TWI311580B - Biomedical devices containing internal wetting agents - Google Patents

Biomedical devices containing internal wetting agents Download PDF

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TWI311580B
TWI311580B TW91120935A TW91120935A TWI311580B TW I311580 B TWI311580 B TW I311580B TW 91120935 A TW91120935 A TW 91120935A TW 91120935 A TW91120935 A TW 91120935A TW I311580 B TWI311580 B TW I311580B
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TW91120935A
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Chinese (zh)
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P Mccabe Kevin
F Molock Frank
A Hill Gregory
Alli Azaam
B Steffen Robert
G Vanderlaan Douglas
A Young Kent
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Johnson & Johnson Vision Care
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Priority claimed from US10/236,538 external-priority patent/US6822016B2/en
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1311580 A7 B7 五、發明說明( 相關專利申諸銮 本專利申請案聲明暮剧止—击^ 536(其係於_年9=日^利中請案第W, 牛月10日提出申請)之優先權。 發明領域 本發明係有關含有內w龙丨* 等之製造方法及用途。1夕氧財凝膠,以及彼 發明背景 力T二年代起,隱形眼鏡已被用作商品來改良視 使用者不:Γ眼鏡係由硬質材料製造,因此或多或少讓 使用者不舒服。現代別 水凝膠,且特別是矽氧 〈土本上為 ..._ 戏水,轉)來製造。魏烧水凝膠 為城之水膨脹之聚合物網絡,且 水性者*料鏡片對W喊者㈣提供很好的舒適 度’但有—些使用者當使収等鏡片時有不舒服的經驗且 過度的眼如積㈣致降狀視錄織。 經濟部智慧財產局員工消費合作社印製 和沉積物與鏡片表社疏謂㈣及«表面與蛋= 脂質及黏液素和眼_親水性表面之交互作用有關_。 某些人已’試減輕此問題,即藉親水性塗覆物(如電聚 塗覆物)塗覆錢貌水卿隱·鏡之表面。具有低表面 沉積物發生之未塗覆隱形眼鏡並未被揭示。 已揭示將㈣親水劑(或制劑)併人含有巨體之反應 混合物中H並非所有包含#氧烧之巨體都表現與親 -3- 本紙張尺度適用中國國豕標準(CNS)A4規格(210x297公幻 經濟部智慧財產局員工消費合作社印製 1311580 A7 B7 五、發明說明(2) 水性聚合物相容。亦已揭示藉添加可聚合之表面活性劑至 用來形成物體之單體混合物中,以修飾聚合性物體之表 面。然而,持續之活體内濕潤度的改善及減少表面沉積物 並不可能。 聚乙烯吡咯啶酮(PVP)或聚-2-乙基-2-哼唑咁已被添 加至一種水凝膠組成物中,以形成一種互穿網絡,其顯示 出一種低度之磨擦力、低度之脫水率及高度之耐生物 '沉積性。然而,所揭示之水凝膠配方為傳統之水凝膠且未 揭示如何組合疏水性成分(諸如石夕氧院單體)而不會失去 單體相容性。 雖然併入諸如内部濕潤劑之高分子量聚合物於矽氧烷水 凝膠鏡片中是可行的,但此種聚合物很難溶解於包含矽氧 <·ν 烷之反應混合物中。為溶解此等濕潤劑,必須使用矽氧烷 巨體或其他預聚物。此等矽氧烷巨體或預聚物必須在另一 步驟中製備,然後接著與矽氧烷水凝膠配方之其餘成分混 合。此額外的步驟(或諸步驟)增加了製造此等鏡片所花 費的成分與時間。再者,此等方法在製造一種充分濕潤足 使其用作無塗覆物之隱形眼鏡的眼用裝置方面已屬失敗。 因此,有利的是找出一種無須使用矽氧烷巨體%其他預 聚物,且適合在無表面處理下供延時配戴之鏡片配方。 發明概述 本發明係有關一種濕潤之矽氧烷水凝膠,其係由包括、 實質上包含或包含至少一種高分子量之親水性聚合物和至 -4- 本纸張尺度適用中國國家標準(CNS)A4規格(210x297公釐)1311580 A7 B7 V. Description of invention (Related patents apply to this patent application statement 暮 — — 击 击 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 536 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method and use containing an inner w*, and the like. In the second half of the second year, contact lenses have been used as commercial products for improved visual use. No: Γ glasses are made of hard materials, so they are more or less uncomfortable for users. Modern water gels, and especially 矽 〈 土 土 土 土 _ _ _ _ _ _ _ _ _ 土 土 土 土 土 土 土 土 土 土 土 土 土 土Weishui hydrogel is the polymer network of the city's water expansion, and the water-based lens provides good comfort to the W-speaker (four). But there are some users who have uncomfortable experience when collecting lenses. And the excessive eye is like the product (4). Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative printing and sediment and lens table society (4) and «surface and egg = lipid and mucin and eye_hydrophilic surface interaction. Some people have tried to alleviate this problem by coating the surface of the money with the hydrophilic coating (such as electropolymer coating). Uncoated contact lenses with low surface deposits have not been disclosed. It has been revealed that (4) the hydrophilic agent (or preparation) and the human body containing the macromolecule in the reaction mixture, H, not all of the macromolecules containing #oxygen burned and the pro--3- paper scale applicable to the China National Standard (CNS) A4 specification ( 210x297 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1311580 A7 B7 V. INSTRUCTIONS (2) Waterborne Polymer Compatibility. It has also been revealed that by adding a polymerizable surfactant to a monomer mixture used to form an object To modify the surface of a polymeric object. However, it is not possible to improve the in-vivo wetness and reduce surface deposits. Polyvinylpyrrolidone (PVP) or poly-2-ethyl-2-carbazole It is added to a hydrogel composition to form an interpenetrating network that exhibits a low degree of friction, a low rate of dehydration, and a high degree of biodegradability. However, the disclosed hydrogel The formulation is a conventional hydrogel and does not reveal how to combine hydrophobic components (such as octagonal monomers) without losing monomer compatibility. Although incorporating high molecular weight polymers such as internal wetting agents in decane Hydrogels It is possible in the film, but such a polymer is difficult to dissolve in the reaction mixture containing oxime <· ν alkane. To dissolve these humectants, a cesium alkane giant or other prepolymer must be used. The oxoxane macro or prepolymer must be prepared in a separate step and then mixed with the remaining ingredients of the decane hydrogel formulation. This additional step (or steps) adds to the cost of making such lenses. Ingredients and time. Furthermore, these methods have failed in the manufacture of an ophthalmic device that is sufficiently moistened to use as a contactless contact lens. Therefore, it is advantageous to find a giant axane that does not require the use of Body % other prepolymers, and suitable for lens formulations for delayed wear without surface treatment. SUMMARY OF THE INVENTION The present invention relates to a wet alkane hydrogel comprising, substantially comprising or comprising at least one High molecular weight hydrophilic polymer and up to -4- paper scales applicable to China National Standard (CNS) A4 specification (210x297 mm)

經濟部智慧財產局員工消費合作社印製 1311580 Αν B7 五、發明說明(3) 少一種含羥基-官能化矽氧烷之單體的反應混合物所形 成。 本發明進一步係有關一種生物醫學裝置,其係由包括、 實質上包含或包含一種高分子量親水性聚合物和一有效量 之含羥基-官能化矽氧烷之單體的反應混合物所形成。 本發明更有關一種製備生物醫學裝置的方法,其包括、 實質上包含或包含混合一種高分子量之親水性聚合物和一 有效量之含羥基-官能化矽氧烷之單體以形成一種透明溶 液,及固化該溶液而成。 本發明又有關一種製備方法,其包括、實質上包含或包 含步驟:(a)混合一種高分子量親水性聚合物和一有效量 之含羥基-官能化矽氧烷之單體及(b)固化步驟(a)之產物以 形成生物醫學裝置。 本發明更有關一種製備方法,其包括、實質上包含或包 含步驟:(a)混合一種高分子量之親水性聚合物和一有效 量之含羥基-官能化矽氧烷之單體及(b)在最低成溫度下或 以上固化步驟(a)之產物以形成一種濕潤之生物醫學裝 置。 本發明係有關一種改良由反應混合物所形成之目用裝置 之濕潤度的方法,其包括、實質上包含或包含添加至少一 種高分子量親水性聚合物和一有效量之至少一種相容性單 體至該反應混合物中而成。 本發明係有關一種改良由反應混合物所形成之眼用裝置 之濕潤度的方法,其包括、實質上包含或包含添加至少一 -5- Q本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives 1311580 Αν B7 V. INSTRUCTIONS (3) The reaction mixture of a monomer containing a hydroxyl-functional azide. The invention further relates to a biomedical device formed by a reaction mixture comprising, consisting essentially of or comprising a high molecular weight hydrophilic polymer and an effective amount of a hydroxyl-functionalized decane-containing monomer. The invention further relates to a method of preparing a biomedical device comprising, consisting essentially of or comprising mixing a high molecular weight hydrophilic polymer and an effective amount of a hydroxyl-functionalized decane-containing monomer to form a transparent solution And curing the solution. The invention further relates to a method of preparation comprising, consisting essentially of or comprising the steps of: (a) mixing a high molecular weight hydrophilic polymer and an effective amount of a hydroxyl-functionalized decane-containing monomer and (b) curing The product of step (a) to form a biomedical device. The invention further relates to a method of preparation comprising, consisting essentially of or comprising the steps of: (a) mixing a high molecular weight hydrophilic polymer and an effective amount of a hydroxyl-functionalized siloxane containing monomer and (b) The product of step (a) is cured at or below the minimum temperature to form a moist biomedical device. The present invention relates to a method for improving the wettability of a substrate formed by a reaction mixture, comprising, consisting essentially of or comprising adding at least one high molecular weight hydrophilic polymer and an effective amount of at least one compatible monomer It is formed into the reaction mixture. The present invention relates to a method for improving the wettability of an ophthalmic device formed from a reaction mixture, comprising, substantially comprising or comprising adding at least one -5-Q of the paper size applicable to the Chinese National Standard (CNS) A4 specification (210x297) MM)

