, worn weekly, bi-weekly or worn on a monthly basis or worn or worn every day. Wear it in two weeks or wear it every month. The wearer of the lens wearer associated with the oxygenated hydrogel contact lens can be at least partially attributed to the combination of the hydrophilic component of the contact lens and the hydrophobic character of the ruthenium containing polymeric material. Non-oxygenated hydrogel contact lenses, such as 2-hydroxyethyl methacrylate (HEMA based hydrogel contact lenses), are often found in non-polar resin contact lens molds (eg, contact lens molds derived from polyolefin-based resins). Produced in. In other words, the lens precursor composition for non-stone-oxygen hydrogel contact lenses is polymerized in a non-polar resin contact lens mold to produce a wealth-based polymeric eye lens product. Due to the hydrophilic nature of the polymeric component of the HEMA-based contact lens, the hema-based spectacles are compatible on the eye and have an ophthalmically acceptable surface wettability, even though produced using a non-polar resin mold. In contrast, the current cut oxygen hydrogel contact lenses obtained from non-polar resin molds have hydrophobic eyeglass surfaces. In other words, the (a) oxygen hydrogel 121841.doc 200813102 has a low wettability on the surface of the contact lens, which is therefore incompatible with the eye or unacceptable to the eye. For example, such lyophilized hydrogel contact lenses can be associated with increased lipid deposition, protein deposition, combination of spectacles and ocular surfaces, and general stimuli for spectacles wearers. • In an effort to overcome these problems, attempts have been made to surface or surface-modify the helium-oxygen hydrogels; 11-eye glasses or lens products to increase the hydrophilicity and wettability of the lens surface. Examples of surface treatments of silicone hydrogel lenses include coating the surface of the lens, adsorbing the chemical onto the surface of the lens, and surface treating, including coating the surface of the polymeric lens with a plasma gas, or using it on the surface of the contact lens mold. The plasma gas is used to treat the mold prior to forming the polymeric glasses. Unfortunately, several drawbacks are associated with this approach. The surface treatment of contact lenses requires more mechanical and time to produce contact lenses than manufacturing methods that do not use surface treatment or modification. In addition, the surface treated hydroxyl hydrogel invisible eyepiece can exhibit reduced surface wettability when the lens is worn and/or touched by the lens wearer. For example, increasing the touch on the U-treated glasses can result in degradation or wear of the hydrophilic surface. Another way to increase the wettability and eye compatibility of the oxygenated hydrogel glasses is to polymerize the oxygen in the presence of a first: composition comprising a polymeric wetting agent such as polyvinylpyrrolidone (pvp). Hydrogel contact lens precursor composition. Such types of spectacles are referred to herein as diarrhea hydrogel contact lenses having a polymeric internal humectant, and typically comprise an interpenetrating polymer network (IPN) comprising a high molecular weight polymer such as pvp. As is generally understood by those skilled in the art, IPN refers to the synthesis of two or more different polymers in a network form. 121841.doc 200813102:, at least one polymer is synthesized in the presence of another polymer and/ 'There is no covalent bond between the two. Cong can consist of two chains that form two adjacent or interpenetrating networks. (d) Examples include step-by-step synchronization of 1PN, half (four) and average 1PN. Although including polymeric humectants IPN, the lithohydrate hydrogel contact lenses avoid problems associated with surface treatment, such lenses may not retain their eye compatibility over a prolonged period of time, including (or Since the internal humectant is not covalently bonded to form = other components of the spectacles', so when worn by the spectacles wearer, it can be self-mirror/removal, and thereby the surface wettability is lowered over time. And the discomfort of the wearer of the lens increases. As an alternative to the surface treatment or the use of polymeric wetting agent IPN as described above, it has been found that a polar resin mold can be used instead of a non-polar resin mold to produce an ophthalmically acceptable surface that is wettable. Hydroxyl hydrogel contact lenses. For example, hydroxyl hydrogel contact lenses formed in ethylene-vinyl alcohol based or polyvinyl alcohol based molds have the desired surface wettability. An example of a polar resin which produces a non-polymerized humectant IPN which is not surface-treated oxime water/spinner fe: contact lens mold of a type of spectacles is a resin of ethylene-vinyl alcohol copolymer Such as ethylene vinyl alcohol copolymer resin sold by Nipp〇n G〇hsei, Ltd under the trade name soarliteTM. In addition to its polarity, SOARLITETM is described as having the following characteristics: · High mechanical strength, antistatic property, when used Low shrinkage during molding, excellent oil and solvent resistance, low coefficient of thermal expansion and good wear resistance. Although SOARLITETM based molds produce an eye on the surface without the use of surface treatment or polymeric wetting agent IPN. Rongzhi Oxygen Hydrogel Contact Lens 121841.doc 200813102 provides an advantageous alternative, but the SOARLITETM mold has less deformability or flexibility than non-polar resin molds (such as polypropylene molds) and is non-polar Resin molds are relatively difficult to work with. From the above, it can be seen that there is a need for an oxygen compatible hydrogel contact lens Y that is more compatible with the oxygenated hydrogel contact lenses obtained from the s〇ARLITETM contact lens mold. Easily produced without the need for surface treatment or the use of polymeric wetting agents IPN (including PVP IPN) to achieve eye compatibility. In addition, it is highly desirable to provide a self-polar tree Or a hydrocarbon-based contact lens mold member for producing an eye-compatible oxygenated hydrogel contact lens, such as a hydroxyl hydrogel contact lens having an eye-compatible surface wettability, which overcomes existing methods Disadvantages, that is, there is a need for an improved method for preparing a compatible lens on the eye which does not require surface treatment of the resulting contact lens product and does not require the use of a polymeric wetting agent (4) as a polymerizable shi A portion of a hydrogel contact lens precursor composition. The present invention satisfies such needs. SUMMARY OF THE INVENTION The present invention provides contact lenses, eyeglass products, compositions, and methods for solving contact with existing lithothere hydrogel contact lenses and their present The need and problems associated with the production method. It has been surprisingly found that 'eye-compatible Shishi oxygen hydrogel contact lenses can provide phase shifting in the pre-extracted polymeric rock hydrogel contact lens product. In addition to the material, the product is then extracted to remove the removable materials and hydrated to produce a sulphuric hydrogel contact lens. Pre-extracted polymeric oxaxy hydrogel lens products having a removable component (i.e., one or more removable materials, including extractable materials and the like) typically contain about 10 weight less to 121841.doc 200813102. /〇Removable components. s ^ Λ u 177 The saddle will extract the polymerized hydrogel lens product from the pre-stroke (to remove the extractable component by this means) and hydrate it to form an eye for use as described herein. A chopped hydrogel contact lens that can be attached to the surface of the f. The Shi Xi Dong: silk _ night / 7 milk water / spin-on spectacles of the present invention have a time for allowing the patient to comfortably wear the glasses for a prolonged period of time, such as at least one day, at least weeks to V two weeks or about one month without self- The eye removes oxygen permeability, surface wettability, modulus, water content, ion flow and design.
在態樣中,本發明係針對可聚合石夕氧水凝膠隱形眼鏡 前驅體組合物。該等前驅體組合物有效形成碎氧水凝膠隱 形眼鏡。聚合之後,前驅體調配物導致形成可萃取之可水 合隱形眼鏡預產物。前驅體組合物包含以下各物:⑴至少 約20重量%之反應性含氟丙烯醯基矽氧大分子單體,至 少約45重量%之不含石夕之單體組合物,其包含親水性含乙 烯基單體、丙烯酸單體及丙烯酸酯官能化之氧化乙烯寡聚 物,及(iii)聚氧化烯矽氧可萃取組份。 在一實施例中,可聚合矽氧水凝膠隱形眼鏡前驅體組合 物包含至少約25重量%,且較佳約25重量%至約35重量% 之反應性含氟二甲基丙烯醯基矽氧大分子單體。本發明之 例示性反應性含氟二甲基丙烯醯基石夕氧大分子單體為α_ω_ 雙(甲基丙烯醯氧基乙基亞胺基羧基乙氧基丙基 >聚(二甲 基矽氧梡)-聚(三氟丙基甲基矽氧烷)-聚(ω_甲氧基·聚(乙二 醇)丙基甲基矽氧烷)(在本文中亦稱為M3U,且CAS註冊號 為 697234-74-5)。 在另一實施例中,本發明之可聚合矽氧水凝膠隱形眼鏡 121841.doc -10- 200813102 則驅體組合物包含約45-55重量%之不含矽之單體組合物。 尤其較佳為包含沭乙烯基甲基乙醯胺、甲基丙烯酸甲 酉曰及一甲基丙烯酸三乙二醇酯之不含矽的親水性組份。 在另一實施例中,可聚合矽氧水凝膠隱形眼鏡前驅體組 合物包含約10重量°/〇至約30重量%之聚氧化烯矽氧可萃取 、、、伤在甚至更特定之實施例中,聚氧化烯石夕氧可萃取組 份視情況包含約〇· 1至6份鏈轉移劑及約99.9至94份聚氧化 烯矽氧。說明性聚氧化烯矽氧可萃取組份包括二甲基矽氧 烷-氧化乙烯嵌段共聚物,諸如含有約75重量%氧化乙烯之 二甲基矽氧烷-氧化乙烯嵌段共聚物。一種該二甲基矽氧 燒-氧化乙烯嵌段共聚物為Dbe 712 (Ge]lest,M〇rrisviUe, PA)。 ’ 本文所述之組合物、眼鏡及方法中所用之鏈轉移試劑包 括硫醇、二硫醚、有機鹵化物、烯丙氧基醚及烯丙氧基 醇。在尤其較佳之實施例令,鏈轉移試劑為烯丙氧基乙 醇。 在本發明之其他實施例中,可聚合矽氧水凝膠隱形眼鏡 前驅體組合物亦可包含一或多個以下各物:紫外線吸收 劑、著色劑或引發劑。紫外線吸收劑可例如為光可聚合羥 基二苯甲酮’諸如2-羥基_4丙烯醯氧基乙氧基二苯甲酮。 本發明所用^色劑可例如為駄菁顏料,諸如醜菁藍。此 外,可聚合矽氧水凝膠隱形眼鏡前驅體調配物中所包含之 引發劑可例如為熱引發劑,諸如2,2,_偶氮雙(2,4_二甲基戊 腈)(VAZO-52)。 土 12184Ldoc -11 - 200813102 在更特定實施例中,本發明之可聚合矽氧水凝膠隱形眼 鏡前驅體組合物包含α-ω·雙(甲基丙烯醯氧基乙基亞胺基羧 基乙氧基丙基聚(二甲基矽氧烷)_聚(三氟丙基甲基矽氧 院)-聚(ω·甲氧基-聚(乙二醇)丙基甲基矽氧烷)、Ν_乙烯基_ . Ν-甲基乙醯胺、甲基丙烯酸甲酯及二甲基丙烯酸三乙二醇 酉旨。 在一較佳實施例中,本發明之前驅體組合物包含心…雙 (甲基丙烯醯氧基乙基亞胺基羧基乙氧基丙基)_聚(二甲基 石夕氧烷)_聚(三氟丙基甲基矽氧烷)-聚(ω-甲氧基-聚(乙二 醇)丙基甲基矽氧烷)、Ν-乙烯基甲基乙醯胺、甲基丙烯 酸甲i旨、二甲基丙烯酸三乙二醇酯及二甲基石夕氧燒-氧化 乙烯嵌段共聚物可萃取組份。 在另一實施例中,可萃取組份包含視情況含有烯丙氧基 乙醇之DBE 712。 在可聚合矽氧水凝膠隱形眼鏡前驅體組合物之更特定實 施例中’ α-ω-雙(甲基丙烯醯氧基乙基亞胺基羧基乙氧基丙 U 基聚(二甲基矽氧烷)_聚(三氟丙基甲基矽氧烷)-聚(ω-甲 氧基-聚(乙二醇)丙基曱基矽氧烷)與]^_乙烯基_Ν•甲基乙醯 ; 胺、甲基丙烯酸甲酯及二甲基丙稀酸三乙二醇酯之組合的 . 比率以重量比計在約〇·50至約〇·65之範圍内。 在一較佳實施例中,可聚合矽氧水凝膠隱形眼鏡前驅體 組合物包含α-ω-雙(甲基丙烯醯氧基乙基亞胺基羧基乙氧基 丙基)-聚(二甲基矽氧烷;)_聚(三氟丙基甲基矽氧烷聚(ω_ 甲氧基-聚(乙二醇)丙基甲基矽氧烷)、Ν_乙烯基_Ν_曱基乙 121841.doc -12- 200813102 酿胺、甲基丙烯酸甲醋、二f基丙婦酸三乙二醇醋、2-經 基-4-丙烯醯氧基乙氧基二苯甲酮、酞菁藍、2,2,_偶氮雙 (2,4-二甲基戊腈)及DBE 712(視情況與烯丙氧基乙醇組 合)。 上述、、且伤在例示性可聚合矽氧水凝膠隱形眼鏡前驅體組 合物中之尤其較佳重量/重量百分比為約(重量比)心①-雙(甲基丙烯醯氧基乙基亞胺基緩基乙氧基丙基)_聚(二甲 基矽氧烷)-聚(二氟丙基甲基矽氧烷)_聚(①_甲氧基_聚(乙二 酵)丙基甲基矽氧烷)、約37%(重量比)Ν_乙烯基_ν_甲基乙 醯胺、、力13·5%(重《比)甲基丙烯酸甲醋、約〇16%(重量 比)二甲基丙烯酸三乙二醇酯、約〇·7%(重量比)2_羥基 丙職氧基乙氧基二苯甲酮、約〇1%(重量比)献菁藍、約 〇 /〇(重里比)2,2丨-偶氮雙(2,4·二甲基戊腈)及約2〇% DBE 712 (視情況與烯丙氧基乙醇組合)。 根據另一態樣,本發明提供自上述可聚合之眼鏡前驅體 組合物中之任一者所產生之矽氧水凝膠隱形眼鏡。 在另一態樣中,本發明提供自如本文所述之不存在可萃 取組份之可聚合之眼鏡前驅體組合物反應所得之矽氧水凝 膠隱形眼鏡。 "根據另一態樣,本發明係針對藉由以下步驟所產生之矽 乳膠隱形眼鏡:聚合如本文所述之可聚合之眼鏡前驅 體組口物以形成預萃取之聚合矽氧水凝膠隱形眼鏡,自預 ★ 开v眼鏡萃取可萃取之組份以形成經萃取之聚合眼 鏡產物,且使經萃取之聚合眼鏡產物水合以形成矽氧水凝 121841.doc • 13 - 200813102 膠隱形眼鏡。所得經萃取之水合隱形眼鏡產物通常具有約 40重量至約48重量%範圍内之平衡水含量及約ι〇〇_ιΐ5 barrer範圍内之透氧性(Dk X 1〇-")。 在本發明之此態樣的一實施例中,根據以上方法產生矽 氧水凝膠隱形眼鏡,其中可聚合之眼鏡前驅體組合物包含 熱引發劑’且聚合步驟進一步包含將可聚合之眼鏡前驅體 組合物加熱至大於約50°C之溫度。 在另一實施例中,藉由以下步驟產生矽氧水凝膠隱形眼 鏡:聚合如上所述之可聚合之眼鏡前驅體組合物以形成預 萃取之聚合矽氧水凝膠隱形眼鏡,其中DBE與烯丙氧基乙 醇組合,自預萃取之聚合矽氧水凝膠隱形眼鏡萃取聚氧化 烯矽氧可萃取組份以形成經萃取之聚合眼鏡產物,且使經 萃取之聚合眼鏡產物水合以形成一批任一或多種以下特徵 具有低可變性之矽氧水凝膠隱形眼鏡:平衡水含量、透氧 性、靜態接觸角、動態接觸角、滯後、折射率、離子流、 模數及抗張強度。例如,視眼鏡產物之特定特徵而定,任 一或多種前述眼鏡特徵之可變性通常均小於約2〇%,且較 佳小於約10%。在一或多個實施例中,眼鏡直徑、平衡水 含篁及/或離子流之任一或多者的可變性均為約5%或小於 5%,更佳為約3%或小於3%,且甚至更佳為約2%或小於 2% 〇 在另一態樣中,本發明提供一種平衡水含量為至少約 4〇%、透氧性(Dk X 1〇·η)為約9〇_12〇 barrer之矽氧水凝膠 隱形眼鏡。 121841.doc -14 - 200813102 在上述之_誊士Α, 貫轭例中,本文提供進一步包含選 各特徵組成之雜& 乂匕$ &自由以下 目…一 或多個特徵之矽氧水凝膠隱形眼鏡: 了…進接觸角為約7〇。至約75。,拉伸模數小於約〇·7 3,且離子流為約 1.5-5(xl〇-3mm2/min)。 、只^例中,本發明之矽氧水凝膠隱形眼鏡亦可且 有圓形外周邊緣,士 1 〃 ^ 、 或可為以下之一者··球面眼鏡、非球面 眼鏡、早焦點眼鏡或旋轉穩定複曲面隱形眼鏡。 實%例中,本發明提供密封包裝之如本文所述之 矽氧水凝膠隱形眼鏡。 在另一實施例中,本發明之矽氧水凝膠隱形眼鏡未經表 面處理。In one aspect, the invention is directed to a polymerizable oxalate hydrogel contact lens precursor composition. The precursor compositions are effective to form a broken oxygen hydrogel contact lens. After polymerization, the precursor formulation results in the formation of an extractable hydratable contact lens preform. The precursor composition comprises the following: (1) at least about 20% by weight of a reactive fluoropropenyl fluorene macromonomer, at least about 45% by weight of a monomer composition free of sulphur, which comprises hydrophilicity A vinyl-containing monomer, an acrylic monomer, and an acrylate-functionalized ethylene oxide oligomer, and (iii) a polyoxyalkylene oxide extractable component. In one embodiment, the polymerizable silicone hydrogel contact lens precursor composition comprises at least about 25% by weight, and preferably from about 25% to about 35% by weight, of reactive fluorine-containing dimethyl propylene fluorenyl hydrazine. Oxygen macromonomer. An exemplary reactive fluorine-containing dimethyl propylene fluorenyl oxalyl macromonomer of the present invention is α_ω_bis(methacryloxyethyliminocarboxycarbonylpropyl) poly(dimethylhydrazine) Oxime)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyloxane) (also referred to herein as M3U, and CAS Registration No. 697234-74-5). In another embodiment, the polymerizable silicone hydrogel contact lens of the present invention 121841.doc -10- 200813102 then the body composition comprises about 45-55 wt% A monomer composition containing ruthenium. Particularly preferred is a hydrazine-free hydrophilic component comprising decyl vinylmethyl acetamide, methacrylate methacrylate and triethylene glycol methacrylate. In one embodiment, the polymerizable silicone hydrogel contact lens precursor composition comprises from about 10 weight percent to about 30 weight percent polyoxyalkylene oxide extractable, in an even more specific embodiment. The polyoxyalkylene oxide-extractable component optionally comprises from about 1 to 6 parts of a chain transfer agent and from about 99.9 to 94 parts of a polyoxyalkylene oxide. The polyoxyalkylene oxime extractable component comprises a dimethyloxane-ethylene oxide block copolymer, such as a dimethyl methoxy olefin-ethylene oxide block copolymer containing about 75% by weight of ethylene oxide. The dimethyloxoxime-oxyethylene block copolymer is Dbe 712 (Ge]lest, M〇rrisviUe, PA). The chain transfer reagents used in the compositions, glasses and methods described herein include mercaptans, Thioether, organic halide, allyloxy ether and allyloxy alcohol. In a particularly preferred embodiment, the chain transfer reagent is allyloxyethanol. In other embodiments of the invention, the polymerizable helium oxygen The hydrogel contact lens precursor composition may also comprise one or more of the following: a UV absorber, a colorant or an initiator. The UV absorber may, for example, be a photopolymerizable hydroxybenzophenone such as 2-hydroxyl. 4 propylene methoxy ethoxy benzophenone. The chromogen used in the present invention may, for example, be a phthalocyanine pigment, such as ugly cyanine blue. In addition, the polymerizable silicone hydrogel contact lens precursor formulation is included The initiator can be, for example, a thermal initiator such as 2 , 2, _ azobis(2,4-dimethylvaleronitrile) (VAZO-52). Soil 12184 Ldoc -11 - 200813102 In a more specific embodiment, the polymerizable silicone hydrogel contact lens precursor of the present invention The composition comprises α-ω·bis(methacryloxyethylethylimidocarboxyethoxypropylpoly(dimethyloxane)-poly(trifluoropropylmethyloxime)- Poly(ω·methoxy-poly(ethylene glycol) propylmethyl decane), Ν_vinyl _. Ν-methyl acetamide, methyl methacrylate and triethylene methacrylate In a preferred embodiment, the precursor composition of the present invention comprises a core... bis(methacryloxyethylethylimidocarboxyethoxypropyl)-poly (dimethyl texa Oxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyloxirane), fluorene-vinylmethylacetamide, The component may be extracted by methacrylic acid, triethylene glycol dimethacrylate and dimethyl oxalate-oxyethylene block copolymer. In another embodiment, the extractable component comprises DBE 712, optionally containing allyloxyethanol. In a more specific embodiment of the polymerizable silicone hydrogel contact lens precursor composition, 'α-ω-bis(methacryloxyethylethylimidocarboxyethoxypropyl)-poly(dimethyl)矽 ) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The ratio of the combination of amine, methyl methacrylate and triethylene glycol dimethyl acrylate is in the range of about 〇·50 to about 〇·65 by weight. In an embodiment, the polymerizable silicone hydrogel contact lens precursor composition comprises alpha-omega-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly(dimethyloxime) Alkane;)_poly(trifluoropropylmethyloxirane poly(ω_methoxy-poly(ethylene glycol) propylmethyloxirane), Ν_vinyl_Ν_曱基乙121841.doc -12- 200813102 Amine amine, methyl methacrylate, bis-f-propylglycolic acid triethylene glycol vinegar, 2-pyridyl-4-propenyloxyethoxybenzophenone, phthalocyanine blue, 2, 2, _ azobis(2,4-dimethylvaleronitrile) and DBE 712 (as appropriate The propoxyethanol combination) is particularly preferred in the exemplary polymerizable hydrogel contact lens precursor composition. The weight/weight percentage is about (weight ratio) heart 1-bis (methyl) Propylene oxiranylethylimidoyl yloxypropyl)-poly(dimethyloxane)-poly(difluoropropylmethyloxirane)-poly(1-methoxy-poly (Ethylene glycol) propylmethyl oxime), about 37% (by weight) Ν _ vinyl _ ν _ methyl acetamide, force 13.5% (heavy ratio) methyl methacrylate , about 16% by weight of triethylene glycol dimethacrylate, about 7% by weight of 2-hydroxypropyl ethoxyethoxy benzophenone, about 1% by weight (weight ratio) Cyanine blue, about 〇/〇 (heavy ratio) 2,2丨-azobis(2,4·dimethylvaleronitrile) and about 2〇% DBE 712 (as appropriate with allyloxyethanol) According to another aspect, the present invention provides a hydrogenated hydrogel contact lens produced from any of the above polymerizable lens precursor compositions. In another aspect, the invention provides a freezer as described herein. Non-existible polymerizable component The ophthalmic hydrogel contact lens obtained by the reaction of the lens precursor composition. According to another aspect, the present invention is directed to a latex contact lens produced by the following steps: polymerizing a polymerizable lens as described herein Precursor group mouth to form a pre-extracted polymeric hemohydrogel contact lens, extracting the extractable component from pre-opening glasses to form an extracted polymeric lens product, and hydrating the extracted polymeric lens product Forming a hemorrhagic hydrogel 121841.doc • 13 - 200813102 Glue contact lens. The resulting extracted hydrated contact lens product typically has an equilibrium water content in the range of from about 40 weights to about 48% by weight and within about ι〇〇_ιΐ5 barrer Oxygen permeability (Dk X 1〇-"). In an embodiment of this aspect of the invention, a helium oxygen hydrogel contact lens is produced according to the above method, wherein the polymerizable lens precursor composition comprises a thermal initiator and the polymerization step further comprises polymerizing the lens precursor The body composition is heated to a temperature greater than about 50 °C. In another embodiment, a helium oxygen hydrogel contact lens is produced by polymerizing a polymerizable lens precursor composition as described above to form a pre-extracted polymeric hemohydrogel contact lens, wherein DBE and The allyloxyethanol combination extracts the polyoxyalkylene oxime extractable component from the pre-extracted polymeric oxime hydrogel contact lens to form an extracted polymeric spectacles product, and hydrates the extracted polymeric spectacles product to form a Batching of one or more of the following characteristics of low-variability helium hydrogel contact lenses: equilibrium water content, oxygen permeability, static contact angle, dynamic contact angle, hysteresis, refractive index, ion current, modulus and tensile strength . For example, depending on the particular characteristics of the lens product, the variability of any one or more of the foregoing lens features is typically less than about 2%, and preferably less than about 10%. In one or more embodiments, the variability of any one or more of the spectacles diameter, equilibrium water enthalpy and/or ion current is about 5% or less, more preferably about 3% or less than 3%. And even more preferably about 2% or less than 2%. In another aspect, the present invention provides an equilibrium water content of at least about 4% and an oxygen permeability (Dk X 1〇·η) of about 9〇. _12〇barrer's oxygen hydrogel contact lens. 121841.doc -14 - 200813102 In the above-mentioned _ 誊 Α, 贯 轭 , , , , 本文 本文 本文 本文 本文 本文 & & & & & & & & & & & & & & & & & & & & & & & & & & & & & Gel contact lenses: The contact angle is about 7 inches. To about 75. The tensile modulus is less than about 〇·7 3 and the ion current is about 1.5-5 (xl 〇 -3 mm 2 /min). In the case of the present invention, the oxygenated hydrogel contact lens of the present invention may have a circular outer peripheral edge, and may be one of the following: · spherical glasses, aspherical glasses, early focus glasses or Rotating stable toric contact lenses. In a practical example, the present invention provides a heralloy hydrogel contact lens as described herein in a sealed package. In another embodiment, the oxygenated hydrogel contact lenses of the present invention are not surface treated.
ϋ 在另一態樣中,本發明提供一種產生可聚合矽氧水凝膠 隱形眼鏡前驅體組合物之方法。該方法包括組合以下各 物··⑴至少約25重量%之反應性含氟二甲基丙烯醯基矽氧 大分子單體、(ii)至少約45重量%之不含矽之大分子單體組 合物及(iii)聚氧化烯石夕氧可萃取組份,以藉此產生可聚合 矽氧水凝膠隱形眼鏡前驅體組合物,其中不含石夕之大分子 單體組合物包含親水性含乙烯基單體、丙烯酸系單體及丙 烯酸酯官能化之氧化乙烯寡聚物。 在本發明之此態樣之一實施例中,以上方法進一步包含 組合大分子單體、不含矽之單體組合物及可萃取組份、紫 外線吸收劑及著色劑。例示性著色劑包括酞菁顏料,諸如 酞菁藍。較佳紫外線吸收劑為光可聚合之羥基二苯曱酮, 諸如2-羥基-4-丙烯醯氧基乙氧基二苯甲酮。 121841.doc 200813102 在該方法之一特定實施例中,該反應性含氟二甲基丙烯 酿基石夕氧大分子單體之量在約25重量%至約35重量%之範 圍内。 在該方法之另一實施例中,該不含矽之單體組合物之量 在約45-55重量%之範圍内。 在該方法之另一實施例中,聚氧化烯矽氧可萃取組份之 量在約10重量%至約3〇重量。/〇之範圍内。 在該方法之一較佳實施例中,反應性含氟二甲基丙烯醯 基石夕氧大分子單體為心仍—雙(甲基丙稀醯氧基乙基亞胺基竣 基乙氧基丙基聚(二甲基矽氧烷)_聚(三氟丙基甲基矽氧 烷)-聚(ω-甲氧基-聚(乙二醇)丙基甲基矽氧烷)(M3U)。 在該方法之另一實施例中,不含矽之單體組份包含冰乙 烯基甲基乙醯胺、甲基丙烯酸甲酯及二甲基丙烯酸三 乙二醇S旨。 在該方法之另一實施例中,聚氧化烯矽氧可萃取組份進 -步包含鏈轉移劑,諸如硫醇、n有機鹵化物或稀 丙氧基醇。在一尤其較佳之實施例中,鏈轉移試劑為烤丙 氧基乙醇。 在該方法之-較佳實施例中’聚氧化料氧可萃取组份 包含約0.05重量%至約7重量%之埽丙氧基乙醇…種說明 性聚氧化料氧可萃取組份為二甲切氧氧化乙稀嵌 段共聚物’例如含有75重量%之氧化乙烯的二甲基矽氧烷 氧化乙烯餘共聚物。尤其較佳用作聚氧化_氧可萃取 組份者為DBE 712。 121841.doc _ 16 _ 200813102 在該方法之另一實施例中,組合步驟進一步包含將引發 劑與其他組份組合。較佳為熱引發劑,諸如2,2,_偶氮雙 (2,4-二甲基戊腈)(VAZO-52)。 在另一態樣中,本文提供一種產生可聚合矽氧水凝膠隱 形眼鏡前驅體組合物之方法。該方法包含將α_ω_雙(甲基丙 烯醯氧基乙基亞胺基羧基乙氧基丙基)_聚(二甲基矽氧烷 聚(三氟丙基曱基矽氧烷)-聚(ω_甲氧基_聚(乙二醇)丙基甲 基矽氧烷)、Ν-乙烯基-Ν-甲基乙醯胺、甲基丙烯酸甲酯及In another aspect, the present invention provides a method of producing a polymerizable silicone hydrogel contact lens precursor composition. The method comprises combining the following: (1) at least about 25% by weight of a reactive fluorine-containing dimethyl propylene fluorenyl siloxane macromonomer, and (ii) at least about 45% by weight of a fluorene-free macromonomer a composition and (iii) a polyoxyalkylene oxide extractable component to thereby produce a polymerizable hydrogel hydrogel contact lens precursor composition, wherein the high molecular weight monomer composition excluding the Shixia comprises hydrophilicity A vinyl-containing monomer, an acrylic monomer, and an acrylate functionalized ethylene oxide oligomer. In one embodiment of this aspect of the invention, the above method further comprises combining a macromonomer, a monomer composition free of bismuth and an extractable component, an ultraviolet absorber, and a color former. Exemplary colorants include phthalocyanine pigments such as phthalocyanine blue. Preferred UV absorbers are photopolymerizable hydroxydibenzophenones such as 2-hydroxy-4-propenyloxyethoxybenzophenone. 121841.doc 200813102 In a particular embodiment of the method, the amount of the reactive fluorine-containing dimethyl propylene geranyl macromonomer is in the range of from about 25% by weight to about 35% by weight. In another embodiment of the method, the amount of the bismuth-free monomer composition is in the range of from about 45 to about 55% by weight. In another embodiment of the method, the polyoxyalkylene oxide extractable component is present in an amount from about 10% by weight to about 3% by weight. / within the scope of 〇. In a preferred embodiment of the method, the reactive fluorine-containing dimethyl propylene fluorenyl oxy-enlarge macromonomer is a core-bis(methyl propyl methoxyethyl imino decyl ethoxy group) Propyl poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) (M3U) In another embodiment of the method, the ruthenium-free monomer component comprises glacial vinylmethyl acetamide, methyl methacrylate, and triethylene glycol dimethacrylate S. In another embodiment, the polyoxyalkylene oxime extractable component further comprises a chain transfer agent such as a thiol, an n organic halide or a diloxypropanol. In a particularly preferred embodiment, the chain transfer reagent In the preferred embodiment of the method, the polyoxygen oxide extractable component comprises from about 0.05% by weight to about 7% by weight of decyloxyethanol. The extractable component is a dimethyl ethoxylated ethylene oxide block copolymer, for example, a dimethyl oxirane ethylene oxide copolymer copolymer containing 75% by weight of ethylene oxide. Particularly preferred for use as the polyoxygen-oxygen extractable component is DBE 712. 121841.doc _ 16 _ 200813102 In another embodiment of the method, the combining step further comprises combining the initiator with the other components. Preferably, it is a thermal initiator such as 2,2,-azobis(2,4-dimethylvaleronitrile) (VAZO-52). In another aspect, provided herein is a method for producing polymerizable helium oxygenated water. A method of a gel contact lens precursor composition comprising: α_ω_bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly(dimethyloxane poly(trifluoropropane) (曱-based oxane)-poly(ω_methoxy-poly(ethylene glycol) propylmethyl decane), Ν-vinyl-Ν-methyl acetamide, methyl methacrylate and
二甲基丙烯酸三乙二醇酯組合,以藉此產生可聚合矽氧水 凝膠隱形眼鏡前驅體組合物。 在以上方法之一實施例中,組合步驟進一步包含將二甲 基矽氧烷-氧化乙烯嵌段共聚物可萃取組份(例如dbe 與其他組份組合。 在上述方法之一實施例中’烯丙氧基乙醇與dbe 712之 相對量在約(M份至約5份稀丙氧基乙醇與約9 之範圍内。 勺95 —在前述方法之另—實施例中,組合步驟進—步包含將敢 菁藍與其他組份組合。 M 例+ ’ M合步驟進—步包含將_ 酿氧基乙氧基二苯甲_與其他組份組合。 烯 在該方法之另一實施例中,組合步驟包含將2,2、偶氮雙 (2,4-一甲基戊腈)添加至組合中。 在前述方法之一 基乙基亞胺基羧基 較佳實施例+,雙(甲基丙烯醯氧 乙氧基丙基)_聚(二甲基矽氧烷)_聚(三氟 121841.doc •17· 200813102 丙基曱基矽氧烷)-聚(ω-曱氧基-聚(乙二醇)丙基曱基矽氧 烷)與Ν-乙烯基-Ν_曱基乙醯胺、甲基丙烯酸甲酯及二甲基 丙烯酸三乙二醇酯之組合的比率以重量比計在約〇·5〇至約 〇·65之範圍内。 在另一態樣中,本文提供一種產生可聚合矽氧水凝膠隱 形眼鏡前驅體組合物之方法,其中該方法包含將心…雙(甲 基丙烯醯氧基乙基亞胺基羧基乙氧基丙基)_聚(二甲基矽氧 烷聚(三氟丙基甲基矽氧烷)_聚(ω_甲氧基_聚(乙二醇)丙 基甲基石夕氧烷)、Ν-乙烯基甲基乙醯胺、甲基丙烯酸甲 酯、二甲基丙烯酸三乙二醇酯、2-羥基_4_丙烯醯氧基乙氧 基二苯甲酮、酞菁藍、2,2,-偶氮雙(2,4_二甲基戊腈)與dbe 712(視情況包含烯丙氧基乙醇)組合,以藉此產生可聚合石夕 氧水凝膠隱形眼鏡前驅體組合物。 在一實施例中,上述方法包括以下相對量之組份:約 28%(重量比)α-ω-雙(甲基丙稀醯氧基乙基亞胺基羧基乙氧 基丙基)-聚(二甲基矽氧烷)-聚(三氟丙基甲基矽氧烷)_聚 (ω-曱氧基-聚(乙二醇)丙基甲基石夕氧烧)、約3 7% (重量 比)Ν-乙烯基甲基乙醯胺、約13.5% (重量比)甲基丙烯 酸曱S曰、約〇. 16% (重量比)二甲基丙烯酸三乙二醇酯、約 〇·7%(重量比)2-羥基-4-丙烯醯氧基乙氧基二苯甲酮、約 0.1%(重量比)酞菁藍、約0.4%(重量比)2,2,_偶氮雙(2,4•二 甲基戊腈)及約20% DBE 712 (視情況包含烯丙氧基乙醇)。 在前述方法之另一實施例中,組合步驟導致組份組合之 形成’且該方法進一步包含混合組份之組合以形成混合 121841.doc -18- 200813102 物。 在另一實施例中,該方法進一步包含過濾混合物。 在另一實施例中,該方法包含聚合可聚合之眼鏡前驅體 組合物以形成預萃取之聚合矽氧水凝膠隱形眼鏡。 在另一實施例中,該方法進一步包含在聚合步驟之前將 可聚合之眼鏡前驅體組合物置放於非極性樹脂隱形眼鏡模 具中。Triethylene glycol dimethacrylate is combined to thereby produce a polymerizable silicone hydrogel contact lens precursor composition. In one embodiment of the above method, the combining step further comprises combining the dimethyloxane-ethylene oxide block copolymer extractable component (eg, dbe with other components. In one embodiment of the above method, 'ene The relative amount of propoxyethanol and dbe 712 is in the range of about (M to about 5 parts of diloxypropoxyethanol and about 9. Spoon 95 - in another embodiment of the foregoing method, the combination step further comprises Combining the cyanine blue with the other components. The M example + 'M combined step-in step comprises combining the ethoxylated ethoxybisbenzophenone with the other components. In another embodiment of the method, The combining step comprises adding 2,2, azobis(2,4-monomethylvaleronitrile) to the combination. One of the foregoing methods, ethyl imino, carboxyl group, preferred embodiment +, bis(methacrylic)醯Oxyethoxypropyl)-poly(dimethyloxane)_poly(trifluoro-121841.doc •17·200813102 propyl-decyloxyl)-poly(ω-decyloxy-poly(B) Glycol) propyl mercapto oxime) with Ν-vinyl-Ν-mercaptoacetamide, methyl methacrylate and triethylene glycol dimethacrylate The ratio of combinations is in the range of from about 〇·5〇 to about 〇·65. In another aspect, a method of producing a polymerizable silicone hydrogel contact lens precursor composition is provided herein, wherein The method comprises the steps of: bis(methacryloxyethylethylimidocarboxyethoxypropyl)-poly(dimethyloxoxane poly(trifluoropropylmethyloxirane)-poly( Ω_methoxy-poly(ethylene glycol) propylmethyl oxalate, Ν-vinylmethyl acetamide, methyl methacrylate, triethylene glycol dimethacrylate, 2- Hydroxy_4_acryloxyethoxybenzophenone, phthalocyanine blue, 2,2,-azobis(2,4-dimethylvaleronitrile) and dbe 712 (optionally containing allyloxy) Ethanol) is combined to thereby produce a polymerizable oxalate hydrogel contact lens precursor composition. In one embodiment, the above method comprises the following relative amounts of components: about 28% by weight alpha-omega- Bis(methylpropoxymethoxyethyliminocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-曱Oxy-poly (ethylene Alcohol) propylmethyl oxime), about 3 7% by weight of Ν-vinylmethyl acetamide, about 13.5% by weight of 甲基S曰 methacrylate, about 16% (%) Weight ratio) triethylene glycol dimethacrylate, about 7% by weight of 2-hydroxy-4-propenyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue , about 0.4% by weight of 2,2,-azobis(2,4•dimethylvaleronitrile) and about 20% DBE 712 (including allyloxyethanol as appropriate). In an embodiment, the combining step results in the formation of a component combination 'and the method further comprises combining the mixed components to form a mixture 121841.doc -18-200813102. In another embodiment, the method further comprises filtering the mixture. In another embodiment, the method comprises polymerizing a polymerizable lens precursor composition to form a pre-extracted polymeric oxygenated hydrogel contact lens. In another embodiment, the method further comprises placing the polymerizable lens precursor composition in a non-polar resin contact lens mold prior to the polymerizing step.