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1311580 A7 B7 五、發明說明(斗) 種 其 垸 南刀子莖親水性聚合物和一有致量之 官能化矽氧烷之單體至該反應混合物中而v種含羥基、 本發明更有關一種由反應混合物所成 包括、實質上包含或包含至少一種含;之眼用骏置, 之單體和足以提供該裝置在無表面處官能化矽氣 低於約70或低於約60之前進接觸角 _ ;約8〇、 水性聚合物。 .置之高分子量覩 本發明更有關-種由反應混合物所 包括、實質上包含或包含至少一種含c ’其 之單體和足以提供該裝置在無表面處理下具有於^夕氣燒 配戴後’淚膜崩潰時間至少約7秒之 ACUVUH®隱形眼鏡之淚膜崩潰時間之用古八3於 水性聚合物。 里、回义子量親 一種包含矽氧烷水凝膠隱形眼鏡之裝 飾下實質上無表面沉積。 ’、…、表面修 釐明之詳細銳 經濟部智慧財產局員工消費合作社印製 現已令人驚訝地發現到’無表面修飾之生物醫學裝置, 特別是具有特別之活體内或臨床濕潤度之㈣裝置―,可 包含-有效量之高分子量親水性聚合物和—有效量: 基-官能切減之單體於㈣料凝膠配方中予= 備。所謂特別之濕潤度,意表前進動態接觸角相較於盈任 何親水性聚合物之類似配方而言,減低至少約ig% ',、、較 佳至少約辦,在某些具體例令至少約观。在本發明 -6- 本紙張尺度適用中國國家標準(CNS)A4規格(2ΤΓχ297公"57 !311580 A71311580 A7 B7 V. DESCRIPTION OF THE INVENTION (Draft) Seeding a hydrophilic polymer of the southern stalk stem and a monomer of a quantity of functionalized oxoxane to the reaction mixture and v containing a hydroxyl group, the invention is more related to The reaction mixture comprises, consists essentially of, or comprises at least one of: an ophthalmic monomer, and a contact angle sufficient to provide the apparatus prior to functionalizing the helium at less than about 70 or less than about 60. _; about 8 〇, water-based polymer. High molecular weight 覩 The present invention is more related to the invention comprising, consisting essentially of, or comprising at least one monomer comprising c' and sufficient to provide the device with a surface-free treatment After the tear film collapse time is at least about 7 seconds, the tear film collapse time of ACUVUH® contact lenses is used in ancient polymers. In the case of a fluorescein-containing contact lens, there is virtually no surface deposition. ',..., the surface of the clarification of the details of the Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative printing has now surprisingly found that 'bio-medical devices without surface modification, especially with special in vivo or clinical moistness (4) The device - may comprise - an effective amount of a high molecular weight hydrophilic polymer and - an effective amount: the base-functionally cut monomer is prepared in a (four) feed gel formulation. The so-called special wetness, the apparent dynamic contact angle is reduced by at least about ig% ', compared with similar formulations of any hydrophilic polymer, at least about, in some specific cases at least about . In the present invention -6- This paper scale applies the Chinese National Standard (CNS) A4 specification (2ΤΓχ297 public "57 !311580 A7

田啰乳既水凝膠所形 技认 1 成之眼用裝置不是必須做表面 乜飾以提供臨床的濕潤度 —^ ^ 就疋必須由至少一種具有羥基 吕此性之含石夕氧烧之巨體所形成。 當於本文中使用時,“ ^A , 生物语學裝置,,意表被設計成於哺 礼動物組織或液體中,哎 ^ 孑季乂佳於人體組織或液體中被使用 ,何物體此等裝置的實例包括但不限於導展管、移植 物⑽她及諸如眼内鏡片和隱形眼鏡之眼用裝置。較佳It is not necessary to make a surface enamel to provide clinical moistness. The ^^ must be composed of at least one kind of hydroxy-containing oxyxy The formation of giants. As used herein, "^A, a biolinguistic device, is intended to be used in animal tissues or in liquids, and is used in human tissues or fluids, and such devices. Examples include, but are not limited to, a guide tube, a graft (10), and an ophthalmic device such as an intraocular lens and a contact lens.

之生物醫學裝置為眼用萝 B 表直,特別是隱形眼鏡,最特別疋 由I氧烧水凝_製造之隱形目Mt。 田於本文中使用時,術語“鏡片,,和‘‘眼用裝置,,指的是存 在於眼目月之上或之中的裝置。此等裝置可提供光學校正, 傷'照遵、藥物傳送、診斷功能、美容增強或效果或此等 特丨生之組合。術語鏡片包括但不限於軟式隱形眼鏡 、硬式 隱系眼鏡、眼内鏡片、外罩鏡片、眼球嵌入物及光學嵌入 物。 經濟部智慧財產局員工消費合作社印製 當於本文中使用時,術語“單體,,為一種包含炱少一種可 t合基團和平均分子量約低於2〇〇〇道耳頓(Daltons)(依 據藉由凝膠滲透層析折射指數偵測法所測定)之化合物。 因此’單體(包括二聚體且在某些情況中為低聚牌_)包括 由多於一個單體性單元所製造之低聚物。 畲於本文中被使用時,片語“無表面處理,,指的是本發明 裝置之外表面並未被分別處理以改良裝置之濕潤度。本發 明可進行之處理包括電漿處理、接枝、塗覆等。然而,提 供除了改良濕潤度以外之特性的塗覆物(諸如但不限於抗 -7- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公楚) !311580 A7 ---- B7 五、發明說明(6) 微生物塗覆物)可被施加至本發明之裝置中。 各種分子量範圍被揭示於本文中。就具有不連續分子結 構之化合物而言,本文中所報導之分子量係基於分子式來 a十算且以克/莫耳予以報導。就聚合物而言,分子量(數 量平均)係藉由凝膠滲透層析折射指數偵測法所測定且以 道耳頓被報導,或藉由動力黏度測量法(如描述於聚合物 科學及工程百科全書’ N-乙烯醯胺聚合物..,第2版,第 Π冊第I98·257頁,John Wiley & Sons股份有限公司中 者)且以K-值予以報導。 高分子詈親水性聚合物 經濟部智慧財產局員工消費合作社印製 #於本文中使用時,“高分子量親水性聚合物,,指的是具 有重量平均分子量不低於約100,000道耳頓者,其中該物 質一旦被組合於矽氧烷水凝膠配方時,會增加已固化石夕氧 貌水凝膠之濕潤度。此等高分子量親水性聚合物之較佳重 量平均分子量為大於約150,000至約2,000,〇〇〇道耳頓, 尤佳介於約300,000至約1,800,000道耳頓之間,最彳土約 500,000 至約 1,500,000 道耳頓。 另外’本發明之親水性聚合物之分子量亦可以κ值予 以表達’其係基於動力黏度測量法(如描述於聚合物科風 及工程百科全書’ Ν-乙烯醯胺聚合物,第2版 干 版,第17冊 第198-257頁’ John Wiley & Sons股份有限公司中者) 當以此方式被表達時,親水性單體具有大於約46, 佳介於約46和150之間的K-值。高分子量親水性聚合2 -8- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 1311580 發明說明(7) 裝置之配方中’其用量足以提供隱形眼鏡在無 少,於使用期間維持實質上無表面沉積物。並型 之使用期間包括至少約8小時,較佳接連配戴數天,純 於:::下,小時或更久。實質上無表面沉積物意表當 以Γ 〇燈觀察時,至少約7〇%,較佳至少約80%,尤 佳^ 9〇%_之被配戴於病患族群中之鏡片,經過配戴時間 之後。,,4 τ被評等為無或輕微的沉積度。 =丙里之阿分子量親水性聚合物包括約1至約15重量 百刀 尤公約3至約15百分比,最佳約5至约12百分 比一為基於所有反應成分之總重量為準。 @刀子里親水性聚合物之實例包括但不限於聚醯胺、聚 内酉曰Uiv亞胺、聚内g㈣及官能化之聚酿胺 、聚内酯、 經濟部智慧財產局員工消費合作社印製 聚鯭亞胺、聚内醯胺,諸如藉DMA與較少莫耳量之羥 官能性單體(如HEMA)之共聚合,然後將形成之共 聚物之經基與包含可聚合基團之材料(如異氰酸醋基乙基 甲基丙烯酸酯或甲基丙烯醯基氣化物)反應之DMA官能 化由DMA或N-乙烯吡咯啶酮與甲基丙烯酸縮水甘油 酉旨所製得之親水性預聚物亦可使用。甲基丙稀酸縮水甘油 西旨可被開環以形成_種二醇,其可於—混合系統中—與其他 親=生預聚物併用以增加高分子量親水性聚合物、含經 基-s忐化矽氧烷單體及任何賦與相容性之其他基團之相 奋1'生較佳之高分子量親水性聚合物為那些於彼等骨架中 =含%狀部分者,尤佳為環狀醯胺或環狀醯亞胺。高分子 里親水性聚合物包括但不限於聚-N-乙烯吡咯啶酮、聚-N- -—. 本紙 -9- 1311580 A7 _________B7 五、發明說明(s) 乙烯-2_六氫吡啶酮、聚-N-乙烯-2-己内醯胺、聚-N-乙烯-3-曱基-2-己内醯胺、聚_N_乙烯_3_曱基六氫吡啶酮、 聚-N-乙烯_4·甲基_2_六氫吡啶酮、聚_N_乙烯_4_曱基_2·己 内醯胺、聚-N-乙烯_3_乙基-2-吡咯啶酮及聚乙烯-4,5-二甲基-2-吡咯啶酮、聚乙烯咪唑、聚_N_N_二曱基丙烯醯 胺、聚乙烯醇、聚丙烯酸、聚氧化乙烯、聚2乙基啐唑 咁、肝素多糖、多糖、其之混合物及共聚物(包括嵌段表 無規’为支、多鍵、梳形或星形)’其中以聚-N-乙烯吡 咯啶酮(PVP)為較佳。共聚物亦可被使用,諸如 PVP之接 枝共聚物。 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 阿刀于置視水性聚合物提供本發明之醫學裝置改良之濕 潤度特別是改良之活體内濕潤度。不欲受制於任何理 咸信高分子量親水性聚合物為氫鍵接受者,其在含水 叫中,氫結合至水’因此有效地變為更加親水性的。缺 t水有助於親水性聚合物組合於反應混合物中。除了特別 指定之高分子魏水絲合物外,期望任何高分子量親水 性聚合物料料本發财,前提是當聚合物被添加至石夕 =凝膠配方時’親水性聚合物⑷不會實質上由反應 ^中相刀離且⑼對形成之固化聚合物賦與濕;間度。 下=具體例中,較佳高分子量親水性聚合物在加工溫度 較佳=於轉射。使財或切溶稀咖之製造方法為 工’因此彼等簡單且縣低。在此等具體例中,在加 •度下為水可溶之高分子量親水性聚合物為較佳的。The biomedical device is an eye-shaped lens B, especially a contact lens, and most particularly, the invisible Mt manufactured by I-oxygenation. As used herein, the terms "lens," and "opial device" refer to devices that are present on or in the eye of the eye. These devices provide optical correction, injury, and drug delivery. , diagnostic function, cosmetic enhancement or effect or a combination of such specialties. The term lenses include, but are not limited to, soft contact lenses, hard contact lenses, intraocular lenses, outer lens lenses, eyeball inserts, and optical inserts. Property Bureau Staff Consumer Cooperative Printed As used herein, the term "monomer," is a type that contains less than one chelating group and an average molecular weight of less than about 2 Daltons (based on A compound as determined by gel permeation chromatography refractive index detection. Thus 'monomers (including dimers and in some cases oligomeric plates) include oligomers made from more than one monomeric unit. As used herein, the phrase "without surface treatment" means that the outer surface of the device of the present invention is not separately treated to improve the wettability of the device. The process of the present invention includes plasma treatment, grafting. , coating, etc. However, coatings other than improved wetness are provided (such as, but not limited to, anti--7 - this paper scale applies to China National Standard (CNS) A4 specification (210x297 public)! 311580 A7 -- -- B7 V. INSTRUCTION DESCRIPTION (6) Microbial coatings can be applied to the apparatus of the present invention. Various molecular weight ranges are disclosed herein. For compounds having a discontinuous molecular structure, as reported herein The molecular weight is based on the formula and is reported in grams per mole. In the case of polymers, the molecular weight (number average) is determined by gel permeation chromatography refractive index detection and reported in Dalton. , or by dynamic viscosity measurement (as described in the Encyclopedia of Polymer Science and Engineering 'N-vinylamine polymer.., 2nd edition, Book No. I98.257, John Wiley & Sons Limited In the company And the K-value is reported. Polymer 詈 Hydrophilic Polymer Economics Department Intellectual Property Bureau Employee Consumption Cooperative Printed # When used herein, "high molecular weight hydrophilic polymer, refers to the weight average molecular weight Not less than about 100,000 Daltons, wherein the substance, once combined with the alkane hydrogel formulation, increases the wettability of the cured Shiyan oxygen hydrogel. Preferably, the high molecular weight hydrophilic polymers have a weight average molecular weight of from greater than about 150,000 to about 2,000, more preferably from about 300,000 to about 1,800,000 Daltons, most preferably from about 300,000 to about 1,800,000 Daltons. 500,000 to about 1,500,000 Daltons. In addition, the molecular weight of the hydrophilic polymer of the present invention can also be expressed by the kappa value, which is based on dynamic viscosity measurement (as described in the Polymer Science and Engineering Encyclopedia 'Ν-vinylamine polymer, 2nd edition dry Edition, Vol. 17, pp. 198-257 - John Wiley & Sons, Inc.) When expressed in this manner, the hydrophilic monomer has a K- greater than about 46, preferably between about 46 and 150. value. High molecular weight hydrophilic polymerization 2 -8- This paper scale is applicable to China National Standard (CNS) A4 specification (210x297 mm) A7 1311580 Invention Description (7) The formula of the device is 'used enough to provide contact lenses in no less, in use During the maintenance period, substantially no surface deposits are maintained. The use period of the combined type includes at least about 8 hours, preferably several days in a row, purely :::: down, hours or longer. Substantially no surface deposits, when viewed with a xenon lamp, at least about 7〇%, preferably at least about 80%, and especially preferably 9%% of the lenses that are worn in the patient population, after wearing After time. , 4 τ was rated as no or slight deposition. = propylene glycol molecular weight hydrophilic polymer comprises from about 1 to about 15 weight percent of from about 3 to about 15 percent, most preferably from about 5 to about 12 percent, based on the total weight of all of the reaction components. Examples of hydrophilic polymers in the @knife include, but are not limited to, polydecylamine, poly-indolizine Uiv imine, poly-g (iv) and functionalized polyamine, polylactone, Ministry of Economic Affairs, Intellectual Property Office, employee consumption cooperative, printed poly a ruthenium imine, a polyendammine, such as a copolymerization of DMA with a less molar amount of a hydroxy functional monomer (such as HEMA), and then a base of the formed copolymer and a material comprising a polymerizable group ( DMA functionalization of DMA or N-vinylpyrrolidone and glycidyl methacrylate prepared by DMA functionalization of hydroxy or methacrylic acid methacrylate Polymers can also be used. Methyl methacrylate glycidol can be ring-opened to form a diol, which can be used in a mixed system with other pro-polymers to increase the high molecular weight hydrophilic polymer, containing a thiol group.忐 矽 矽 矽 单体 单体 及 及 及 及 及 及 及 及 及 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳Cyclic guanamine or cyclic quinone imine. Hydrophilic polymers in polymers include, but are not limited to, poly-N-vinylpyrrolidone, poly-N---. Paper-9-1311580 A7 _________B7 V. Description of invention (s) Ethylene-2_hexahydropyridone, poly -N-ethylene-2-caprolactam, poly-N-vinyl-3-mercapto-2-caprolactam, poly-N_ethylene_3_mercaptohexahydropyridone, poly-N-ethylene _4·methyl_2_hexahydropyridone, poly_N_ethylene_4_mercapto-2·caprolactam, poly-N-ethylene_3_ethyl-2-pyrrolidone and polyethylene -4,5-Dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N_N_didecyl acrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethyl 2 oxazolidine, heparin Polysaccharides, polysaccharides, mixtures and copolymers thereof (including block tables which are randomly 'branched, multi-bonded, comb-shaped or star-shaped)' are preferably poly-N-vinylpyrrolidone (PVP). Copolymers can also be used, such as graft copolymers of PVP. The Ministry of Economics, the Ministry of Finance, the Bureau of Fisheries, and the Consumers' Association for the Production of Waterborne Polymers provide the improved moisture content of the medical device of the present invention, especially the improved in vivo moistness. It is not intended to be subject to any salty high molecular weight hydrophilic polymer being a hydrogen bond acceptor, in which water is hydrogen bonded to water' thus effectively becoming more hydrophilic. The lack of water helps the hydrophilic polymer to be combined in the reaction mixture. In addition to the specially designated high molecular weight water-wet compound, it is expected that any high molecular weight hydrophilic polymer material will be rich, provided that the hydrophilic polymer (4) does not substantially consist of when the polymer is added to the Shixi = gel formulation. The phase of the reaction is separated and (9) imparts a wetness to the formed cured polymer. In the lower = specific example, the preferred high molecular weight hydrophilic polymer is preferably at the processing temperature = in the conversion. The manufacturing method of making money or cutting the thin coffee is a workmanship, so they are simple and the county is low. In these specific examples, a water-soluble high molecular weight hydrophilic polymer at a degree of addition is preferred.

、發明說明(9) 當於本文中被使用時,“人、_ 為—種包含至少—種具有平=基=能化石夕氧炫之單體,’ (依據藉由凝膠滲透層析:子量約低於灣道耳頓 佳低於約 3〇〇。;=可::指數谓測法所測定) 且較 含括於水凝膠配方中之 ^團之化合物,其可使被 在改良親,狀料親錢聚合物相容。 此,杳-較佳具體例中,本二宫:性是極有效的。因 :單體包含至少-個趣基和;能切氣燒 佳矽和其所附接之氧 乂個-s·,基圏。較 單體之H)重量百分比了 ΐ4含經基-官能化石夕氧貌之 在含經基-宫能化石夕氧产之20重量百分比。 很重要的,為f 中之&對〇Η之比例是 之善經基_官能化^夕氧^—種可提供所期望程度之相容性 _高,官::==::_ 物方面能力很差,導致早體在相錢親水性聚合 鬌 些具體例中,㈣〇Γ 不相容。因此,在某 至約㈣之門對;^比例低於約15:1,較佳介於約Μ U·1之間。在某些具體例中,一級 二級醇有改良m❹該項技術;^ 官能化魏…體的繼驅將視 聚合物來達成所期欤、 了优而要多少親水性 聚合物不相容親水性 體含減·官能切氡院之單體之實例包括式!及η之單 |_ -11- 本紙張尺㈣时關賴準^ 1311580(Invention) (9) As used herein, "human, _ is a species containing at least one type of monomer having a ping = base = energy fossil," (based on gel permeation chromatography: The sub-amount is less than about 3 〇〇 湾 〇〇 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾 湾The modified pro- and pro-forms are compatible with the polymer. Therefore, in the preferred embodiment, the second house: the sex is extremely effective. Because: the monomer contains at least one interesting group; And the oxygen 乂-s·, 圏 圏 圏 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 较 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含Percentage. It is important that the ratio of the & 〇Η to f is the basis of the _ _ functionalization oxime oxy-type can provide the desired degree of compatibility _ high, official::==:: _ The ability of the object is very poor, leading to the early body in the hydrophilic polymerization of some of the specific examples, (4) 〇Γ incompatible. Therefore, in a certain to about (4) the door; ^ ratio is less than about 15:1, Good between about Μ U·1 In some specific examples, the primary secondary alcohol has an improved m❹ technology; ^ the functionalized Wei... the secondary drive will depend on the polymer to achieve the desired enthalpy, which is better than the hydrophilic polymer. Examples of monomers that contain hydrophilic and functional cleavage and cleavage of the brothel include the formula! and η of the single |_ -11- The paper ruler (four) is related to the ^^ 1311580