在另一實施例中,前述方法包括萃取預萃取之聚合隱形 眼鏡以形成不存在可萃取組份之經萃取聚合眼鏡產物,且 使經萃取之聚合眼鏡產物水合以形成矽氧水凝膠隱形眼 鏡0 在另一態樣,本發明提供一種改良用於矽氧水凝膠隱形 眼鏡製備中之二甲基矽氧烷-氧化乙烯嵌段共聚物的效能 之方法。該方法包含將約〇1重量%至約1〇重量。义之烯丙氧 基乙醇添加至二甲基矽氧烷_氧化乙烯嵌段共聚物中之步 驟以提供用於製備矽氧水凝膠隱形眼鏡產物之烯丙氡基乙 醇_二甲基矽氧烷氧化乙烯嵌段共聚物。 用於添加步驟中之稀丙氧基乙醇之量較佳有效產生膨服 係數在約G.9G至約^0(諸如約Q %至社Q5)之範圍内的經 t取水切氧水凝膠隱形眼鏡產物。在至少-實施例中, 膨脹係數為約〇·98至約1〇2。 本發明之眼鏡、目尽於太^ 由以下"同物、組合物及方法之其他實施例 田从下描述、圖示、杳& ^丄 實例及申請專利範圍顯而易見。如由 上及以下描述可暸龃 瞭解本文所述之各個及每一特徵及該 121841.doc -19- 200813102 等特徵中之兩者或兩者以上之各個及每—組合均包括在本 發明之範彆内,其限制條件為該組合中所包括之特徵彼此 -致。此外’任何特徵或特徵組合可特定排除在本發明之 任何實施例之外。尤其當結合隨附實例及圖示考慮日^,本 發明之其他態樣及優勢在以下實施方式及中請專利範 闡明。 【實施方式】 本發明現將在下A中更全面地描述。然而,本發明可以 多種不同形式具體化,且不應理解為限於本文所提出之實 施例,·相反,提供該等實施例以使本揭示案詳盡且完整^ 且對熟習此項技術者完全傳達本發明之範疇。 定義 須注意,除非上下文另外明確指示,否則如本說明書中 所用之單數形式"一"及"該"包括複數指示物。因此,舉例 而言’提及|,隱形眼鏡"包括單一眼鏡以及兩個或兩個以上 相同或不同之眼鏡,提及"前驅體組合物"係指單一組合物 以及兩種或兩種以上相同或不同之組合物,及其類似物。 在描述且主張本發明時,以下術語將根據下文所述之定 義來使用。 如本文所用之術語,,水凝膠”係指通常為聚合物鏈網路或 基質之能夠在水中膨脹或遇水膨脹之聚合物質。網路或基 質可交聯或可不交聯。水凝膠係指遇水可膨脹或遇水膨脹 之聚a物貝,包括隱形眼鏡。因此,水凝膠可⑴未經水合 且遇水可膨脹,或(ii)部分水合且遇水膨脹,或(丨⑴完全水 121841.doc -20- 200813102 合且遇水膨脹。 如(例如)"經取代之烷基”中之術語,,經取代,,係指經一或 多個非干擾取代基取代之部分(例如烷基),該等取代基諸 如(但不限於)CrC8環烷基(例如環丙基、環丁基及其類似 • 物)、鹵基(例如氟基、氯基、溴基及碘基)、氰基、烷氧 基、低碳苯基、經取代之苯基及其類似物。對於苯環上之 取代而言,取代基可在任何方位上(亦即鄰、間或對)。 術語”石夕氧水凝膠”或,,矽氧水凝膠物質”係指包括矽(Si) 〇 組份或矽氧組份之特定水凝膠。舉例而言,矽氧水凝膠通 常係藉由將含矽物質與習知親水性水凝膠前驅體組合來製 備。矽氧水凝膠隱形眼鏡為包含矽氧水凝膠物質之隱形眼 鏡,包括矯正視力之隱形眼鏡。矽氧水凝膠隱形眼鏡之特 性不同於習知之水凝膠基眼鏡。 ’’含矽氧組份,,為在單體、大分子單體或預聚物中含有至 少-個[-Si-O-Si]鍵聯之組份,#中各矽原+視情況可具有 一或多個可相同或不同之有機基團取代基(Rl、R2)或經取 U 代之有機基團取代基,例如-SiRihO-。 本文所用之術語”鍵聯劑”係指用以鍵聯互連部分之原子 :或原子集合,諸如聚合物末端及重複單元嵌段。鍵聯劑部 : >可為水解穩定的或τ包括生理學上彳水解或可酶促降解 之鍵聯。較佳鍵聯劑為水解穩定的。 可认或視情況”意謂隨後所述之事件可能發生或可能 不發生,以使得此描述包括事件發生之情況及事件不發生 之情況。 121841.doc 21- 200813102 例如在提及諸如鍵聯劑中具有特定原子長度(例如長度 在2至50個原子範圍内)之原子集合時,術語,,長度,,係基於 原子集合之最長鏈中的原子數目,而與取代基無關。舉例 而5,由於氫原子為碳上之取代基且在鏈之近似總體長度 中不考慮,因此認為-CHaCH2·具有兩個碳原子之長度,即 使各亞甲基自身含有總共三個原子。類似地,認為鍵聯 劑-0-C(0)-CH2CH2C(0)NH-具有由下劃線指示之6個原子 的鏈長度。 在本發明聚合物之情形下的”分子質量”係指聚合物之標 稱平均分子質量,it常藉由尺寸排阻層析法、光散射技術 或在1,2,4-二氯苯中之内在速度測定法來測定。在聚合物 情形下之分子量可表述為數量平均分子量或重量平均分子 量,且在廠商供應之物質的情況下,將視供應商而定。若 並非以封裝物質形式提供,則任何該等分子量測定之基礎 均可易於由供應商提供。通常本文提及之大分子單體或聚 合物之分子量在本文中係指重量平均分子量。數量平均分 子量及重量平均分子量之分子量測定均可使用凝膠滲透層 析技術或其他液相層析技術來量測。亦可使用其他量測分 子量值之方法,諸如使用端基分析或量測依數性(例如凝 固點下降、沸點升高或滲透壓)來測定數量平均分子量, 或使用光散射技術、超速離心法或黏度測定法來測定重量 平均分子量。 親水性聚合物之”網路”或"基質"通常意謂在聚合物鏈之 間由共價鍵或物理鍵(例如氫鍵)形成之交聯。 121841.doc -22· 200813102 π非干擾性取代基,’為存在於分子中時通常與同一分子中 所含之其他官能基不反應之彼等基團。 ’’親水性π物質為喜水性物質。該等化合物對水具有親矛 力且常帶電或具有吸引水之極性側鏈基團。 。 本發明之”親水性聚合物"定義為能夠在水中膨服但 在水中可溶之聚合物。 @ Ο "親水性組份"為可為或可不為聚合物之親水性物質。親 水性組份包括在與剩餘反應性組份組合時能夠對所得水: 眼鏡提供至少約20%(例如至少約25%)之水含量的:7等二 水性組份。 ” 如本文所用之,,眼睛上相容之矽氧水凝膠隱形眼鏡”係指 可配戴於人眼上而人不經歷或報導實質性不適(包括眼^ 刺激及類似不適)的梦氧水凝膠隱形眼鏡。眼睛上相容: 矽氧水凝膠隱形眼鏡具有眼用可接受之表面可濕性,且通 常不引起顯著角膜腫脹、角膜脫水("乾眼病,,)、上方角: 上皮弓狀病變("SEAL”)或其他顯著不適或與該等病相 關。 ^ ”實質上”或"基本上”或"約,,意胃幾乎全部或完全,例如 某一給定量之95%或95%以上。 /烧基"係指長度通常在約ι20個原子範圍内之煙鍵。 =等輕鏈較佳但並非必需飽和,且雖然通常直鍵較佳,但 可為支鏈或直鏈。例示性烧基包括甲基、乙基、丙基、丁 :戊基、曱基丁基、乙基丙基、3_甲基戊基及類似 燒基1提及三個或三個以上碳原子時,如本文所用之 121841.doc -23- 200813102 烷基π包括環烷基。 ’’寡聚物’’為由有限數目之單體亞單元組成之分子,且通 常由約2至約8個單體亞單元組成。 ’’低碳烷基”係指含有1至6個碳原子之烷基,且可為直鏈 或支鏈,例如甲基、乙基、正丁基、異丁基、第三丁基。In another embodiment, the foregoing method comprises extracting a pre-extracted polymeric contact lens to form an extracted polymeric lens product in the absence of an extractable component, and hydrating the extracted polymeric lens product to form a helium oxygen hydrogel contact lens In another aspect, the present invention provides a method of improving the efficacy of a dimethyloxane-ethylene oxide block copolymer for use in the preparation of a hydrogel contact lens. The method comprises from about 1% by weight to about 1% by weight. a step of adding allylicoxyethanol to a dimethyloxane-ethylene oxide block copolymer to provide an allyl mercaptoethanol-dimethyloxoxime for preparing a hydroxyl hydrogel contact lens product Alkylene oxide block copolymer. The amount of diloxypropoxyethanol used in the addition step is preferably effective to produce a t-water-cut oxygen hydrogel having a swelling coefficient in the range of from about G.9G to about 0 (such as from about Q% to Q5). Contact lens products. In at least embodiment, the coefficient of expansion is from about 98 98 to about 1 〇 2 . The spectacles of the present invention are intended to be exemplified by the following "combination, composition, and other embodiments of the method. The following description, the drawings, the 。& It is to be understood that the individual and each feature described herein, and each of the two or more features of the features, such as 121841.doc -19-200813102, and each of the combinations are included in the present invention. Within the scope, the constraints are that the features included in the combination are mutually exclusive. Furthermore, any feature or combination of features may be specifically excluded from any embodiment of the invention. In particular, other aspects and advantages of the present invention are set forth in the following embodiments and in the claims. [Embodiment] The present invention will now be described more fully in the following A. However, the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Instead, the embodiments are provided so that this disclosure will be thorough and complete and fully conveyed to those skilled in the art. The scope of the invention. DEFINITIONS It should be noted that the singular forms """ &""""""" Thus, for example, 'reference|, contact lens" includes a single eyeglass and two or more identical or different glasses, reference to "precursor composition" refers to a single composition and two or two The same or different compositions above, and analogs thereof. In describing and claiming the present invention, the following terms will be used in accordance with the definitions set forth below. As used herein, the term "hydrogel" refers to a polymeric material that is typically a polymer chain network or matrix capable of swelling or swelling with water. The network or matrix may or may not be crosslinked. A poly-a shell that is water-swellable or water-swellable, including contact lenses. Therefore, a hydrogel may (1) be unhydrated and swellable with water, or (ii) partially hydrate and expand with water, or (丨(1) Complete water 121841.doc -20- 200813102 Combined with water swelling. As the term, for example, "substituted alkyl,", substituted, is substituted by one or more non-interfering substituents. Part (eg, alkyl) such as, but not limited to, CrC8 cycloalkyl (eg, cyclopropyl, cyclobutyl, and the like), halo (eg, fluoro, chloro, bromo and Iodo), cyano, alkoxy, lower phenyl, substituted phenyl and the like. For substitution on the phenyl ring, the substituent can be in any orientation (ie, ortho, in between, or in the opposite). The term "Shixi oxygen hydrogel" or "hydroxyl hydrogel material" is meant to include bismuth (Si) a specific hydrogel of a bismuth component or a bismuth component. For example, a hydrazine hydrogel is usually prepared by combining a hydrazine-containing substance with a conventional hydrophilic hydrogel precursor. A contact lens is a contact lens comprising a silicone hydrogel material, including a contact lens for correcting vision. The characteristics of a silicone hydrogel contact lens are different from those of conventional hydrogel-based glasses. ''Oxygen-containing component, In order to contain at least one [-Si-O-Si] linkage component in a monomer, a macromonomer or a prepolymer, each of the oxime in # may have one or more of the same or different The organic group substituent (R1, R2) or the substituted organic group substituent, for example, -SiRihO-. The term "bonding agent" as used herein refers to an atom used to bond the interconnecting moiety: or A collection of atoms, such as polymer ends and repeating unit blocks. Bonding agent: > may be hydrolytically stable or tau include physiologically hydrolyzed or enzymatically degradable linkages. Preferred linkages are hydrolytically stable. "recognised or as appropriate" means that the events described later may or may not occur, so that this The description includes the occurrence of the event and the occurrence of the event. 121841.doc 21- 200813102 For example, when referring to a collection of atoms having a specific atomic length (for example, a length ranging from 2 to 50 atoms) in a bonding agent, the term , , length, based on the number of atoms in the longest chain of the set of atoms, independent of the substituent. For example, 5, since the hydrogen atom is a substituent on carbon and is not considered in the approximate overall length of the chain, it is considered - CHaCH2· has a length of two carbon atoms, even though each methylene group itself contains a total of three atoms. Similarly, the linking agent-0-C(0)-CH2CH2C(0)NH- is considered to have 6 underlines The chain length of an atom. The "molecular mass" in the context of the polymer of the invention refers to the nominal average molecular mass of the polymer, which is often by size exclusion chromatography, light scattering techniques or at 1, 2, 4 - Intrinsic velocity measurement in dichlorobenzene. The molecular weight in the case of a polymer can be expressed as a number average molecular weight or a weight average molecular weight, and in the case of a material supplied by a manufacturer, it will depend on the supplier. The basis for any such molecular weight determination can be readily provided by the supplier if it is not provided in the form of an encapsulating material. Generally, the molecular weight of a macromonomer or polymer as referred to herein means the weight average molecular weight. The molecular weight determination of the number average molecular weight and the weight average molecular weight can be measured using a gel permeation chromatography technique or other liquid chromatography techniques. Other methods of measuring molecular weight values may also be used, such as using end group analysis or measurement dependencies (eg, freezing point drop, boiling point increase, or osmotic pressure) to determine the number average molecular weight, or using light scattering techniques, ultracentrifugation, or Viscosity measurement to determine the weight average molecular weight. The "network" or "matrix" of a hydrophilic polymer generally means cross-linking formed by covalent bonds or physical bonds (e.g., hydrogen bonds) between polymer chains. 121841.doc -22· 200813102 π non-interfering substituents, 'are those groups which are normally not reactive with other functional groups contained in the same molecule when present in the molecule. The hydrophilic π substance is a water-repellent substance. These compounds have a pro-spraying effect on water and are often charged or have polar side chain groups that attract water. . The "hydrophilic polymer" of the present invention is defined as a polymer which is capable of swelling in water but soluble in water. @ Ο "Hydrophilic component" is a hydrophilic substance which may or may not be a polymer. Hydrophilic The sexual component comprises, when combined with the remaining reactive components, capable of providing at least about 20% (e.g., at least about 25%) water content to the resulting water: spectacles: a quaternary component such as 7 or the like." As used herein, "Oxygen-compatible hydrogel contact lenses" refers to dream oxygen hydrogel contact lenses that can be worn on the human eye without human experience or substantial discomfort (including eye irritation and similar discomfort). Compatibility: Hydroxyl hydrogel contact lenses have an ophthalmically acceptable surface wettability and usually do not cause significant corneal swelling, corneal dehydration ("dry eye disease,), upper angle: epithelial arch lesion (" ;SEAL") or other significant discomfort or related to these diseases. ^ "Substantially" or "basically" or "about," means that the stomach is almost all or completely, such as 95% or more of a certain given amount. / Burning base is usually about ι20 in length. Smoke bonds in the atomic range. = The light chain is preferably but not necessarily saturated, and although the direct bond is generally preferred, it may be branched or straight chain. Exemplary alkyl groups include methyl, ethyl, propyl, and butyl groups. When pentyl, nonylbutyl, ethylpropyl, 3-methylpentyl and similar alkyl 1 refer to three or more carbon atoms, as used herein, 121841.doc-23-200813102 alkyl π includes a cycloalkyl group. ''Oligomer'' is a molecule composed of a limited number of monomeric subunits, and usually consists of from about 2 to about 8 monomeric subunits. ''Lower alkyl' refers to An alkyl group having 1 to 6 carbon atoms, and may be a straight chain or a branched chain such as a methyl group, an ethyl group, a n-butyl group, an isobutyl group, or a t-butyl group.
認為如本文所用之特定批次聚氧化烯矽氧(例如矽油)之”效 能”為其在給定濃度(且所有其他因數均相同)下提供具有所 用隱形眼鏡模具直徑〇.98至1()2倍範圍内之直徑的最終經 萃取水合眼鏡產物之能力。最終眼鏡產物之眼鏡直徑減: 愈大,則聚氧化烯矽氧之”效能,,愈大。 如本文所用之術語"膨脹係數"係指水切氧水凝膠隱形 眼鏡之外徑與心形成隱形眼鏡模具之眼鏡形成表面的一 形眼鏡模具插入物之外徑的比率。因此,當隱形眼 鏡模具插入物具有142 mm 眼鏡具有14.2_之外,,時,障广夕乳水凝膠隱形 1 〇〇。 二夺L、形眼鏡之膨脹係數為 其他定義亦可見於以下部分中。 本發明之綜述 如先前所論述,本文提供之 王目,7成03 夕#分基於以下發 現即.可使用避免與極性樹 複雜且昂貴之聚人後…關之問S、避免對 來σ後耘序之需要且解決盥取入 相關之問題的方法來製備眼睛上相容之石夕、二…間劑ΙΡΝ 鏡。令人驚奇地,已發現藉由將特乳水凝膠隱形眼 氧水凝谬隱形眼鏡之調配物 、广入用以製造石夕 自所得經模製之隱形 121841.doc -24- 200813102 眼鏡產物移除㈣崎(與其他未反叙崎—起),藉此 可產生眼睛上相容之隱形眼鏡產物。 特定言之,本發明者已發現一種藉由將相對大量之一或 多種可移除物質併入可聚合矽氧隱形眼鏡前驅體組合物中 來提供眼睛上相容之矽氧水凝膠隱形眼鏡的方法。雖然該 等物質賦予所得最終隱形眼鏡產物所需之特徵,但其實際 上係(例如)藉由萃取自其中移除以提供經萃取之隱形眼鏡 產物,其接著經水合以產生具有眼用可接受之表面可濕性 、及如本文所述之其他有盈特徵之最終矽氧水凝膠隱形眼 鏡產物。 在一相關態樣中,纟文提供一種改良用於石夕氧水凝膠隱 形眼鏡製備中之二甲基石夕氧I氧化乙烯嵌段共聚物效能 的方法其中忒方法包含將約0· 1重量。/。至約丨〇重量%之烯 丙氧基乙醇添加至二甲基石夕氧^氧化乙烯嵌段共聚物中 以提供用於製備矽氧水凝膠隱形眼鏡產物之烯丙氧基乙 醇_二甲基矽氧烷氧化乙烯嵌段共聚物。已有利地發現, 例如在與可聚合隱形眼鏡前驅體組合物之其他組份混合之 前向二甲基矽氧烷-氧化乙烯嵌段共聚物中添加烯丙氧基 乙醇有效使得自使用特定批次或貨號或類似之二甲基矽氧 烷-氧化乙烯嵌段共聚物或其類似物所得之任何潛在不利 作用”正規化",以藉此提供對一或多種眼鏡尺寸或各種物 理特性變化具有可接受之耐受性的最終眼鏡產物。 在以下部分詳細描述且例示本發明之此等及其他重要態 樣。 Μ 121841.doc 25- 200813102 可聚合矽氧水凝膠隱形眼鏡前驅體組合物之組份 本發明之矽氧水凝膠隱形眼鏡通常自本文稱為”可聚合 矽氧水凝膠隱形眼鏡前驅體組合物”或”前驅體組合物,,之 物質而產生。前驅體組合物為用以製備石夕氧水凝膠隱形眼 • 豸之各種試劑的混合物,亦即在反應(在本發明之狀況下 為聚合反應)前之反應混合物。 ' 本發明之前驅體組合物通常包含至少以下組份:⑴至少 約25重量%之反應性含氟二甲基丙烯醯基矽氧大分子單 -·體,且較佳約25重量%至約35重量%之該反應性含氟二甲 基丙烯醯基矽氧大分子單體,(ii)至少約45重量%之不含矽 之單體組合物,及(iii)聚氧化烯矽氧可萃取組份。不含矽 之單體組合物包括親水性含乙烯基單體、丙烯酸系單體及 丙烯酸酯官能化之氧化乙烯募聚物。 反應性含氟丙締醯基發氧大分子單體 如上所述,自包含反應性含氟丙烯醯基矽氧大分子單體 《前驅體組合物製備本發明之矽氧隱形眼鏡。雖然並非必 需,但大分子單體通常表示為矽氧烷嵌段共聚物或三嵌段 \ 5物亦即由兩個或二個不同之石夕氧烧聚合物“後段” ' 或區奴組成且在線性大分子單體之一個末端具有至少一個 ' &應性丙烯醯基且較佳在兩末端均具有反應性丙稀醯基的 大分子單體。 用於本發明之含氟矽氧大分子單體通常具有至少一個氟 取代基。氟取代基較佳存在於嵌段聚合物之重複單元之一 者上,以使得總體大分子單體具有一個以上氟原子。較佳 121841.doc -26 - 200813102 之含氟大分子單體為具有約1重量%至約^ 〇重量%之氟且較 佳具有約1重量%至約5重量❶/。之氟的彼等大分子單體。 一般而言’共聚物或三嵌段聚合物之嵌段之至少一者具 有重複單元-[Si(CH3)2〇]-,而至少一個其他嵌段包含矽原 子’其具有含氟取代基、較佳具有氟烷基取代基、最佳其 中烧基為低碳烷基。在大分子單體為三嵌段聚合物之情況 下’較佳一個嵌段具有重複單元4Si(CH3)2〇]_,第二嵌段 為其中矽原子具有氟烷基取代基之嵌段,最佳其中烷基為 低破烧基,且第三嵌段具有經包含親水性組份(例如短聚 乙二醇(PEG)鏈(CH2CH2〇)p)之烷基取代之矽原子。以上提 及之第三嵌段較佳包含經共價連接至聚乙二醇之伸烷基鍵 聯劑取代之矽原子,其中PEG視情況經封端基團(諸如低碳 烧基或苯甲基)封端且伸烷基鍵聯劑部分最接近矽原子。 聚乙二醇區段通常具有約1至約25個亞單元,且更佳約2至 約12個亞單元。PEG區段最佳具有約4至約1〇個亞單元。 以上提及之三個矽氧烷嵌段可呈任何次序。 上文之例示性矽氧大分子單體描述於美國專利第 6,867,245號及國際專利公開案第w〇 20〇6/〇26474號中, 該兩專利之内容均以引用的方式併入本文中。其中所述之 任一或多個矽大分子單體適用於本發明之組合物及隱形眼 鏡中,且尤其是彼等含有(_si〇_)嵌段之矽大分子單體,其 中夕原子具有一取代基,該取代基為經一或多個氟原子取 代之伸烧基或其他烴鏈。 舉例而言,代表性矽氧大分子單體包含以下三嵌段之重 121841.doc -27- 200813102 複單元:The "efficiency" of a particular batch of polyoxyalkylene oxide (e.g., eucalyptus) as used herein is believed to provide a contact lens mold diameter of 98.98 to 1 () at a given concentration (and all other factors being the same). The ability of the final extracted hydrated lens product in a diameter within 2 fold. The diameter of the final glasses product is reduced: the larger the polyoxyalkylene is, the greater the efficiency, the larger the term "expansion coefficient" as used herein refers to the outer diameter and heart of the water-cut oxygen hydrogel contact lens. The ratio of the outer diameter of the lens-shaped insert of the lens forming surface forming the contact lens mold. Therefore, when the contact lens mold insert has a 142 mm eyeglass having a 14.2_, the barrier is invisible 1 〇〇. The expansion coefficient of two L-shaped glasses is also found in the following sections. Summary of the Invention As previously discussed, the Wang Wang, 7 to 03 夕# points provided in this article are based on the following findings. Use the method of avoiding complicated and expensive polar trees with the polar tree... to avoid the need for the post-sequence and to solve the problem of taking in the relevant problems to prepare the compatible Shishi, Er... ΙΡΝ 镜 。 。 。 令人 令人 令人 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 841 - 200813102 Eyewear products Remove (four) Saki (with other non-reverse kiosks), thereby producing a compatible contact lens product on the eye. In particular, the inventors have discovered that one can be removed by relatively large amounts or ones. A method of incorporating a substance into a polymerizable silicone contact lens precursor composition to provide an ophthalmically compatible hydroxyl hydrogel contact lens. While such materials impart the desired characteristics to the resulting final contact lens product, in practice The contact lens product is provided, for example, by extraction therefrom to provide an extracted contact lens product, which is then hydrated to produce a final enamel having an ophthalmically acceptable surface wettability, and other gain characteristics as described herein. Oxygen hydrogel contact lens product. In a related aspect, the invention provides a method for improving the performance of dimethyl oxaxiglass I oxyethylene block copolymer used in the preparation of a lithothermic hydrogel contact lens. The hydrazine method comprises adding from about 0.1% by weight to about 5% by weight of allyloxyethanol to the dimethyl oxalate ethylene oxide block copolymer to provide a hydroxyl hydrogel for use in the preparation of a helium oxygen hydrogel. Contact lens Isopropoxyethanol dimethyl oxa oxide oxyethylene block copolymer. It has been advantageously found, for example, to dimethyl methoxyoxane prior to mixing with other components of the polymerizable contact lens precursor composition. - The addition of allyloxyethanol to the ethylene oxide block copolymer is effective to achieve any potential adverse effects from the use of a particular batch or grade or similar dimethyloxane-oxyethylene block copolymer or analog thereof" Normalize " to thereby provide a final lens product that is acceptable to one or more eyeglass sizes or variations in various physical properties. These and other important aspects of the invention are described and illustrated in detail in the following section. Μ 121841.doc 25- 200813102 Composition of Polymerizable Oxygenated Hydrogel Contact Lens Precursor Compositions The hydroxyl hydrogel contact lenses of the present invention are generally referred to herein as "polymerizable silicone hydrogel contact lens precursors" The composition "or" precursor composition is produced. The precursor composition is a mixture of various reagents for preparing the invisible eye of the australis hydrogel, that is, in the reaction (in the state of the present invention) The reaction mixture before the polymerization reaction. The precursor composition of the present invention usually comprises at least the following components: (1) at least about 25% by weight of a reactive fluorine-containing dimethyl methacryloyloxyl macromonomer mono-body And preferably from about 25% by weight to about 35% by weight of the reactive fluorine-containing dimethyl propylene fluorenyl siloxane macromonomer, and (ii) at least about 45% by weight of the quinone-free monomer composition, And (iii) a polyoxyalkylene oxime extractable component. The ruthenium-free monomer composition comprises a hydrophilic vinyl-containing monomer, an acrylic monomer, and an acrylate functionalized ethylene oxide polymer. Fluoropropyl thiol oxy macromonomer As described above, the self-contained reactive fluoropropenyl fluorenyloxy macromonomer "precursor composition" is used to prepare the oxime contact lens of the present invention. Although not essential, the macromonomer is usually represented by a siloxane block. The copolymer or triblock \5 is also composed of two or two different oxaxy-oxygenated polymers "post-stage" or zone slaves and has at least one at one end of the linear macromonomer. The propylene oxime group and preferably the macromolecular monomer having a reactive acrylonitrile group at both ends. The fluorine-containing fluorenyloxy macromonomer used in the present invention usually has at least one fluorine substituent. The fluorine substituent is preferably. Existing on one of the repeating units of the block polymer such that the overall macromonomer has more than one fluorine atom. Preferably, the fluorine-containing macromonomer of 121841.doc -26 - 200813102 has about 1% by weight to A macromonomer of about 5% by weight of fluorine and preferably having from about 1% by weight to about 5% by weight of fluorine. Generally, at least one of the blocks of the 'copolymer or triblock polymer. Have a repeating unit -[Si(CH3)2〇]-, and at least The other blocks comprise a halogen atom which has a fluorine-containing substituent, preferably has a fluoroalkyl substituent, preferably wherein the alkyl group is a lower alkyl group. In the case where the macromonomer is a triblock polymer' Preferably, one block has a repeating unit 4Si(CH3)2〇]_, and the second block is a block in which a halogen atom has a fluoroalkyl substituent, preferably wherein the alkyl group is a low-cracking group, and the third inlay The segment has a ruthenium atom substituted with an alkyl group comprising a hydrophilic component (eg, a short polyethylene glycol (PEG) chain (CH2CH2 〇) p). The third block mentioned above preferably comprises covalently attached to the poly A ruthenium atom substituted with an alkyl group-bonding agent of ethylene glycol, wherein PEG is optionally blocked with a blocking group such as a lower alkyl group or a benzyl group and the alkyl group-bonding moiety is closest to the ruthenium atom. The polyethylene glycol segment typically has from about 1 to about 25 subunits, and more preferably from about 2 to about 12 subunits. The PEG segment preferably has from about 4 to about 1 unit subunit. The three oxoxane blocks mentioned above may be in any order. The above-described exemplary aerobic macromonomers are described in U.S. Patent No. 6,867,245, the disclosure of which is incorporated herein by reference. Any one or more of the macromonomers described therein are suitable for use in the compositions and contact lenses of the present invention, and especially those having a (_si〇_) block of a macromonomer having A substituent which is an exothermic or other hydrocarbon chain substituted with one or more fluorine atoms. For example, a representative alkoxy macromonomer comprises the weight of the following triblocks. 121841.doc -27- 200813102 Complex unit:
其中Rl、R2、R3、R4、RdR6各自獨立地選自_H、低碳烷 圍内,P(氧化乙烯重複單元之數目)在約1至約25之範圍 内,且Y為Η、低碳烷基或苯曱基。變數n、m&h對應於各 敗段之重複單7〇的數目;且各自獨立地在約3至約2〇〇之範 圍内。較佳共價連接至各嵌段n、m&h之Si_〇的至少一個 R基為低碳烷基,且甚至更佳為曱基。亦即,較佳地,在 嵌段η中,1^或化2中之至少一者為甲基;在嵌段m中,化或 R4中之至少一者為甲基;且在嵌段h中,r5或尺6中之至少 一者為甲基。較佳地,嵌段n、h中之至少一者具有重 複單元-Si(CH3)2〇-,其中共價連接至矽之兩個r基為甲 基。例如,較佳之大分子單體包含以下聚合物三嵌段:Wherein R1, R2, R3, R4, and RdR6 are each independently selected from the group consisting of _H and a lower alkyl group, and P (the number of ethylene oxide repeating units) is in the range of from about 1 to about 25, and Y is ruthenium and low carbon. Alkyl or phenyl fluorenyl. The variables n, m &h correspond to the number of repeats 7 各 of each defeated segment; and are each independently within the range of about 3 to about 2 。. Preferably, at least one R group of the Si_〇 which is covalently bonded to each block n, m&h is a lower alkyl group, and even more preferably a fluorenyl group. That is, preferably, in the block η, at least one of 1 or 2 is a methyl group; in the block m, at least one of the group or R4 is a methyl group; and in the block h In the middle, at least one of r5 or the ruler 6 is a methyl group. Preferably, at least one of the blocks n, h has a repeating unit -Si(CH3)2?-, wherein the two r groups covalently bonded to the oxime are methyl. For example, preferred macromonomers comprise the following polymer triblocks:
其中Ri、R3及R5各自獨立地選自-H、低碳烷基、氟烷基 (包括二氟烷基及三氟烷基)及(-CHOJOCH^CHdpO-Y,其 中〇在1至10之範圍内,p(氧化乙烯重複單元之數目)在約2 至約12之範圍内,且Y為Η、低碳烷基或苯曱基,其限制 條件為⑴I、R3及Rs中之至少一者為_Η或低碳烷基, 121841.doc -28- 200813102 (··) 1 R3及R5中之至少一者為氟焼基,且(出)1、以3及 中之至少一者為(-ch2)0(〇ch2ch2)p〇_y,其中特定變數之 值如上所述。用於本發明之一種尤其較佳大分子單體t 3以上一欣奴聚合物結構之大分子單體,其中Rl為曱基, R3 為氟烷基,且 R5 為(-CH2)0(OCH2CH2)pO-Y,且 η在 50 至 . 200之範圍内,茁在2至50之範圍内,且h在1至15之範圍 • 内。 在提及含氟丙烯醯基矽氧大分子單體時,大分子單體之 f; sl-0-sla卩为通《佔矽氧大分子單體組份之總分子量的約大 於20重量%,例如大於3〇重量%。本發明之矽氧大分子單 體包含丙烯醯基,且較佳具有兩個丙烯醯基,即每一末端 一個’其中丙烯醯基部分之一或多個烯烴碳視情況經有機 基團(諸如烷基)取代。 丙烯醯基部分為衍生自丙烯酸之部分,例如 R7\ /R9 R/c=c\,Wherein Ri, R3 and R5 are each independently selected from -H, lower alkyl, fluoroalkyl (including difluoroalkyl and trifluoroalkyl) and (-CHOJOCH^CHdpO-Y, wherein 〇 is in the range of 1 to 10 In the range, p (the number of ethylene oxide repeating units) is in the range of from about 2 to about 12, and Y is an anthracene, a lower alkyl group or a benzoinyl group, the limitation being at least one of (1) I, R3 and Rs Is _Η or lower alkyl, 121841.doc -28- 200813102 (··) 1 At least one of R3 and R5 is a fluoroindolyl group, and at least one of (out) 1, 3, and 3 is ( -ch2)0(〇ch2ch2)p〇_y, wherein the value of the specific variable is as described above. A macromonomer for use in a particularly preferred macromonomer t 3 or more than a Xinnu polymer structure of the present invention, Wherein R1 is a fluorenyl group, R3 is a fluoroalkyl group, and R5 is (-CH2)0(OCH2CH2)pO-Y, and η is in the range of 50 to 200, 茁 is in the range of 2 to 50, and h is Range of 1 to 15 • Within the reference to the fluoropropenyl fluorenyl oxy macromonomer, the macromonomer f; sl-0-sla 卩 is the "occupying oxime macromonomer component The total molecular weight is greater than about 20% by weight, for example greater than 3 〇 The oxime macromonomer of the present invention comprises an acrylonitrile group, and preferably has two propylene fluorenyl groups, that is, one at each end, wherein one of the propylene sulfhydryl moieties or a plurality of olefin carbons is optionally organic. Substituted by a group such as an alkyl group. The propylene fluorenyl moiety is a moiety derived from acrylic acid, such as R7\ /R9 R/c=c\,
II U ° ’其中在丙烯酸中,、r8及r9各自為 Η。然而,根據本發明,丙烯醯基部分為其中在以上結構 中R9為Η或烷基,較佳為低碳烷基,且心及心各自獨立地 . 為Η、烷基或羧基者,但其限制條件為R7*R8中僅一者可 ▲ 缝基。W為氧或氮。在Μ氮之情況下,相應丙烯醯基 部分稱為丙烯醯胺。在一較佳實施例中,心及以各自為 氫,且R9為低碳烷基,例如甲基、乙基或丙基。&較佳為 曱基,且以上提及之丙烯醯基部分係存在於線性大分子單 121841.doc •29- 200813102 體之兩末端上。在大分子單體所含之各丙烯醯基中,I、 R8及R9之值係獨立的。亦即,對具有一個以上丙烯醯基之 大分子單體而言,各丙烯醯基部分之心、心及心之值係經 獨立選擇。然而’在_較佳實施例中,各丙烯醯基中各 R7、R8及I之值相同,因而大分子單體被視為均雙官能基 者-意謂末端之反應性基團相同。在末端之反應性基團不 相同之情況下,該等大分子單體被視為雜雙官能基者。可 存在於矽氧大分子單體末端上之說明性丙烯醯基可聚合官 能基包括甲基丙烯酸酯基、丙烯醯胺基及甲基丙烯醯胺 基。 合適之含矽氧單體的其他實例為聚矽氧烷基烷基(甲基) 丙烯酸單體,其包括(但不限於)經氟取代之甲基丙烯醯氧 基丙基參(二甲基石夕烧氧基)石夕烧、甲基丙烯酸五甲基二石夕 氧烷基甲酯及甲基二(三甲基矽烷氧基)甲基丙烯醯氧基甲 基石夕燒。 一類適用之含矽氧組份為聚(有機矽氧烷)預聚物,諸如 經氟取代之L雙甲基丙烯醯氧基-丙基聚二甲基矽氧烷。 另一實例為經氟取代之mPDMS (經單曱基丙烯醯氧基丙基 封端之單正丁基封端之聚二甲基矽氧烷)。 刀子早體之碎氧烧聚合物部分(亦即一或多個碎氧燒 聚合物嵌段)通常藉由插入鍵聯劑鍵聯至丙烯醯基末端。 各鍵聯劑通常具有約4個原子至約20個原子之長度,其中 說明性鍵聯劑可包括以下之一或多者:_〇_c(〇)_、 O- ^ -C(〇)-NH. . .〇.C(0)-NH- > -C(0).〇.(CH2)a ^ -C(〇). 121841.doc •30- 200813102 0-(CH2)aNH-C(0)(0)-(CH2)b-〇-(CH2)c-、-〇-C(〇)-〇-(CH2)a- 、-0-C(0)-0-(CH2)aNH-C(0)(0)-(CH2)b及其類似物,其中 a、b及c各自獨立地在1至約10之範圍内。亦即,a、b&c 各自獨立地選自1、2、3、4、5、6、7、8、9及ι〇。鍵聯 劑較佳為直鏈而非支鏈,且視情況含有一或多個雜原子〇 或N。因此,除包含一或多個伸烷基鏈區段以外,鍵聯劑 視情況可含有一或多個選自(例如)羧基、醯胺基、胺基甲 酸酯基及碳酸酯基之官能基。 石夕氧大分子單體組份之分子量通常在約8,000道爾頓 ((1已11:〇11)至約25,000道爾頓之範圍内,且較佳在約1〇,〇〇〇道 爾頓至約20,000道爾頓之範圍内。一種用於本發明之尤其 較佳矽氧烷大分子單體具有約16,000道爾頓之分子量。 一類尤其較佳之矽氧烷大分子單體為具有以下通式之三 嵌段聚合物: 0 ch3 ο ϋ 〒Η3 CS-Λ -ch3 . Si—〇 .1 ch3 ch3 j 與下行結構連續 CH2CH2CF3 續 -Sj—0-|4si-Ο ch3 ch2ch2ch2(〇ch2ch2)poch3 o o /CH3 II || ch3 *Si^~(CH2)3〇(CH2)2〇CNH(CH2)2OC—-i=CH2 CH3 其中n、m、h及p之值如上所述。以上大分子單體稱為心 ω-雙(甲基丙烯酸氧基乙基亞胺基叛基乙氧基丙基)·聚(二 甲基矽氧烷)_聚(三氟丙基甲基矽氧烷)_聚(仍_甲氧基-聚(乙 121841.doc -31 _ 200813102II U ° 'wherein in acrylic acid, r8 and r9 are each Η. However, according to the present invention, the fluorenyl fluorenyl moiety is one in which R9 is fluorene or alkyl, preferably lower alkyl, and the heart and heart are each independently Η, alkyl or carboxyl, but The restriction is that only one of R7*R8 can be sewed. W is oxygen or nitrogen. In the case of hydrazine nitrogen, the corresponding propylene sulfhydryl moiety is referred to as acrylamide. In a preferred embodiment, the core is each hydrogen and R9 is a lower alkyl group such as methyl, ethyl or propyl. & is preferably a fluorenyl group, and the above-mentioned acryl-based moiety is present on both ends of the linear macromonomer 121841.doc • 29-200813102. Among the propylene groups contained in the macromonomer, the values of I, R8 and R9 are independent. That is, for macromonomers having more than one propylene fluorenyl group, the values of the heart, heart and heart of each propylene thiol moiety are independently selected. However, in the preferred embodiment, the values of R7, R8 and I in the respective acrylonitrile groups are the same, and thus the macromonomer is regarded as a homobifunctional group - meaning that the reactive groups at the terminal are the same. Where the reactive groups at the ends are different, the macromonomers are considered to be heterobifunctional. Illustrative acryl-based polymerizable functional groups which may be present at the end of the oxime macromonomer include methacrylate groups, acrylamido groups and methacrylamide groups. Further examples of suitable oxo-containing monomers are polydecyloxyalkyl (meth) acrylate monomers which include, but are not limited to, fluoro substituted methacryloxypropyl thiols (dimethyl) Shi Xi alkoxy, Shi Xizhuo, pentamethyl oxalyl alkyl methacrylate and methyl bis(trimethyl decyloxy) methacryloxymethyl ketone. One type of suitable rhodium-containing component is a poly(organosiloxane) prepolymer such as L bis methacryloxy-propyl polydimethyl decane substituted by fluorine. Another example is a fluorine-substituted mPDMS (mono-n-butyl propyleneoxy propyl-terminated mono-n-butyl-terminated polydimethyl methoxy oxane). The oxy-fired polymer portion of the knives of the knives (i.e., one or more oxy-fired polymer blocks) is typically bonded to the propylene thiol end by insertion of a linking agent. Each of the linking agents typically has a length of from about 4 atoms to about 20 atoms, wherein the illustrative linking agent can include one or more of the following: _〇_c(〇)_, O-^-C(〇) -NH. . . . . . . . (( ( ( ( ( ( ( ( ( ( ( ( ( (0)(0)-(CH2)b-〇-(CH2)c-, -〇-C(〇)-〇-(CH2)a-,-0-C(0)-0-(CH2)aNH -C(0)(0)-(CH2)b and analogs thereof, wherein a, b and c are each independently in the range of from 1 to about 10. That is, a, b&c are each independently selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, and ι. The linking agent is preferably a straight chain rather than a branched chain, and optionally contains one or more heteroatoms 或 or N. Thus, in addition to comprising one or more alkylene chain segments, the linking agent may optionally contain one or more functionalities selected from, for example, a carboxyl group, a guanylamino group, a urethane group, and a carbonate group. base. The molecular weight of the osmolality component is typically in the range of from about 8,000 Daltons ((1:11:11) to about 25,000 Daltons, and preferably about 1 Torr, 〇〇〇Door Up to about 20,000 Daltons. A particularly preferred oxoxane macromer for use in the present invention has a molecular weight of about 16,000 Daltons. A particularly preferred class of oxirane macromonomers has the following Triblock polymer of the general formula: 0 ch3 ο ϋ 〒Η3 CS-Λ -ch3 . Si—〇.1 ch3 ch3 j and continuous structure CH2CH2CF3 continued -Sj—0-|4si-Ο ch3 ch2ch2ch2(〇ch2ch2) Poch3 oo /CH3 II || ch3 *Si^~(CH2)3〇(CH2)2〇CNH(CH2)2OC—i=CH2 CH3 where n, m, h and p have the same values as above. The monomer is called heart ω-bis (oxyethyl imido thioglycol methacrylate) · poly (dimethyl methoxy oxane) _ poly (trifluoropropyl methyl oxa oxide) _ poly (still _ methoxy-poly (B 121841.doc -31 _ 200813102
二醇)丙基曱基矽氧烷)或M3U。在一尤其較佳之實施例 中,η為約121,m為約7·6,h為約4.4,且p為約7 4。M3U 可易於根據國際專利公開案第WO 2006/026474號實例1中 陳述之程序來合成。 本文所提供之可聚合矽氧水凝膠前驅體組合物通常含有 至少約20重量%之含氟丙烯醯基矽氧大分子單體,且較佳 含有至少約25重量%之含氟丙烯醯基矽氧大分子單體。本 發明之組合物較佳含有約25重量%至約4〇重量%之含氟丙 烯醯基矽氧大分子單體,且更佳含有約25重量%至約35重 量%之大分子單體。 無矽氧之單體組合物 人除矽氧大分子單體以外,本發明之眼鏡、眼鏡產物及組 合物進一步包括由大量添加劑組成之無矽單體組份或組合 物不含矽之單體組合物通常包含一種以上親水性化合 親水[生組伤包括在與其他前驅體調配物組份組合時能 夠對所得水合眼鏡提供至少約2〇%(或甚至至少約25%)水 έ畺之彼4組份。以各前驅體組合物組份之分子量計,無 矽之單體組合物(意謂組成單體組合物之各化合物)一般組 成至少約45重量%之眼鏡前驅體組合物。無矽之單體組合 物較佳佔前驅體組合物之約45重量%至55重量%。本發明 之無矽單體組合物排除含有一或多個矽原子之親水性化合 物。因此,本發明之單體組合物在本文中稱為,,不含矽之 組合物”。 可包括在無矽之單體組合物中之單體通常具有至少一個 121841.doc -32- 200813102 可聚合之雙鍵及至少一個親水性官能基。可聚合雙鍵之實 例包括丙烯酸、甲基丙烯酸、乙烯基、〇-乙烯基乙醯基及 N-乙烯基内醯胺、N_乙烯基醯胺基雙鍵及其類似物。該等 親水性單體可為但並非必需為交聯劑。認為作為如上所述 之丙烯醯基部分之子集,,,丙烯酸型,,或”含丙烯酸”或含丙 烯酸酯之單體為含有丙烯酸基團(CR,H=CRCOW)之單體, 其中R為Η或CH3,R,為H、烷基或羰基,且W為0或N。 本發明之親水性組份一般包含以下各不含矽之組份,其 D 中一或多種組份為親水性的··含親水性乙烯基(CH2=CH-) 之單體、丙烯酸系單體及丙稀酸酯官能化之氧化乙烯 (_(〇CH2CH2)n)寡聚物。 說明性丙烯酸系單體包括N,N-二甲基丙稀醯胺(DMA)、 丙烯酸2-羥乙酯、甲基丙烯酸甘油酯、2-羥乙基甲基丙烯 醯胺、甲基丙浠酸、丙浠酸、曱基丙烯酸甲酉旨(MMA)及其 混合物。 如上所述,包括所有個別親水性及非親水性組份之單體 / \ 組合物包含至少約45重量%之前驅體組合物。因此,組成 單體組合物之各組份的重量百分比將在此範圍内變化。單 ; 體組合物較佳佔前驅體組合物之約45重量%至約55重量 % ’且因此’其各組份之重量百分比自前驅體組合物之約 0.05重量%至約40重量%或約〇 〇5重量%至約5〇重量%之間 變化’以達到前驅體組合物之所需總重量百分比。丙烯酸 系單體組份較佳以佔用以製備矽氧眼鏡產物之前驅體組合 物之約7重量%至約20重量❶/❶的量存在,且甚至更佳以佔前 12l841.doc -33- 200813102 驅體組合物之約10重量%至約18重量%的量存在。以總前 驅體調配物計,丙烯酸系單體之說明性重量百分比包括以 下·約 10%、11%、12%、13%、14%、15%、16%、17%或 18%。 如上所述’單體組合物亦包含親水性含乙烯基單體。可 併入本發明之眼鏡物質中的親水性含乙烯基單體包括以下 各物· N-乙烯基内醢胺(例如N-乙稀基吼洛唆_ (NVP))、 N-乙烯基-N-甲基乙醯胺(VMA)、N-乙烯基-N·乙基乙醯 胺、N-乙烯基-N-乙基甲醯胺、N-乙浠基甲醯胺、胺基甲 酸N_2_羥乙基乙烯酯、N-羧基-β-丙胺酸N-乙烯酯。一種尤 其較佳之含乙烯基單體為Ν-乙烯基-Ν-甲基乙醢胺 (VMA)。VMA之結構對應於CH3C(0)N(CH3)-CH=CH2。 單體組合物之含乙烯基單體組份較佳以佔用以製備矽氧 眼鏡產物之前驅體組合物約20重量%至約5〇重量%範圍内 之量存在,且甚至更佳以佔前驅體組合物約25重量%至約 42重量%範圍内之量存在。含乙烯基單體之代表性重量包 括以下各重量:前驅體組合物之約25重量%、26重量%、 27重1 %、28重量%、29重量%、30重量%、3 1重量%、32 重量%、3 3重量%、3 4重量%、3 5重量%、3 6重量%、3 7重 量%、38重量%、39重量%、40重量%、41重量%或42重量 % 〇 單體組合物額外包含丙烯酸酯官能化之氧化乙烯寡聚 物’亦即具有約2至約8個連續氧化乙烯(ch2CH20-)單體亞 單元且末端經反應性基團(諸如丙稀酸酯基)官能化之氧化 121841.doc -34- 200813102 乙烯寡聚物。募聚物之一或兩端可經丙烯酸酯基官能化。 實例包括與一或多莫耳當量之能夠將一或多個反應性丙烯 酸S曰基引入养t物之 或兩個末端的試劑(例如曱基丙烯 酸異氰酸酯基乙酯(nIEMn)、甲基丙烯酸酐、甲基丙浠醯 基氣或其類似物)反應以產生在一或兩個末端上具有丙浠 酸基之氧化乙烯寡聚物的氧化乙烯募聚物。代表性募聚物 : 由以下通式描述: R7\ = /R9Glycol) propyl decyl oxane or M3U. In a particularly preferred embodiment, η is about 121, m is about 7.6, h is about 4.4, and p is about 7.4. The M3U can be easily synthesized according to the procedure set forth in Example 1 of International Patent Publication No. WO 2006/026474. The polymerizable hydroxyl hydrogel precursor compositions provided herein typically comprise at least about 20% by weight of a fluoropropenyl fluorene macromonomer, and preferably at least about 25% by weight of a fluoropropenyl group. Oxygen macromonomer. The compositions of the present invention preferably comprise from about 25% to about 4% by weight of the fluorine-containing fluorenylfluorenyloxy macromonomer, and more preferably from about 25% to about 35% by weight of the macromonomer. Non-aerobic monomer composition The glasses, lens products and compositions of the present invention, in addition to the oxime macromonomer, further comprise a ruthenium-free monomer component or a composition-free monomer comprising a plurality of additives. The composition typically comprises more than one hydrophilic combination of hydrophilicity [the biopsy includes the ability to provide at least about 2% (or even at least about 25%) of the water hydration to the resulting hydrated eyeglass when combined with other precursor formulation components. 4 components. The inorganic monomer composition (meaning each compound constituting the monomer composition) generally comprises at least about 45% by weight of the lens precursor composition, based on the molecular weight of each precursor composition component. The inert monomer composition preferably comprises from about 45% to about 55% by weight of the precursor composition. The ruthenium-free monomer composition of the present invention excludes a hydrophilic compound containing one or more ruthenium atoms. Thus, the monomer composition of the present invention is referred to herein as a composition free of ruthenium. The monomers which may be included in the monomer composition of the ruthenium-free monomer generally have at least one of 121841.doc-32-200813102 Polymerized double bond and at least one hydrophilic functional group. Examples of polymerizable double bond include acrylic acid, methacrylic acid, vinyl, fluorene-vinyl ethyl fluorenyl and N-vinyl decylamine, N-vinyl decylamine Base double bonds and analogs thereof. These hydrophilic monomers may be, but are not necessarily, cross-linking agents. It is considered to be a subset of the acryl-based moiety as described above, acrylic type, or "acrylic-containing" or The acrylate monomer is a monomer containing an acrylic group (CR, H = CRCOW), wherein R is hydrazine or CH3, R is H, an alkyl group or a carbonyl group, and W is 0 or N. Hydrophilicity of the present invention The component generally comprises the following components which do not contain bismuth, and one or more components of D are hydrophilic. The monomer containing hydrophilic vinyl (CH2=CH-), acrylic monomer and acrylic acid Ester-functionalized ethylene oxide (_(〇CH2CH2)n) oligomer. Illustrative acrylic monomers including N, N - dimethyl propyl decylamine (DMA), 2-hydroxyethyl acrylate, glyceryl methacrylate, 2-hydroxyethyl methacrylamide, methacrylic acid, propionic acid, methacrylic acid The composition (MMA) and mixtures thereof. As described above, the monomer/\ composition comprising all of the individual hydrophilic and non-hydrophilic components comprises at least about 45% by weight of the precursor composition. Thus, the composition of the monomer composition The weight percentage of each component will vary within this range. The mono-body composition preferably comprises from about 45% to about 55% by weight of the precursor composition 'and thus the weight percent of each component from the precursor The composition varies from about 0.05% to about 40% by weight or from about 5% to about 5% by weight to achieve the desired total weight percent of the precursor composition. The acrylic monomer component is preferred. Existing in an amount of from about 7 wt% to about 20 wt%/❶ of the precursor composition of the precursor composition for the preparation of the xenon glasses product, and even more preferably about 10% of the precursor composition of the first 12l841.doc-33-200813102 5% by weight to about 18% by weight. Served with total precursor The illustrative weight percentage of the acrylic monomer includes the following: about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% or 18%. As described above, the monomer composition Also included is a hydrophilic vinyl-containing monomer. Hydrophilic vinyl-containing monomers which can be incorporated into the spectacles of the present invention include the following: N-vinyl decylamine (e.g., N-ethylene fluorene oxime _ (NVP)), N-vinyl-N-methylacetamide (VMA), N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-B Mercaptocarboxamide, N 2 -hydroxyethyl vinyl carbamate, N-carboxy-β-alanine N-vinyl ester. A particularly preferred vinyl containing monomer is fluorenyl-vinyl-indole-methylacetamide (VMA). The structure of the VMA corresponds to CH3C(0)N(CH3)-CH=CH2. The vinyl-containing monomer component of the monomer composition is preferably present in an amount ranging from about 20% by weight to about 5% by weight of the precursor composition prior to the preparation of the hydrogen spectacles product, and even more preferably in the precursor The bulk composition is present in an amount ranging from about 25% to about 42% by weight. A representative weight of the vinyl-containing monomer includes the following weights: about 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, of the precursor composition, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight or 42% by weight The bulk composition additionally comprises an acrylate functionalized ethylene oxide oligomer 'i.e., having from about 2 to about 8 continuous ethylene oxide (ch2CH20-) monomeric subunits and terminally reactive groups (such as acrylate groups) ) Functionalized Oxidation 121841.doc -34- 200813102 Ethylene oligomer. One or both ends of the polymer can be functionalized with an acrylate group. Examples include reagents with one or more molar equivalents capable of introducing one or more reactive acrylonitrile groups to either or both ends of the nutrient (eg, isocyanatoethyl methacrylate (nIEMn), methacrylic anhydride) The methyl propyl sulfhydryl gas or the like is reacted to produce an ethylene oxide condensate of an ethylene oxide oligomer having a propionate group at one or both ends. Representative polymer: It is described by the following formula: R7\ = /R9
〇 R/C—、/(沉邮灿―F〇 R/C—,/(Shen Mailcan-F
——一 II 其中s介於2至約8之範圍内,較佳為2至約4,且1為1^或 烷基,較佳為低碳烷基,且心及尺8各自獨立地為H、烷基 或羧基,其限制條件為R7或Rs中僅一者可為羧基。&較佳 為低碳烷基,諸如甲基,且R?及Rs各自為H。變數F係選 自_〇H、諸如燒氧基之封端基團或如下文所示之㈣酸醋 c; 基。以下結構表明在各末端具有相同丙烯酸酯基之均雙官 能基氧化乙婦寡聚物。然而,理論上,各末端之丙稀酸醋 部分可相同或可不同。- II, wherein s is in the range of 2 to about 8, preferably 2 to about 4, and 1 is 1 or an alkyl group, preferably a lower alkyl group, and the heart and the ruler 8 are each independently H, an alkyl group or a carboxyl group, with the proviso that only one of R7 or Rs may be a carboxyl group. & is preferably a lower alkyl group such as a methyl group, and each of R? and Rs is H. The variable F is selected from the group consisting of 〇H, a capping group such as an alkoxy group or a (iv) vinegar c group as shown below. The following structure shows a homo-functional ethoxylated ethoxylate oligomer having the same acrylate group at each end. However, in theory, the acetoacetate moieties at each end may be the same or different.
/C=C ,R9/C=C ,R9
A II ο ,(〇ch2ch2): C- II o / c==c r8 較佳用於本發明 之丙烯酸酯官能化氧化乙烯寡聚物包括 121841.doc -35- 200813102 寡-氧化乙稀單曱基丙烯酸酯及寡-氧化乙烯二甲基丙稀酸 醋。較佳用於本發明之丙烯酸酯官能化氧化乙烯寡聚物為 —曱基丙細酸丙二酵酉旨。A II ο , (〇ch2ch2): C-II o / c==c r8 Preferred for use in the acrylate functionalized ethylene oxide oligomer of the present invention includes 121841.doc -35- 200813102 oligo-oxyethylene oxide monoterpene Acrylate and oligo-ethylene oxide dimethyl acrylate. The acrylate functionalized oxyethylene oligomer preferably used in the present invention is a thioglycolic acid propylene glycol.
丙烯酸酯官能化氧化乙烯募聚物通常以相對小之量存在 於前驅體組合物中。舉例而言,募聚物以約〇 〇5重量%至 約10重量%範圍内,較佳約0.075重量%至約5重量%範圍内 之量存在於前驅體組合物中。募聚物組份之代表性量包括 以下量:前驅體組合物之約〇· 1重量%、0·2重量%、〇 3重 量%、0.4重量%、〇·5重量%、〇·8重量%、〇9重量%、1重 量%、2重量❽/。、3重量%、4重量%或5重量〇/〇。 聚氧化烯矽氧可萃取組份 如先前所述,本發明之前驅體組合物特別包括聚氧化烯 矽氧(PAOS)可移除或可萃取組份。(兩術語"可移除"及"可 萃取在本文中可互換使用,且係'指在眼鏡前驅體組合物 聚合後移除之組份)。本發明之PA〇s可萃取組份表示為聚 氧化稀矽氧,纟中聚氧化烯可為聚乙二醇、聚丙二醇、乙 二醇與丙二醇之共聚物、聚乙二醇與聚丙二醇之三聚物, 包括欲段共聚物及三喪段聚合物。該等聚氧化㈣氧在本 文中有時可稱為石夕油;如本文所用之術語,,石夕油"旨在涵蓋 任何該等聚氧化烯矽氧。 -般而言,聚氧化浠石夕氧之特徵在於具有聚二甲 烷(PDMS)主鏈,其中一定百 刀比之曱基經如上所述之聚 烯虱基置換。在一較佳實施例中, T汆烯虱基經由間隔基共 秘連接至矽氧烷主鏈。該等間 寻間隔基長度一般為約2至約u 121841.doc • 36 - 200813102 個原子,且通常用以便於聚氧化烯鏈與矽氧烷主鏈之連 接。例示性間隔基包括伸烧基鏈、經取代之伸烧基鏈、胺 基酸及其類似物。較佳間隔基為低碳烷基,諸如乙基、丙 基、丁基、戊基、己基等。或者,用於本文之聚氧化烯石夕 氧可為二甲基矽氧烷氧化乙烯嵌段共聚物,諸如購自 Gelest (Morrisville,PA)之彼等。一般而言,本發明之聚氧 化稀石夕氧將含有至少約2 5重量%之聚氧化稀,且更通常將 含有約30重量%至約90重量%之聚氧化烯。較佳之聚氧化 烯矽氧含有約50重量%或50重量%以上之聚氧化烯。說日月 性聚氧化稀石夕氧含有約25% (重量%)聚氧化烯、40重量 %、50重量%、60重量%、70重量%、75重量%、8〇重量% 或85重量%之聚氧化烯。一般而言,具有約55重量%或55 重量%以上之氧化乙烯的物質為水溶性的。尤其較佳用於 本發明者為其中聚氧化烯為聚乙二醇或氧化丙烯-氧化乙 烯嵌段共聚物之聚氧化烯矽氧。 例示性聚氧化烯矽氧可自Gelest (PA,USA)獲得。代表 性聚氧化烯矽氧包括二曱基矽氧烷(75%氧化乙烯)嵌段共 聚物(PDMS-共-PEG);二曱基矽氧烷[65-70% (60%氧化丙 烯/40%氧化乙烯)]嵌段共聚物(PDMS-共-PPO-PEG);二曱 基矽氧烷(25-30%氧化乙烯)嵌段共聚物(PDMS·共-PEG); 二曱基矽氧烷[50-55% (60%氧化丙烯/40%氧化乙烯)]嵌段 共聚物(PDMS-共-PPO-PEG);二甲基矽氧烷(50-55%氧化 乙烯)嵌段共聚物(PDMS-共-PEG);二甲基矽氧烷(80-85% 氧化乙烯)嵌段共聚物(PDMS-共-PPO-PEG)及二曱基矽氧 121841.doc -37- 200813102 烷(8〇°/q氧化乙烯)嵌段共聚物(Pdms_共_PEG)。上述聚氧 化稀石夕氧分別對應於以下縮寫(Gelest) : DBE-712、DBP- 732 、 DBE-224 、 DBP-534 、 DBE-621 、 DBE-821 及 DBE· 814。較佳之聚氧化烯矽氧為二甲基矽氧烷氧化乙烯) 後段共聚物(DBE-712)。 雖然PAOS可萃取組份可以任何量存在於前驅體組合物 中但較佳可萃取組份以約2重量%至約3 〇重量%,較佳約 1 〇重里%至約3 〇重量%範圍内之量存在。可萃取組份更佳 以約10重量%至約28重量%範圍内之量存在。可萃取組份 在前驅體組合物中之例示性量包括以下重量% ••約1〇重量 /〇 、力12重里%、約1 5重量%、約20重量%、約25重量%、 約29重量%或約3〇重量〇/〇。 在某些情況下,PAOS可移除組份除包含聚氧化烯矽氧 以外,亦包含鏈轉移試劑。鏈轉移試劑為促進自由基物質 與非自由基物質之間反應的試劑。用於本發明之例示性鏈 轉移試劑包括硫醇、二硫醚、有機_化物及烯丙氧基化合The acrylate functionalized ethylene oxide polymer is typically present in the precursor composition in relatively small amounts. For example, the polymeric polymer is present in the precursor composition in an amount ranging from about 5% by weight to about 10% by weight, preferably from about 0.075% by weight to about 5% by weight. A representative amount of the polymer component includes the following amounts: about 1% by weight of the precursor composition, 0.2% by weight, 3% by weight, 0.4% by weight, 〇·5% by weight, 〇·8 by weight %, 〇9 wt%, 1 wt%, 2 wt❽/. 3 wt%, 4 wt% or 5 wt〇/〇. Polyoxyalkylene Oxide Extractable Components As previously described, the precursor compositions of the present invention specifically include polyoxyalkylene oxide (PAOS) removable or extractable components. (The terms "removable" and "extractable are used interchangeably herein and refer to a component that is removed after polymerization of the lens precursor composition. The PA〇s extractable component of the present invention is represented by polyoxygen oxide, and the polyoxyalkylene in the oxime may be polyethylene glycol, polypropylene glycol, copolymer of ethylene glycol and propylene glycol, polyethylene glycol and polypropylene glycol. Terpolymer, including a segment of the copolymer and a three-stage polymer. Such polyoxy(tetra)oxygens may sometimes be referred to herein as lycopene; as the term is used herein, lithium oil " is intended to encompass any such polyoxyalkylene oxime. In general, polyoxonite oxygen is characterized by having a polydimethylene (PDMS) backbone in which a certain hundred moles of sulfhydryl groups are replaced by a polyalkylene group as described above. In a preferred embodiment, the T terpene fluorenyl group is attached to the oxane backbone via a spacer. The intervening spacers are typically from about 2 to about 121,841.doc • 36 to 200813,102 atoms and are typically used to facilitate attachment of the polyoxyalkylene chain to the siloxane backbone. Exemplary spacers include extended alkyl chains, substituted alkyl groups, amino acids, and the like. Preferred spacers are lower alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl and the like. Alternatively, the polyoxyalkylene oxide used herein may be a dimethyloxane oxyethylene block copolymer such as those available from Gelest (Morrisville, PA). In general, the polyoxygen oxides of the present invention will contain at least about 25 weight percent polyoxydioxide, and more typically will comprise from about 30 weight percent to about 90 weight percent polyoxyalkylene. Preferably, the polyoxyalkylene oxide contains about 50% by weight or more of the polyoxyalkylene. It is said that the solar polyoxygen oxide contains about 25% by weight of polyoxyalkylene, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 75% by weight, 8% by weight or 85% by weight. Polyoxyalkylene. In general, materials having about 55% by weight or more by weight of ethylene oxide are water soluble. Particularly preferred for use in the present invention are polyoxyalkylene oxides in which the polyoxyalkylene is a polyethylene glycol or a propylene oxide-ethylene oxide block copolymer. Exemplary polyoxyalkylene oxides are available from Gelest (PA, USA). Representative polyoxyalkylene oxime includes dimercapto oxane (75% ethylene oxide) block copolymer (PDMS-co-PEG); dimercapto oxime [65-70% (60% propylene oxide / 40) % ethylene oxide) block copolymer (PDMS-co-PPO-PEG); dimercapto oxirane (25-30% ethylene oxide) block copolymer (PDMS · co-PEG); Alkane [50-55% (60% propylene oxide / 40% ethylene oxide)] block copolymer (PDMS-co-PPO-PEG); dimethyloxane (50-55% ethylene oxide) block copolymer (PDMS-co-PEG); dimethyloxane (80-85% ethylene oxide) block copolymer (PDMS-co-PPO-PEG) and dimercapto oxime 121841.doc -37- 200813102 alkane ( 8 〇 / q ethylene oxide) block copolymer (Pdms_co-PEG). The above-mentioned polyoxygen oxides correspond to the following abbreviations (Gelest): DBE-712, DBP-732, DBE-224, DBP-534, DBE-621, DBE-821 and DBE·814. The preferred polyoxyalkylene oxime is dimethyl oxirane ethylene oxide) post-copolymer (DBE-712). While the PAOS extractable component may be present in the precursor composition in any amount, preferably the extractable component is present in an amount ranging from about 2% by weight to about 3% by weight, preferably from about 1% by weight to about 3% by weight. The amount exists. The extractable component is more preferably present in an amount ranging from about 10% by weight to about 28% by weight. Exemplary amounts of the extractable component in the precursor composition include the following weight % ••about 1〇weight/〇, force 12% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 29% % by weight or about 3 〇 〇 / 〇. In some cases, the PAOS removable component also contains a chain transfer reagent in addition to the polyoxyalkylene oxide. The chain transfer reagent is an agent that promotes a reaction between a radical species and a non-radical species. Exemplary chain transfer reagents for use in the present invention include thiols, disulfides, organic compounds, and allylooxylates.