R1 R2 R-R6-C-R8-Si-R3 R5 R4 R1 R2 R2 R7_R6.i_R8_^_'j]n_R8_^ R5 R4 ^ ^R1 R2 R-R6-C-R8-Si-R3 R5 R4 R1 R2 R2 R7_R6.i_R8_^_'j]n_R8_^ R5 R4 ^ ^

II 其中·: n為介於3和35之間的整數,較佳介於4和25之間. R1 i氫、Cw烷基; ’ R2,R\及R4互相獨立地為Cm烧基、三Ci 6烷基矽氧基、 苯基、奈基、經取代之C,.6烧基、經取之苯基或經取 代之萘基, 經濟部智慧財產局員工消費合作社印製 其中院基取代基係選自-或多個由基、 C,-6烷基、c,_6烷氧墓、醯胺基、豳素、羥基、羧 基、Cu烷基羰基及甲醯所組成之組群的成員,且 其中芳香族取代基係選自一或多個由c16院氧幾基 Cl—6烧基、C!.6院氧基、醯胺基、齒素、經基、叛 基、C!·6院基羰基及甲醯所組成之組群的成員, R5為羥基、一包含一或多個羥基之烷基;或(CH2(CR9 -12- Ιί.本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公爱) 經濟部智慧財產局員工消費合作社印製 1311580 Αν B7 五、發明說明(11) R'OXVR11,其中y為1至5,較佳1至3,X為1至100 之整數,較佳2至90且尤佳10至25 ; R9-Rn互相獨立 地選自H、具有至多達10個碳原子之烷基及至多達10 個碳原子且經至少一個極性官能基取代之烷基, R6為包含至多達20個碳原子之二價基圑; R7為可進行自由基及/或陽離子性聚合且包含至多20個 碳原子之單價基圑; -一 一' ‘ R8為包含至多20個碳原子之二價或三價基團。 本發明之反應混合物可包括多於一個含羥基-官能化矽 氧烷之單體。 就單官能性之含羥基-官能化矽氧烷之單體而言,較佳 R1 .為--氫且較佳R2, R3及R4為Cy烷基及三CN6烷基矽氧 严、 基,最佳為甲基和三甲基矽氧基。就多官能性(二官能或 更而言,R^R4獨立地包含乙烯性不飽和可聚合基 團,尤佳包含丙烯酸酯基、苯乙烯基、Cu烷基丙烯酸酯 基、丙烯醯胺、CN6烷基丙烯醯胺、Ν-ζ>烯内醯胺、N-乙 稀酿胺、C2-I2稀基、C2-12稀基苯基、C2-I2稀基蒸基或匸2_ 6稀·基苯基Ci 烧基。 較佳R5為羥基、-CH2OH或CH2CHOHCH2OH,_以羥基 最佳。 較佳之R6為二價之Cm烷基、CN6烷基氧基、CN6烷基 氧基Cw烷基、伸苯基、萘、C,_12環烷基、烷氧基羰 基、醯胺基、羧基、CN6烷基羰基、羰基、Q.6烷氧基、 經取代之CN6烷基、經取代之CN6烷基氧基、經取代之 -13- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)II wherein: n is an integer between 3 and 35, preferably between 4 and 25. R1 i hydrogen, Cw alkyl; 'R2, R\ and R4 are independently Cm alkyl, three Ci 6 alkyl decyloxy, phenyl, naphthyl, substituted C, .6 alkyl, substituted phenyl or substituted naphthyl, Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in the yard base substituent a member selected from the group consisting of a group consisting of a group consisting of a group consisting of a group consisting of a group of C, -6 alkyl groups, c, -6 alkoxides, amidino groups, halogens, hydroxyl groups, carboxyl groups, Cu alkylcarbonyl groups, and formazan. And wherein the aromatic substituent is selected from one or more of the group consisting of c16, an oxygen group, a C6 group, a C..6 alkoxy group, a guanamine group, a dentate group, a ruthenium group, a ruthenium group, a C!6 A member of a group consisting of a carbonyl group and a formamidine, R5 is a hydroxyl group, an alkyl group containing one or more hydroxyl groups; or (CH2 (CR9 -12- Ι.) This paper scale applies to the Chinese National Standard (CNS) A4 Specifications (210 297 297 public) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1311580 Αν B7 V. Invention Description (11) R'OXVR11, where y is 1 to 5, preferably 1 to 3, and X is 1 to 100 Integer, preferably 2 to 90 Preferably, R9-Rn are independently selected from H, an alkyl group having up to 10 carbon atoms, and an alkyl group up to 10 carbon atoms substituted with at least one polar functional group, and R6 is included up to 20 a divalent group of carbon atoms; R7 is a monovalent group of radicals capable of undergoing free radical and/or cationic polymerization and containing up to 20 carbon atoms; -1' R8 is a divalent group containing up to 20 carbon atoms or The trivalent group. The reaction mixture of the present invention may comprise more than one monomer containing a hydroxy-functional oxoxane. For monofunctional hydroxy-functional oxane-containing monomers, R1 is preferred. Is -hydrogen and preferably R2, R3 and R4 are Cy alkyl and three CN6 alkyl anthracene, preferably methyl and trimethyldecyloxy. In terms of polyfunctionality (difunctional or more) R^R4 independently comprises an ethylenically unsaturated polymerizable group, particularly preferably an acrylate group, a styryl group, a Cu alkyl acrylate group, a acrylamide, a CN6 alkyl acrylamide, a ruthenium-ruthenium> Alkene decylamine, N-ethylene thin amine, C2-I2 dilute group, C2-12 dilute phenyl group, C2-I2 dilute base group or 匸2-6 phenylene group Ci alkyl group Preferably, R5 is hydroxy, -CH2OH or CH2CHOHCH2OH, and _ is preferably hydroxy. Preferably, R6 is a divalent Cm alkyl group, a CN6 alkyloxy group, a CN6 alkyloxy Cw alkyl group, a phenylene group, a naphthalene group, C, _12 cycloalkyl, alkoxycarbonyl, decylamino, carboxy, CN6 alkylcarbonyl, carbonyl, Q.6 alkoxy, substituted CN6 alkyl, substituted CN6 alkyloxy, substituted -13- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm)

1311580 A7 B7 經濟部智慧財產局員工消費合作社印製 i r-y 五、發明説明(12)1311580 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed i r-y V. Invention description (12)

Cu烷基氣基Ck烷基、經取代之伸笨基、經取代之萘、 經取代之CV12環烷基,其中係選自一或多個由Ck烷氧 羰基、Cl-6烷基、CN6烷氧基、醯胺基、函素、羥基、羧 基、Cm烷基羰基及曱醯所組成之組群的成員。特佳之R6 為二價曱基(亞曱基)。 較佳R7包含一自由基反應性基團,諸如丙烯酸酯、苯 乙烯基、乙烯基一乙稀醚、衣康酸酯基團、Cu烷基丙烯 酸酯基、而烯醯胺、Ck院基丙烯醯胺、N-乙烯内醯胺二 N-乙烯酸胺、C2-12烯基、C2_12烯基苯基、C2-12烯基萘基 或C2-6歸基苯基Cw烧基或一陽離子性反應性基團,諸如 乙烯醚或環氧化基團。特佳R7為甲基丙烯酸酯。 R8為二價之Cl·6烷基、Cw烷基氧基、Cl_6烷基氧基 Cl-6炫基、伸苯基、萘、CM2環烷基、c16烷氧基羰基、 醯胺基、羧基、Cm烷基羰基、羰基、Cl 6烷氧基、經取 代之C“6烷基、經取代之Cu烷基氧基、經取代之c丨·6烷 基氧基C,·6烷基、經取代之伸笨基、經取代之萘、經取代 之Cm2環烷基,其中係選自—或多個由Ci 6烷氧羰基、 Cm烧基、Cw烷氧基、醯胺基、鹵素、羥基、複基、^ 6烷基羰基及甲醯所組成之k群的成員。特佳之R8為c 炫基氧基Ck烧基。 特佳之式【之含經基-官能化石夕氧院之單體的實例為^ 丙烯酸、2-甲基-、2_經基·ΗΗι,3,3,3四甲基小[(三甲笑 甲石夕院基)氧基]二胡氧烧基]丙氧基]㈣(其亦被稱為^ 曱基丙烯氧基-2-經基丙基氧基)丙基雙(三甲基石夕氧基)甲 -14- _本紙張尺度適用中國國家標準(CNS)A4規格(210x297 -------- _Cu alkyl group-based Ck alkyl, substituted alkyl, substituted naphthalene, substituted CV12 cycloalkyl, wherein one or more selected from Ck alkoxycarbonyl, Cl-6 alkyl, CN6 A member of a group consisting of an alkoxy group, a decylamino group, a hydroxyl group, a hydroxyl group, a carboxyl group, a Cm alkylcarbonyl group, and an anthracene. Particularly preferred R6 is a divalent fluorenyl group (anthracene group). Preferably, R7 comprises a radical-reactive group such as acrylate, styryl, vinyl-ethylene ether, itaconate group, Cu alkyl acrylate group, and eneamine, Ck-based propylene. Indoleamine, N-vinyl indoleamine di N-vinylamine, C2-12 alkenyl, C2-12 alkenylphenyl, C2-12 alkenylnaphthalenyl or C2-6 decylphenyl Cw alkyl or a cationic A reactive group such as a vinyl ether or an epoxidized group. Tejia R7 is a methacrylate. R8 is a divalent C.6 alkyl group, a Cw alkyloxy group, a C1-6 alkyloxy group, a phenyl group, a phenyl group, a naphthyl group, a phenyl 2 cycloalkyl group, a c16 alkoxycarbonyl group, a decylamino group, a carboxyl group. , Cm alkylcarbonyl, carbonyl, Cl 6 alkoxy, substituted C "6 alkyl, substituted Cu alkyloxy, substituted c 丨 6 alkyloxy C, · 6 alkyl, Substituted, substituted naphthalene, substituted Cm2 cycloalkyl, selected from - or a plurality of Ci 6 alkoxycarbonyl, Cm alkyl, Cw alkoxy, decyl, halogen, a member of the k group consisting of a hydroxyl group, a complex group, a 6-alkylcarbonyl group and a formazan group. Particularly preferred R8 is a c-histyloxy Ck alkyl group. A particularly good formula [containing a thiol-functionalized fossil Examples of the body are: acrylic acid, 2-methyl-, 2-yl-based, ΗΗι, 3,3,3 tetramethyl-[(三甲笑甲石院)oxy] bis(oxyalkyl)]propoxy (4) (also known as ^ mercaptopropenyloxy-2-p-propyloxy)propyl bis(trimethylsulphonyl)methyl-14- _ This paper scale applies to China National Standard (CNS) A4 Specifications (210x297 -------- _

1311580 Λ7 B7 五、發明說明(η 〇 〇-Si(CH3)3 Φ - CH3 丨丨 OH 61311580 Λ7 B7 V. INSTRUCTIONS (η 〇 〇-Si(CH3)3 Φ - CH3 丨丨 OH 6

Si(CH3)3 上述化合物,(3-甲基丙烯氧基-2-羥基丙基氧基)丙基雙 (三曱基矽氧基)甲基矽烷係由一種環氧化物所形成,其產 生一種上示化合物之80:20混合物和(2-曱基丙烯氧基-3-羥基丙基氧基)丙基雙(三甲基矽氧基)甲基矽烷。在本發 明之某些具體例中,較佳具有一些量之一級羥基存在 ,較佳大於約10重量%且尤佳至少約20重量%。 其他適合之含羥基-官能化矽氧烷之單體包括(3-曱基丙 烯氧基-2-羥基丙基氧基)丙基雙(三曱基矽氧基)甲基矽烷 〇 p^Si(CH3)3 丨丨 OH ΟSi(CH3)3 The above compound, (3-methacryloxy-2-hydroxypropyloxy)propylbis(tridecylmethoxy)methyl decane is formed from an epoxide, which is produced. An 80:20 mixture of the above compound and (2-mercaptopropoxy-3-hydroxypropyloxy)propylbis(trimethyldecyloxy)methylnonane. In some embodiments of the invention, it is preferred to have some amount of a hydroxyl group present, preferably greater than about 10% by weight and particularly preferably at least about 20% by weight. Other suitable hydroxyl-functionalized alkoxylated monomers include (3-mercaptopropoxy-2-hydroxypropyloxy)propyl bis(tridecyloxy)methylnonane 〇p^Si (CH3)3 丨丨OH Ο

Si(CH3)3 雙-3-曱基丙烯氧基-2-羥基丙基氧基丙基聚二曱基矽氧烷Si(CH3)3 bis-3-mercaptopropenyloxy-2-hydroxypropyloxypropylpolydidecyloxane

經濟部智慧財產局員工消費合作社印製 甲基丙烯氧基-2-(2-羥基乙氧基)丙基氧基)丙基雙(三甲 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 B7 五、發明說明(Η 基石夕氧基)甲基石夕烧 人Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printing Methyl Propenyloxy-2-(2-hydroxyethoxy)propyloxy)propyl bis (Thirteen-15) - This paper scale applies to China National Standard (CNS) A4 Specifications (210x297 mm) 1311580 A7 B7 V. Description of invention (Η基石夕氧) methyl Shi Xia

Si、 ^ ^OH I η ——Si—Si, ^ ^OH I η - Si-

Ν,Ν,Ν’,Ν’-四(3-曱基丙烯氧基-2-羥基丙基)_〇〇,〇)_雙_3_胺基 丙基-聚二曱基矽氧烷。 I 曱基丙烯酸縮水甘油酯與胺基官能性聚二曱基石夕氧烧之 反應產物亦可被用作含羥基-官能性矽氧烧之單體。其他 含羥基-官能性矽氧烷之單體包括那些被描述於us 5,994, 488第6,7及8攔中者及描述於4,259,467; 4,260,725; 4,261,875; 4,649,184; 4,139,513; 4,139,692; US 2002/ 0016383; 4,139,513及4,139,692中之單體。於本文中引述之此等及任 何其他專利案或申請案併入本文作為參考。 適合之含羥基-官能化矽氧烷之單體的其他結構包括那 些類似描述於 Pro. ACS Div. Polym. Mat. Sci. Eng., April 13-17, 1997,p. 42中之化合物且具有下列結構: 裴 訂 線 經濟部智慧財產局員工消費合作社印製 OR OR 〇Ν,Ν,Ν',Ν'-tetrakis(3-mercaptopropenyloxy-2-hydroxypropyl)_〇〇,〇)_bis-3_aminopropyl-polydidecyloxane. The reaction product of glycidyl methacrylate with an amine functional polythioxanthine can also be used as a monomer having a hydroxyl group-functional oxime. Other hydroxy-functional oxane-containing monomers include those described in U.S. Patent No. 5,994,488, the disclosure of U.S. Pat. Nos. 6, s. Monomers in 4,139,513 and 4,139,692. These and any other patents or applications cited herein are hereby incorporated by reference. Other structures of suitable hydroxy-functional azide-containing monomers include those similarly described in Pro. ACS Div. Polym. Mat. Sci. Eng., April 13-17, 1997, p. 42 and having The following structure: 裴 线 经济 经济 经济 经济 经济 经济 智慧 OR OR OR

OR .16- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 經濟部智慧財產局員工消費合作社印製 1311580 Λ7 B7 五、發明說明(15) 其中η = 1-50且R獨立地包含Η或一可聚合之不飽和基 團,其中至少一個R包含可聚合基團且至少一個R (較 佳3-8個R)包含Η。 另外適合之含羥基-官能化矽氧烷之單體被揭示於美國 專利案4,235,985中。 此等成分可藉由已知方法,諸如液相層析、蒸顧、再結 晶或萆取—而自含羥基-官能化矽氧烷之單體中被去除, 或彼等之形成可藉小心選擇反應條件及反應比例予以避 免。 適合之單官能性羥基-官能化矽氧烷單體於商業上可購 自Gelest公司(Morrisville, ΡΑ)。適合之多官能性經基-官 能化矽氧烷單體於商業上可購自Gelest公司(Morrisville, PA)或可利用描述於5,994,488及5,962,548中之程序予以 製造。適合之PEG型羥基-官能化矽氧烷單體可利用描述 PCT/JP02/02231中之程序來製造。 雖然含羥基-官能化矽氧烷之單體業已發現特別適合提 供生物醫學裝置(特別是眼用裝置)之相容聚合物,但任 何含官能化矽氧烷之單體(其當被聚合或被形成一種最終 物體時與選擇之親水性成分相容)可被使用。適_合之羥 基-官能化矽氧烷單體可利用下列單體相容性試驗來選 擇。在此試驗中,單-3-曱基丙烯氧基丙基終端、單-丁基 終端之聚二甲基矽氧烷(mPDMS分子量800-1000)和一 種待試驗之單體各1克與1克之3,7-二甲基-3-辛醇在約 20°C下一起混合。將12重量份之K-90 PVP和60重量份 -17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X297公釐)OR .16- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1311580 Λ7 B7 V. Invention Description (15) where η = 1-50 and R independent The ground layer comprises hydrazine or a polymerizable unsaturated group, wherein at least one R comprises a polymerizable group and at least one R (preferably 3-8 R) comprises hydrazine. Further suitable hydroxy-functionalized decane-containing monomers are disclosed in U.S. Patent No. 4,235,985. These components can be removed from the monomer containing the hydroxy-functional oxane by known methods such as liquid chromatography, evaporation, recrystallization or extraction - or they can be formed with care The reaction conditions and reaction ratios are selected to avoid. Suitable monofunctional hydroxy-functionalized decane monomers are commercially available from Gelest Corporation (Morrisville, ΡΑ). Suitable polyfunctional trans-functionalized oxosiloxane monomers are commercially available from Gelest Corporation (Morrisville, PA) or can be made using the procedures described in 5,994,488 and 5,962,548. Suitable PEG type hydroxy-functionalized decane monomers can be made using the procedure described in PCT/JP02/02231. While monomers containing hydroxy-functional oxane have been found to be particularly suitable for providing compatible polymers for biomedical devices, particularly ophthalmic devices, any monomer containing a functionalized oxane (which when polymerized or It can be used when it is formed into a final object that is compatible with the selected hydrophilic component. Suitable hydroxy-functionalized oxoxane monomers can be selected using the following monomer compatibility tests. In this test, a mono-3-mercapto oxypropyl terminal, a mono-butyl terminal polydimethyl methoxy oxane (mPDMS molecular weight 800-1000) and a monomer to be tested each 1 gram and 1 The 3,7-dimethyl-3-octanol was mixed together at about 20 °C. 12 parts by weight of K-90 PVP and 60 parts by weight -17- This paper size is applicable to China National Standard (CNS) A4 specification (210 X297 mm)