物。鏈轉移劑之某些說明性實例包括硫醇,諸如丁硫醇、 月桂硫醇、硫代乙醇酸辛酯、乙二醇雙(硫代乙醇酸酯)、 M-丁二醇雙(硫代丙酸酯)、三羥曱基丙烷參(硫代乙醇酸 酯)、三羥甲基丙烷參(β-硫代丙酸酯)、異戊四醇肆硫代 丙酸酯)及其類似物;二硫醚,諸如二笨基二硫醚;函化 物,諸如四氣化碳、四漠化碳、氣仿、二氣笨及其類似 物;及烯丙氧基化合物,諸如烯丙氧基醇及其類似物。此 等鏈轉移劑可個別使用或以任一前述各物之混合物形式使 121841.doc -38· 200813102 :。較佳用於本發明者為烯丙氧基化合 多個稀丙氧基部分之化合物β P“-或 構包含至少一個稀丙氧基部分之化合物具有以下通用結 h2c:Things. Some illustrative examples of chain transfer agents include mercaptans such as butanol, lauryl mercaptan, octyl thioglycolate, ethylene glycol bis(thioglycolate), M-butanediol bis(thiopropyl) Acid ester), trihydrocarbyl propane ginseng (thioglycolate), trimethylolpropane ginseng (β-thiopropionate), pentaerythritol thiopropionate) and the like; Disulfide, such as di-p-butyl disulfide; a complex such as tetra-carbonized carbon, four-alkaline carbon, gas-like, dioxane, and the like; and an allyloxy compound, such as allyloxy alcohol And its analogues. These chain transfer agents can be used individually or in the form of a mixture of any of the foregoing. 121841.doc -38· 200813102 :. Preferred compounds for use in the present invention that are allylicoxylated to a plurality of diloxyoxyl moieties, β P "- or a compound comprising at least one diloxyoxy moiety, have the following generalized knot h2c:
:CH 〇r〇:CH 〇r〇
ο 八中框付部分對應於稀丙氧基部分,且Q表示母體分子之 =物或殘基,例如醇或任何有機小分子,當其與嫌丙負 土一分連接在—起時’能夠充當鏈轉移劑。Q較佳衍生自 :’諸如乙醇、丙醇、丁醇及其類似物或其經取代之妒 式^較佳為乙醇之殘基,且具有結構(_CH2CH20H),= 使仔鏈轉移試劑對應於2·烯丙氧基乙醇。 本I明者已發現’視情況向可萃取組份(諸如本文所述 彼等可萃取組份)中添加鏈轉移試劑有效地提供尺寸及 匆理特可變性減少之經萃取水合③氧隱形眼鏡體。因 匕添加鏈轉移劑用以"正規化”或,,微調”前驅體眼鏡組合 物,以使仟所得經萃取水合隱形眼鏡群體通常具有小於 20%之任—或多種以下特徵之可變性:平衡水含量、透氧 靜二接觸角、動悲接觸角(前進接觸角或後退接觸 角 '滯後、折射率、離子流、模數、拉伸強度及其類似 特徵。例如,視眼鏡產物之特定特徵而定,任一或多種前 述眼鏡特徵之可變性通常均小於約20%,且較佳小於約 10/〇。在一或多個實施例中,眼鏡直徑、平衡水含量及/或 121841.d〇< -39- 200813102 離子流中任一或多者之可變性均為約5%或小於5%,更俨 為約3%或小於3%,且甚至更佳為約2%或小於2%。眼鏡^ 體中眼鏡直徑較佳具有小於約1 ·5%之可變性。 如本文所用之批次或群體係指複數個隱形眼鏡。可瞭 . 解,當隱形眼鏡批次或群體中之隱形眼鏡數量足以提供有 t義之標準誤差時,達成經改良之統計學數值。在某些情 況下,一批隱形眼鏡係指至少10個隱形眼鏡、至少100個 隱形眼鏡、至少1000個隱形眼鏡或更多。 n 因A,在一態樣中,本發明提供-種改良聚氧化烯矽氧 效,之方法,該方法係藉由向其中添加約01重量%至約10 重里°/°之鏈轉移劑,較佳為烯丙氧基化合物,且更佳為烯 氧基醇以提供用於製備矽氧水凝膠隱形眼鏡產物之鏈 f移4劑聚氧化烯石夕氧。較佳以約01重量%至約6重量% 乾圍内之1添加鏈轉移劑。認為如本文所用之特定批次聚 乳化稀石夕氧(例如石夕油)之,,效能,,為其在給定濃度(且所有其 / ,、數均相同)下提供具有隱形眼鏡模具之眼鏡形成表面 2 L形眼鏡插入物之模具形成表面之外徑約〇·卯至約 入(諸如、、々0.95至約le05倍)範圍内之外徑的最終經萃取水 ' 〃見產物之能力。在至少—實施例+,水合眼鏡產物之 7為所用隱形眼鏡模具或用以形成該隱形眼鏡模具之模 八〆、、物之外彳!的約G·98至1 ·〇2倍。最終眼鏡產物之眼鏡 直控減小命士 丨 〆 -大則t氧化烯矽氧之”效能”愈大。雖然最終 =鏡直技為對於鏈轉移劑提供具有如上所述在臨床可接受 "内之所需特性之石夕氧隱形眼鏡產物之能力的一種量 121841.doc 200813102 測’但在與前驅體組合物之其他組份混ο 八中框付部分 corresponds to the dilute propoxy moiety, and Q represents the parent molecule's = or residue, such as an alcohol or any small organic molecule, when it is connected to the susceptor Acts as a chain transfer agent. Q is preferably derived from: 'such as ethanol, propanol, butanol and the like or a substituted oxime thereof, preferably a residue of ethanol, and having the structure (_CH2CH20H), = corresponding to the chain transfer reagent 2. Allyloxyethanol. It has been found that the addition of a chain transfer reagent to an extractable component, such as the extractable components described herein, as appropriate, effectively provides an extracted hydrated 3 oxygen contact lens having reduced size and haste variability. body. Because the chain transfer agent is added to "normalize" or, the precursor lens composition is fine-tuned such that the resulting extracted hydrated contact lens population typically has a variability of less than 20% - or more of the following characteristics: Equilibrium water content, oxygen permeable static contact angle, dynamic sad contact angle (forward contact angle or receding contact angle 'lag, refractive index, ion current, modulus, tensile strength, and the like. For example, the specificity of the spectacles product Depending on the characteristics, the variability of any one or more of the aforementioned spectacles features is typically less than about 20%, and preferably less than about 10 Å. In one or more embodiments, the spectacles diameter, equilibrium water content, and/or 121841. D〇<-39- 200813102 The variability of any one or more of the ion currents is about 5% or less, more preferably about 3% or less than 3%, and even more preferably about 2% or less. 2%. Glasses The diameter of the lens in the body preferably has a variability of less than about 1.5%. The batch or group system as used herein refers to a plurality of contact lenses. Yes, when the contact lens is in a batch or group When the number of contact lenses is sufficient to provide a standard error of t, A modified statistical value is achieved. In some cases, a batch of contact lenses refers to at least 10 contact lenses, at least 100 contact lenses, at least 1000 contact lenses or more. n Because A, in one aspect The present invention provides a method for improving the oxygenation of polyoxyalkylene by adding a chain transfer agent of from about 01% by weight to about 10% by weight, preferably an allyloxy compound, More preferably, it is an oxyl alcohol to provide a chain shift of 4 doses of polyoxyalkylene oxide for the preparation of a hydroxyl hydrogel contact lens product. Preferably, it is from about 01% by weight to about 6% by weight dry circumference. 1 Addition of a chain transfer agent. It is considered that the specific batch of polyemulsified rare earth oxide (such as Shixia oil) as used herein, the efficiency, is at a given concentration (and all / /, the same number) Providing a lens-forming surface having a contact lens mold 2 The final extracted water of the outer diameter of the mold-forming surface of the lens-shaped insert of the L-shaped lens insert is about 〇·卯 to an outer diameter in the range of (such as, 々0.95 to about le05 times) ' The ability to see the product. At least - Example +, hydrated glasses 7 is the contact lens mold used or the mold to form the contact lens mold, and the object is G!, about G·98 to 1 · 〇 2 times. The final glasses product glasses directly control to reduce the number of people The greater the "efficiency" of 丨〆-大和t oxyalkylene oxime. Although the final = mirroring technique is to provide the chain transfer agent with the desired properties of the above-mentioned clinically acceptable " An amount of product capacity 121841.doc 200813102 measured 'but mixed with other components of the precursor composition
=中添加鏈轉移劑額外有效地提供最二二氧:烯 性,大-致'_即可變C 〇·ι至約5份鏈轉移劑及約 即旦鏈轉移劑·聚氧化婦梦氧之混合物可含有任。亦 不量之鏈轉移劑:、0.2、〇.3、G.4、Q 5 1下例 ΟAdding a chain transfer agent to additionally provide the most dioxane: olefinic, large-to- _ can be changed C 〇 · ι to about 5 parts of chain transfer agent and about dad chain transfer agent · polyoxidation The mixture may contain any. Also, the amount of chain transfer agent: 0.2, 〇.3, G.4, Q 5 1
Γ、。Ι ^.5 + 2.5^3.5+4:5-: 97.5、97、96.5、96、95.5 或 95。 矽氧水凝膠隱形眼鏡前驅體組合物之額外組份 本發明之眼鏡前驅體組合物亦可包括額外組份,例 外線(UV)吸㈣或uv輻射或能量吸㈣蝴著色劑, 吸收劑可為(例如)在約320_380奈米之υν·Α範圍内展示相 對高之吸收值,但在約380 nm以上相對透明之強υν吸收 劑。實例包括光可聚合之經基二苯甲酮及光可聚合之笨幷 三唑,諸如2-羥基-4-丙烯醯氧基乙氧基二苯甲_ (以 CYASORB® UV416購自 Cytec lndustries)、2_ 經基 _4 (2羥 基-3-甲基丙烯醯氧基)丙氧基二苯甲酮及光可聚合之笨幷 二唑(以NORBLOC® 7966購自Noramco)。適用於本發明之 其他光可聚合UV吸收劑包括可聚合之烯系不飽和三嗅、 水揚酸酯、經芳基取代之丙烯酸酯及其混合物。一般而 言,UV吸收劑若存在,則以對應於約〇·5重量%之前驅體 121841.doc -41- 200813102 組合物至約1.5重量%之組合物的量提供。尤其較佳者為包 括約0.6重量%至約1 ·〇重量% UV吸收劑之組合物。 本發明之前驅體組合物亦可包括著色劑,儘管涵蓋彩色 眼鏡產物及透明眼鏡產物。著色劑較佳為對所得眼鏡產物 有效提供顏色之反應性染料或顏料。反應性染料為與石夕氧 水凝膠眼鏡物質鍵結且不滲色之彼等染料。例示性著色劑 包括以下各物·苯石黃酸、4-(4,5 -二氫-4-((2-甲氧基甲 基-4-((2-(磺氧基)乙基)磺醯基)苯基)偶氮-3-甲基侧氧 基_1Η-σΛ。坐-1-基);[2 -萘石黃酸,7-(乙酿胺基)-4 -經基_3_ ((4_((磺氧基乙基)石黃醯基)苯基)偶氮)_] ; [5_((4,6-二氯- 1,3,5-二嗓-2-基)胺基-4-經基-3-((1-石黃基-2-萘基)偶氮-2,7-萘-二磺酸,三鈉鹽];[銅,29H,31H_酞菁基(2-)-N29,N30,N31,N32)·,磺基((4((2-磺氧基)乙基)石黃醯基)苯基) 胺基)磺醯基衍生物]及[2,7-萘磺酸,4-胺基-5-羥基-3,6-雙 ((4-((2•(磺氧基)乙基)石黃醯基)苯基)偶氮)-四納鹽]。 用於本發明之尤其較佳著色劑為酞菁顏料,諸如酞菁藍 及酞菁綠、氧化鉻-氧化鋁-氧化亞鈷、氧化鉻及紅色、黃 色、棕色及黑色之各種鐵氧化物。亦可併入諸如二氧化鈦 之不透明劑。對於某些應用而言,可採用顏色之混合物以 更佳模擬自然虹膜之外觀。 此外’本發明之前驅體組合物可包含一或多種引發劑化 合物’亦即能夠引發前驅體組合物聚合之化合物。較佳為 熱引發劑’亦即具有”聚合開始”溫度之引發劑。藉由選擇 具有較南開始分解溫度之熱引發劑且使用相對低量之引發 121841.doc -42- 200813102 別’可此減少本發明眼鏡之離子流,藉此可影響在萃取步 驟移除或萃取之可移除物質的量。舉例而言,用於本發明 前驅體組合物中之一種例示性熱引發劑為2,2,_偶氮雙(2,4_ 二甲基戊腈)(VAZO㊣-52)。VAZO®-52具有約50°c之開始 .. 刀解度’其為如驅體組合物中之反應性組份開始聚合之 μ度。另一適用於本發明組合物之熱引發劑為偶氮二異丁 腈(VAZO⑧-88),其具有約9〇°C之開始分解溫度。亦合適 之引發劑為VAZO®-64,2,2,-偶氮二異丁腈。本文所述之 額外熱引發劑包括腈類,諸如1,1,_偶氮雙(環己腈)及2,2,_ 偶氮雙(2-曱基丙腈),以及其他類型之引發劑,諸如可購 自SigmaAldrich之彼等引發劑。眼睛上相容之矽氧水凝膠 隱形眼鏡可自包含約0.2-0.7份VAZO-52(或約〇·1至約〇·8重 量%)或約0· 1份至約0.6份VAZO-88(約0.05至約〇·5重量%) 之前驅體組合物而獲得。 本發明之前驅體組合物亦可包含脫模助劑,亦即有效使 Ij 得固化隱形眼鏡更易於自其模具中移除之一或多種化合 物。例示性脫模助劑包括親水性碎氧、聚氧化晞及其組 * 合0 、 前驅體組合物可額外包含選自由以下各物組成之群之稀 釋劑:己醇、乙氧基乙醇、異丙醇(IPA)、丙醇、癸醇及 其組合。若使用稀釋劑,則其通常以約10%至約30%(重量 比)範圍内之量存在。具有相對較高濃度稀釋劑之組合物 傾向於(但並非必需)具有較低離子流值、減少之模數及增 121841.doc -43- 200813102 加之伸長率以及大於20秒之水BUT。 適用於製備秒氧水凝膠隱形眼鏡之其他物f描述於美國 專利第M67,245號中。Oh,. Ι ^.5 + 2.5^3.5+4:5-: 97.5, 97, 96.5, 96, 95.5 or 95. Additional Components of the Oxygenated Hydrogel Contact Lens Precursor Composition The lens precursor compositions of the present invention may also include additional components, exceptional line (UV) absorption (four) or uv radiation or energy absorption (four) butterfly colorants, absorbents It can be, for example, a relatively high absorption value exhibiting a relatively high absorption value in the range of 320ν·Α of about 320 380 nm, but relatively transparent at about 380 nm. Examples include photopolymerizable benzophenones and photopolymerizable clumole triazoles such as 2-hydroxy-4-propenyloxyethoxybenzhydryl (purchased from Cytec Industries by CYASORB® UV416) 2, via — 4 (2hydroxy-3-methylpropenyloxy)propoxybenzophenone and photopolymerizable albendazole (purchased from Noramco as NORBLOC® 7966). Other photopolymerizable UV absorbers suitable for use in the present invention include polymerizable ethylenically unsaturated tris, salicylates, aryl substituted acrylates, and mixtures thereof. In general, the UV absorber, if present, is provided in an amount corresponding to about 5% by weight of the precursor 121841.doc -41 - 200813102 composition to about 1.5% by weight of the composition. Particularly preferred are compositions comprising from about 0.6% by weight to about 1% by weight of the UV absorber. The precursor compositions of the present invention may also include colorants, although encompassing colored eyeglass products and clear lens products. The colorant is preferably a reactive dye or pigment that effectively provides color to the resulting lens product. The reactive dyes are dyes that are bonded to the materials of the spectacles and do not bleed. Exemplary colorants include the following materials: benzoquinic acid, 4-(4,5-dihydro-4-((2-methoxymethyl-4-((2-(sulfooxy)ethyl))) Sulfhydryl)phenyl)azo-3-methylxyloxy_1Η-σΛ. sit-1-yl); [2-naphthoic acid, 7-(ethinyl)-4-yl group _3_ ((4_((sulfoethyl) fluorenyl)phenyl)azo)_] ; [5_((4,6-dichloro-1,3,5-diin-2-yl)amine 4--4-yl-3-((1-Drytyl-2-naphthyl)azo-2,7-naphthalene-disulfonic acid, trisodium salt]; [copper, 29H, 31H_phthalocyanine (2-)-N29, N30, N31, N32)·, sulfo((4((2-sulfo)oxy)ethyl)indolyl)phenyl)amino)sulfonyl derivatives] and [2, 7-naphthalenesulfonic acid, 4-amino-5-hydroxy-3,6-bis((4-((2)(sulfooxy)ethyl) fluorenyl)phenyl)azo)-tetrasodium salt] Particularly preferred colorants for use in the present invention are phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, chromium oxide-alumina-cobalt oxide, chromium oxide, and various iron oxides of red, yellow, brown, and black. An opacifier such as titanium dioxide may also be incorporated. For some applications, a mixture of colors may be employed. More preferably, the appearance of the natural iris is simulated. Furthermore, the precursor composition of the present invention may comprise one or more initiator compounds, i.e., compounds capable of initiating polymerization of the precursor composition. Preferably, the thermal initiator 'i. Start the "temperature initiator" by selecting a thermal initiator having a souther decomposition temperature and using a relatively low amount of initiation 121841.doc -42 - 200813102 to reduce the ion current of the glasses of the present invention, thereby affecting The amount of removable material removed or extracted in the extraction step. For example, one exemplary thermal initiator used in the precursor composition of the present invention is 2,2,-azobis (2,4-dimethyl) Valeronitrile) (VAZO-n-52). VAZO®-52 has a beginning of about 50°c.. Knife-degree is 'μ degree as the reactivity of the reactive component in the body composition begins. The thermal initiator of the composition of the present invention is azobisisobutyronitrile (VAZO8-88) having a decomposition temperature of about 9 ° C. A suitable initiator is VAZO®-64, 2, 2, - Azobisisobutyronitrile. The additional thermal initiators described herein include nitriles such as 1 1, 1, azobis(cyclohexanecarbonitrile) and 2,2,_ azobis(2-mercaptopropionitrile), and other types of initiators, such as those available from Sigma Aldrich. A compatible oxygenated hydrogel contact lens may comprise from about 0.2 to about 0.7 parts of VAZO-52 (or from about 1 to about 8% by weight) or from about 0.1 part to about 0.6 parts of VAZO-88. 0.05 to about 5% by weight) obtained from the precursor composition. The precursor compositions of the present invention may also comprise a release aid, i.e., effective to make the cured contact lens of Ij easier to remove one or more compounds from its mold. Exemplary release aids include hydrophilic crushed oxygen, polyyttrium oxide, and combinations thereof. The precursor composition may additionally comprise a diluent selected from the group consisting of hexanol, ethoxyethanol, and iso Propanol (IPA), propanol, decyl alcohol, and combinations thereof. If a diluent is used, it is usually present in an amount ranging from about 10% to about 30% by weight. Compositions having relatively high concentrations of diluent tend to (but are not required to) have lower ion current values, reduced modulus, and increased elongation and water BUT greater than 20 seconds. Other materials suitable for the preparation of a second oxygen hydrogel contact lens are described in U.S. Patent No. M67,245.
本申請案内纟中之術語,,添加劑”係#在本發明之可聚合 矽氧水凝膠隱形眼鏡前驅體組合物或預萃取之聚合矽氧水 凝=形眼鏡產物中提供但並非製切氧水凝㈣形眼鏡 所必需之化合物或任何化學藥劑。雖然對於製備矽氧水凝 膠隱形眼鏡而言可能並非必需,但此決不表明由於本發明 之組合物中包括一或多種添加劑而不對前驅體組合物或所 得眼鏡產物賦予一或多種優勢。舉例而言,包括可移除之 添加劑可(例如)便於在製造隱形眼鏡期間對其進行加工, 與在無添加敎情況下自㈣前驅體組合物獲得之矽氧水 凝膠隱形眼鏡相比可增強矽氧水凝膠隱形眼鏡之_或多種 特性:或其、组合。如本文所用之添加劑為可自預萃取之聚 合石夕氧水凝膠隱形眼鏡產物中移除之添加劑。舉例而言, 添加劑實質上可為非反應性的或可不與可聚切氧減膠 眼鏡前驅體組合物之其他組份反應,以使得添加劑實質上 :成為所得聚合眼鏡產物之共價結合構成部分。視直分子 量及形狀而定,大部分(若非全部)添加劑可自聚合梦氧水 凝膠隱形眼鏡產物中萃取。因此’在萃取程序期間,本發 =組合物中之添加劑可自聚切氧水凝膠隱形眼鏡產物中 卒取。因&,亦認為如先前描述為可移除或可萃取組份之 聚氧化烯矽氧為如本文所用之”添加劑,,。 除PAOS可萃取組份以外 添加劑之實例包括(但不限於) 121841.doc •44- 200813102 硬脂酸乙二醇酯、單月桂酸二乙二醇酯、C2_Cm醇及/或The term "additive" in the present application is provided in the polymerizable silicone hydrogel contact lens precursor composition of the present invention or the pre-extracted polymeric helium oxygenated gel-shaped lens product. A compound or any chemical agent necessary for hydrogel (tetra) glasses. Although not necessarily necessary for the preparation of a hydrogel contact lens, this does not in any way indicate that the composition of the present invention does not include a precursor to one or more additives. The body composition or the resulting lens product imparts one or more advantages. For example, the inclusion of a removable additive can, for example, facilitate processing of the contact lens during manufacture, and in combination with the (four) precursor in the absence of added enamel. The obtained hydroxyl hydrogel contact lens can enhance the _ or a plurality of characteristics of the hydroxyl hydrogel contact lens: or a combination thereof. The additive used herein is a self-pre-extracted polymeric oxime oxygen gel. An additive that is removed from the contact lens product. For example, the additive may be substantially non-reactive or may not be combined with a polymerizable oxygen-reducing lens precursor composition. The component reacts such that the additive is essentially: a covalently bonded constituent of the resulting polymeric lens product. Depending on the molecular weight and shape, most, if not all, of the additives can be self-polymerized in the dream hydrogel contact lens product. Extraction. Therefore, during the extraction procedure, the additive in the composition can be drawn from the polyoxygenated hydrogel contact lens product. Because & is also considered to be a removable or extractable component as previously described. Polyoxyalkylene oxime is an "additive," as used herein. Examples of additives other than the PAOS extractable component include, but are not limited to, 121841.doc • 44- 200813102 ethylene glycol stearate, diethylene glycol monolaurate, C2_Cm alcohol, and/or
CrC24胺。添加劑亦可含有一或多種極性或親水性端基, 諸如(但不限於)羥基、胺基、硫氫基、磷酸酯基及羧酸 基,以便於添加劑與組合物中所存在之其他物質混溶。 添加劑可呈液體或固體形式,且包括疏水性或兩親媒性 化合物或藥劑。 在某些實施例中,添加劑可稱為稀釋劑,實質上非反應 性劑或可萃取劑。除先前所述之PA0S可萃取組份以外, 本發明之前驅體組合物亦可含有醇類或非醇類稀釋劑。若 使用該等其他稀釋劑,則其通常以在小於約10%(重量比) 之i存在本發明之組合物中所提供之添加劑可提供任一 或多種以下功能,例如其可⑴諸如藉由促進形成均質組合 物或未經相分離之組合物而有助於形成可聚合之矽氧水凝 膠隱形眼鏡前驅體組合物;(ii)諸如藉由促進含有隱形眼 鏡產物之隱形眼鏡模具脫模,及/或促進隱形眼鏡產物自 隱形眼鏡模具中脫鏡而增強預萃取之聚合石夕氧水凝膠隱形 、兄產物之可加工性,(U1)諸如藉由減少隱形眼鏡群體中 (例如不同批次之隱形眼鏡中)隱形眼鏡物理參數之可變性 而改良對隱形眼鏡之物理參數的控制;(iv)諸如藉由增強 隱形眼鏡表面之可濕性而增強隱形眼鏡之可濕性;⑺諸如 猎由視需要減少模數或增加模數而積極影響隱形眼鏡之模 ㈣可諸如猎由與自不包括添加劑之眼鏡產物所獲 靶hi眼鏡相比減少隱形眼鏡之離子流而積極影響隱形 乂、見離子流。因此,本發明組合物中所提供之添加劑可 121841.doc -45- 200813102 充當相容劑、脫模助劑、脫鏡助劑、物理參數控制劑、可 濕性增強劑、模數影響劑、離子流減少劑或前述任一或多 者之組合。 相容劑可改良或增強本發明前驅體組合物之組份的混溶 f生舉例而吕’與無相容劑之調配物相比,相容劑可減少 與合秒聚合物及其他眼鏡形成組份相關之相分離。 添加劑較佳均勻分布於整個聚合組合物中且在萃取程序 期間自聚合產物中實質性(若非完全)移除。因此,本發明 之隱形眼鏡較佳因各批次之間之小的物理或尺寸可變性而 產生’藉此改良臨床上可接受之眼睛上相容之矽氧水凝膠 隱形眼鏡的產量。 本發明之例示性前驅體組合物於實例1、3及4中提供。 本發明前驅體組合物之某些實施例包括於非極性樹脂隱 形眼鏡模具中所提供之可聚合矽氧水凝膠隱形眼鏡前驅體 組合物。其他實施例包括在儲存容器(諸如瓶子及其類似 物)中或分配裝置(諸如人工或自動移液裝置)中之該等組合 物。 形成矽氧水凝膠隱形眼鏡之方法 一般而言,在產生矽氧水凝膠隱形眼鏡中,將石夕氧水凝 膠隱形眼鏡前驅體組合物之組份各自稱重且接著組人。接 著通常(例如)使用磁力或機械混合來混合所得前驅體組合 物’且視情況過濾以移除微粒。 本發明之眼鏡可(例如)如圖丨中所說明來產生。圖丨為說 明產生矽氧水凝膠隱形眼鏡之方法的方塊圖。特定令之, 121841.doc •46- 200813102 圖1說明一種澆鑄成型矽氧水凝膠隱形眼鏡之方法。澆鑄 成型隱形眼鏡可自身以適於直接置放於人眼上之形式產 生’而無需進一步加工來改質眼鏡而使眼鏡適用於眼睛 上。使用諸如圖1所說明之程序的澆鑄成型程序而產生的 本發明之矽氧水凝膠隱形眼鏡在本文被認為係,,澆鑄成型 石夕氧水凝膠隱形眼鏡’’。若不使用加工來改變使眼鏡產物 自模具構件脫鏡後之眼鏡設計,則將本發明之眼鏡理解為 "完全成型之矽氧水凝膠隱形眼鏡,,。 用於產生隱形眼鏡(諸如矽氧水凝膠隱形眼鏡)之說明性 方法描述於以下專利中:美國專利第4,121,896號、第 4,495,313 號、第 4,565,348 號、第 4,640,489 號、第 4,889,664 號、第 4,985,186 號、第 5 〇39 459 號 第 5,〇80,839 號、第 5,094,609 號、第 5 26〇 〇〇〇 號第 5,607,5 18 號、第 5,760,100 號、第 5,85〇,1〇7 號、第 5,935,492 號、第 6,099,852 E、帛 6 367 929 號第 6,822,016 號、第 6,867,245 號、第 6,869 549 號、第 6,939,487號及美國專利公開案第2〇〇3〇125498號、第 20050154080 號及第 20050191335 號。 回到圖1,現簡單描述方塊圖中概述之方法。所說明之 方法包括步驟1〇2,即··將可聚合矽氧水凝膠眼鏡前驅體 組合物(202,如圖2中所示)置放於隱形眼鏡模具構件上或 内部。可聚合矽氧水凝膠眼鏡前驅體組合物係指適於聚合 之預聚合或預固化組合物。如本文所用之本發明之可聚合 組合物亦可稱為”單體混合物”或”反應混合物,,。在組合^ 121841.doc -47- 200813102 固化或聚合之前,可聚合組合物或眼鏡前驅體組合物較佳 未經聚合至任何顯著程度。然而,在某些情況下,可聚合 組合物或眼鏡前驅體組合物可在經受固化之前部分聚合。 在固化或聚合程序之前,本發明之眼鏡前驅體組合物可 提供於容器、分配裝置或隱形眼鏡模具中。 . 回到圖1步驟102,將眼鏡前驅體組合物置放於凹形隱形 • 目艮鏡模具構件之眼鏡形成表面上。凹形隱形眼鏡模具二 -般係指第一隱形眼鏡模具構件或前部隱形眼鏡模具構 - -件。舉例而言,凹形隱形眼鏡模具構件具有眼鏡形成表 面,該表面界定自隱形眼鏡模具所產生之隱形眼鏡的前表 面。 第一隱形眼鏡模具構件與第二隱形眼鏡模具構件接觸置 放以形成具有隱形眼鏡狀空腔之隱形眼鏡模具。因此,圖 中所況月之方法包括步驟1〇4,即:藉由將兩隱形眼鏡模 具構件彼此接觸置放以形成隱形眼鏡狀空腔來封閉隱形眼 鏡模具。可聚合矽氧水凝膠眼鏡前驅體組合物2〇2位於隱 I 料鏡狀空腔中。第二隱形眼鏡模具構件係指凸形隱形眼 鏡模具構件或後部隱形眼鏡模具構件。舉例而言,第二隱 形眼鏡模具構件包括眼鏡形成表面,該表面界定隱形眼鏡 .. 模具中所產生之隱形眼鏡的後表面。 如本文所用之,,非極性樹脂隱形眼鏡模具”或”疏水性樹 脂隱形眼鏡模具”係指由非極性或疏水性樹脂形成或產生 之隱形眼鏡模具。因此,非極性樹脂基隱形眼鏡模具可包 έ非極丨生或水性樹脂。舉例而言,該等隱形眼鏡模具可 121841.doc -48- 200813102 包含一或多種聚烯烴,或可由聚烯烴樹脂物質形成。用於 本申請案之情形+的非極性樹脂隱形眼鏡模具之實例包括 聚乙烯隱形眼鏡模具、聚丙烯隱形眼鏡模具及聚苯乙烯隱 形眼鏡模具。非極性樹脂基隱形眼鏡模具通常具有疏水性 表面。舉例而言,如使用俘獲氣泡法所測定,非極性樹脂 模具或疏水性樹脂模具可具有約9〇。或更大之靜態接觸 角。在該等接觸角下,該等模具中所產生之習知石夕氧水凝 膠隱形眼鏡具有臨床上不可接受之表面可濕性。 1 — 該方法進一步包括固化1 驅體組合物以形成預萃取之聚合石夕氧水凝膠隱形眼鏡產物 204(如圖2中所示)。在固化期間,可聚合石夕氧水凝膠眼鏡 前驅體組合物之眼鏡形成組份聚合以形成聚合眼鏡產物。 因此,固化亦可理解為聚合步驟。固化1〇6可包括將可聚 合之眼鏡前驅體組合物暴露於輕射,諸如熱輕射或任何其 他有效聚合眼鏡前驅體組合物之組份的方式。舉例而言, ”106可包括將可聚合之眼鏡前驅體組合物暴露於聚合 ’ ϊ之熱或紫外(UV)光。固化可視情況在無氧環境中進行。 牛!1而。SMb可在惰性氣氛T (例如在氮、氬或其他惰 性氣體下)進行。 預萃取之聚合矽氧水凝膠隱形眼鏡產物204係指在經受 自聚合產物移除實質上所有可移除/可萃取組份之萃取程 序之前的聚合產物。在與萃取組合物接觸之前,預萃取之 聚合石夕氧水凝膠隱形眼鏡產物可提供於隱形眼鏡模具、萃 取盤或其他裝置上或内部。舉例而言,在固化程序之後, 121841.doc -49- 200813102 預萃取之聚合⑦氧錢膠隱形眼鏡產物可提供於隱形眼鏡 模具之眼鏡狀空腔中;在隱形眼鏡模具脫模之後,可提供 於一種隱形眼鏡模具構件上或内部;或在脫鏡程序之後且 在萃取程序之前,可提供於萃取盤或其他裝置上或内部。 預萃取之聚合⑦氧水凝膠隱形眼鏡產物包括眼鏡形成組份 (諸如呈眼鏡狀之含矽聚合網路或基質)及可自眼鏡形成組 伤移除之可移除組份。可移除組份除PA〇s可萃取組份以 外亦包括未反應之單體、寡聚物、部分反應之單體或相對CrC24 amine. The additive may also contain one or more polar or hydrophilic end groups such as, but not limited to, a hydroxyl group, an amine group, a sulfhydryl group, a phosphate group, and a carboxylic acid group to facilitate mixing of the additive with other materials present in the composition. Dissolved. The additive may be in liquid or solid form and includes a hydrophobic or amphiphilic compound or agent. In certain embodiments, the additive may be referred to as a diluent, substantially a non-reactive agent or an extractable agent. In addition to the previously described PAOS extractable components, the precursor compositions of the present invention may also contain an alcohol or non-alcohol diluent. If such other diluents are used, they may generally provide one or more of the following functions in an amount of less than about 10% by weight of the present invention provided in the compositions of the present invention, for example, Promoting the formation of a homogeneous composition or a composition that is not phase separated to aid in the formation of a polymerizable silicone hydrogel contact lens precursor composition; (ii) demolding, for example, by promoting contact lens molds containing contact lens products And/or promoting the release of the contact lens product from the contact lens mold to enhance the processability of the pre-extracted polymeric rock-oxygen hydrogel invisible, brother product, (U1), such as by reducing contact lens populations (eg, different In a batch of contact lenses, the variability of the physical parameters of the contact lens improves the control of the physical parameters of the contact lens; (iv) enhances the wettability of the contact lens, such as by enhancing the wettability of the surface of the contact lens; (7) Hunting by actively reducing the modulus or increasing the modulus and actively affecting the contact lens model (4) can reduce the invisibility compared to the target hi glasses obtained from the glasses product that does not include the additive. Mirror ion flow and positive influence qe invisible, see ion flow. Therefore, the additive provided in the composition of the present invention can be used as a compatibilizer, a mold release aid, a mirror release aid, a physical parameter control agent, a wettability enhancer, a modulus influencer, and the like. 121841.doc -45-200813102 Ion flow reducing agent or a combination of any one or more of the foregoing. The compatibilizing agent can improve or enhance the miscibility of the components of the precursor composition of the present invention. The compatibilizer can reduce the formation of the polymer and other glasses in comparison with the formulation without the compatibilizer. Component related phase separation. The additive is preferably evenly distributed throughout the polymeric composition and is substantially (if not completely) removed from the polymeric product during the extraction procedure. Thus, the contact lenses of the present invention are preferably produced by small physical or dimensional variability between batches' thereby improving the yield of clinically acceptable ocular oxygen-compatible hydrogel contact lenses. Exemplary precursor compositions of the present invention are provided in Examples 1, 3 and 4. Certain embodiments of the precursor compositions of the present invention comprise a polymerizable silicone hydrogel contact lens precursor composition provided in a non-polar resin contact lens mold. Other embodiments include such compositions in storage containers such as bottles and the like, or in dispensing devices such as manual or automatic pipetting devices. Method of Forming a Hydroxyl Hydrogel Contact Lens In general, in the production of a helium oxygen hydrogel contact lens, the components of the Shiqi Oxygen Hydrogel Contact Lens Precursor Composition are each weighed and then assembled. The resulting precursor composition is then typically mixed, for example, using magnetic or mechanical mixing and optionally filtered to remove particulates. The spectacles of the present invention can be produced, for example, as illustrated in Figure 。. The figure is a block diagram illustrating a method of producing a helium oxygen hydrogel contact lens. Specific Orders, 121841.doc • 46- 200813102 Figure 1 illustrates a method of casting a silicone hydrogel contact lens. The cast molded contact lens can be self-produced in a form suitable for direct placement on the human eye' without the need for further processing to modify the lens to make the lens suitable for use on the eye. The hydroxyl hydrogel contact lenses of the present invention produced using a casting process such as the procedure illustrated in Figure 1 are herein considered to be, cast, and formed as the aerogel contact lens. The glasses of the present invention are understood to be "fully formed hydroxyl hydrogel contact lenses, if no processing is used to alter the design of the lens that causes the lens product to be removed from the mold member. Illustrative methods for producing contact lenses, such as neohydrogenated hydrogel contact lenses, are described in U.S. Patent Nos. 4,121,896, 4,495,313, 4,565,348, 4,640,489, 4,889,664. , 4, 985, 186, 5, 39, 459, 5, 〇 80, 839, 5, 094, 609, 5, 26, 5, 607, 5 18, 5, 760, 100, 5, 85 , No. 1, No. 5, No. 5, 935, 492, No. 6, 099, 852 E, No. 6, 367, 929, No. 6, 822, 016, No. 6, 867, 245, No. 6, 869 549, No. 6, 939, 487, and U.S. Patent Publication No. 2, pp. 20050154080 and 20050191335. Returning to Figure 1, the method outlined in the block diagram will now be briefly described. The illustrated method includes the step of step 2, i.e., placing the polymerizable silicone hydrogel lens precursor composition (202, as shown in Figure 2) on or in the contact lens mold member. The polymerizable silicone hydrogel lens precursor composition refers to a prepolymerized or precured composition suitable for polymerization. The polymerizable composition of the present invention as used herein may also be referred to as a "monomer mixture" or "reaction mixture," a polymerizable composition or a lens precursor prior to curing or polymerization of the combination of ^121841.doc-47-200813102. Preferably, the composition is not polymerized to any significant extent. However, in some cases, the polymerizable composition or lens precursor composition can be partially polymerized prior to being subjected to curing. Prior to curing or polymerization procedures, the lens precursor of the present invention The body composition can be provided in a container, dispensing device or contact lens mold. Returning to step 102 of Figure 1, the lens precursor composition is placed on the lens forming surface of the concave invisible • eyepiece mold member. Concave invisible Eyeglass molds generally refer to a first contact lens mold member or a front contact lens mold member. For example, a concave contact lens mold member has a lens forming surface that defines an invisible shape produced by a contact lens mold. a front surface of the lens. The first contact lens mold member is placed in contact with the second contact lens mold member to form a contact lens-like space The contact lens mold of the cavity. Therefore, the method of the month in the figure includes the step 1〇4, that is, the contact lens mold is closed by placing the two contact lens mold members in contact with each other to form a contact lens-like cavity. The hydroxyl hydrogel lens precursor composition 2〇2 is located in the hidden mirror cavity. The second contact lens mold member refers to a convex contact lens mold member or a rear contact lens mold member. For example, the second The contact lens mold member includes a lens forming surface that defines a contact lens: a rear surface of the contact lens produced in the mold. As used herein, a non-polar resin contact lens mold or a "hydrophobic resin contact lens mold" Refers to a contact lens mold formed or produced from a non-polar or hydrophobic resin. Thus, non-polar resin based contact lens molds can be included in non-polar or aqueous resins. For example, the contact lens molds may comprise one or more polyolefins, or may be formed from a polyolefin resin material. Examples of non-polar resin contact lens molds for use in the context of the present application include polyethylene contact lens molds, polypropylene contact lens molds, and polystyrene contact lens molds. Non-polar resin based contact lens molds typically have a hydrophobic surface. For example, the non-polar resin mold or the hydrophobic resin mold may have about 9 Torr as determined by the trapping bubble method. Or a larger static contact angle. At these contact angles, the conventional Shihee hydrogel contact lenses produced in such molds have clinically unacceptable surface wettability. 1 - The method further comprises curing the l-body composition to form a pre-extracted polymeric oxime hydrogel contact lens product 204 (as shown in Figure 2). During curing, the lens forming components of the polymerizable oxalate hydrogel lens precursor composition are polymerized to form a polymeric lens product. Therefore, curing can also be understood as a polymerization step. Curing 1 〇 6 can include exposing the polymerizable lens precursor composition to a light shot, such as a thermal light shot or any other component that effectively polymerizes the lens precursor composition. For example, "106" can include exposing the polymerizable lens precursor composition to a polymeric 'hot or ultraviolet (UV) light. Curing can be carried out in an oxygen-free environment as appropriate. Cattle! 1 and SMb can be inert The atmosphere T is carried out, for example under nitrogen, argon or other inert gas. The pre-extracted polymeric hydrogel contact lens product 204 means substantially all of the removable/extractable components are removed from the self-polymerized product. The polymerization product prior to the extraction procedure. The pre-extracted polymeric oxime hydrogel contact lens product can be provided on or within the contact lens mold, extraction tray or other device prior to contact with the extraction composition. For example, in curing After the procedure, 121841.doc -49- 200813102 pre-extracted polymeric 7 oxygenated contact lens product can be provided in the lens-like cavity of the contact lens mold; after the contact lens mold is released, it can be provided in a contact lens mold member Upper or inner; or after the devitrification procedure and prior to the extraction procedure, may be provided on or in the extraction tray or other device. Pre-extracted polymeric 7-oxygen hydrogel invisible The mirror product comprises a lens forming component (such as a enamel-containing polymeric network or matrix in the form of a spectacles) and a removable component that can be removed from the spectacles forming group. The removable component is in addition to the PA 〇s extractable component. Also includes unreacted monomers, oligomers, partially reacted monomers or relative
C 於眼鏡形成組份未共價連接或固定之其他藥劑。可移除組 份亦可包括-或多種添加劑,包括有機添加劑,包括稀釋 劑’其可如先前論述在萃取程序期間自聚合眼鏡產物萃 取。因此’可包含可移除組份之物質不僅包括聚氧化稀妙 氧可萃取組份’亦可包括相對於鏡體之聚合物主鏈、網路 或基質而言未交聯或固定之可萃取物質的線性未交聯、交 聯及/或分枝聚合物。 此外二可移除組份可包括其他物質,諸如揮發性物質, 其可在萃取之刖自預萃取之聚合碎氧水㈣隱形眼鏡產物 被動或主動_除。舉例而言,-部分可移除組份可在脫 模步驟與萃取步驟之間蒸發。 在口化可聚合之眼鏡前驅體組合物之後,進行隱形眼鏡 模具之脫模108。脫模係指分離含有預萃取之聚合隱形眼 鏡產物之楔具或聚合裝置的兩個模具構件(諸如凸形及凹 :模具構件)之方法。預萃取之聚合石夕氧水凝膠隱形眼鏡 產物位於經脫模之4具構件之—者上。舉例而言’聚合石夕 121841.doc -50- 200813102 氧水;邊膠隱形眼鏡產物可位於凸形模具構件或凹形模且構 件上。 ’ 接著在脫鏡步驛110(如圖1所示)期間將預萃取之聚合石夕 氧味-凝母贵形兔-鏡-Jr翁划4言^:貫定‘位-之-蓚取眼〜鏡模其蒼 件分離。預萃取之聚合隱形眼鏡產物可自凸形模具構件或 凹形模具構件脫鏡,此取決於聚合隱形眼鏡產物在隱形眼 鏡模具脫模期間保持黏附之模具構件。 在預萃取之矽氧水凝膠隱形眼鏡產物脫鏡之後,該方法 Ο 〇 包括自預萃取之矽氧水凝膠隱形眼鏡產物萃取112可萃取 物質。萃取步驟112導致經萃取之矽氧水凝膠隱形眼鏡產 物206(如圖2所示)。萃取步驟112係指使預萃取之聚合矽氧 水凝膠隱形眼鏡產物與一或多種萃取組合物接觸之程序, 且可包括單一萃取步驟或若干次連續萃取。舉例而言,聚 a矽氧水凝膠隱形眼鏡產物或一批聚合矽氧水凝膠隱形眼 鏡產物與一或多體積之液體萃取介質接觸。萃取介質通常 包括一或多種溶劑。舉例而言,萃取介質包括乙醇、甲 醇、丙醇及其他醇。萃取介質亦可包括醇類與水之混合 物,諸如5〇%乙醇與50%去離子水之混合物,或7〇%乙醇 與3 0。/。去離子水之混合物,或9()%乙醇與跳去離子水之 112可在各種溫度(包括室溫)下進行。$例而言,萃取可在 混合物。或者,萃取介質可實質上或完全無醇,且可包括 一或多種有利於自聚合矽氧水凝膠眼鏡產物移除疏水性未 反應組份之藥劑。舉例而言,萃取介質可包含水、緩衝溶 液及其類似物、基本上由其組成或完全由其組成。萃取 121841.doc -51- 200813102 室溫(例如約20°C )下發生’或其可在高溫(例如約25。〇至約 100 C )下發生。此外,在某些實施例中,萃取步驟1 η可 包括使眼鏡產物與醇與水之混合物接觸,在某些情況下, -_其^_包^萃一取序文嘴〜一·,步—。-------------〜-------------— 在萃取預萃取之聚合矽氧水凝膠隱形眼鏡產物以提供經 萃取之聚合碎乳水/旋膠隱形眼鏡產物之後,該方法包括水 : 合114經萃取之聚合矽氧水凝膠隱形眼鏡產物。水合步驟 114例如可包括使經萃取之聚合矽氧水凝膠隱形眼鏡產物 p 或一或多批該等產物與水或水溶液接觸以形成水合石夕氧水 凝膠隱形眼鏡208(如圖2中所示)。例如,經萃取之聚合石夕 氧水凝膠隱形眼鏡產物可藉由置放於兩單獨體積或兩單獨 體積以上之水(包括去離子水)中來水合。在某些實施例 中,水合步驟114與萃取步驟112組合,以使得兩步驟在隱 形眼鏡生產線中之單一位置上進行。水合步驟114可在容 器中於室溫或高溫下且必要時在高壓下進行。舉例而言, 水合可在約120°C(例如121。〇之溫度及1〇3 kPa (15 psi)之 ϋ 壓力下於水中發生。 因此,如由上文顯而易見,認為預萃取之聚合矽氧水凝 : ㈣形眼鏡產物及經萃取之聚合魏水«隱形眼鏡產物 ' &水可膨脹性之產物或元件,錢為水合錢水凝膠隱形 眼鏡為遇水可膨脹之產物或元件。如本文所用之石夕氧水凝 膠隱形眼鏡係指已經歷水合步驟之石夕氧水凝膠元件。因 此,石夕氧水凝膠隱形眼鏡可為完全水合之石夕氧水凝膠隱形 眼鏡、部分水合之石夕氧水凝膠隱形眼鏡或脫水之石夕氧水凝 121841.doc -52- 200813102 膠隱形眼鏡。脫水之^夕氧水凝膠隱形眼鏡係指已經歷水人 程序且隨後經脫水以自眼鏡移除水之隱形眼鏡。 在水合經萃取之矽氧水凝膠隱形眼鏡產物以產生石夕氧水 -务膠普帝娘翁之稜~^^^戈•括對言^广氧^求貫膠慕-形-眼-鏡一一一一 • 208之步驟116。舉例而言,矽氧水凝膠隱形眼鏡2〇8可置 放於包括一定體積液體(諸如生理食鹽水溶液,包括經缓 衝之生理食鹽水溶液)之發泡包裝或其他合適容器中。適 合於本發明眼鏡之液體的實例包括磷酸鹽緩衝生理食鹽水 疒_及獨酸鹽緩衝生理食鹽水。如步驟118所示,接著密封發 /包包裝或谷器,且隨後殺菌。舉例而言,經封裝之石夕氧水 凝膠隱形眼鏡可諸如藉由高壓釜處理、γ輻射、電子束輻 射或紫外輻射而暴露於殺菌量之輻射,包括熱輻射。 矽氧水凝膠眼鏡之特性 如上所論述,本文所提供之組合物及方法提供眼睛上相 容之石夕氧水凝膠隱形眼鏡。將具有如本文所述之可移除組 份的預萃取聚合石夕氧水凝踢眼鏡產物萃取且水合以形成具 有眼用可接受之表面可濕性的石夕氧水凝膠隱形眼鏡。本發 明之眼鏡具有透氧性、表面可濕性、模數、水含量、離子 μ 及其組合’其使得本發明之眼鏡適合患者眼睛 適地配戴延長之時期,諸如至少一天、至少一週、至少兩 週或勺個月,而無需自眼睛中移除眼鏡。 可配t=所用 < 目艮睛上相容之矽氧水凝膠隱形眼鏡"係指 =:人眼上而人不經歷或報導實質性不適(包括眼睛 別激及類似不適)的石夕氧水凝膠隱形眼鏡。眼睛上相容之 121841.doc •53- 200813102 夕乳水凝勝隱形眼鏡具有眼 常不引起顯著角膜腫表濕性,且通 上皮弓狀病即ς、 水("乾眼病")、上方角臈 皮弓狀病k(,SEAL”)或其他顯 具寺眼讲可K 个週U孚病狀不相 係产不奋 ^^性之砍氧謂膠隱翁競- 者:^不利影響眼鏡配戴者眼睛之淚膜至導致眼鏡配戴 關之導與眼睛上置放或配戴石夕氧水凝膠隱形眼鏡相 广之私度的矽氧水凝膠隱形眼鏡。眼睛上相容之矽 乳水旋膠隱形眼鏡滿足針 之臨床上可接受之㈣。配戴或長期配戴隱形眼鏡 2明之⑦氧水凝膠隱形眼鏡包含鏡體,其具有具眼用 σ文之表面可濕性(0ASW)的表面,諸如前表面及後表 面可4性係指隱形眼鏡之一或多個表面的親水性。在一 種量測方法中,若眼鏡在如下進行之可濕性檢定中得到3 或X上之6平分’則可認為眼鏡表面為可濕性的,或可認 為其具有眼用可接受之可濕性。將隱形眼鏡浸入蒸館水 C; 中,自水中移除,且測定水膜自眼鏡表面後退所耗之時間 長度(例如水驅散時間(水贿或WBUT))。檢定提供卜狀 線性範圍内的眼鏡等級,其中1〇分係指其中水滴需輝或 更長時間自眼鏡後退之眼鏡。雖㈣斯之活體外評估僅 為對於OASW之-種1測方法或指示,但可認為具有$秒 以上(諸如至少10秒或更理想為至少約15秒)水BUT之矽氧 水凝膠隱形眼鏡具有眼用可接受之表面可濕性。或者,可 在活體内評估0綱。若眼鏡可在患者眼睛上配戴至少6 小時而患者未報導不適或刺激,則認為眼鏡具有〇ASW。 121841.doc -54- 200813102 可λ、、〖生亦可藉由里測一或兩個眼鏡表面上之接觸角來測 疋接觸角可為動悲或靜態接觸角。較低接觸角一般係指 隱形眼鏡表面之可濕性增加。舉例而言,矽氧水凝膠隱: 资鏡之号’最牷表贡於妁12-〇.σ之接 本發明眼鏡之某些實施例巾,眼鏡具有不大於9g。之接觸 角’且在其他實施例中,本發明之矽氧水凝膠隱形眼鏡具 有小於約80。且甚至更佳小於約75。之前進接觸 角。 本發明之矽氧水凝膠隱形眼鏡包含具有眼用可接受之表 面可濕性的鏡體。舉例而言,本發明之矽氧水凝膠隱形眼 鏡之鏡體通常具有前表面及後表面,各表面均具有眼用可 接受之表面可濕性。 在一實施例中,矽氧水凝膠隱形眼鏡之鏡體包含矽氧水 旋膠物質。鏡體具有不大於萃取前鏡體乾重9〇%之乾重。 舉例而言,預萃取之聚合矽氧水凝膠隱形眼鏡產物之鏡體 可具有乾重X。萃取程序之後,經萃取之聚合矽氧水凝膠 隱形眼鏡產物之鏡體具有小於或等於0·9Χ之乾重。如上所 娜述,在萃取步驟期間,預萃取之聚合矽氧水凝膠隱形眼 鏡產物可與大量多種有機溶劑接觸,繼而進行水合步驟以 產生矽氧水凝膠隱形眼鏡。接著,將水合矽氧水凝膠隱形 眼鏡脫水且稱重以測定矽氧水凝膠隱形眼鏡之鏡體乾重。 舉例而言,在某些方法中,將預萃取之聚合矽氧水凝膠 隱形眼鏡產物自隱形眼鏡模具構件脫鏡,且稱重以提供預 萃取之聚合矽氧水凝膠隱形眼鏡產物之乾重。接著使預萃 121841.doc -55- 200813102 取之眼鏡產物與醇接觸約6小時,且接著與水進行水合。 接著在約80 °C下乾燥水合眼鏡約1小時,且接著在真空下 於約80°C下乾燥約2小時。稱重經乾燥之眼鏡以測定石夕氧 水凝膠隱形眼鏡之鏡體乾重。接著比較該等乾重以確定預 卒取之聚合石夕氧水凝膠隱形眼鏡產物中所存在之可萃取物 貝的里。具有約40%可萃取組份含量之預萃取聚合眼鏡產 物產生乾重為預萃取眼鏡產物約60%之矽氧水凝膠隱形眼 鏡的鏡體。具有約70%可萃取組份含量之預萃取聚合眼鏡 產物產生乾重為預萃取眼鏡產物約30%之矽氧水凝膠隱形 眼鏡的鏡體,等等。 預萃取之聚合矽氧水凝膠隱形眼鏡產物中所存在之可萃 取物之量或可萃取組份含量可使用以下等式來確定: 預萃取眼鏡產物之乾重-經萃取及水合之隱形眼鏡 之乾重)/預萃取眼鏡產物之乾重)X 1〇〇。 Ε為預萃取眼鏡產物中所存在之可萃取物的百分比。 舉例而言,預萃取之聚合矽氧水凝膠隱形眼鏡產物可具 有約20 mg之乾重。若自彼產物所獲得之矽氧水凝膠隱形 眼鏡具有約17 mg之乾重,則彼矽氧水凝膠隱形眼鏡包含 乾重為預萃取眼鏡產物乾重85 %之鏡體。應瞭解,該預萃 取眼鏡產物具有約15 %(重量比)之可萃取組份含量。作為 另一實例,預萃取之聚合矽氧水凝膠隱形眼鏡產物可具有 約18 mg之乾重,且若自該眼鏡產物所獲得之經脫水之石夕 氧水凝膠隱形眼鏡具有約13 mg之乾重,則該石夕氧水凝膠 隱形眼鏡包含乾重為預萃取之眼鏡產物約72%之鏡體。該 121841.doc -56- 200813102 預萃取之聚合石夕氧水凝膠隱形眼鏡產物具有約2 8 % (重量 比)之可萃取組份含量。 在某些實施例中,矽氧水凝膠隱形眼鏡(亦即已經受萃 取及水合程序之矽氧水凝膠隱形眼鏡)之鏡體乾重大於鏡 體在萃取之乾重的4 0 %。舉例而言,萃取後之鏡體乾重 可為預萃取之鏡體乾重的約4〇%至約9〇%。本發明眼鏡之 : 某些實施例包含乾重為預萃取鏡體乾重之約50%至約80% 的鏡體。 (、—一 如本文所論述,當預萃取眼鏡產物中之可萃取組份含量 (例如未反應之試劑,諸如相對於鏡體之聚合物主鏈、網 路或基質未交聯或固定之可萃取物質的線性未交聯、交聯 或分枝聚合物)大於10%,諸如至少15%,至少2〇%,至少 25 /〇或更多時,自無聚氧化烯矽氧可萃取組份之眼鏡前驅 體組合物或預萃取之矽氧水凝膠隱形眼鏡產物所獲得之矽 氧水凝膠隱形眼鏡(例如自”大批調配物”所獲得之眼鏡產 、 物)可具有眼用可接受之表面可濕性。申請者已發現,與C Other agents that are not covalently attached or immobilized to the lens forming component. The removable component may also include - or a plurality of additives, including organic additives, including diluents' which may be extracted from the polymeric lens product during the extraction procedure as previously discussed. Thus, a substance which may comprise a removable component includes not only a polyoxygen oxide extractable component but also an extractable or unremovable extractable relative to the polymer backbone, network or matrix of the lens body. Linear uncrosslinked, crosslinked, and/or branched polymers of the material. Further, the second removable component may include other materials, such as volatile materials, which may be passively or actively removed from the pre-extracted polymeric hydrogen peroxide water (IV) contact lens product after extraction. For example, the -partial removable component can evaporate between the demolding step and the extraction step. After the polymerizable lens precursor composition is singulated, the release lens 108 of the contact lens mold is performed. Demolding refers to the method of separating two mold members (such as male and female: mold members) of a wedge or polymerization device containing a pre-extracted polymeric contact lens product. The pre-extracted polymeric rock-oxygen hydrogel contact lens product is located on the four members of the demolded mold. For example, 'polymerization shi shi 121841.doc -50- 200813102 oxygen water; the edge contact lens product can be located on the male mold member or the concave mold and the member. 'Next, during the de-mirror step 110 (shown in Figure 1), the pre-extracted polymerized stone-oxygen-condensed female-shaped rabbit-mirror-Jr Weng 4 words ^: '定'位-之-取取Eye ~ mirror mold its separation of the pieces. The pre-extracted polymeric contact lens product can be removed from the convex mold member or the female mold member depending on the mold member that the polymeric contact lens product remains adhered during the release of the contact lens mold. After the pre-extracted deoxygenated hydrogel contact lens product is demired, the method comprises extracting 112 extractable material from the pre-extracted neohydrogen hydrogel contact lens product. Extraction step 112 results in an extracted oxygenated hydrogel contact lens product 206 (shown in Figure 2). Extraction step 112 refers to the process of contacting the pre-extracted polymeric hydrogel contact lens product with one or more extraction compositions, and may include a single extraction step or several sequential extractions. For example, the polyaerogel hydrogel contact lens product or a batch of polymeric hydrogel hydrogel contact lens product is contacted with one or more volumes of liquid extraction media. The extraction medium typically includes one or more solvents. For example, the extraction medium includes ethanol, methanol, propanol, and other alcohols. The extraction medium may also include a mixture of an alcohol and water, such as a mixture of 5 % ethanol and 50% deionized water, or 7 % ethanol and 30. /. A mixture of deionized water, or 9 (%) ethanol and deionized water 112 can be carried out at various temperatures including room temperature. For example, the extraction can be in the mixture. Alternatively, the extraction medium can be substantially or completely alcohol free and can include one or more agents that facilitate removal of the hydrophobic unreacted component from the polymerized hydrogel hydrogel lens product. For example, the extraction medium can comprise, consist essentially of, or consist entirely of water, a buffer solution, and the like. Extraction 121841.doc -51- 200813102 occurs at room temperature (e.g., about 20 ° C) or it can occur at elevated temperatures (e.g., from about 25 Torr to about 100 C). In addition, in some embodiments, the extracting step 1 η may include contacting the lens product with a mixture of alcohol and water, and in some cases, - _ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ . -------------~------------- - Extraction of pre-extracted polymeric hydrogel contact lens products to provide extracted polymeric ground milk After the water/spinning contact lens product, the method comprises the step of: extracting the polymerized hydroxyl hydrogel contact lens product. The hydrating step 114 can, for example, comprise contacting the extracted polymeric hydrogel head contact lens product p or one or more batches of the product with water or an aqueous solution to form a hydrated rock oxygen hydrogel contact lens 208 (as in Figure 2). Shown). For example, the extracted polymeric oxyhydrogel contact lens product can be hydrated by being placed in two separate volumes or two separate volumes of water, including deionized water. In certain embodiments, the hydrating step 114 is combined with the extraction step 112 such that the two steps are performed at a single location in the contact lens production line. The hydration step 114 can be carried out in a container at room temperature or elevated temperature and, if necessary, under high pressure. For example, hydration can occur in water at a temperature of about 120 ° C (e.g., a temperature of 121 ° C and a pressure of 1 〇 3 kPa (15 psi). Therefore, as apparent from the above, it is considered that the pre-extracted polymer is oxygenated. Hydrogel: (4) Shaped glasses products and extracted polymeric Weishui «contact lens products" & water-swellable products or components, money for hydrated water hydrogel contact lenses are water-swellable products or components. As used herein, a Shixia oxygen hydrogel contact lens refers to a Shixia oxygen hydrogel element that has undergone a hydration step. Therefore, the Shixi oxygen hydrogel contact lens can be a fully hydrated Shixia oxygen hydrogel contact lens, Partially hydrated Shixia Oxygen Hydrogel Contact Lens or Dehydrated Stone Oxygen Condensate 121841.doc -52- 200813102 Glue Contact Lens. Dehydrated Oxygen Hydrogel Contact Lens means that it has undergone a water human procedure and subsequently Dehydration to remove water contact lenses from the glasses. In the hydration of the extracted hydrogel hydrogel contact lens products to produce Shi Xi oxygen water - Gongjia Pu Di Niang Weng ~ ^ ^ ^ Ge • brackets to speak ^ Guang Oxygen ^ seeking through the plastic - shape - eye - mirror one by one • 208 steps 116. For example, the hydroxyl hydrogel contact lens 2〇8 can be placed in a blister pack or other suitable container that includes a volume of liquid, such as a physiological saline solution, including a buffered physiological saline solution. Examples of the liquid of the spectacles of the present invention include phosphate buffered physiological saline 疒 and monoacid buffered physiological saline. Then, as shown in step 118, the hair/package or the granule is sealed, and then sterilized. For example, The encapsulated oxime hydrogel contact lens can be exposed to a sterilizing amount of radiation, including heat radiation, such as by autoclave treatment, gamma radiation, electron beam radiation, or ultraviolet radiation. The characteristics of the oxygenated hydrogel glasses are as described above. Disclosed, the compositions and methods provided herein provide an eye-compatible Shishi oxygen hydrogel contact lens. Pre-extracted polymeric rock-enriched hydrocele gel product extraction with a removable component as described herein. And hydrating to form an Oxime Hydrogel contact lens having an ophthalmically acceptable surface wettability. The glasses of the present invention have oxygen permeability, surface wettability, modulus, water content, Ion μ and combinations thereof - which make the spectacles of the present invention suitable for the patient's eye to be properly worn for extended periods of time, such as at least one day, at least one week, at least two weeks, or scoop months without the need to remove the spectacles from the eye. The < eye-catching compatible oxygenated hydrogel contact lens" means: the human eye does not experience or report substantial discomfort (including eye irritations and similar discomfort) Glue contact lenses. Eyes compatible 121841.doc •53- 200813102 Essence water gel contact lens has eye damage that does not cause significant corneal swelling, and epithelial arch disease is sputum, water (" dry eye disease "), the upper corner of the sacral arch disease k (, SEAL) or other sacred temples can be said that K weeks U flu symptoms are not compatible with the production of ^ ^ sexual culmination :: adversely affect the lens of the wearer's eye tear film to lead the glasses to wear the guide to the eye or put on the eye or wear Shixia oxygen hydrogel contact lens wide-ranging private oxygen hydrogel contact lens . The eye is compatible with the blister contact lens to meet the clinically acceptable needle (4). Wearing or long-wearing contact lenses 2 Ming 7 oxygen hydrogel contact lenses comprise a mirror body having a surface with an ophthalmic surface wettability (0ASW), such as a front surface and a rear surface. The hydrophilicity of one or more surfaces of the contact lens. In a measuring method, if the spectacles obtain 6 amps on 3 or X in the wettability test performed as follows, the surface of the spectacles may be considered to be wettable, or it may be considered to be wettable for ophthalmology. Sex. Immerse the contact lens in the steaming water C; remove it from the water and measure the length of time it takes for the water film to recede from the surface of the lens (eg water dispersal time (water bribe or WBUT)). The test provides the level of the glasses in the linear range of the shape, where the 1〇 point refers to the glasses in which the water droplets need to glow or take longer to retreat from the glasses. Although the in vitro evaluation of (4) is only for the OASW method or indication, it can be considered to have an invisible hydrogel of water BUT of more than $second (such as at least 10 seconds or more preferably at least about 15 seconds). The glasses have an ophthalmically acceptable surface wettability. Alternatively, the 0 class can be evaluated in vivo. If the eyewear can be worn on the patient's eye for at least 6 hours and the patient does not report discomfort or irritation, the eyeglass is considered to have a 〇ASW. 121841.doc -54- 200813102 λ, 〖, can also be measured by measuring the contact angle on the surface of one or two glasses to detect the contact angle can be a sad or static contact angle. A lower contact angle generally refers to an increase in the wettability of the contact lens surface. For example, the hydroxyl hydrogel is hidden: the number of the lens is the best of the 贡12-〇.σ. In some embodiments of the glasses of the present invention, the glasses have a size of no more than 9g. The contact angle' and in other embodiments, the oxygenated hydrogel contact lenses of the present invention have a thickness of less than about 80. And even more preferably less than about 75. Before entering the contact angle. The hydroxyl hydrogel contact lenses of the present invention comprise a lens body having an ophthalmically acceptable surface wettability. For example, the mirror body of the helium oxygen hydrogel contact lens of the present invention typically has a front surface and a back surface, each surface having an acceptable surface wettability for the eye. In one embodiment, the lens body of the helium oxygen hydrogel contact lens comprises a hydroxyl hydrogel material. The mirror body has a dry weight of not more than 9〇% of the dry weight of the lens body before extraction. For example, the mirror body of the pre-extracted polymeric hemohydrogel contact lens product can have a dry weight X. After the extraction procedure, the mirror of the extracted polymeric hydrogel hydrogel contact lens product has a dry weight of less than or equal to 0.99 。. As noted above, during the extraction step, the pre-extracted polymeric hydrogel hydrogel contact lens product can be contacted with a wide variety of organic solvents, followed by a hydration step to produce a helium oxygen hydrogel contact lens. Next, the hydrated hydrogel hydrogel contact lenses were dehydrated and weighed to determine the dry weight of the lens body of the hydroxyl hydrogel contact lenses. For example, in some methods, the pre-extracted polymeric hemohydrogel contact lens product is removed from the contact lens mold member and weighed to provide a pre-extracted polymeric hydrogel contact lens product. weight. The pre-extracted 121841.doc -55-200813102 lens product was contacted with the alcohol for about 6 hours and then hydrated with water. The hydrated spectacles are then dried at about 80 ° C for about 1 hour and then dried under vacuum at about 80 ° C for about 2 hours. The dried glasses were weighed to determine the dry weight of the mirror body of the Shihe oxygen hydrogel contact lens. The dry weights are then compared to determine the amount of extractable material present in the polymerized lyophilized hydrogel contact lens product. The pre-extracted polymeric lens product having a level of extractable component of about 40% produces a lens body having a dry weight of about 60% of the oxygenated hydrogel invisible eyeglasses of the pre-extracted lens product. The pre-extracted polymeric lens product having an extractable component content of about 70% produces a lens body having a dry weight of about 30% of the oxygenated hydrogel contact lens of the pre-extracted lens product, and the like. The amount of extractable material or extractable component present in the pre-extracted polymeric hydrogel contact lens product can be determined using the following equation: Dry weight of the pre-extracted lens product - extracted and hydrated contact lens Dry weight) / pre-extracted dry weight of the lens product) X 1〇〇. Ε is the percentage of extractables present in the pre-extracted lens product. For example, the pre-extracted polymeric oxygenated hydrogel contact lens product can have a dry weight of about 20 mg. If the hydrogenated hydrogel contact lens obtained from the product has a dry weight of about 17 mg, the hydrogenated hydrogel contact lens comprises a lens body having a dry weight of 85% of the dry weight of the pre-extracted lens product. It will be appreciated that the pre-extracted lens product has an extractable component content of about 15% by weight. As another example, the pre-extracted polymeric hydrogel contact lens product can have a dry weight of about 18 mg, and if the dehydrated oxaxy hydrogel contact lens obtained from the lens product has about 13 mg For dry weight, the Shixi oxygen hydrogel contact lens comprises a mirror body having a dry weight of about 72% of the pre-extracted lens product. The 121841.doc -56-200813102 pre-extracted polymeric rock hydrogel contact lens product has an extractable component content of about 28% by weight. In certain embodiments, the mirror body of the helium-oxygen hydrogel contact lens (i.e., the oxygenated hydrogel contact lens that has been subjected to the extraction and hydration procedures) is substantially more than 40% of the dry weight of the lens in the extraction. For example, the dry weight of the lens body after extraction can be from about 4% to about 9% by weight of the pre-extracted lens body. The lenses of the present invention: Certain embodiments comprise a lens body having a dry weight of from about 50% to about 80% of the dry weight of the pre-extracted lens body. (a) as discussed herein, when the extractable component content of the pre-extracted lens product (eg, unreacted reagents, such as polymer backbone, network or matrix relative to the lens body, is not crosslinked or fixed) The linear uncrosslinked, crosslinked or branched polymer of the extracted material) is greater than 10%, such as at least 15%, at least 2%, at least 25 / Torr or more, from the non-polyoxyalkylene oxime extractable component The ophthalmic hydrogel contact lens obtained from the lens precursor composition or the pre-extracted oxygenated hydrogel contact lens product (for example, the lens product obtained from the "mass formulation") can be ophthalmically acceptable Surface wettability. Applicants have discovered that
Cj 大批調配物眼鏡產物相比,前驅體組合物或經聚合之預萃 取眼鏡產物中包括一或多種可移除/可萃取添加劑增加可 萃取組份之含量,且產生具有眼用可接受之表面可濕性的 . 矽氧水凝膠隱形眼鏡。 雖然本發明之預萃取聚合矽氧水凝膠隱形眼鏡產物具有 相對大量之可萃取物質,但本發明之石夕氧水凝膠隱形眼鏡 之經萃取形式在所得鏡體中具有極少之可萃取物質。在某 些實施例中,經萃取之眼鏡中剩餘之可萃取物質的量為約 121841.doc -57- 200813102 0.1%至約4%,諸如約〇·4%至約2% (重量比)。該等額外可 萃取物質可藉由使經萃取之隱形眼鏡與額外體積之強溶劑 (諸如氯仿)接觸來測定。 此外,由於可萃取組份存在且分布在整個可聚合之矽氧 水凝膠眼鏡前驅體組合物及預萃取之聚合矽氧水凝膠隱形 眼鏡產物中,因此本發明之眼鏡產物及隱形眼鏡可區別於 經表面處理之矽氧水凝膠隱形眼鏡。由於可萃取組份可自 眼鏡產物萃取且實質上不存在於經水合之隱形眼鏡中,因 此本發明之眼鏡產物及隱形眼鏡可區別於具有聚合濕潤劑 IPN之矽氧水凝膠隱形眼鏡。 本發明之矽氧水凝膠隱形眼鏡可包含自非極性樹脂隱形 眼鏡模具所獲得之鏡體,該等鏡體在水合及脫水狀態下檢 查時具有實質上相同之表面形態。此外,該等水合鏡體可 具有略微小於脫水鏡體之表面粗糙度的表面粗糙度。舉例 而言,本發明之眼鏡之鏡體可具有包括奈米大小峰之表 面,該等奈米大小峰在分析眼鏡表面之均方根(RMS)粗糙 度資料時顯而易見。鏡體可包含在各峰之間差異性隆起之 違等峰之間的區域,以提供減少之粗趟度而實質上類似之 表面形態。舉例而言,雖然在鏡體水合時峰高可減少,但 峰形狀實質上保持相同。 或者或另外,本發明之經非極性樹脂模製之矽氧水凝膠 隱形眼鏡的實施例可包含具有在用電子顯微鏡(諸如掃描 電子顯微鏡、透射電子顯微鏡或掃描透射電子顯微鏡)觀 察時可視覺辨別之富矽區及貧矽區的鏡體。基於化學分 121841.doc -58- 200813102 析,可瞭解貧石夕區為實質上或完全無石夕之眼鏡内區域。貧 石夕區可能比經表面處理之石夕氧水凝膠隱形眼鏡或包含聚合 濕潤劑腦之石夕氧水凝膠隱形眼鏡中的該等區大。可使用 習知影像分析軟體及裝置(諸如可購自 (Tennessee)之影像分析系統)測定富矽區、貧矽區或兩者 之大小。影像分析軟體系統可用以勾勒出富石夕區及貧石夕區 • t邊界輪廓且敎該等區之橫截面積、直徑、體積及其類 似物。在某些實施例中,貧石々P* g 士 ^ T貞夕^具有比其他矽氧水凝膠隱 Ο --形眼鏡之貧石夕區大至少鄕、至少鄉、至少70%、至少 80%或至少90%之橫截面積。 本發明之未經表面處理之鏡體通常提供眼用彳接受之表 面可濕性。換言之,在-實施例中,本發明之石夕氧水凝膠 隱形眼鏡之鏡體為未經表面處理之鏡體。換言之,在不進 行鏡體之表面處理下產生鏡體以提供 濕性。舉例而言,說明性鏡體不包括用以使== 冑上更可接受之電漿處理或額外塗層1而,由於因預萃 ° $之聚合石夕氧水凝膠隱形眼鏡產物中所存在《可移除物質 之量而使本發明之眼鏡具有眼用可接受之表面可濕性,因 \ 此必要時某些實施例可包括表面處理。 '本發明之眼鏡之某些實施例包含自非極性樹脂隱形眼鏡 帛具獲得之洗鑄成型元件鏡體。聚切氧水凝膠隱形眼鏡 產物係指在非極性樹脂隱形眼鏡模具中聚合或固化之產 物。或者,以另一種方式說明,聚合石夕氧水凝膠隱形眼鏡 產物在非極性樹脂隱形眼鏡模具中產生。如本文所論述, 121841.doc -59- 200813102 4等fe形眼鏡模具為使用非極性或疏水性樹脂物質或基於 非極性或疏水性樹脂物質而產生之模具。該等物質通常在 其眼鏡形成表面上具有相對大之接觸角。The Cj bulk formulation lens product includes one or more removable/extractable additives in the precursor composition or the polymerized pre-extracted lens product to increase the extractable component content and produce an ophthalmically acceptable surface Wettable. Hydroxyl hydrogel contact lenses. Although the pre-extracted polymeric hydrogel contact lens product of the present invention has a relatively large amount of extractable material, the extracted form of the As-Silicon hydrogel contact lens of the present invention has very little extractable material in the resulting lens body. . In some embodiments, the amount of extractable material remaining in the extracted spectacles is from about 121841.doc -57 to 200813102 from 0.1% to about 4%, such as from about 4% to about 2% by weight. The additional extractable material can be determined by contacting the extracted contact lens with an additional volume of a strong solvent such as chloroform. In addition, since the extractable component is present and distributed throughout the polymerizable silicone hydrogel lens precursor composition and the pre-extracted polymeric oxygenated hydrogel contact lens product, the lens product and contact lens of the present invention can be Different from surface treated helium hydrogel contact lenses. Since the extractable component can be extracted from the lens product and is substantially absent from the hydrated contact lens, the lens products and contact lenses of the present invention can be distinguished from the oxygenated hydrogel contact lens having the polymeric wetting agent IPN. The silicone hydrogel contact lenses of the present invention may comprise lens bodies obtained from non-polar resin contact lens molds having substantially the same surface morphology upon inspection in the hydrated and dehydrated state. Further, the hydrated mirror bodies may have a surface roughness slightly smaller than the surface roughness of the dehydrated mirror body. For example, the lens body of the glasses of the present invention may have a surface comprising a nanometer size peak, which is apparent when analyzing the root mean square (RMS) roughness data of the surface of the lens. The mirror body may contain regions between the unbalanced peaks of the differential ridges between the peaks to provide reduced roughness and substantially similar surface morphology. For example, although the peak height can be reduced when the lens body is hydrated, the peak shape remains substantially the same. Alternatively or additionally, embodiments of the non-polar resin molded oxygenated hydrogel contact lenses of the present invention may comprise visually visible when viewed with an electron microscope such as a scanning electron microscope, a transmission electron microscope, or a scanning transmission electron microscope. Identify the mirrors of the rich and poor areas. Based on the analysis of the chemical points 121841.doc -58- 200813102, it can be understood that the pelagic area is a region of the eyeglasses that is substantially or completely free of stone. The plutonium area may be larger than the surface treated zephyrheal hydrogel contact lenses or those in the oxidizing agent brain containing the polymeric humectant. Conventional image analysis software and devices, such as the image analysis system available from Tennessee, can be used to determine the size of the rich zone, the barren zone, or both. The image analysis software system can be used to outline the cross-sectional area, diameter, volume, and the like of the rich boundary area and the peat area. In certain embodiments, the prickly 々P* g 士 ^ T贞 ^ ^ has at least 鄕, at least 70%, at least 70%, at least 70% smaller than other anaerobic hydrogel concealed glasses. 80% or at least 90% of the cross-sectional area. The untreated surface of the present invention generally provides surface wettability acceptable to the eye. In other words, in the embodiment, the mirror body of the Shixia oxygen hydrogel contact lens of the present invention is a mirror body which is not surface-treated. In other words, the mirror body is produced to provide moisture without surface treatment of the mirror body. For example, the illustrative mirror body does not include a plasma treatment or additional coating 1 to make the == 胄 more acceptable, due to the pre-extraction of the polymerized stone hydrogel contact lens product There is a "removable amount of material" to provide the spectacles of the present invention with an ophthalmically acceptable surface wettability, as certain embodiments may include surface treatment if necessary. Some embodiments of the lenses of the present invention comprise a wash-molded component mirror body obtained from a non-polar resin contact lens cookware. Polyoxygenated Hydrogel Contact Lens The product refers to a product that is polymerized or cured in a non-polar resin contact lens mold. Alternatively, in another manner, the polymeric rock oxide hydrogel contact lens product is produced in a non-polar resin contact lens mold. As discussed herein, 121841.doc-59-200813102 4 is a mold produced using a non-polar or hydrophobic resin material or based on a non-polar or hydrophobic resin material. These materials typically have a relatively large contact angle on their lens forming surface.