經濟部智慧財產局員工消費合作杜印製 1311580 Αν B7 五、發明說明(16) 之DMA之混合物於攪拌中逐滴添加至疏水性成分溶液 中,直到溶液於攪拌3分鐘後維持混濁為止。所添加之 PVP和DMA之摻合物之質量以克數來測定,且被記錄為 單體相容性指數。任何具有大於0.2克,尤佳大於約0.7 克且最佳大於約1.5克之含羥基-官能化矽氧烷之單體將 適合於本發明之使用。 本發明之含羥基-官能化矽氧烷之單體的」‘丰放量”或“相 容化有效量”為相容化或溶解高分子量親水性聚合物所需 要的量。因此,含經基-官能性石夕氧烧之單體的量將部分 視所使用之親水性聚合物的量而定,但更多的含經基-官 能化矽氧烷之單體被需要與較高濃度之親水性聚合物相 容。聚合物配方中含羥基-官能化矽氧烷之單體的有效量 包括約5% (重量百分比,基於反應成分之重量百分比為 準)'至約90%,較佳約10%至約80%,最佳約20%至約 50%。 除了本發明之高分子量親水性聚合物和含羥基-官能化 矽氧烷之單體以外,其他親水性和疏水性單體、交聯劑、 添加劑、稀釋劑、聚合引發劑可被用來製備本發明之生物 醫學裝置。除了高分子量親水性聚合物和含羥基官能化 矽氧烷之單體以外,水凝膠配方可包括含其他矽氧烷之單 體、親水性單體及交聯劑以提供本發明之生物醫學裝置。 含其他矽氧烷之單體 有關含其他矽氧烷之單體,描述於美國專利案4,711, -18- U l本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative Printing, Printing 1311580 Αν B7 V. Mixture of DMA of Invention (16) was added dropwise to the hydrophobic component solution with stirring until the solution remained turbid after stirring for 3 minutes. The mass of the blend of PVP and DMA added was determined in grams and recorded as the monomer compatibility index. Any monomer having a hydroxyl-functionalized oxoxane having greater than 0.2 grams, particularly preferably greater than about 0.7 grams, and most preferably greater than about 1.5 grams, will be suitable for use in the present invention. The "concentration amount" or "compatibilization effective amount" of the hydroxy-functionalized siloxane-containing monomer of the present invention is the amount required to compatibilize or dissolve the high molecular weight hydrophilic polymer. - the amount of functional oxime-oxygenated monomer will depend, in part, on the amount of hydrophilic polymer used, but more trans-functionalized siloxane-containing monomers are required and at higher concentrations The hydrophilic polymer is compatible. The effective amount of the hydroxyl-functionalized oxane-containing monomer in the polymer formulation comprises from about 5% by weight, based on the weight percent of the reaction component, to from about 90%, preferably. From about 10% to about 80%, optimally from about 20% to about 50%. In addition to the high molecular weight hydrophilic polymer of the present invention and the hydroxyl-functionalized alkoxylated monomer, other hydrophilic and hydrophobic monomers , a crosslinking agent, an additive, a diluent, a polymerization initiator can be used to prepare the biomedical device of the present invention. In addition to the high molecular weight hydrophilic polymer and the monomer containing a hydroxyl functionalized siloxane, the hydrogel formulation can be Including monomers containing other siloxanes, hydrophilic monomers and crosslinkers The biomedical device of the present invention is provided. The monomer containing other oxane is related to other siloxane containing monomers, and is described in U.S. Patent No. 4,711, -18- U l. This paper scale applies to China National Standard (CNS) A4 specification. (210x297 mm)

13115801311580

943中之觀醯胺類似物、描述於美國專利案5,070’ 犯中之乙烯胺基甲酸m酸賴似物及被包含於美國 專利案M2M45中之切氧解體為有㈣,所述及之 專利案以及其他在本朗書巾所述之專職都併人本文作 為參考。尤特別地, 3-甲基丙稀氧基二(二甲基石夕氧基)石夕烧(TRIS), 單曱-基丙烯氧基丙基終端之聚二曱基矽氧烷, 聚一甲基矽氧烷,3-曱基丙烯氧基丙基雙(三曱基矽氧基) 曱基矽烷, 1 曱基丙烯氧基丙基五甲基二矽氧烷及其之組合物特別可用 作本發明之其他含矽氧烷單體。含其他矽氧烷之單體可存 在孓量為約0至約75重量%,尤佳約5和約6〇,且最佳 約10和約40重量%。 親水性單體 經濟部智慧財產局員工消費合作社印製 另外,本發明之反應成分亦可包括任何用來製備傳統水 凝膠之親水性單體。例如可使用包含丙稀酸基(⑶尸⑶ COX ’其中R為氫或Ci_6烷基且X為〇或]^)或乙稀基 (-OCH2)之單體。其他親永性單體之實例包括n,n-二甲 基丙烯醯胺、2-經基乙基曱基丙稀酸酯、單甲基丙烤酸甘 油酯、2-經基乙基曱基丙稀醯胺、聚伸乙基單甲笑丙稀酽 甘油酯、曱基丙烯酸、丙烯酸、N-乙烯吡哈。定綱、N_乙 烯-N-曱基乙醯胺、N-乙烯-N-乙基乙醯胺、Ν·乙稀^乙 基曱乙醯胺及彼等之組合物。 -19-134本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 經濟部智慧財產局員工消費合作社印製 1311580 - B7 五、發明說明(18) 除了上述之其他親水性單體外,可使用具有一或多個終 端羥基被含有可聚合雙鍵之官能基所取代之聚氧乙烯多元 醇。實例包括聚乙二醇(如揭示於美國專利案5,484,863 中者);乙氧基化烷基葡萄糖苷(如揭示於美國專利案 5,690,953、5,304,584中者):和乙氧基化聯苯酚A,如 揭示於美國專利案5,565,539中者;其經與一或多個莫耳 當量之末端加蓋基圑(如異氰酸S旨基乙基甲基丙稀酸自旨_、一y_n. '甲基丙烯酸酐、曱基丙烯醯氯化物、乙烯苯曱醯氯化物) 等反應,產生一種聚伸乙基多元醇,其具有一或多個終端 可聚合烯烴基透過聯結部分,如胺基曱酸酯、脲或酯基, 被鍵結至聚伸乙基多元醇。 又v其他實例包括被描述於美國專利案5,070,215中之 親水性碳酸乙烯酯或胺基甲酸乙烯酯單體、描述於美國專 利桌4,910,277中之親水性哼唑酮單體(彼等之内容併入 本文參考)及聚葡萄糖。 較佳之其他親水性單體為Ν,Ν-二甲基丙烯醯胺 (DMA)、2-羥基乙基曱基丙烯酸酯(ΗΕΜΑ)、曱基丙烯酸 甘油酯、2-羥基乙基曱基丙烯醯胺、N-乙烯吡咯啶酮 (NVP)、聚伸乙基單甲基丙稀酸甘油酯、甲基丙烯、丙 烯酸及彼等之組合物,包含DMA之親水性單體特佳。其 他親水性單體可存在之量為約0至約70重量%,尤佳約 5和約60,最佳約10和約50重量%。 交聯劑 -20- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)The guanamine product of 943, the vinyl carbamic acid m-acid lysate described in U.S. Patent No. 5,070', and the oxidative disintegration contained in U.S. Patent No. M2M45 are (IV), and the patents mentioned therein The case and other full-time jobs described in this booklet are for reference. In particular, 3-methylpropoxy bis(dimethyl oxa oxy) tartan (TRIS), monofluorenyl allyoxypropyl terminated polydidecyl fluorene, poly Methyl methoxy oxane, 3-mercapto propyleneoxypropyl bis(trimethyl decyloxy) decyl decane, 1 decyl propyleneoxy propyl pentamethyldioxane, and combinations thereof, particularly Used as other oxosiloxane-containing monomers of the present invention. The monomer containing other oxane may be present in an amount of from about 0 to about 75% by weight, particularly preferably from about 5 to about 6 Torr, and most preferably from about 10 and about 40% by weight. Hydrophilic Monomers Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed In addition, the reactive components of the present invention may also include any hydrophilic monomer used to prepare conventional hydrogels. For example, a monomer containing an acrylic acid group ((3) cadaverine (3) COX ' wherein R is hydrogen or Ci-6 alkyl group and X is ruthenium or osmium) or ethylene group (-OCH 2 ) can be used. Examples of other pro-permanent monomers include n,n-dimethylpropenylamine, 2-ethylidene decyl acrylate, monomethylpropionate, 2-aminoethyl fluorenyl Acrylamide, polyethylidene ethyl acetophenone glyceride, methacrylic acid, acrylic acid, N-vinylpyrazine. Nitrite, N-ethylene-N-mercaptoacetamide, N-ethylene-N-ethylacetamide, hydrazine, ethyl ethane acetamide, and combinations thereof. -19-134 This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 1311580 - B7 V. Invention Description (18) In addition to the other hydrophilic monomers mentioned above A polyoxyethylene polyol having one or more terminal hydroxyl groups substituted by a functional group containing a polymerizable double bond can be used. Examples include polyethylene glycol (as disclosed in U.S. Patent No. 5,484,863); ethoxylated alkyl glucosides (as disclosed in U.S. Patent Nos. 5,690,953, 5,304,584): and ethoxylated biphenol A, such as It is disclosed in U.S. Patent No. 5,565,539, which is incorporated by reference to the end of one or more molar equivalents (e.g., isocyanate S-ethyl ethyl methacrylate), a y_n. Reaction with acrylic acid anhydride, mercaptopropene hydrazine chloride, ethylene benzoquinone chloride, etc. to produce a polyethylidene polyol having one or more terminally polymerizable olefin groups through a linking moiety, such as an amino phthalate , urea or ester group, bonded to the polyethylidene polyol. Still other examples include the hydrophilic vinyl carbonate or vinyl urethane monomers described in U.S. Patent No. 5,070,215, the hydrophilic oxazolone monomers described in U.S. Patent 4,910,277, the disclosure of which is incorporated herein by reference. Reference herein) and polydextrose. Preferred other hydrophilic monomers are hydrazine, hydrazine-dimethyl decylamine (DMA), 2-hydroxyethyl decyl acrylate (fluorene), glyceryl methacrylate, 2-hydroxyethyl decyl propylene hydride. Amine, N-vinylpyrrolidone (NVP), polyethylidene monomethacrylate, methacrylic acid, acrylic acid, and combinations thereof, are particularly preferred as hydrophilic monomers comprising DMA. Other hydrophilic monomers may be present in an amount from about 0 to about 70% by weight, particularly preferably from about 5 to about 60, most preferably from about 10 and about 50% by weight. Crosslinker -20- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm)