Ο 本發明之矽氧水凝膠隱形眼鏡亦可包括一或多種舒適增 強劑,其相對於無舒適增強劑之矽氧水凝膠隱形眼鏡增強 眼鏡配戴者或眼鏡配戴者群體所感受之隱形眼鏡的舒適 度。舒適增強劑之實例包括脫水減少齊卜淚膜穩定劑或既 減 > 脫水亦穩定隱形眼鏡所置放之眼睛的淚膜之藥劑。該 等舒適增_包括對水具有親和力之聚合物質。在某些實 &例中’聚合物質包含_或多種兩親媒性基團。適用作舒 適增強劑之物質的實例包括可聚合構脂,諸如包括鱗酸膽 鹼、、且伤之物質。在某些實施例中,前驅體組合物包含甲基 丙婦酸_酸膽驗單體,以使得在此狀況下兩親媒性物ί 磷酸膽鹼包括於所得交聯網路中。 、 如本文所論述,本發明之⑨氧水凝膠眼鏡之舒適度亦可 f由在眼鏡前㈣組合物及财取之⑦氧水㈣隱形眼鏡 物中包括-或多種可移除之舒適增強劑來增強。舉例而 言:本文所述之某些可移除物質包括與自無可移除物質之 — 艮鏡相比減少本發明之眼鏡的離子流 之樂劑。減少眼鏡之籬;a 兄之離子流可有助於減少眼鏡配戴 膜脫水且減少配戴眼於 冉 戳目艮鏡所導致之角膜染色。 如本文所論述,本發明 期之計…“ 月之眼鏡具有允許眼鏡配戴延長時 gp ^ °本表月之眼鏡可作為每天配 戴眼鏡、母週配戴眼鏡、 笑迴配戴眼鏡或母月配戴眼鏡來 121841.doc -60 - 200813102 酉己戴。本發日月> 、 、、兄匕έ具有有助於眼鏡舒適度及可用性 之表面可濕性、槎 雜工、*左卜 、數、離子&、透氧性及水含量的水合鏡 體。在某些實施例中,木 、 Τ奉毛明之眼鏡包含具有選自由以下 、^、成之群之特徵的水合鏡體:小於約95。之前進接 : 2 ]於約1,6 MPa之拉伸模數、小於約7 X ΙΟ.3 : 111之離子、流、至少約70 barrer之透氧性(Dk卜至少 約3(^置%之水含量及其組合。然而,在其他實施例中, 離子流可大於7 X 1(r3mm2/min,但仍未引起角膜脫水染色 Γ、 _ 或其他臨床問題。 二本發明之眼鏡可包含前表面、後表面或前及後表面上之 前進接觸角小於120。之水合鏡體。在某些實施例中,鏡體 /、有】於90之鏡表面前進接觸角,例如鏡體具有約85。、 、勺80約75。、約70。、約65°、約60。、約55。或約50。之鏡 表面前進接觸角。鏡體亦可具有小於80。之鏡表面後退接 觸角,例如鏡體可具有約75。、約7〇。、約65。、約6〇。、約 55°、約5〇。或約45。之鏡表面後退接觸角。作為前進接觸 角與後退接觸角之間的差異之滯後可為約5。至約35。。然 而’在某些實施例,滯後可大於25。,但仍為臨床上可接 • 受的。 可使用一般熟習此項技術者已知之常規方法測定前進接 觸角。舉例而言,可使用習知液滴形狀法(諸如固著液滴 法或俘獲氣泡法)來量測隱形眼鏡之前進接觸角及後退接 觸角。矽氧水凝膠隱形眼鏡之前進及後退水接觸角可使用矽 The oxygenated hydrogel contact lens of the present invention may also include one or more comfort enhancers that enhance the feel of the lens wearer or the wearer of the eyeglasses relative to the silicone hydrogel contact lens without the comfort enhancer. The comfort of contact lenses. Examples of comfort enhancers include dehydration to reduce the tear film stabilizer or to reduce > dehydrate and stabilize the tear film of the eye placed by the contact lens. These comforts include a polymeric substance that has an affinity for water. In some embodiments, the 'polymeric substance' contains _ or a plurality of amphiphilic groups. Examples of the substance which is suitable as a relaxing enhancer include a polymerizable structure such as a substance including choline citrate, and which is damaged. In certain embodiments, the precursor composition comprises a methyl aceto-acid citrate monomer such that in this case the amphiphilic choline choline is included in the resulting cross-linked network. As discussed herein, the comfort of the 9-oxygel eyeglasses of the present invention may also include - or a plurality of removable comfort enhancements in the front (4) composition of the lens and the 7 oxygen water (four) contact lens. Agent to enhance. By way of example, some of the removable materials described herein include an agent that reduces the flow of ions of the lenses of the present invention as compared to a krypton mirror of a non-removable material. Reduce the barrier of the glasses; a brother's ion flow can help reduce the lens dehydration of the lens and reduce the cornea stain caused by wearing the eye. As discussed herein, the period of the invention... "The glasses of the moon have the ability to allow the glasses to be worn extended. gp ^ ° The glasses of this month can be used as glasses for daily wear, glasses for maternal week, glasses for laughter or mater Wearing glasses for the month 121841.doc -60 - 200813102 酉己戴. The date of the hair, 、,, brothers and sisters have surface wettability, handyman, * Zuo Bu, which contributes to the comfort and usability of the glasses. Hydrating mirror body of number, ion & oxygen permeability and water content. In certain embodiments, the wood, Τ毛毛明 glasses comprise a hydrated mirror body having a characteristic selected from the group consisting of: About 95. Previously: 2] at a tensile modulus of about 1,6 MPa, less than about 7 X ΙΟ.3: 111 ions, flow, at least about 70 barrer oxygen permeability (Dk at least about 3 ( The water content and its combination are set. However, in other embodiments, the ion current may be greater than 7 X 1 (r3 mm 2 /min, but still does not cause corneal dehydration staining, _ or other clinical problems. May include a front surface, a back surface, or a front contact angle of less than 120 on the front and back surfaces. In some embodiments, the mirror body has a contact angle of 90 on the surface of the mirror, such as a mirror body having about 85., a spoon 80 of about 75, about 70, about 65, and about 60. A mirror surface advancing contact angle of about 55. or about 50. The mirror body may also have a mirror surface receding contact angle of less than 80. For example, the mirror body may have about 75., about 7 〇, about 65., about 6 〇., about 55°, about 5〇, or about 45. The mirror surface recedes the contact angle. The hysteresis as the difference between the advancing contact angle and the receding contact angle may be about 5 to about 35. However, 'in some In some embodiments, the hysteresis can be greater than 25. However, it is still clinically acceptable. The advancing contact angle can be determined using conventional methods known to those skilled in the art. For example, conventional droplet shape methods can be used. (such as the fixed droplet method or the trapping bubble method) to measure the contact angle and the receding contact angle of the contact lens. The front and back water contact angles of the oxygenated hydrogel contact lens can be used.
Kruss DSA 100 器具(Kruss GmbH,Hamburg)且如 D. A. 121841.doc -61 - 200813102Kruss DSA 100 appliance (Kruss GmbH, Hamburg) and as D. A. 121841.doc -61 - 200813102
Brandreth: "Dynamic contact angles and contact angle hysteresis*’,Journal of Colloid and Interface Science,第 62 卷,1977,第 205-212 頁及 R. Knapikowski,M. Kudra:Brandreth: "Dynamic contact angles and contact angle hysteresis*', Journal of Colloid and Interface Science, Vol. 62, 1977, pp. 205-212 and R. Knapikowski, M. Kudra:
Kontaktwinkelmessungen nach dem Wi lhel my-Pr inzip-Ein statistischer Ansatz zur Fehierbeurteilung’’, Chem. Technik,第45卷,1993,第179-185頁及美國專利第 6,43 6,481號中所述來測定。 例如,前進接觸角及後退接觸角可使用俘獲氣泡法使用 磷酸鹽緩衝生理食鹽水(PBS ; pH=7.2)來測定。使眼鏡平 鋪在石英表面上且在測試之前用PB S再水合1 〇分鐘。使用 自動/主射糸統將氣泡置放於眼鏡表面上。可增加及減小氣 泡大小以獲得後退角(當增加氣泡大小時獲得平臺)及前進 角(當減小氣泡大小時獲得平臺)。 或者或另外,本發明之眼鏡可包含展示大於5秒之水驅 散時間(BUT)的鏡體。舉例而言,包含水but為至少15秒 (諸如20秒或更長時間)之鏡體的本發明之眼鏡的實施例可 具有眼用可接受之表面可濕性。 本發明之眼鏡可包含模數小於1.6 MPa之鏡體。在某些 實鉍例中,鏡體之模數小於丨·〇 MPa。舉例而言,鏡體可 具有約 G.9 MPa、約 〇·8 MPa、狀7 Mpa、狀6 Mpa、約 ^ & 、力〇·4 MPa或約0.3 MPa之模數。本發明之鏡體之 模數較佳為約〇·4至敎8 Mpa,且甚至更佳在社4與約 ΜΡ&之間。在一實施例中,鏡體具有約0.4與0.5 MPa之 間的模數。選擇鏡體模數以提供當置放於眼睛上時舒適之 121841.doc -62 - 200813102 眼鏡且使眼鏡配戴者可適應眼鏡之操作。 可使用一般熟習此項技術者已知之常規方法測定鏡體之 模數。舉例而言,寬度約4 mm之隱形眼鏡片可自眼鏡中心 部分切割,且拉伸模數(單位:MPa)可自藉由使用Instron 3342 (Instron Corporation)在 25°C 下在至少 75%濕度之空氣 中以10 mm/min之速率進行拉伸測試所獲得之應力應變曲 線的初始斜率來測定。 本發明之眼鏡之鏡體的離子流通常小於約5 X 1 〇·3 mm2/min。雖然某些本發明之眼鏡的鏡體可具有高達約7 X 1〇_3 mm2/min之離子流,但咸信當離子流小於約5 X 1〇-3 mm2/min,且當隱形眼鏡不包括MPC時,可減少角膜脫水 染色。在某些實施例中,鏡體之離子流為約4.5 X 10·3 mm2/min、約 4 X l〇-3mm2/min、約 3·5 x 1〇-3mm2/min、約 3 x l(T3mm2/min或更少。然而,如本文所述,離子流可大 於7X10·3 mm2/min,但仍未引起角膜脫水染色或其他臨床 問題。 本發明之眼鏡之鏡體的離子流可使用一般熟習此項技術 者已知之常規方法來測定。舉例而言,隱形眼鏡或鏡體之 離子流可使用實質上類似於美國專利第5,849,81丨號中所述 之1’Ionoflux Technique”的技術來量測。舉例而言,待量測 之眼鏡可置放在保留眼鏡之裝置中的凸形與凹形部分之 間。凸形及凹形部分包括位於眼鏡與各凸形或凹形部分之 間的可撓性密封環。在將眼鏡定位於保留眼鏡之裝置中之 後,將保留眼鏡之裝置置放於帶螺紋之蓋中。將蓋擰至玻 121841.d〇( -63- 200813102 管上以界定原料物質腔室。原料物質腔室中可填充有i6 〇·ι莫耳濃度之NaC1溶液。接收腔室可填充有8〇 mi去離 子水。將電導計之導線浸人接收腔室之去離子水中,且將 授拌杯添加至接收腔室中。將接收腔室置放在丨1溫箱令, 2溫度保持在約3rc。最後,將原料物質腔室浸入接收 中可在將原料物質腔室浸入接收腔室後10分鐘開 始,每隔兩分鐘進行電導率之量測,歷時約20分鐘。電導 率與時間之關係資料應實質上呈線性。 本發明之眼鏡之鏡體通常具有高透氧性。舉例而言,鏡 體具有Dk不小於60 barrer之透氧性。本發明之眼鏡的實施 例包含 Dk為約 80 barrer、約 90 barrer、約100 barrer、約 110 barrer、約 120 barrer、約 13〇 barrer、約 14〇 或更 大之鏡體。 可使用一般熟習此項技術者已知之常規方法來測定本發 明之眼鏡之Dk。舉例而言,Dk值可使用如美國專利第 5,817,924號中所述之Mocon方法來測定。Dk值可使用型號 名稱為Mocon Οχ-Tran System之市售器具來測定。 本發明之眼鏡亦包含具有眼用可接受之水含量的鏡體。 舉例而5,本發明之眼鏡之實施例包含水含量不小於3 〇 % 之鏡體。在某些實施例中,鏡體具有約35%、約40%、約 45%、約50%、約55%、約60%或約65%之水含量。 可使用一般熟習此項技術者已知之常規方法來測定本發 明之眼鏡之水含量。舉例而言,水合矽氧水凝膠隱形眼鏡 可自水性液體中移除,擦拭以移除過量表面水,且稱重。 121841.doc -64- 200813102 接著可將經稱重之眼鏡在烘箱中於8(rc真空中乾燥,且接 著可稱重經乾燥之眼鏡。藉由自水合眼鏡重量減去乾燥眼 鏡重篁來測定重量差。水含量(%)為(重量差/水合重 量)χ 100。 : 除上文所確定之特定值以外,本發明之眼鏡可具有在上 文所確定之特定值之任何組合之間範圍内之值。舉例而 «,本發明之隱形眼鏡可具有約45%至約55%之水含量, 約3至約4之離子流值,約35。至約45。之靜態接觸角,約 ^ — 55。至約8〇。之前進接觸角,約47。至約55。之後退接觸角, 約11。至约25。之滯後,約〇·47 MPa至約〇·51 _之楊氏模 數(Young’s m〇duli)、約14〇%至約245%之伸長率及其組 合。 在本毛明之矽氧水凝膠隱形眼鏡之某些特定實施例中, 鏡體具有小於0.5 MPa之模數,小於4之離子流及約42_46% 之水含量。 纟發明之石夕氧水凝膠隱形眼鏡為矯正視力或增強視力之 L形眼鏡眼鏡可為球面眼鏡或非球面眼鏡。眼鏡可為單 焦點眼鏡或多焦點眼鏡,包括雙焦點眼鏡。在某些實施例 . t ’本發明之眼鏡為旋轉穩定眼鏡,諸如旋轉穩定複曲面 • 形眼鏡。紋轉穩定隱形眼鏡可為包含包括壓載物之鏡體 的隱形眼鏡。舉例而言,鏡體可具有稜鏡壓載物、周圍壓 载物及/或一或多個薄化上方及下方區域。 本發明之眼鏡亦包含包括外周邊緣區域之鏡體。外周邊 緣區域可包括圓形部分。舉例而言,外周邊緣區域可包含 121841.doc -65 - 200813102 圓形後邊緣表面、圓形前邊緣表面或其組合。在某些實施 例中,外周邊緣自前表面至後表面完全成圓形。因此,可 瞭解本發明之眼鏡之鏡體可包含圓形外周邊緣。 本發明之眼鏡可包含其厚度分布解決與現㈣氧水凝膠 : S形眼鏡相關之問題但對眼鏡配戴者而言仍舒適之鏡體。 : # =改變鏡體厚度及鏡體模數,可控制鏡體之硬度。舉例 而言’隱形眼鏡之-區域的硬度可定義為眼鏡之揚氏模數 與指定區域之眼鏡厚度平方的乘積。因此,本發明之眼鏡 P —之某些實施例可包含中心硬度(例如眼鏡中心或視區中心 之硬度)小於約0.007 MPa_mm2、眼鏡接面硬度小於約〇〇3 MPa-mm或其組合之鏡體。眼鏡接面可定義為眼鏡區與斜 面或(對於無斜面之眼鏡而言)距離眼鏡邊緣約1.2 mm之點 的接面(參見美國專利第6,849,671號)。在其他實施例中, 本發明之眼鏡可包含中心、硬度大於G•⑽7 Mpa_mm2、眼鏡 接面硬度大於約0.03 MPa_mm2或其組合之鏡體。 <、 μ的疋,在眼鏡或大批眼鏡中,本發明之矽氧水凝膠 ’ 隱形眼鏡之物理參數(諸如物理尺寸及其類似物)具有小的 可變性。舉例而言,在某些實施例中,將諸如鏈轉移劑之 . 添加劑添加至可聚合矽氧水凝膠隱形眼鏡前驅體組合物中 .卩減少眼鏡物理屬性之可變性。使用該等控制物理參數之 添加劑,任兩批眼鏡之間的可變性較佳小於2%。舉例而 或夕批本發明之眼鏡之可變性可為約〇 · 5 %至約 I.9%。舉例而言,本發明之眼鏡之直徑及基礎曲線可控制 在預定值之L6%内。更特定言之’若目標隱形眼鏡直徑為 121841.doc -66- 200813102 14.0 mm,且若一批隱形眼鏡中隱形眼鏡之實際直徑在約 13.6 mm至約14_4 mm之間變化,則可在隱形眼鏡產生期間 使用一或多種添加劑以減少可變性,且產生直徑在約Η 8 mm至約i4.2 mm範圍内之隱形眼鏡。可提供類似控制以減 : 少眼鏡厚度、徑向深度、基礎曲率及其類似物之變化。 本發明之矽氧水凝膠隱形眼鏡可提供於密封包裝中。舉 例而言,本發明之矽氧水凝膠隱形眼鏡可提供於密封發泡 包裝或適於傳遞給眼鏡配戴者之其他類似容器中。眼鏡可 (\ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 適浴液包括磷酸鹽緩衝生理食鹽水溶液及硼酸鹽緩衝溶 液。必要時,溶液可包括消毒劑或可無消毒劑或防腐劑。 必要時,溶液亦可包括界面活性劑,諸如泊洛沙姆 (poloxamer)及其類似物。 禮封包裝内之眼鏡較佳無菌。舉例而言,眼鏡可在密封 G裝之如权菌或可在密封包裝内殺菌。經殺菌之眼鏡可為 〇 6暴露於殺菌量之輻射之眼鏡。舉例而言,眼鏡可為經高 M爸處理之眼鏡、經γ輻射之眼鏡、、經紫外輕射暴露之眼 鏡及其類似物。 實例 以下μ例說明本發明之某些態樣及優勢,然而絕不認為 本發明限於以下所述之特定實施例。 —除非另外指出,否則本發明之實踐將採用此項技術技能 耗圍内之聚合物合成、水凝膠形成及其類似物之習知技 術該等技術在文獻中充分說明。除非相反特定說明,否 121841.doc -67· 200813102 則試劑及物質為市售的。 製備隱形眼鏡(例如矽氧水凝膠隱形眼鏡)之方法描述於 以下專利中:美國專利第4,121,896號、第4,495,313號、第 4,565,348 號、第 4,64〇,489 號、第七889,664 號、第 • 4,985,186 號、第 5,039,459 號、第 5,080,839 號、第 5,094,609 號、第 5 26〇,〇〇〇 號、第 5,6〇7,518 號、第 • 5,760,100 號、第 5,850,107 號、第 5,935,492 號、第 6,099,852 號、第 6 367,929 號、第 6,8225016 號、第 —6,867,245 ^^ ^ ^ 公開案第20030125498號、第20050154080號及第 20050191335號。 在以下實例中,雖然已努力確保與所用數字(例如量、 溫度等)相關之精確性,但仍應解決某些實驗誤差及偏 差。除非另外指出,否則溫度以。c計,且壓力在海平面下 為大氣壓力或接近大氣壓力。 以下熟知之化學物質在實例中提及,且在某些情況下, 由其如下提出之縮寫提及。 物質及方法 、 縮寫 . AE :烯丙氧基乙醇 DI :去離子化 HEMA:曱基丙烯酸2-羥乙酯 IPA :異丙醇 MMA :甲基丙烯酸甲酯 121841.doc .68- 200813102 M3U: M3-U; α-ω-雙(曱基丙烯醯氧基乙基亞胺基羧基 乙氧基丙基)_聚(二甲基矽氧烷聚(三氟丙基甲基矽氧烷)-聚(ω-甲氧基-聚(乙二醇)丙基甲基矽氧烷;含二甲基丙烯 醯基矽氧大分子單體 以下實例中所用之M3U由下式表示,其中η為121,m為 7.6,h 為 4.4,p 為 7·4,且 Μη=12,800,且 Mw=16,200 (Asahikasei Aime Co” Ltd” Japan) 〇 C3H6(OC2H4)pOCH3 CH3 〇H3 CH3 C2H4CF3 ch3 ch3 H2C=CCOOC2H4NHCOOC2H4OC3H6〒iO—(〒iO)n-十0)m—〒0)h—fi—C3H6OC2H4OCONHC2H4OCOC=CH2 ch3 ch3 ch3 ch3 ch3 M3U著色:β銅酞菁於M3U中之分散液(重量%)。銅酞菁 可自 BASF以 Heliogen Blue Κ7090獲得。 N,N-DMF : DMF ; N,N-二甲基甲醯胺 NVP: 1-乙烯基-2-吡咯啶酮(在真空下新鮮蒸餾) PDMS :聚二甲基矽氧烷 PDMS-共-PEG:聚二甲基矽氧烷與PEG之嵌段共聚物, 其含有 75% PEG 且 MW 為 600 (來自 Gelest 之 DBE712) PEG :聚乙二醇 PP :丙基丙烯 Pr :丙醇 TEGDMA :二甲基丙烯酸三乙二醇酯 TEGDVE :三乙二醇二乙烯醚 TPO:聯苯基(2,4,6-三甲基苯甲醯基)氧化膦 TPTMA :三經甲基丙烧三甲基丙稀g复酯 121841.doc -69- 200813102 UV416:丙烯酸2-(4-苯曱醯基-3-羥基苯氧基)乙酯 Vazo-52 : 2,2’-偶氮雙(2,4-二甲基戊腈)(V-52 ;熱引發 劑)Kontaktwinkelmessungen nach dem Wi lhel my-Pr inzip-Ein statistischer Ansatz zur Fehierbeurteilung'', Chem. Technik, Vol. 45, 1993, pp. 179-185 and U.S. Patent No. 6,43,481. For example, the advancing contact angle and the receding contact angle can be measured using a capture bubble method using phosphate buffered physiological saline (PBS; pH = 7.2). The glasses were spread on a quartz surface and rehydrated with PB S for 1 minute before testing. Use the Auto/Main System to place the bubbles on the surface of the glasses. The bubble size can be increased and decreased to obtain a receding angle (a platform is obtained when the bubble size is increased) and an advancing angle (a platform is obtained when the bubble size is reduced). Alternatively or additionally, the spectacles of the present invention may comprise a lens body exhibiting a water scatter time (BUT) of greater than 5 seconds. For example, embodiments of the lenses of the present invention comprising a mirror body having a water but of at least 15 seconds (such as 20 seconds or more) may have an ophthalmically acceptable surface wettability. The spectacles of the present invention may comprise a lens body having a modulus of less than 1.6 MPa. In some practical examples, the modulus of the mirror body is less than 丨·〇 MPa. For example, the mirror body can have a modulus of about G.9 MPa, about 88 MPa, 7 Mpa, 6 Mpa, about ^ &, force 4 4 MPa or about 0.3 MPa. The modulus of the mirror body of the present invention is preferably from about 〇4 to M8 Mpa, and even more preferably between the society 4 and about ΜΡ& In one embodiment, the mirror body has a modulus between about 0.4 and 0.5 MPa. The mirror body modulus is chosen to provide a comfortable lens that can be adapted to the operation of the eyewear when placed on the eye. The modulus of the mirror body can be determined using conventional methods known to those skilled in the art. For example, a contact lens having a width of about 4 mm can be cut from the center portion of the lens, and the tensile modulus (unit: MPa) can be at least 75% humidity at 25 ° C by using Instron 3342 (Instron Corporation). The initial slope of the stress-strain curve obtained by tensile testing at a rate of 10 mm/min in air was measured. The ion current of the lens body of the glasses of the present invention is typically less than about 5 X 1 〇·3 mm 2 /min. While some of the scopes of the lenses of the present invention can have ion currents of up to about 7 X 1 〇 3 mm 2 /min, the ion current is less than about 5 X 1 〇 -3 mm 2 /min, and when the contact lenses are not Corneal dehydration staining can be reduced when MPC is included. In some embodiments, the ion current of the mirror body is about 4.5 X 10·3 mm 2 /min, about 4 X l〇-3 mm 2 /min, about 3·5 x 1 〇 -3 mm 2 /min, about 3 x 1 (T3 mm 2 /min or less. However, as described herein, the ion current can be greater than 7 x 10 · 3 mm 2 / min, but still does not cause corneal dehydration staining or other clinical problems. The ion current of the lens body of the glasses of the present invention can be used generally The method is known in the art to determine the ion flux of a contact lens or a mirror body, for example, using a technique substantially similar to the 1 'Ionoflux Technique" described in U.S. Patent No. 5,849,81. For example, the spectacles to be measured may be placed between the convex and concave portions of the device that retains the spectacles. The convex and concave portions are located between the spectacles and the respective convex or concave portions. Flexible seal ring. After positioning the glasses in the device that retains the glasses, place the device that retains the glasses in the threaded cover. Screw the cover onto the glass 121841.d〇 (-63- 200813102 tube to define Raw material chamber. The raw material chamber can be filled with NaC1 with i6 ι·1 molar concentration. Solution. The receiving chamber can be filled with 8 〇mi deionized water. The conductor of the conductivity meter is immersed in the deionized water of the receiving chamber, and the mixing cup is added to the receiving chamber. The receiving chamber is placed in the 丨1 thermostat, 2 temperature is maintained at about 3 rc. Finally, immersing the raw material chamber into the receiving chamber can start measuring the conductivity every two minutes after immersing the raw material chamber into the receiving chamber for 10 minutes. About 20 minutes. The relationship between conductivity and time should be substantially linear. The lens body of the glasses of the present invention generally has high oxygen permeability. For example, the lens body has oxygen permeability of Dk not less than 60 barrer. Embodiments of the eyeglasses include a lens body having a Dk of about 80 barrer, about 90 barrer, about 100 barrer, about 110 barrer, about 120 barrer, about 13 barrer, about 14 inches or more. Conventional methods are known for determining the Dk of the glasses of the present invention. For example, the Dk value can be determined using the Mocon method as described in U.S. Patent No. 5,817,924. The Dk value can be modeled as Mocon®-Tran System. city The lens of the present invention also comprises a lens body having an ophthalmically acceptable water content. For example, an embodiment of the eyeglasses of the present invention comprises a lens body having a water content of not less than 3 %. In certain embodiments The mirror body has a water content of about 35%, about 40%, about 45%, about 50%, about 55%, about 60% or about 65%. It can be determined using conventional methods known to those skilled in the art. The water content of the glasses of the present invention. For example, a hydrated hydrogel hydrogel contact lens can be removed from an aqueous liquid, wiped to remove excess surface water, and weighed. 121841.doc -64- 200813102 The weighed glasses can then be dried in an oven at 8 (rc vacuum, and then the dried glasses can be weighed. Determined by subtracting the dry glasses from the weight of the hydrated glasses) The difference in weight. The water content (%) is (weight difference / hydration weight) χ 100. : In addition to the specific values determined above, the spectacles of the invention may have a range between any combination of the specific values determined above. By way of example, the contact lens of the present invention may have a water content of from about 45% to about 55%, an ion current value of from about 3 to about 4, a static contact angle of from about 35 to about 45. — 55.至约8〇. Before entering the contact angle, about 47. to about 55. After the contact angle, about 11. to about 25. The lag, about 〇·47 MPa to about 〇·51 _ of the Young's die Number (Young's m〇duli), elongation of about 14% to about 245%, and combinations thereof. In certain specific embodiments of the present invention, the lens body has a mode of less than 0.5 MPa. Number, less than 4 ion currents and about 42_46% water content. 纟Invented Shixi oxygen hydrogel contact lenses for correction L-eye glasses for force or enhanced vision may be spherical or aspherical glasses. The glasses may be single focus glasses or multifocal glasses, including bifocal glasses. In some embodiments, the lens of the present invention is a rotationally stable eyeglass. , such as a rotationally stable toric lens; a styrofoam stable contact lens can be a contact lens comprising a mirror body comprising a ballast. For example, the mirror body can have a ballast, surrounding ballast and/or One or more thinned upper and lower regions. The spectacles of the present invention also include a mirror body including a peripheral edge region. The peripheral edge region may include a circular portion. For example, the peripheral edge region may include 121841.doc -65 - 200813102 a circular trailing edge surface, a rounded leading edge surface, or a combination thereof. In some embodiments, the peripheral edge is completely rounded from the front surface to the back surface. Thus, it can be appreciated that the mirror body of the eyeglasses of the present invention can comprise a circular perimeter The spectacles of the present invention may comprise a lens body whose thickness distribution solves the problems associated with the current (IV) oxyhydrogel: S-shaped spectacles but which is still comfortable for the wearer of the spectacles. : # = The thickness of the mirror body and the modulus of the mirror body can control the hardness of the mirror body. For example, the hardness of the contact lens-area can be defined as the product of the Young's modulus of the glasses and the square of the thickness of the glasses in the specified area. Spectacles of the invention P - some embodiments may comprise a mirror body having a central hardness (e.g., the hardness of the center of the eyeglass or the center of the viewing zone) of less than about 0.007 MPa_mm2, a lens joint hardness of less than about 〇〇3 MPa-mm, or a combination thereof. The junction can be defined as the junction of the eyeglass region and the bevel or (for non-beveled glasses) a point of about 1.2 mm from the edge of the lens (see U.S. Patent No. 6,849,671). In other embodiments, the spectacles of the present invention may comprise a mirror body having a center, a hardness greater than G•(10)7 Mpa_mm2, a lens joint hardness greater than about 0.03 MPa mm2, or a combination thereof. <, μ of 疋, in the glasses or a large number of glasses, the physical parameters of the oxygenated hydrogel' contact lenses of the present invention, such as physical dimensions and the like, have small variability. For example, in certain embodiments, an additive such as a chain transfer agent is added to the polymerizable silicone hydrogel contact lens precursor composition. The variability in the physical properties of the lens is reduced. The variability between any two batches of glasses is preferably less than 2% using such additives that control physical parameters. For example or alternatively, the variability of the lenses of the present invention may range from about 〇 5% to about I. 9%. For example, the diameter and base curve of the glasses of the present invention can be controlled within L6% of the predetermined value. More specifically, if the target contact lens diameter is 121841.doc -66- 200813102 14.0 mm, and if the actual diameter of the contact lens in a batch of contact lenses varies from about 13.6 mm to about 14_4 mm, then the contact lens can be used. One or more additives are used during production to reduce variability and produce contact lenses having a diameter ranging from about 8 mm to about i4.2 mm. Similar controls can be provided to reduce: variations in lens thickness, radial depth, base curvature, and the like. The oxygenated hydrogel contact lenses of the present invention can be provided in a sealed package. For example, the oxygenated hydrogel contact lenses of the present invention can be provided in a sealed foamed package or other similar container suitable for delivery to a lens wearer. Glasses can be (\^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ bath solution including phosphate buffered saline solution and borate buffer solution. If necessary, the solution may include disinfectant or may Disinfectant or preservative. If necessary, the solution may also include a surfactant such as poloxamer and the like. The lenses in the package are preferably sterile. For example, the glasses can be sealed in G Such as the bacterium or can be sterilized in a sealed package. The sterilized glasses can be glasses that are exposed to the sterilizing amount of radiation. For example, the glasses can be glasses treated with high-M da, gamma-radiated glasses, Glasses exposed by ultraviolet light and the like. EXAMPLES The following examples illustrate some aspects and advantages of the invention, but the invention is not considered to be limited to the specific embodiments described below. - Unless otherwise indicated, The practice of the invention will employ well-known techniques for polymer synthesis, hydrogel formation, and the like within the skill of the art. Such techniques are fully described in the literature. Unless specifically stated to the contrary, no. 121841.doc -67· 200813102 then Reagents and materials are commercially available. Methods for preparing contact lenses, such as neohydrogenated hydrogel contact lenses, are described in U.S. Patent Nos. 4,121,896, 4,495,313, 4,565,348, 4, 64〇, 489, 7889, 664, 4,985,186, 5,039,459, 5,080,839, 5,094,609, 5,26, nickname, 5,6,7,518, 5, 760, 100, 5, 850, 107, 5, 935, 492, 6, 099, 852, 6 367, 929, 6,8225016, -6, 867, 245 ^ ^ ^ ^ Publications No. 20030125498, No. 20050154080, and No. 20050191335 In the following examples, while efforts have been made to ensure accuracy with respect to the numbers used (eg, amount, temperature, etc.), certain experimental errors and deviations should be resolved. Unless otherwise noted, the temperature is in .c and the pressure is Below sea level is atmospheric pressure or near atmospheric pressure. The following well-known chemical substances are mentioned in the examples, and in some cases, are mentioned by the abbreviations mentioned below. Substances and methods, abbreviations. AE: allyloxyethanol DI: deionized HEMA: 2-hydroxyethyl methacrylate IPA: isopropanol MMA: methyl methacrylate 121841.doc .68- 200813102 M3U: M3-U; α-ω - bis(fluorenyl propylene oxyethyl imino carboxy ethoxy propyl) _ poly (dimethyl methoxy oxane poly(trifluoropropyl methyl decane) - poly (ω-methoxy - poly(ethylene glycol) propylmethyl decane; dimethyl methacrylate oxime macromonomer The M3U used in the following examples is represented by the following formula, wherein η is 121 and m is 7.6, h is 4.4, p is 7.4, and Μη=12,800, and Mw=16,200 (Asahikasei Aime Co" Ltd" Japan) 〇C3H6(OC2H4)pOCH3 CH3 〇H3 CH3 C2H4CF3 ch3 ch3 H2C=CCOOC2H4NHCOOC2H4OC3H6〒iO—(〒iO)n -10) m-〒0)h-fi-C3H6OC2H4OCONHC2H4OCOC=CH2 ch3 ch3 ch3 ch3 ch3 M3U coloring: dispersion of β copper phthalocyanine in M3U (% by weight). Copper phthalocyanine is available from BASF as Heliogen Blue® 7090. N,N-DMF : DMF ; N,N-dimethylformamide NVP: 1-vinyl-2-pyrrolidone (fresh distillation under vacuum) PDMS : polydimethyl methoxy hydride PDMS-total - PEG: block copolymer of polydimethylsiloxane and PEG, which contains 75% PEG and MW 600 (DBE712 from Gelest) PEG: polyethylene glycol PP: propyl propylene Pr: propanol TEGDMA: two Triethylene glycol methacrylate TEGDVE: triethylene glycol divinyl ether TPO: biphenyl (2,4,6-trimethylbenzylidene) phosphine oxide TPTMA: trimethyl methacrylate trimethyl Propylene g-ester 121841.doc -69- 200813102 UV416: 2-(4-phenylmercapto-3-hydroxyphenoxy)ethyl acrylate Vazo-52 : 2,2'-azobis (2,4 - dimethyl valeronitrile) (V-52; thermal initiator)
Vazo-64 :偶氮二異丁腈(V-64 ;熱引發劑) VMA ·· N-乙烯基-N-甲基乙醯胺(在真空下新鮮蒸餾) VM :甲基丙烯酸乙烯酯 表徵眼鏡產物之方法 前進接觸角/後退接觸角可使用一般熟習此項技術者已 知之常規方法測定前進接觸角。舉例而言,可使用習知液 滴形狀法(諸如固著液滴法或俘獲氣泡法)來量測本文所提 供之隱形眼鏡之前進接觸角及後退接觸角。矽氧水凝膠隱 形眼鏡之前進及後退水接觸角可使用Kruss DSA 100器具 (Kruss GmbH,Hamburg)且如 D. A. Brandreth: ’’Dynamic contact angles and contact angle hysteresis’’,Journal of Colloid and Interface Science,第 62卷,1977,第 205-212 頁及 R. Knapikowski,M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung",Chem. Technik,第 45 卷,1993,第 179-185頁及美國專利第6,436,481號中所述來測定。 例如,前進接觸角及後退接觸角可使用俘獲氣泡法使用 磷酸鹽緩衝生理食鹽水(PBS ; ρΗ=7·2)來測定。使眼鏡平 鋪在石英表面上且在測試之前用PBS再水合10分鐘。使用 自動注射系統將氣泡置放於眼鏡表面上。可增加及減小氣 泡大小以獲得後退角(當增加氣泡大小時獲得平臺)及前進 121841.doc -70- 200813102 角(當減小氣泡大小時獲得平臺)。 模數可使用一般熟習此項技術者已知之常規方法測定鏡 體之模數。舉例而言,寬度約4 mm之隱形眼鏡片可自眼鏡 中心部分切割,且拉伸模數(單位:MPa)可自藉由使用Vazo-64: azobisisobutyronitrile (V-64; thermal initiator) VMA ··N-vinyl-N-methylacetamide (fresh distillation under vacuum) VM: vinyl methacrylate characterization glasses Method of Advancing Contact Angle/Retraction Contact Angle The advancing contact angle can be determined using conventional methods known to those skilled in the art. For example, a conventional droplet shape method such as a sessile drop method or a trapping bubble method can be used to measure the contact angle and the receding contact angle of the contact lens provided herein. The Kruss DSA 100 appliance (Kruss GmbH, Hamburg) and the DA Brandreth: ''Dynamic contact angles and contact angle hysteresis'', Journal of Colloid and Interface Science, can be used for the front and back water contact angles of the hydrogel contact lenses. Vol. 62, 1977, pp. 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung", Chem. Technik, Vol. 45, 1993, pp. 179-185 and Measured as described in U.S. Patent No. 6,436,481. For example, the advancing contact angle and the receding contact angle can be measured using a capture bubble method using phosphate buffered physiological saline (PBS; ρ Η = 7.2). The lenses were spread on a quartz surface and rehydrated with PBS for 10 minutes prior to testing. The bubble is placed on the surface of the lens using an automatic injection system. The bubble size can be increased and decreased to obtain the receding angle (the platform is obtained when the bubble size is increased) and the advancement (the platform is obtained when the bubble size is reduced). The modulus can be determined using conventional methods known to those skilled in the art to determine the modulus of the lens. For example, a contact lens with a width of about 4 mm can be cut from the center of the lens, and the tensile modulus (in MPa) can be used by itself.
Instron 3342(Instron Corporation)在 25°C 下在至少 75%濕度 之空氣中以10 mm/min之速率進行拉伸測試所獲得之應力 4 應變曲線的初始斜率來測定。 離子流本發明之眼鏡之鏡體的離子流可使用一般熟習此 〇…項技術者已知之常規方法來測定。舉例而言,隱形眼鏡或 鏡體之離子流可使用實質上類似於美國專利第5,849,811號 中所述之nI〇noflux Teehnique,,的技術來量測。舉例而言, 待量測之眼鏡可置放在保留眼鏡之裝置中的凸形與凹形部 分之間。凸形及凹形部分包括位於眼鏡與各凸形或凹形部 分之間的可撓性密封環。在將眼鏡定位於保留眼鏡之裝置 中之後,將保留眼鏡之裝置置放於帶螺紋之蓋中。將蓋擰 、 至玻璃官上以界定原料物質腔室。原料物質腔室中可填充 有16 ml 0·1莫耳濃度之NaC1溶液。接收腔室可填充有80 離子水,將電導計之導線浸入接收腔室之去離子水 ' 二且將攪拌棒添加至接收腔室中。將接收腔室置放在恆 '皿相中1將溫度保持在約35°C。最後,將原料物質腔室 /文接收腔至中。可在將原料物質腔室浸入接收腔室後1〇 分鐘開始’每隔兩分鐘進行電導率之量測,歷時約2〇分 鐘、電導率與時間之關係資料應實質上呈線性。 透氧1±可使用_般熟習此項技術者已知之常規方法來測 121841.doc -71 - 200813102 定本發明之眼鏡之Dk。舉例而言,Dk值可使用如美國專 利第5,817,924號中所述之Mocon方法來測定。Dk值可使用 型號名稱為Mocon Ox-Tran System之市售器具來測定。 平衡水含量可使用一般熟習此項技術者已知之常規方法 來測定本發明之眼鏡之水含量。舉例而言,水合石夕氧水凝 膠隱形眼鏡可自水性液體中移除,擦拭以移除過量表面 水,且稱重。接著可將經稱重之眼鏡在烘箱中於8〇°c真空 中乾燥,且接著可稱重經乾燥之眼鏡。藉由自水合眼鏡重 量減去乾燥眼鏡重量來測定重量差。水含量(%)為(重量差/ 水合重量)χ 100。 實例1 低模數可聚合矽氧水凝膠隱形眼鏡前驅體組合物之製備 使用以下指定之試劑及相對量來製備可聚合矽氧水凝膠 隱形眼鏡前驅體組合物。歸因於所得水合隱形眼鏡產物之 低模數,此調配物在本文稱為”低模數調配物"或”LMF,,。 表1 化合物(縮寫) 單位量 重量°/❶(重量比) M3U 35 27.8 VMA 47 37.4 MMA 17 13.5 TEGDMA 0.2 0.2 VAZO-52 0.5 0·4 UV416 0.9 0.7 TlNT(PB15 ;酞菁藍,m3u 运7 0.1 0.1 DBE712(梦油) 25 19.9Instron 3342 (Instron Corporation) was determined by initial slope of the stress 4 strain curve obtained by tensile testing at a rate of 10 mm/min in air at least 75% humidity at 25 °C. Ion Current The ion current of the lens body of the glasses of the present invention can be determined using conventional methods known to those skilled in the art. For example, the ion current of the contact lens or lens body can be measured using a technique substantially similar to nI〇noflux Teehnique, described in U.S. Patent No. 5,849,811. For example, the spectacles to be measured can be placed between the convex and concave portions of the device that retains the spectacles. The male and female portions include a flexible sealing ring between the eyeglasses and each of the male or female portions. After positioning the glasses in the means for retaining the glasses, the means for retaining the glasses is placed in a threaded cover. Screw the cover onto the glass to define the material chamber. The raw material chamber can be filled with 16 ml of 0. 1 molar NaC1 solution. The receiving chamber can be filled with 80 ionized water, the conductor of the conductivity meter is immersed in the deionized water of the receiving chamber and the stir bar is added to the receiving chamber. The receiving chamber was placed in a constant dish 1 to maintain the temperature at about 35 °C. Finally, the raw material chamber/texture chamber is brought to the center. The conductivity can be measured every two minutes after immersing the material chamber in the receiving chamber for a period of about two minutes. The relationship between conductivity and time should be substantially linear. Oxygen Permeation 1 can be measured using conventional methods known to those skilled in the art. 121841.doc -71 - 200813102 The Dk of the glasses of the present invention is determined. For example, the Dk value can be determined using the Mocon method as described in U.S. Patent No. 5,817,924. The Dk value can be measured using a commercially available instrument of the Mocon Ox-Tran System model name. The equilibrium water content can be determined using conventional methods known to those skilled in the art to determine the water content of the lenses of the present invention. For example, a hydrazine hydrated hydrogel contact lens can be removed from an aqueous liquid, wiped to remove excess surface water, and weighed. The weighed glasses can then be dried in an oven at 8 ° C in vacuum and the dried glasses can then be weighed. The weight difference was determined by subtracting the weight of the dry glasses from the weight of the hydrated glasses. The water content (%) is (weight difference / hydration weight) χ 100. EXAMPLE 1 Preparation of a Low Modulus Polymerizable Hydroxyl Hydrogel Contact Lens Precursor Composition A polymerizable silicone hydrogel contact lens precursor composition was prepared using the reagents and relative amounts specified below. Due to the low modulus of the resulting hydrated contact lens product, this formulation is referred to herein as a "low modulus formulation" or "LMF,". Table 1 Compound (abbreviation) Unit weight ° / ❶ (weight ratio) M3U 35 27.8 VMA 47 37.4 MMA 17 13.5 TEGDMA 0.2 0.2 VAZO-52 0.5 0·4 UV416 0.9 0.7 TlNT (PB15; phthalocyanine blue, m3u transport 7 0.1 0.1 DBE712 (dream oil) 25 19.9
U 織汀 125.17份 稱重表!中之組份且混合以形成混合物。經由〇2_2〇〇微 米注射過濾器將混合物過濾至瓶中,且儲存長達約2週。 121841.doc -72- 200813102 (此混合物在本文稱為可聚合石夕氧水凝膠隱形眼鏡前驅體 組合物)。在表!中,除各自重量百分比(以重量/重量表 示;重量比)以外,提供單位量之各化合物。 在最終之矽氧水凝膠隱形眼鏡中,各化學組份之百分比 ; 貞組合才勿中所存在之單位量而非相應、重量π分比更密切相 關。 實例2 矽氧水凝膠隱形眼鏡之製造 f) 一 使用重複真空/氮沖洗程序使來自實例1之大量前驅體組 合物脫氣。接著將經脫氣之前驅體組合物置放至凹形非極 性樹脂模具構件中。接著藉由在達成緊密配合所需之壓力 下與非極性樹脂凸形模具構件接觸置放來封閉經填充之凹 形模具構件。接著在氮批料烘箱中以如下循環進行固化·· 室溫下30 min比淨化,550C下30 min&8(rc下6〇 min。藉 由敲擊隱形眼鏡模具之凹形模具構件進行脫模,以使得凸 賴具構件自其釋放,其中聚合㈣水凝膠隱形眼鏡產物 黏附於凸形模具構件。藉由浮離法或使用機械脫鏡設備進 行脫鏡。浮離法包括將含有乾燥眼鏡之凸形模具構件浸泡 於桶水中。眼鏡通常在約10分鐘内離開模具。藉由壓縮 及旋轉聚合矽氧水凝膠隱形眼鏡產物黏附至其之凸形模具 構件,引導氣體介於隱形眼鏡產物與旋轉凸形模具構件之 間且對隱形眼鏡產物之暴露表面施加真空來進行機械脫 鏡。接著將經分離之眼鏡負載至塑料盤上以進行萃取及水 合0 121841.doc •73- 200813102 般t室溫下’將含有聚合矽氧水凝膠隱形眼鏡產物之眼鏡 皿改入溶劑液體(諸如含有95%乙醇及5%甲醇之工業甲基 =精_))中歷時45 min。接著排出溶劑且用新鮮^ r且用1⑽(3次)、1:1醇/水(3次)及DI水(3次)重複該 方法。 將水合眼鏡儲存於含有财之玻璃小瓶或發泡包裝中或 儲存於pH為7.1·7·5之㈣鹽緩衝生理食鹽水中。在12代 Ο 下將密封容器高壓釜處理30 在高壓釜處理24 h後, 進行眼鏡量測。 水 重 %重所得水合矽氧水凝膠隱形眼鏡, ,且再次稱重以測定經脫水之矽氧水 且接著在烘箱中脫 凝膠隱形眼鏡之乾 如本文所述,敎眼鏡特性,諸如接觸角(包括動態接 觸角及靜態接觸角),性、離子流、模數、伸長率、 拉伸㈣ '水含量及其類似特性。水切氧水凝膠隱形眼 鏡之可濕性亦藉由量測眼鏡之水驅散時間來檢測。 在分配研究期間,進-步檢測眼睛相容性,其中將隱形 眼鏡置放於人眼上歷時i小時、3小時或6小時或更長時 間,且接著進行臨床評估。 由本發明之調配物所產生之石夕氧水凝膠隱形眼鏡具有眼 用可接受之表面可濕性。該等矽氧水凝膠隱形眼鏡具有 44仏2%之平衡水濃度(EWC),且、經測定具有48 9+/_〇 7% 之可萃取物含量。 所得水合隱形眼鏡具有以下特性·· 121841.doc -74- 200813102 表2 特性 值 平衡水含量(EWC) 43-45% 透氧性(Dk) 109 barrer 靜態接觸角(俘獲氣泡濕潤角) 36° 動態接觸角(前進接觸角) 71° 動態接觸角(後退接觸角) 49° 滯後(前進-後退) 22° 折射率 L398 離子流 3-4 模數 0.4-0.5 Mpa 拉伸強度 0.55-0.6 Mpa 在最終之眼鏡中,在萃取程序後,將大部分(若非所有) 矽油與未反應之單體或線性聚合物組份一起萃取。在本實 例中,萃取後未偵測到矽油。 製備一系列數批眼鏡以用於臨床評估。自如實例1中所 述之前驅體組合物製備眼鏡。該數批眼鏡經表徵且具有以 下特性。 Ο 121841.doc 75- 200813102U Weining 125.17 copies Weighing table! The ingredients are combined and mixed to form a mixture. The mixture was filtered into a vial via a 〇2 2 〇〇 microinjection filter and stored for up to about 2 weeks. 121841.doc -72- 200813102 (This mixture is referred to herein as a polymerizable lithothere hydrogel contact lens precursor composition). In the table! In addition to the respective weight percentages (expressed by weight/weight; weight ratio), a unit amount of each compound is provided. In the final oxime hydrogel contact lens, the percentage of each chemical component is more closely related to the unit amount present rather than the corresponding π ratio. Example 2 Manufacture of a Hydroxyl Hydrogel Contact Lens f) A large number of precursor compositions from Example 1 were degassed using a repeated vacuum/nitrogen rinsing procedure. The degassed precursor composition is then placed into a concave non-polar resin mold member. The filled female mold member is then closed by contact with a non-polar resin male mold member under the pressure required to achieve a tight fit. Then, the mixture was cured in a nitrogen batch oven in the following cycle: • 30 min at room temperature, 30 min & 8 at 550 C (6 sec at rc. Demold by tapping the concave mold member of the contact lens mold) So that the protruding member is released therefrom, wherein the polymeric (tetra) hydrogel contact lens product adheres to the convex mold member. The lens is removed by a floatation method or using a mechanical lens removal device. The floatation method includes containing dry glasses. The convex mold member is immersed in the bucket water. The spectacles typically leave the mold within about 10 minutes. The gas is interposed between the contact lens products by compressing and rotating the polymerized hydrogel contact lens product to its convex mold member. A mechanical vacuum is applied between the rotating male mold member and the exposed surface of the contact lens product. The separated lens is then loaded onto a plastic tray for extraction and hydration. 0 121841.doc •73- 200813102 Change the glassware containing the polymerized hydrogel contact lens product to a solvent liquid (such as industrial methyl = fine _ with 95% ethanol and 5% methanol) for 45 min at room temperatureThe solvent was then drained and the procedure was repeated with fresh <1>10 (3 times), 1:1 alcohol/water (3 times) and DI water (3 times). The hydrated spectacles are stored in a glass vial or blister pack containing the money or stored in a (4) salt buffered physiological saline solution having a pH of 7.1·7·5. The sealed vessel autoclave treatment was carried out under 12 passages. After the autoclave treatment for 24 h, the glasses were measured. The water weighs the resulting hydrated hydrogel contact lens, and is weighed again to determine the dehydrated hydrogen peroxide water and then de-gel the contact lens in an oven as described herein, 敎 glasses characteristics, such as contact Angle (including dynamic contact angle and static contact angle), sex, ion current, modulus, elongation, tensile (IV) 'water content and similar characteristics. The wettability of the water-cut oxygen hydrogel invisible eyeglasses is also detected by measuring the water dispersing time of the glasses. Eye compatibility was further tested during the dispensing study, where the contact lenses were placed on the human eye for i hours, 3 hours or 6 hours or longer, and then clinical evaluation was performed. The oxime oxygen hydrogel contact lenses produced by the formulations of the present invention have an ophthalmically acceptable surface wettability. The hydrogel contact lenses have an equilibrium water concentration (EWC) of 44% and have an extractable content of 48 9+/_〇 7%. The resulting hydrated contact lens has the following characteristics: 121841.doc -74- 200813102 Table 2 Characteristic value Balanced water content (EWC) 43-45% Oxygen permeability (Dk) 109 barrer Static contact angle (capture bubble wetting angle) 36° Dynamic Contact angle (advancing contact angle) 71° Dynamic contact angle (reverse contact angle) 49° Hysteresis (forward-reverse) 22° Refractive index L398 Ion flow 3-4 Modulus 0.4-0.5 Mpa Tensile strength 0.55-0.6 Mpa at the end In the glasses, after the extraction procedure, most, if not all, of the eucalyptus oil is extracted with the unreacted monomer or linear polymer component. In this example, no oil was detected after extraction. A series of lenses were prepared for clinical evaluation. Spectacles were prepared from the precursor composition as described in Example 1. The batch of glasses is characterized and has the following characteristics. Ο 121841.doc 75- 200813102
v£< 25C1FB07 I 43.69士 0.37 36.4 土 0.1 76.1 土 4·0 47.9 土 0.7 28.2 0.45 土 0.03 340.2土 161.0 0.58 士 0.26 3.04 土 0.10 8272 25C1FB06 43.84士 0.42 36.7 土 0·6 67.4 士 4·4 ί 47.4 士 L8 20.1 0.41 土 0·02 466.9土 43·7 0.66 土 0·04 3.04 士 0.07 7883 25C1FB05 43.85士 0.38 36·7 士 0.5 7U 士 5·5 48.4 士 1.0 22.7 0·57 土 0.03 508.6土 93.2 1.18士 0.25 3.08 土 0· 18 6742 25C1FB04 44.37土0.36 | 37.6 士 0.3 66.5 士 2.1 48.0 土 0·4 18.5 0.53 士 0.07 395.7土 60.2^ 0.78 土 0.21 3.21 士 0.19 8291 25C1FB03 45.52土 0.70 36.0 士 0.5 | 1 72.3 土 1.8 1 | 46.7士0.1 | | 25.5 1 0.39 士 0·07 449.4士 53.7 0.70 土 0.15 2.36 士 0.29 11148 25C1FB02 45·0 士 0·51 36.3 士 1.3 ί 65·5 士 1.2 | 47.7士0.7 | 17.8 0.39 土 0.01 302土 181.9 0.43 士 0.18 3.18 士 0.07 9855 25C1FB01 43.79士 0·33 36.0 土 1.4 66.9 土 2·8 | 47.6土0.7 | |193_I 0.47 土 0.01 170.2±100.2 0.33 土 0.11 2.65 土 0.13 11482 眼鏡 靜態(°) 前進(ADV,。) 後退(REC,勹 滯後(〇) 模數(mPa) 伸長率(%) 拉伸強度(mPa) J S S fH # GPC讀數(每毫克乾燥眼鏡之反應) I25C1FB14 43.42d=0.72 37.0 士 0.8 70·7 士 4.7 1 47.1 士 0.6 I 23.6 0.49 士 0·02 496.8±89.4 0.92 土 0.20 2·72 土 0.14 10005 25C1FB13 44·48±〇·42 38·1 士 0.6 | 75.1 士2.2 1 48.6 士 1.4 26.5 0.46 土 0.03 i 340.9±117.7 0·59 土 0.21 2.7 士 0· 14 9735 25C1FB12 42.68土 0·70 1 36.5 土 0.9 67·8 士 3.0 | 47.5土0·8 | [204____1 0.52 土 0·12 ί 256.3土 191.1 0.61 土 0·50 2.60 土 0.04 7020 25C1FB11 43·32 士 0.76 36.9 土 0.6 73.3 土 0.4 49.2 士 1·0 24.1 0.48±0.13 412·8 土 7·3 0.70 士 0.23 1 2.62 士 0.20 7810 25C1FB10 44.56士 0.39 | 35.9土 1·9 i | 57.9土3.5 | | 47·7士 1·2 1 1 10.2 1 0.55 士 0.03 443.1±51.3 | 0.92士0.20 | 2.81 土 0.02 10879 25C1FB09 46.1 士 0·37 37.5 土 0·3 ί 72.5 土 3.7 1 47.6±〇.l ] 24.9 0·43 士 0·02 151.8 士 100.7 0.30 土 0.12 2.65 士 0.18 11514 25C1FB08 45.14 士 0.43 | | 35.9土 1.0 | 69.6 土 3.7 48·1 士 0·6 21.5 0.44 士 0.05 | 412.3士63.0 | 0.63 土 0·07 3.32 土 0·29 10340 眼鏡 Μ 靜態(°) 前進(ADV,。) 後退(REC,Q) 滯後(0) 模數(mPa) 伸長率(%) 拉伸強度(mPa) 離子流(1(T3 mm2/min) GPC讀數(每毫克乾燥眼鏡之反應) 121841.doc -76- 200813102 ue< 1 25C1FB18 1 43.90土 0·85 | 36.5士0·8 I I 67.5±1.9 I 49.1±0.5 18.4 0.41 土 0.06 458.4士 85.1 0.81 土 0.23 2.15 士0.15 10671 25C1FB17 43.59土 0.63 37.1 士 0.7 73·7 土 3.5 47.8±0.5 j 25.9 0.51±0.10 455.4 土 43.6 0.92 士 0.11 2.47 士 0.09 11598 25C1FB15 43.23土 0.60 36.7 士 0.3 73.5 士 2.5 | 47.3±0.2 | 26.2 I 0.43 土 0.05 424.5土 22.2 0.71 土 0.05 2.74 士 0.09 10741 眼鏡 靜態(°) 前進(ADV,0) 後退(REC,°) 滯後(。) 模數(mPa) 伸長率(%) 拉伸強度(mPa) J S S 錐 GPC讀數(每毫克乾燥眼鏡之反應) 121841.doc -77- 200813102 在上述各表中,GPC值為萃取及水合後殘餘可移除物含 量之相對讀數。使用氯仿作為用以接觸先前萃取之隱形眼 鏡的最終萃取溶劑,萃取及水合後之總殘餘/可萃取物含 量在約0.4%至2%之範圍内。對各組眼鏡而言,量測3至5 個重複樣品。 實例3 ; 微調低模數可聚合矽氧水凝膠隱形眼鏡前驅體組合物之 製備 (; 使用以下指定之試劑及量來製備可聚合矽氧水凝膠隱形 眼鏡前驅體組合物。歸因於所得水合矽氧水凝膠隱形眼鏡 產物中之低模數及低批次間變化,此調配物在本文中稱為 π微調低模數調配物π或nMLMFn。 表4 化合物(縮寫) 單位量 重量%(重量比) M3U 35 VMA 47 MMA 17 TEGDMA 0.2 VAZO-52 0.5 UV416 0.9 TINT(PB15 ;酞菁藍,m3u 藍) 0.1 DBE712(矽油)+ AE1 25 121841.doc -78- 1 AE與矽油之比率在0.1至5份AE與99.9至95份矽油之範 圍内。 總計:125.17份 稱重上表4中之組份且混合以形成混合物。經由0.2-5.0 微米注射過濾器將混合物過濾至瓶中,且儲存長達約2 週。 200813102 别驅體組合物血膏柄〗由 /、貫例1中所述之丽驅體組合物的不同之 處在於石夕油組份中包括ΑΕ。將心添加至石夕油中,之後將 石夕油與前驅體調配物中所含之其他化學試劑混合,且有利 也用乂減夕所知水合隱形眼鏡產物之尺寸及物理特性的可 變性。 基本上如以上實例2中所述進行隱形眼鏡之調配。所得 水合隱形眼鏡具有類似於實例2中所述眼鏡之物理特性, 其具有以下有利之例外情況-眼鏡直徑、讀及離子流之 任一或多者的可變性通常低於在AE不存在下所製備之調 配物中之彼等的可變性。 實例4 含有變化量之稀丙氧基乙醇之微調低模數可聚合發氣水 凝谬隱形眼鏡前媒趙組合物之製備及所得梦氧水凝膠隱形 眼鏡產物之表徵 進行以下實驗以進—步研究向石夕油中添加不同量之稀丙 氧基乙n此減少最終經萃取水合隱形眼鏡產物中之尺 寸及物理特性之批次變化的作用。 如實例1及3中所述來製備單體混合物(可聚合矽氧水凝 膠前驅體組合物)。調配物組份與以上實例丨中所述者相 同’其令例外為可萃取之石夕油組份在梦油中視情況含有各 種量之婦丙氧基乙醇·· 〇、2、4及6%。調配物詳情提供於 下表4及5中。將各種里之烯丙氧基醇添加至三種不同貨號 之石夕油(Gelest)的每一者中。 將單體混合物過遽且脫氣,分散於凹形聚丙稀隱形眼鏡 121841.doc -79- 200813102 模具構件之眼鏡形成表面上,且將凸形模具構件與凹形模 具構件嚙合以形成在隱形眼鏡狀腔室中含有單體混合物之 隱形眼鏡模具。工具之EF(膨脹係數)為約1.1%或鋼質隱形 眼鏡模具插入物之外徑為約14.3 mm。在分批烘箱中在N2 下進行固化。通常將經填充之模具置放於N2批料烘箱内, « 且用N2淨化30 min以將氧含量減少至小於1000 ppm,繼而 * 第一次加熱至55 °C歷時30 min,繼而加熱至80 °C歷時60 min 〇 表5 具有各種AE濃度之25°C調配物 〇 腔室 參考號 M3U貨號 矽油貨號 ΑΕΛΟ/〇 1 25C-0AE-A1 050906 5L-7902 0 2 25C-2AE-A1 050906 5L-7902 2 3 25C-4AE-A1 050906 5L-7902 4 4 25C-6AE-A1 050906 5L-7902 6 1 25C-0AE-B1 050906 7H-11038 0 2 25C-2AE-B1 050906 7H-11038 2 3 25C-4AE-B1 050906 7H-11038 4 4 25C-6AE-B1 050906 7H-11038 6 1 25C-0AE-C1 050906 7E-10627 0 2 25C-2AE-C1 050906 7E-10627 2 3 25C-4AE-C1 050906 7E-10627 4 4 25C-6AE-C1 050906 7E-10627 6 〇 *烯丙氧基乙醇百分比(AE%)係指矽油中所含烯丙氧基 ,乙醇之重量百分比 121841.doc -80- 200813102 表6 具有各種烯丙氧基乙醇濃度之25°C調配物 腔室 參考號 M3U貨號 矽油貨號 %矽油/AE 1 25C-20SO-A1 50906 5L-7902 WITH 4%AE 20 2 25C-23SO-A1 50906 5L-7902 WITH 4%AE 23 3 25C-26SO-A1 50906 5L-7902 WITH 4%AE 26 4 25C-29SO-A1 50906 5L-7902 WITH 4%AE 29 1 25C-20SO-A1 50906 10627 WITH 0.1%AE 20 25C-23SO-A1 50906 10627 WITH 0.1 %AE 23 3 25C-26SO-A1 50906 10627 WITH 0.1%AE 26 Li_ 25C-29SO-A1 50906 10627 WITH 0.1 %AE 29 1 25C-20SO-A1 040819bR 5L-7902 WITH 4%AE 20 2 25C-23SO-A1 040819bR 5L-7902 WITH 4%AE 23 3 25C-26SO-A1 040819bR 5L-7902 WITH 4%AE 26 4 25C-29SO-A1 040819bR 5L-7902 WITH 4%AE 29 1 25C-20SO-A1 040819bR 10627 WITH 0.1 %AE 20 2 25C-23SO-A1 040819bR 10627 WITH 0.1%AE 23 25C-26SO-A1 040819bR 10627 WITH 0.1 %AE 26 4 25C-29SO-A1 040819bR 10627 WITH 0.1 %AE 29 固化後,在臺式脫模機上進行脫模及脫鏡。所有調配物 之眼鏡均顯示良好之脫模/脫鏡特徵。 將乾燥眼鏡負載於聚丙烯盤中,且相繼使用乙醇、乙 醇-水及水各自循環洗滌約30分鐘來萃取及水合,且與熱 水接觸。接著將經萃取及水合之眼鏡置放於含有pH 7.2 PBS緩衝液(含有界面活性劑)之小瓶中且經高壓釜處理。 量測眼鏡且在高壓蚤處理後1天進行檢查。僅量測未變 形眼鏡之尺寸及物理特性,包括直徑、基礎曲線、平衡水 含量、靜態及動態接觸角、拉伸特性(模數、拉伸強度及 伸長率)及離子流。 結果 研究向矽油中添加各種量之烯丙氧基乙醇為一種⑴減少 所得經萃取/水合矽氧水凝膠隱形眼鏡產物中各批次之間 121841.doc -81 - 200813102 的差異,及(ϋ)提供具有所需尺寸及物理特性之隱形眼鏡 的方式。 萃取水合隱形眼鏡之高壓蚤處理後的直徑及物理特性 提供於表7中。直徑、平衡水含量及離子流與烯丙氧基乙 • 醇含量之關係分別顯示於圖4、5及6中。v£< 25C1FB07 I 43.69 ± 0.37 36.4 Soil 0.1 76.1 Soil 4·0 47.9 Soil 0.7 28.2 0.45 Soil 0.03 340.2 Soil 161.0 0.58 ± 0.26 3.04 Soil 0.10 8272 25C1FB06 43.84 ± 0.42 36.7 Soil 0·6 67.4 ± 4·4 ί 47.4士L8 20.1 0.41 土0·02 466.9土43·7 0.66 土0·04 3.04 士0.07 7883 25C1FB05 43.85士0.38 36·7 士0.5 7U 士5·5 48.4 士1.0 22.7 0·57 土0.03 508.6土93.2 1.18士0.25 3.08 soil 0· 18 6742 25C1FB04 44.37 soil 0.36 | 37.6 ± 0.366.5 ± 2.1 48.0 soil 0·4 18.5 0.53 ± 0.07 395.7 soil 60.2^ 0.78 soil 0.21 3.21 ± 0.19 8291 25C1FB03 45.52 soil 0.70 36.0 ± 0.5 | 1 72.3 Earth 1.8 1 | 46.7士 0.1 | | 25.5 1 0.39 士0·07 449.4士53.7 0.70 土 0.15 2.36 士 0.29 11148 25C1FB02 45·0 士0·51 36.3 士1.3 ί 65·5 士 1.2 | 47.7士0.7 | 17.8 0.39土0.01 302 soil 181.9 0.43 ± 0.18 3.18 ± 0.07 9855 25C1FB01 43.79 ± 0 · 33 36.0 soil 1.4 66.9 soil 2 · 8 | 47.6 soil 0.7 | | 193_I 0.47 soil 0.01 170.2 ± 100.2 0.33 soil 0.11 2.65 soil 0.13 11482 glasses static (°) (ADV,.) Back ( REC, 勹 hysteresis (〇) Modulus (mPa) Elongation (%) Tensile strength (mPa) JSS fH # GPC reading (reaction per milligram of dry glasses) I25C1FB14 43.42d=0.72 37.0 ± 0.8 70·7 ± 4.7 1 47.1 ± 0.6 I 23.6 0.49 ± 0 · 02 496.8 ± 89.4 0.92 soil 0.20 2 · 72 soil 0.14 10005 25C1FB13 44 · 48 ± 〇 · 42 38 · 1 ± 0.6 | 75.1 ± 2.2 1 48.6 ± 1.4 26.5 0.46 soil 0.03 i 340.9 ± 117.7 0·59 Soil 0.21 2.7 士 0· 14 9735 25C1FB12 42.68 土 0·70 1 36.5 地 0.9 67·8 士士 3.0 | 47.5土0·8 | [204____1 0.52 土0·12 ί 256.3土191.1 0.61 土0·50 2.60 Soil 0.04 7020 25C1FB11 43·32 ± 0.76 36.9 Soil 0.6 73.3 Soil 0.4 49.2 ±1·0 24.1 0.48±0.13 412·8 Soil 7·3 0.70 ± 0.23 1 2.62 ± 0.20 7810 25C1FB10 44.56 ± 0.39 | 35.9 Soil 1·9 i | 57.9土3.5 | | 47·7士1·2 1 1 10.2 1 0.55 士0.03 443.1±51.3 | 0.92士 0.20 | 2.81 土0.02 10879 25C1FB09 46.1 士0·37 37.5 土0·3 ί 72.5 土3.7 1 47.6 ±〇.l ] 24.9 0·43 士0·02 151.8 士100.7 0.30 土 0.12 2.65 士 0.18 11514 25C1FB08 45.14士 0.43 | | 35.9土1.0 69.6 Soil 3.7 48·1 士 0·6 21.5 0.44 士 0.05 | 412.3士63.0 | 0.63 土 0·07 3.32 土 0·29 10340 Glasses Μ Static (°) Forward (ADV,. ) Back (REC, Q) Hysteresis (0) Modulus (mPa) Elongation (%) Tensile strength (mPa) Ion flow (1 (T3 mm2/min) GPC reading (reaction per milligram of dry glasses) 121841.doc -76- 200813102 ue< 1 25C1FB18 1 43.90 soil 0·85 | 36.5 ± 0·8 II 67.5 ± 1.9 I 49.1 ± 0.5 18.4 0.41 soil 0.06 458.4 ± 85.1 0.81 soil 0.23 2.15 ± 0.15 10671 25C1FB17 43.59 soil 0.63 37.1 ± 0.7 73 ·7 soil 3.5 47.8±0.5 j 25.9 0.51±0.10 455.4 soil 43.6 0.92 ± 0.11 2.47 ± 0.09 11598 25C1FB15 43.23 soil 0.60 36.7 ± 0.3 73.5 ± 2.5 | 47.3 ± 0.2 | 26.2 I 0.43 soil 0.05 424.5 soil 22.2 0.71 soil 0.05 2.74 0.09 10741 Glasses static (°) Advance (ADV, 0) Back (REC, °) Hysteresis (.) Modulus (mPa) Elongation (%) Tensile strength (mPa) JSS Cone GPC reading (reaction per milligram of dry glasses) 121841.doc -77- 200813102 In the above tables, the GPC value is the relative reading of the residual removable content after extraction and hydration. Using chloroform as the final extraction solvent for contact with previously extracted contact lenses, extraction and hydration The total residual/extractable content afterwards is about 0.4% to Within 2% range. For each group of glasses, 3 to 5 replicate samples were measured. Example 3; Preparation of fine-tuned low modulus polymerizable silicone hydrogel contact lens precursor composition (; Reagents and amounts to prepare a polymerizable silicone hydrogel contact lens precursor composition. This formulation is attributed to the low modulus and low batch-to-batch variation in the resulting hydrated hydrogel hydrogel contact lens product. It is called π fine-tuning low-modulus formulation π or nMLMFn. Table 4 Compound (abbreviation) Unit weight% (weight ratio) M3U 35 VMA 47 MMA 17 TEGDMA 0.2 VAZO-52 0.5 UV416 0.9 TINT (PB15; Phthalocyanine blue, m3u Blue) 0.1 DBE712 (矽油) + AE1 25 121841.doc -78- 1 The ratio of AE to oyster sauce is in the range of 0.1 to 5 parts AE and 99.9 to 95 parts eucalyptus oil. Total: 125.17 parts The components in Table 4 above were weighed and mixed to form a mixture. The mixture was filtered into a vial via a 0.2-5.0 micron syringe filter and stored for up to about 2 weeks. 