A7 1311580 五、發明說明(l9) 經濟部智慧財產局員工消費合作社印製 適合之交聯劑為具有兩或多個可聚合官能基之化合物。 交聯劑可為親水性或疏讀的,且在本糾之某些具體例 中’親水性和疏水性之—狀齡物t經發現可提供呈 改良光學透明度(相較於CSI薄鏡片有降低之霧度)之 石夕氧烧水凝膠。適合之親水性交聯劑之實例包括具有兩或 多個可聚合之官能基以及親水性官能基(諸如聚醚、酿胺 或經基基團)之化合物。特殊之實例包括(四 伸乙基二醇二甲基丙烯酸酯)、TrEGDMA (三伸乙基二 醇二曱基丙烯酸酯)、伸乙基二醇二曱基丙烯酸酯 (EGDMA)、伸乙基一胺二曱基丙烯醢胺、二曱基丙稀酸 甘油酯及彼等之組合物。適合之疏水性交聯劑之實例包括 多官能性之含羥基-官能化矽氧烷之單體、多官能性聚醚_ 聚一甲基石夕氧院肷段共聚物及彼等之組合物等。特殊之疏 水i交聯劑包括丙烯氧基丙基終端之聚二甲基矽氧貌 (n=10或20)(acPDMS)、羥基丙烯酸酯基官能化之矽氧燒 巨體、甲基丙烯氧基丙基終端PDMS、丁二醇二甲基内締 酸酯、二乙烯苯、1,3-雙(3-甲基丙烯氧基丙基)四(三甲基 碎氧基)一'碎氧烧及彼專之組合物。較佳之交聯劑包括 TEGDMA、EGDMA、acPDMS及彼等之組合物。—親水性 交聯劑之用量通常為約0至約2重量%,較佳約〇.5至約 2重量%,而疏水性交聯劑之用量通常為約〇至約5重量 % ’其可另外以莫耳%表示,為約〇·〇1至約〇.2毫莫耳 /克反應成分’較佳約0.02至約〇.1重量%,尤佳〇 〇3 至約0.6毫莫耳/克。 -21- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 1311580 五、發明說明(20 在最終聚合物中增加交聯劑之濃度業經發現可降低霧 度。惟’當交聯劑濃度增加約0.15毫莫耳/克反應成分 以上’模數增加在—般期望之程度以上(大於約9〇磅/平 方英对)°因此’在本發明中,交聯劑組成及用量係經選 擇以提供反應混合物中之交聯劑濃度介於約〇.〇1和約〇1 4莫耳/克交聯劑之間。 一备技藝中所熟知的其他成分或添加物亦可被含括。添 加物包括但不限於紫外線吸收化合物及單體、反應性染料 、抗微生物化合物、顏料、光發色劑、釋離劑及彼等之組 合物等。 其他成分包括透氧成分,諸如包含碳碳三鍵之單體及一 般抹藝中所熟知的含氟單體,包括含氟之(甲基)丙烯酸 户. 酯’尤佳包括例如含氟之(曱基)丙烯酸C2-C12烷酯(諸如 2,2,2-三氣乙基(甲基)丙烯酸酯、2,2,2,2,,2,,21_六氟異丙基 (曱基)丙烯酸酯、2,2,3,3,4,4,4-七氟丁基(曱基)丙烯酸酯、 2,2,3,3’4’4’5’5,6,6,7,7,8,8,8-十五氟辛基(甲基)丙婦酸酯、 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-十六氟壬基(甲基)丙烯酸醋 等。 經濟部智慧財產局員工消費合作社印製 稀釋劑· — 反應成分(含羥基-官能化矽氧烷之單體、親水性聚合 物、父聯劑及其他成分)常於缺乏水下且選擇性地在至少 -種稀釋劑的存在下被混合及反應,以㈣__種反應混合 物。所使用之稀釋劑的種類及用量亦影響形成之聚合物及 -22- 本紙張尺度適用中國囷家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1311580 Λ7 B7 五、發明說明(21) 物體之特性。最終物體之霧度及濕潤度可藉選擇相當疏水 性之稀釋劑及/或降低所使用之稀釋劑之濃度予以改良。 如上所述,增加稀釋劑之疏水性亦可容許相容性差之成分 (如藉相容性試驗所測定者)被加工以形成一種可相容之 聚合物及物體。然而,當稀釋劑變得更疏水時,則需要以 水取代稀釋劑之加工步驟將必須使用溶劑,而不是水。此 可能非所欲地增加製造過程的複雜度及成本-I因此,很重 '要的是要在必要程度之加工便利下選擇可提供與成分之期 望相容性之稀釋劑。可用於製備本發明裝置之稀釋劑包括 醚類、酯類、烴類、烷基i化物、矽烷類、醯胺類、醇類 及彼等之組合物。醯胺類及醇類為較佳之稀釋劑,而二級 和三級醇為最佳之醇稀釋劑。可用作本發明稀釋劑之醚類 的實例包括四氫吱喃、三丙二醇甲_、二丙二醇甲鍵、乙 二si正丁醚、二乙二醇正丁醚、二乙二醇.曱醚、乙二醇苯 醚、丙二醇曱醚、丙二醇曱醚乙酸酯、二丙二醇曱醚乙酸 g旨、丙二醇正丙醚、二丙二醇正丙謎、三丙二醇正丁醚、 丙二醇苯醚、二丙二醇二曱醚、聚乙二醇、聚丙二醇及彼 等之混合物。可用於本發明之酯之實例包括乙酸乙酯、乙 酸丁酯、乙酸戊酯、乳酸曱酯、乳酸乙酯、乳酸異__丙酯。 可用作本發明稀釋劑之烷基鹵化物之實例包括二氯曱烷。 可用作本發明稀釋劑之矽烷的實例包括八曱基環四矽氧 烷。 可用作本發明稀釋劑之醇類的實例包括那些具有下式者 -23- 本紙張尺度適用中國國家標準(CNS)A4規格(210 x297公釐)A7 1311580 V. INSTRUCTIONS (l9) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. Suitable crosslinkers are compounds with two or more polymerizable functional groups. The cross-linking agent can be hydrophilic or sparse, and in some specific examples of this correction, 'hydrophilic and hydrophobic--aged t have been found to provide improved optical clarity (compared to CSI thin lenses) Reduced haze) of Shixia oxygenated hydrogel. Examples of suitable hydrophilic crosslinking agents include compounds having two or more polymerizable functional groups and hydrophilic functional groups such as polyethers, captanamines or transradical groups. Specific examples include (tetraethyl glycol dimethacrylate), TrEGDMA (tri-ethyl glycol dimercapto acrylate), ethylene glycol dimercapto acrylate (EGDMA), ethyl Monoamine dimercaptopropenylamine, dimercapto glyceride and combinations thereof. Examples of suitable hydrophobic crosslinking agents include polyfunctional hydroxy-functionalized decane-containing monomers, polyfunctional polyethers - polymethyl oxalate oxime copolymers, and combinations thereof, and the like. . Special hydrophobic i crosslinkers include propyleneoxypropyl terminated polydimethyl oxime (n=10 or 20) (acPDMS), hydroxy acrylate functionalized oxime, giant methacrylate Propyl terminal PDMS, butanediol dimethyl endoate, divinylbenzene, 1,3-bis(3-methylpropoxypropyl)tetrakis(trimethylsuccinyloxy)-a Burn and its special composition. Preferred crosslinking agents include TEGDMA, EGDMA, acPDMS, and combinations thereof. The hydrophilic crosslinking agent is usually used in an amount of from about 0 to about 2% by weight, preferably from about 5% to about 2% by weight, and the hydrophobic crosslinking agent is usually used in an amount of from about 5% to about 5% by weight. The molar % indicates that it is from about 〇·〇1 to about 〇.2 mmol/g of the reaction component, preferably from about 0.02 to about 0.1% by weight, particularly preferably from 3 to about 0.6 mmol/g. -21- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) A7 1311580 V. Description of invention (20) Increasing the concentration of crosslinker in the final polymer has been found to reduce haze. The concentration of the binder is increased by about 0.15 millimoles per gram of the reaction component above the 'modulus increase is above the above-mentioned desired level (greater than about 9 pounds per square inch). Therefore, in the present invention, the composition and amount of the crosslinking agent It is selected to provide a crosslinker concentration in the reaction mixture between about 〇.〇1 and about 莫1 4 mol/g of crosslinker. Other ingredients or additives well known in the art can also be Additives include, but are not limited to, ultraviolet absorbing compounds and monomers, reactive dyes, antimicrobial compounds, pigments, photochromic agents, excipients, and combinations thereof, etc. Other ingredients include oxygen permeable components such as A monomer containing a carbon-carbon triple bond and a fluorine-containing monomer well-known in the general scouring process, including a fluorine-containing (meth)acrylic acid ester. The ester preferably includes, for example, a fluorine-containing (fluorenyl)acrylic acid C2-C12 alkane. Ester (such as 2,2,2-trisylethyl) Acrylate, 2,2,2,2,,2,,21_hexafluoroisopropyl(indenyl)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (曱) Acrylate, 2,2,3,3'4'4'5'5,6,6,7,7,8,8,8-pentadecafluorooctyl (methyl)propionate, 2 , 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl (meth)acrylic acid vinegar, etc. Consumer Cooperatives Print Diluent — The reactive components (hydroxy-functionalized alkoxylated monomers, hydrophilic polymers, parent binders, and other ingredients) are often lacking in water and selectively in at least one diluent Mix and react in the presence of (4) __ kinds of reaction mixture. The type and amount of diluent used also affect the polymer formed and -22- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1311580 Λ7 B7 V. INSTRUCTIONS (21) Characteristics of objects. The haze and wetness of the final object can be selected by using a relatively hydrophobic thinner and/or lowering The concentration of the diluent used is improved. As mentioned above, increase The hydrophobicity of the release agent may also allow for poorly compatible ingredients (as determined by compatibility testing) to be processed to form a compatible polymer and object. However, when the diluent becomes more hydrophobic, then The processing steps that require the replacement of the diluent with water will necessitate the use of solvents rather than water. This may undesirably increase the complexity and cost of the manufacturing process - therefore, it is very important to have the necessary degree of processing convenience. A diluent is provided which provides the desired compatibility with the ingredients. The diluents useful in the preparation of the devices of the present invention include ethers, esters, hydrocarbons, alkyl i radicals, decanes, guanamines, alcohols, and the like. Composition. Indoleamines and alcohols are preferred diluents, while secondary and tertiary alcohols are preferred alcohol diluents. Examples of the ether which can be used as the diluent of the present invention include tetrahydrofuran, tripropylene glycol methyl, dipropylene glycol methyl bond, ethylene di-n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol, decyl ether, Ethylene glycol phenyl ether, propylene glycol oxime ether, propylene glycol oxime ether acetate, dipropylene glycol oxime ether acetic acid g, propylene glycol n-propyl ether, dipropylene glycol n-propyl ray, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol diterpene Ether, polyethylene glycol, polypropylene glycol and mixtures thereof. Examples of the ester which can be used in the present invention include ethyl acetate, butyl acetate, amyl acetate, decyl lactate, ethyl lactate, iso-propyl lactic acid. Examples of the alkyl halide which can be used as the diluent of the present invention include dichlorodecane. Examples of the decane which can be used as the diluent of the present invention include octadecylcyclotetraoxane. Examples of the alcohol which can be used as the diluent of the present invention include those having the following formula -23- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm).