200813102 The composition of the blood-slurry of the body composition is different from that of the body composition described in Example 1, in which the scorpion oil component includes strontium. The heart is added to the Shixia oil, and then the Shixia oil is mixed with other chemical agents contained in the precursor formulation, and is advantageously used for the variability of the size and physical properties of the hydrated contact lens product. The dispensing of the contact lenses was carried out essentially as described in Example 2 above. The resulting hydrated contact lens has physical properties similar to those described in Example 2, with the following advantageous exceptions - the variability of either or both of the spectacles diameter, read and ion flow is generally lower than in the absence of AE Their variability in the formulations prepared. Example 4 Preparation of a finely tuned low modulus polymerizable gas condensed contact lens pre-media composition containing varying amounts of dilute propoxyethanol and characterization of the resulting dream oxygen hydrogel contact lens product The following experiment was carried out to The step study adds a different amount of dilute propoxyethyl n to the Shixia oil which reduces the effect of batch variations in the size and physical properties of the final extracted hydrated contact lens product. A monomer mixture (polymerizable hydrophobic hydrogel precursor composition) was prepared as described in Examples 1 and 3. The composition of the formulation is the same as that described in the above example 其 'The exception is that the extractable Shixia oil component contains various amounts of praline propoxyethanol·· 2、, 2, 4 and 6% in the dream oil. . Details of the formulations are provided in Tables 4 and 5 below. Various isopropoxy alcohols were added to each of the three different grades of Gelest. The monomer mixture is smashed and degassed, dispersed on the lens forming surface of the concave polypropylene contact lens 121841.doc-79-200813102, and the male mold member is engaged with the concave mold member to form the contact lens A contact lens mold containing a monomer mixture in the chamber. The EF (expansion coefficient) of the tool is about 1.1% or the outer diameter of the steel contact lens mold insert is about 14.3 mm. Curing was carried out under N2 in a batch oven. The filled mold is usually placed in an N2 batch oven, « and cleaned with N2 for 30 min to reduce the oxygen content to less than 1000 ppm, then * first heated to 55 °C for 30 min, then heated to 80 °C for 60 min 〇 Table 5 25 °C formulation with various AE concentrations 〇 chamber reference number M3U article number 矽 oil number ΑΕΛΟ / 〇 1 25C-0AE-A1 050906 5L-7902 0 2 25C-2AE-A1 050906 5L- 7902 2 3 25C-4AE-A1 050906 5L-7902 4 4 25C-6AE-A1 050906 5L-7902 6 1 25C-0AE-B1 050906 7H-11038 0 2 25C-2AE-B1 050906 7H-11038 2 3 25C-4AE -B1 050906 7H-11038 4 4 25C-6AE-B1 050906 7H-11038 6 1 25C-0AE-C1 050906 7E-10627 0 2 25C-2AE-C1 050906 7E-10627 2 3 25C-4AE-C1 050906 7E-10627 4 4 25C-6AE-C1 050906 7E-10627 6 Percentage of 烯* allyloxyethanol (AE%) means the allyloxy group contained in eucalyptus oil, the weight percentage of ethanol 121841.doc -80- 200813102 Table 6 has various Allyloxyethanol concentration 25 ° C formulation chamber reference number M3U article number 矽 oil article number 矽 oil / AE 1 25C-20SO-A1 50906 5L-7902 WITH 4% AE 20 2 25C-23SO-A1 50906 5L-7902 WITH4% AE 23 3 25C-26SO-A1 50906 5L-7902 WITH 4% AE 26 4 25C-29SO-A1 50906 5L-7902 WITH 4% AE 29 1 25C-20SO-A1 50906 10627 WITH 0.1% AE 20 25C-23SO -A1 50906 10627 WITH 0.1 %AE 23 3 25C-26SO-A1 50906 10627 WITH 0.1%AE 26 Li_ 25C-29SO-A1 50906 10627 WITH 0.1 %AE 29 1 25C-20SO-A1 040819bR 5L-7902 WITH 4%AE 20 2 25C-23SO-A1 040819bR 5L-7902 WITH 4%AE 23 3 25C-26SO-A1 040819bR 5L-7902 WITH 4%AE 26 4 25C-29SO-A1 040819bR 5L-7902 WITH 4%AE 29 1 25C-20SO- A1 040819bR 10627 WITH 0.1 %AE 20 2 25C-23SO-A1 040819bR 10627 WITH 0.1%AE 23 25C-26SO-A1 040819bR 10627 WITH 0.1 %AE 26 4 25C-29SO-A1 040819bR 10627 WITH 0.1 %AE 29 After curing, at Demolding and mirror removal on a benchtop stripper. All formulations of the glasses showed good release/off mirror characteristics. The dried glasses were loaded in a polypropylene pan, and successively washed with ethanol, ethanol-water and water for about 30 minutes to extract and hydrate, and contacted with hot water. The extracted and hydrated lenses were then placed in vials containing pH 7.2 PBS buffer (containing surfactant) and autoclaved. The glasses were measured and examined one day after the high pressure helium treatment. Only the dimensions and physical properties of the unshaped glasses are measured, including diameter, base curve, equilibrium water content, static and dynamic contact angles, tensile properties (modulus, tensile strength and elongation), and ion current. RESULTS: Various amounts of allyloxyethanol were added to the eucalyptus oil as one (1) to reduce the difference between the batches of 121841.doc -81 - 200813102 in the obtained extracted/hydrated hydrogel hydrogel contact lens products, and (ϋ A way to provide contact lenses of the desired size and physical properties. The diameter and physical properties of the high pressure enthalpy of the extracted hydrated contact lenses are provided in Table 7. The relationship between diameter, equilibrium water content, and ion current and allyloxyethanol content are shown in Figures 4, 5 and 6, respectively.
121841.doc -82 - 200813102121841.doc -82 - 200813102
U g VO o T-H 赛 <N 〇 g-N > Q OO r—H ON (N 41 v〇 s cn 〇 cn +1 β m g ? 4 g 3 卜 ο (N O ro 00 o 跻 Uij^ (N m Λ Ό σ; in 0¾ in PH s i 鹚 S o 2 r-H o o 等 o 磁 w 寸 O 00 ro o 屮 cn 沄 o 'O Q\ <N Ο -Η g (Ν u o CN Ό σ\ 〇 Co 〇 -Ή vq Ο cn ο 去 (Ν cn 寸 /g\ 羞 •Η On Os 卜 ν〇 cn S —IT) A H < ώ < o ό (N H < ώ < (N ό to CN Η < ώ < 寸 ό (Ν τ-Η < ώ ό CN 0 U g vo o r-H 〇 r-H 1 (〇)AQV 寸 cn 寺 iri (N m cr; 00 1 r-H r-H Λ m ov o 衷 v〇 m s m 〇 o 卜 ^-H 〇 r-H T-H Λ (N On 央 in m Β U s § 寸 ο s § C±1 寸 o 屮 錄 (N r-H c5 -Ή o cn 00 (N o r-H (N r- o -H m ^s〇 t-H o -H r-H υ Μ (N CN o 0 -Ή ON 01 in oo O -Ή s r-H v〇 m S m o 寸 /gs ί Η 卜 r-H 莩 rn cn cn B1系列 (M3U:050906, SO:11038) < ώ < O ό in <N r-H < (N ό CN Τ-Ή < ώ c 寸 ό (N r-H < 'O ό - -83-U g VO o TH Race <N 〇gN > Q OO r-H ON (N 41 v〇s cn 〇cn +1 β mg ? 4 g 3 οο (NO ro 00 o 跻Uij^ (N m Λ 03 σ; in 03⁄4 in PH si 鹚S o 2 rH oo et al o magnetic w inch O 00 ro o 屮cn 沄o 'OQ\ <N Ο -Η g (Ν uo CN Ό σ\ 〇Co 〇-Ή vq Ο cn ο go (Ν cn inch / g \ 羞 • Η On Os 卜〇cn S — IT) AH < ώ < o ό (NH < ώ < (N ό to CN Η < ώ < ό ό (Ν τ-Η < ώ ό CN 0 U g vo o rH 〇rH 1 (〇) AQV inch cn temple iri (N m cr; 00 1 rH rH Λ m ov o 〇 v〇msm 〇o 卜 ^ -H 〇rH TH Λ (N On in in Β U s § inchο s § C±1 inch o 屮录 (N rH c5 -Ή o cn 00 (N o rH (N r- o -H m ^s 〇tH o -H rH υ Μ (N CN o 0 -Ή ON 01 in oo O -Ή s rH v〇m S mo inch /gs ί Η 卜rH 莩rn cn cn B1 series (M3U:050906, SO:11038 < ώ < O ό in <N rH < (N ό CN Τ-Ή < ώ c inch ό (N rH < 'O ό - -83-
^s U g ν〇 o 寸 o (〇)Λαν m CO o? t-H 卜 (N r-H 此 00 v〇 o m 1—H o 岑 in cn Ph 1 o (N 00 d 等 s r-H in r-H o cn 00 r-H Λ in CL, s o ▼-H 寸 o r-H o o r-H in o 錄 <N (N 〇 00 〇\ (N 00 o -H ON (N 〇 -H cn in t-H g 〇 -Ή m cn r-H U U 〇 o +1 寸 — 寸 (N cn 〇 -H (N 寸 ?; 〇 (N 〇 o ▼-H 〇 /g\ 1 cn 00 oo rn 卜 cn cn rn r-H A1系列 (M3U:050906, 1 SO: 10627) < ώ ό ^T) (N < w < <N ΰ (N < 寸 ό (N r-H < ό (N^s U g ν〇o 寸o (〇)Λαν m CO o? tH 卜(N rH this 00 v〇om 1—H o 岑in cn Ph 1 o (N 00 d et s rH in rH o cn 00 rH Λ in CL, so ▼-H 寸o rH oo rH in o Record <N (N 〇00 〇\ (N 00 o -H ON (N 〇-H cn in tH g 〇-Ή m cn rH UU 〇o +1 inch - inch (N cn 〇-H (N inch?; 〇(N 〇o ▼-H 〇/g\ 1 cn 00 oo rn 卜 cn rn rH A1 series (M3U:050906, 1 SO: 10627) < ώ ό ^T) (N < w <<N ΰ (N < inch ό (N rH < ό (N
121841.doc 200813102 如圖3中所示,在所有三種調配物(系列A1、B1&C1)中 均使用25份矽油/AE混合物;眼鏡直徑隨混合物中AE含量 增加而減少。各系列對應於由給定貨號之矽油所製備之隱 形眼鏡,其中用於各系列Al、B1及C1之矽油均不同。121841.doc 200813102 As shown in Figure 3, 25 parts of the eucalyptus/AE mixture were used in all three formulations (Series A1, B1 &C1); the diameter of the spectacles decreased as the AE content in the mixture increased. Each series corresponds to a contact lens prepared from a given article of eucalyptus oil, wherein the eucalyptus oils used in each series of Al, B1 and C1 are different.
U A系列產生之眼鏡比系列B或c產生之眼鏡大。早期使用 未添加有AE之系列A矽油製得25C眼鏡之臨床試驗導致眼 鏡具有相對較高之脫水染色速率,而由系列c矽油製得之 眼鏡具有更令人滿意(較低)之脫水染色速率。因此,理想 的是,確定應增加系列A貨號矽油之效能以達成甚至更為 所需之眼鏡臨床特性。(認為特定批次之聚氧化烯石夕氧(例 如矽油)之效能為其在給定濃度下產生具有自所用之隱形 眼鏡模具直徑減小之直徑的最終經萃取水合眼鏡產物:能 力。最終眼鏡產物之眼鏡直徑減小愈大,聚氧化稀石夕氧之 ㈣則愈大。尤其較佳者為產生具有所用隱形眼鏡模具直 徑〇.98M.G2倍範圍内之直徑的最終眼鏡產物之梦油)。、舉 例而言,參看圖3,向系列a石夕油貨號中添加4% ae產生^ 本上與在添加烯丙氧基乙醇之前由系列以夕油貨號產生二 眼鏡直徑相同的眼鏡直徑。 EW=6中所示及圖4及圖5中分別圖示說明,觀測到諸如 EWC/。及離子流之特性的類似趨勢。 因此,向聚氧化烯石夕氧可萃取組份中添 (諸如太眚為丨士 M m W移_劑 例示㈣丙氧基乙醇)有效地細微調 二K驅體組合物提供具有類似有益物理特性之最 、、絲形眼鏡產物之能力。尤其較佳者為平衡水含量在 121841.doc -84 - 200813102 約40-5 0%之範圍内、離子流在約2至約5之範圍内且模數小 於約1.2 Mpa之經萃取水合隱形眼鏡。 如早期所示,可藉由添加4% AE來調節5 L批次之SO。 如對於SO批次10627及1 1038而言,其已具有高效能,且因 此僅添加0.1%之AE來用於微調。為進一步證實此微調概 * 念,將4%AE添加至SO 5L批次中,且將0.1°/〇之AE添加至 ·· SO 10627批次中。兩批M3U用以製成具有20、23、26及29 份微調SO(或S0/AE混合物)之25C眼鏡,如表5中所列。眼 f' 鏡特性列於表8中。 表8具有不同AE-SO負載之眼鏡特性The glasses produced by the U A series are larger than those produced by the series B or c. Early clinical trials using 25A glasses without the addition of AE's Series A enamel resulted in glasses with a relatively high rate of dehydration dyeing, while glasses made from the series c oyster sauce had a more satisfactory (lower) dehydration dyeing rate. . Therefore, it is desirable to determine that the efficacy of Series A No. 矽 oil should be increased to achieve even more desirable clinical characteristics of the lens. (The efficacy of a particular batch of polyoxyalkylene oxide (e.g., eucalyptus) is believed to produce the final extracted hydrated spectacles product at a given concentration having a diameter that is reduced from the diameter of the contact lens mold used: the ultimate spectacles The larger the diameter of the lens of the product is, the larger the polyoxygen oxide (4) is. The better is to produce the final eyeglass product with the diameter of the contact lens mold diameter of 98.98 M.G2 times. ). For example, referring to Fig. 3, 4% ae is added to the series a Shixia oil number to produce the same diameter of the glasses as the diameter of the second pair of glasses produced by the series of the oils before the addition of allyloxyethanol. As shown in EW=6 and illustrated in Figures 4 and 5, respectively, such as EWC/ is observed. And a similar trend in the characteristics of the ion current. Thus, the addition of a polyoxyalkylene oxide extractable component (such as a toluene to a gentleman M m W shifting agent to an exemplary (iv) propoxyethanol) effectively fine-tunes the di-K-drive composition to provide similar beneficial physics. The most characteristic, the ability of wire-shaped glasses products. Particularly preferred are extracted hydrated contact lenses having an equilibrium water content in the range of from about 40,184.doc -84 to 200813102 of about 40 to about 50%, an ion current in the range of from about 2 to about 5, and a modulus of less than about 1.2 MPa. . As indicated earlier, the SO of the 5 L batch can be adjusted by adding 4% AE. For SO batches 10627 and 1 1038, it is already highly efficient, and therefore only 0.1% of AE is added for fine tuning. To further confirm this fine tuning concept, 4% AE was added to the SO 5L batch and AE of 0.1 °/〇 was added to the SO 10627 batch. Two batches of M3U were used to make 25C glasses with 20, 23, 26 and 29 fine-tuned SO (or S0/AE mixtures) as listed in Table 5. The eye f' mirror characteristics are listed in Table 8. Table 8 Characteristics of glasses with different AE-SO loads
A1 (M3U: 050906, SO: 5L-7902) D (mm) EWC% 離子流 模數(mPA) 20SO-A1 14.52 44.47士 0.64 3.35 土 0.1 0.42 士 0.01 23SO-A1 14.3 44.78士 0.39 26SO-A1 14.16 43.42士 0.50 2.61 士 0.19 0.41 士 0.03 29SO-A1 13.99 43.45士 0.42 B1 (M3U: 050906, SO: 10627) D(mm) EWC% 離子流 模數(mPA) 20SO-B1 14.4 42.94士 0.40 3.31±0.2 0·46 士 0.04 23SO-B1 14.34 42.91 士 0.66 26SO-B1 14.14 43.10 士 0·77 3.23 士 0.3 0·54 士 0.03 29SO-B1 13.95 43.10 土 0.44A1 (M3U: 050906, SO: 5L-7902) D (mm) EWC% Ion flow modulus (mPA) 20SO-A1 14.52 44.47 ± 0.64 3.35 Soil 0.1 0.42 ± 0.01 23SO-A1 14.3 44.78 ± 0.39 26SO-A1 14.16 43.42 ± 0.50 2.61 ± 0.19 0.41 ± 0.03 29SO-A1 13.99 43.45 ± 0.42 B1 (M3U: 050906, SO: 10627) D (mm) EWC% Ion flow modulus (mPA) 20SO-B1 14.4 42.94 ± 0.40 3.31 ± 0.2 0 · 46 士0.04 23SO-B1 14.34 42.91 士0.66 26SO-B1 14.14 43.10 士0·77 3.23士士 0.3 0·54 士0.03 29SO-B1 13.95 43.10 土0.44
Cl (M3U: 040819bR, SO: 5L-7902) D (mm) EWC% 離子流 模數(mPA) 20SO-C1 14,55 44.97土 0.38 3.56 士 0·19 0.52 士 0.03 23SO-C1 14.3 44.88士 0.80 26SO-C1 14.14 44.23士 0.56 2.66 士 0·26 0.51 士 0.04 29SO-C1 13.91 43.73士 0·30 D1 (M3U: 040819bR, SO: 10627) D(mm) EWC% 離子流 模數(mPA) 20SO-D1 14.44 43.89士 0.69 3.16 士 0.17 0·49 士 0.02 23SO-D1 14.3 44.45士 0.93 26SO-D1 14.1 43.16 土 0.89 2.43 土 0.11 0.55 士 0.05 29SO-D1 13.85 42.06士 0·97 121841.doc -85- 200813102 曰艮鏡直徑與s 〇含 、 - 、,丨 日义續:且促 隨SO負載增加而減少,此主要歸因於8〇之稀釋作用。稀 釋劑負載愈高,萃取後所移除之物質的量則愈大,且因 此,最終眼鏡之直徑則愈小。&於石夕、油負载含量為20%及 29。/。之直徑資料’彳見兩種微調矽油之效能近乎相同。該 等結果證實向碎油可萃取組份中添加4% AE有效地"微調二 或細微調節例示性可萃取組份s〇 5L以匹配僅含〇·丨% AE之 SO 10627的效能。 Γ Ο 見轉向例不性含氟二曱基丙烯醯基矽氧大分子單體 M3U,錢表明對於不同批次之咖而言,眼鏡直徑在約 内變化。如圖6及7中可見,〇對湖之斜率為約 _〇·〇6讀❻SO。由此資料外推,為了提供具有類似直徑之 眼鏡,選擇約25%士4%之SO(預調節)含量。 3、中所列之所有25C調配物的直徑及離子流與平衡水 量之一般關係圖示㈣8中。參看圖8,可見直徑與水含量 :二在強相關性’且離子流與水含量之間亦存在強相關 此,基於此圖,顯然離子流一般可基於平衡水含量 來預測。 3里 冰白本發明所屬領域之技術者將瞭解,本發明之多種修 及其他實施例具有前述描述中呈現之教示的益處。因 助於=本文所揭示之_施例,如藉 但應理__施例。雖然論㈣示性實施例, 改、替彳、这實轭方式之目的在於覆蓋實施例之所有修 、及等放物,如其他揭示案所定義可屬於本發明之 121841.doc -86- 200813102 精神及範疇内。雖然本文採用特定術語,但其僅以通用及 描述性意義使用且非限制目的。 已在上文引用大量公開案及專利。所引用之公開案及專 利各自以全文引用的方式併入本文中。 【圖式簡單說明】 圖1為說明產生石夕氧水凝膠隱形眼鏡之例示性方法的方 • 塊圖。 圖2為說明本發明之組合物、眼鏡產物及隱形眼鏡的方 (、 塊圖。 囷3為表明在用作用以形成矽氧水凝膠隱形眼鏡之可萃 取組份的聚氧化烯矽氧中增加烯丙氧基乙醇含量之作用與 如實例4所述之所得經萃取水合高壓釜處理後之隱形眼鏡 產物之直徑的關係曲線圖。 圖4為表明在用作用以形成矽氧水凝膠隱形眼鏡之可萃 取組份的聚氧化烯石夕氧中增加稀丙氧基乙醇含量之作用與 #實例4所述之所得經萃取水合高壓爸處理後之隱形眼鏡 """" 產物之平衡水含量的關係曲線圖。 囷5為表明在用作用以形成矽氧水凝膠隱形眼鏡之可萃 ' 取組伤的聚氧化烯矽氧中增加烯丙氧基乙醇含量之作用與 ' 如貝例4所述之所得經萃取水合高壓爸處理後之隱形眼鏡 產物之離子流的關係曲線圖。 、圖6為表明料取水合隱㈣鏡之直徑(mm)與如實例4所 述之使用特定含氟二曱基丙烯酿基石夕氧大分子單體(存放 』3MU)之可聚合前驅體組合物中例示性聚氧化烯矽氧/烯 121841.doc -87- 200813102 丙氧基乙醇可萃取組份百分比的關係曲線圖。 囷7表明經萃取水合隱形眼鏡之直徑(mm)與如實例4所述 之使用特定含氟二甲基丙烯醯基矽氧大分子單體(黃色 M3U)之可聚合前驅體組合物中例示性聚氧化烯矽氧/烯丙 氧基乙醇可萃取組份百分比的關係。 囷8為表明平衡水含量分別與自聚氧化烯矽氧/烯丙氧基 乙醇可萃取組份百分比變化之各種可聚合前驅體組合物產Cl (M3U: 040819bR, SO: 5L-7902) D (mm) EWC% Ion flow modulus (mPA) 20SO-C1 14,55 44.97 soil 0.38 3.56 ±0·19 0.52 ±0.03 23SO-C1 14.3 44.88士0.80 26SO -C1 14.14 44.23士0.56 2.66士0·26 0.51士0.04 29SO-C1 13.91 43.73士0·30 D1 (M3U: 040819bR, SO: 10627) D(mm) EWC% Ion flow modulus (mPA) 20SO-D1 14.44 43.89士0.69 3.16士士 0.17 0·49士士0.02 23SO-D1 14.3 44.45士0.93 26SO-D1 14.1 43.16 土0.89 2.43 土 0.11 0.55士 0.05 29SO-D1 13.85 42.06士0·97 121841.doc -85- 200813102 The diameter and s 〇 、, - , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The higher the diluent loading, the greater the amount of material removed after extraction and, therefore, the smaller the diameter of the final lens. & Yu Shixi, oil loading content of 20% and 29. /. The diameter data is similar to the performance of the two fine-tuning oyster sauces. These results confirmed that the addition of 4% AE to the crushed oil extractable component effectively "fine-tuned or fine-tuned the exemplary extractable component s〇 5L to match the efficacy of SO 10627 containing only 〇·丨% AE. Γ Ο See the case of the non-fluorinated dimercaptopropenyl fluorenyloxy macromonomer M3U. The money indicates that the diameter of the glasses varies within about a batch of coffee. As can be seen in Figures 6 and 7, the slope of the lake to the lake is about _〇·〇6 reading ❻SO. With the extrapolation of this data, in order to provide glasses with similar diameters, an SO (pre-conditioning) content of about 25% and 4% is selected. 3. The general relationship between the diameter and ion current and equilibrium water volume of all 25C formulations listed in (4) 8 is shown. Referring to Figure 8, it can be seen that the diameter and water content: two are in strong correlation' and there is also a strong correlation between ion current and water content. Based on this figure, it is apparent that the ion current can generally be predicted based on the equilibrium water content. It will be appreciated by those skilled in the art to which the present invention pertains that various modifications and other embodiments of the present invention have the benefit of the teachings presented in the foregoing description. Because of the help of the _ example disclosed in this article, such as borrowing but __ example. Although the fourth embodiment is modified, replaced, and the conjugated manner is intended to cover all modifications and equivalents of the embodiments, as defined by other disclosures, may belong to the invention 121841.doc -86-200813102 Spirit and scope. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not limiting. A large number of publications and patents have been cited above. The cited publications and patents are each incorporated herein by reference in their entirety. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram illustrating an exemplary method of producing a Nishui Hydrogel contact lens. Figure 2 is a block diagram showing the composition of the present invention, the lens product, and the contact lens. 囷3 is shown in the polyoxyalkylene oxime used as the extractable component for forming a hydrogen peroxide hydrogel contact lens. The effect of increasing the allyloxyethanol content as a function of the diameter of the contact lens product obtained after the extraction of the obtained hydration autoclave as described in Example 4. Figure 4 is a graph showing the invisible shape used to form the hydrogel. The effect of increasing the content of the dilute propoxyethanol in the polyoxyalkylene oxide of the extractable component of the glasses and the contact lens obtained by the extraction of the hydrated high pressure dad described in Example 4 """ The relationship between the equilibrium water content and 囷5 is to show the effect of increasing the allyloxyethanol content in the polyoxyalkylene oxide used as the extractable group for forming the helium-oxygen hydrogel contact lens. FIG. 6 is a graph showing the relationship between the ion flux of the contact lens obtained after the extraction of the hydrated high pressure dad, and the diameter of the hydrated (four) mirror (mm) and the use as described in Example 4. Specific fluorine Exemplary polyoxyalkylene oxime/ene in the polymerizable precursor composition of the acrylonitrile-based macro-monomer (stored 3MU) 121841.doc -87- 200813102 The relationship between the percentage of extractable components of propoxyethanol Graph 。7 indicates the diameter (mm) of the extracted hydrated contact lens and the polymerizable precursor composition using a specific fluorine-containing dimethyl propylene fluorenyloxyl macromonomer (yellow M3U) as described in Example 4. The relationship between the percentage of extractable components of the exemplary polyoxyalkylene oxime/allyloxyethanol. 囷8 indicates that the equilibrium water content varies with the percentage of the self-polyoxyalkylene oxime/allyloxyethanol extractable component. Various polymerizable precursor compositions
生的最終經萃取水合隱形眼鏡產物之直徑及離子流各自的 一般關係曲線。 【主要元件符號說明】 (/ 102 置放 104 封閉 106 固>ί匕 108 脫模 110 脫鏡 112 萃取 114 水合 116 封裝 118 密封及殺菌 202 可聚合矽氧水凝膠眼鏡前驅體組合物 204 預萃取之聚合矽氧水凝膠隱形眼鏡產 206 經萃取之矽氧水凝膠隱形眼鏡產物 208 水合矽氧水凝膠隱形眼鏡 121841.doc -88-The general relationship between the diameter of the final extracted hydrated contact lens product and the ion current. [Key component symbol description] (/ 102 placement 104 sealing 106 solid > 匕 108 stripping 110 mirror 112 extraction 114 hydration 116 package 118 sealing and sterilization 202 polymerizable oxygenated hydrogel glasses precursor composition 204 pre Extraction of polymeric oxygenated hydrogel contact lenses 206 Extraction of hydrogenated hydrogel contact lens products 208 Hydrated hydrogel contact lenses 121841.doc -88-
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| TW96121908A TWI444408B (en) | 2006-06-15 | 2007-06-15 | Wettable silicone hydrogel contact lenses and related compositions and methods |
| TW96121939A TWI443116B (en) | 2006-06-15 | 2007-06-15 | Wettable silicone hydrogel contact lenses and related compositions and methods |
| TW103118502A TWI512017B (en) | 2006-06-15 | 2007-06-15 | Wettable silicone hydrogel contact lenses and related compositions and methods |
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Also Published As
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| TWI429713B (en) | 2014-03-11 |
| JP2008003612A (en) | 2008-01-10 |
| JP5982684B2 (en) | 2016-08-31 |
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| JP5224090B2 (en) | 2013-07-03 |
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| JP2008050576A (en) | 2008-03-06 |
| TWI444408B (en) | 2014-07-11 |
| JP5024702B2 (en) | 2012-09-12 |
| TWI512017B (en) | 2015-12-11 |
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