13115801311580

五、發明說明(V. Description of the invention (

RR

C-OH 其中R,R及R"獨立地選自H、具有j至1〇個碳之直 鏈、分支、或環狀單價烷基,其可選擇性地經一或多個包 括由素、喊、m--芳基、胺、醯胺、烯、炔、羧酸、醇、 酿、㈣之基團予以取代,或R,R> R"之任二者或三者 可-起結合形成-或多個環狀結構,諸如亦可如前述經取 代之具有1至10個碳原子之烷基,前提是R, R,或R"之 不多於一個為Η。 粒佳R, R'和R"獨立地選自Η或未經取代之具有1至: 個碳之直鏈、分支、或環狀單價烧基。尤佳R,IT和γ 獨立地選自Η或未經取代之具有i至7個碳之直鍵、分 支、或環狀單價炫基。在某些具體例中,較佳之稀釋劑具 有4或更多,尤佳5或更多之總碳數,因為愈高分子量之 稀釋劑有愈低之揮發性及愈低之可祕。# R, r,和r"之 一為Η時,結構即形成—種二級醇。當R,r,和r無—為 Η時,結構即形成—種三級醇。三級醇優於二級醇_ 劑較佳為惰性的且當碳之總數為5或更少日 水置換。 ’、义奋勿掖 有用之二級醇之實例包括2_丁醇、2_丙醇、甲醇、環己 醇、環戊醇及外降料醇、2_戊醇、3_戊醇、2_ ^ 醇、3-己醇、3-甲基_2_ 丁醇、2_庚醇、:辛醇、2_壬醇' -24- 本紙張尺度_ 111 ® 家辟(CNS)A4 (21G X 297^57 13 π 580C-OH wherein R, R and R" are independently selected from H, a linear, branched, or cyclic monovalent alkyl group having from j to 1 carbon, which may optionally be substituted by one or more Shouting, m--aryl, amine, decylamine, alkene, alkyne, carboxylic acid, alcohol, brewing, (4) groups are substituted, or R, R > R" either or both can be combined Or a plurality of cyclic structures such as an alkyl group having 1 to 10 carbon atoms which may be substituted as described above, provided that no more than one of R, R, or R" is hydrazine. The particles R, R' and R" are independently selected from fluorene or unsubstituted linear, branched, or cyclic monovalent alkyl groups having from 1 to: carbon. More preferably R, IT and γ are independently selected from fluorene or unsubstituted direct bonds, branches, or cyclic monovalent groups having from i to 7 carbons. In some embodiments, preferred diluents have a total carbon number of 4 or more, particularly preferably 5 or more, because the higher the molecular weight diluent, the lower the volatility and the lower the secret. When one of # R, r, and r" is Η, the structure forms a secondary alcohol. When R, r, and r are not - Η, the structure forms a tertiary alcohol. The tertiary alcohol is preferred over the secondary alcohol. The agent is preferably inert and when the total number of carbons is 5 or less, the water is replaced. Examples of secondary alcohols that are useful for the purpose include 2-butanol, 2-propanol, methanol, cyclohexanol, cyclopentanol and decyl alcohol, 2-pentanol, 3-pentanol, 2_ ^ Alcohol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,: octanol, 2-sterol' -24- The paper size _ 111 ® Home (CNS) A4 (21G X 297 ^57 13 π 580

五、發明說明(23 2-癸醇、3-辛醇、降花烯醇等。 有用之三級醇之實例包 匕*何乐一』醇、第三酿、2-甲 基_2_戊醇、, —戊和甲 己醇、2-甲基-2-醇广”二;甲广3_戊醇、卜甲基環 丙醇、一庚醇、,Μ:辛^ 2- 甲基-2·癸醇、3-C、η甲基I壬醇、 •4“ ^基-3-己醇、3_甲基-3-庚醇、4-曱基- 4-庚醇、3-甲基-3-辛醇、4 且 4 m . K甲基-4-辛醇、3-甲基-3-壬醇〜 4-甲基-4-壬醇、3-甲其q立1 ," 基辛醇、3·乙基-3-己醇、3-曱基- 3- 庚醇、4-乙基-4-庚醢.^ . 古 厌蛘、4-丙基-4-庚醇、4_異丙基_4_庚 醇、2,4-二甲基-2-戊醇、j美 1甲基蜋戊酵、1-乙基環戊醇、 1-乙基i哀戊醇、3-羥基_3_甲其 3曱基-1-丁烯、4-羥基-4-甲基-1- 衣戍 本基_2·丙醇、2_甲氧基-2-甲基-2-丙醇、2,3,4_ 二甲基-3-戊醇、3,7--甲其,立f w ' —甲基_3-辛醇、2-苯基_2_ 丁醇、2-曱 基-1-苯基-2-丙醇和3_乙基_3_戊醇等。 單一醇或兩或多個上列醇類或兩或多個根據以上結構之 醇類之混合物可被用作製造本發明聚合物之稀釋劑。 一在某一 例中’較佳之醇稀釋劑為具有至少*個石炭之 t級和三級醇類。更佳之醇稀釋劑包括第三丁醇、第三戊 醇:2:丁醇、2-甲基_2、戊醇、2,3_二曱基_2_丁醇、!_曱基_ 3-戊醇、3-乙基_3_戊醇、3,7_二甲基_3_辛醇。~ 目前’最佳之稀釋劑為己醇、庚醇、辛醇、壬醇、癸 醇、第三丁醇、3_甲基-3-戊醇、異丙醇、第三戊醇、乳 酸乙醋、乳酸甲醋、乳酸異丙酉旨、3义二甲基_3^二 甲基甲醯胺、二甲基乙醯胺、二甲基丙醯胺、N-甲基吡 -25- 訂 線 1 t 經濟部智慧財產局員工消費合作社印製 參紙張尺度適用中國國家標準(CNS)A4規格(7f〇 χ 297公楚) Α7 !31158〇 五、發明說明(24) 咯啶酮及彼等之混合物。可用於本發明之其他稀釋劑被栺 述於美國專利案6,020,445,其併入本文作為參考。 在本發明之一具體例中,稀釋劑在加工條件下為水圩溶 的,且在一短時間内易於以水由鏡片洗出。適合之水可溶 稀釋劑包括Κ乙氧基_2_丙醇、1-曱基-2-丙醇 '第三、戍 醇、三丙二醇甲醚、異丙醇、1-甲基-2-吡咯啶酮、'队 —曱基丙SI胺、乳酸乙醋、二丙..二5睁..甲醚及其混合物等。 水可瘩稀釋劑的使用允許橫模塑加工只利用水或包含水作 為一實質成分之水溶液來進行。 在一具體例中,稀釋劑的用量通常低於反應混合物之約 5〇重里%且較佳低於約4〇 %,尤佳介於約10和約3 〇 %之 間。·- 严!· 稀釋劑亦可包含其他成分,諸如釋離劑。適合之釋離劑 為i可浴且幫助鏡片去枯連(deblocking)。 經濟部智慧財產局員Η消費合作社印製 聚合引發劑包括諸如月桂基過氧化物、苯曱醯過氣化 物、碳酸異丙酯、偶氮雙異丁醯腈等之化合物,其在適声 咼溫下產生自由基,以及光引發劑系統,諸如&羥= 嗣、院氧基氧基安息香、苯乙酮、乙醯基氧化鱗、及第: 胺加上二酮,其之混合物等。光引發劑之說明實倒為了 經基環己基笨酮、2-經基·2_甲基笨基_丙·㈣、雙、(仏 二甲氧基苯甲酿基)-2,4-4-三甲基戊基氧^匕膦 _BAP0)、雙(2,4,6三甲基苯甲醯基)_笨基氧 (1职_ 819) ' 2,4,6_三甲鮮基二苯基氧化膦和二 甲基苯甲喊二苯基氧化膦、安息香甲_及樟腦酿和^ -26- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇χ297公楚)- ~~~—— _ A7 1311580 五、發明說明(25) 基4-(N,N-二曱基胺基)苯甲酸酯之組合物。商業上可得之 可見光引發劑系統包括 Irgacure 819、Irgacure 1700、Irgacure 1800、Irgacure 819、Irgacure 1850 (全部來自汽巴特用化學品 公司)及Lucirin TPO引發劑(可得自BASF)。商業可得 之UV光引發劑包括Darocur 1173和Darocur 2959 (汽巴特 用化學品公司)。引發劑以有效量被用於反應混合物中, 以弓卜發及’應混合物之光聚合,例如每1 〇〇份反應單體由釣 ’ 〇.1至,約2重量份。反應混合物之聚合可利用適當選擇之 熱或可見光或紫外光或其他視所使用之聚合引發劑而定之 方法來引發。另外,引發作用可在無光引發劑下,利用如 電子束來進行。然而,當使用光引發劑時,較佳之引發劑 為,1 -趟基環己基苯酮和雙(2,6-二甲氧基苯甲醯基)-2,4-4-三甲基戊基氧化膦(DMBAPO)之組合物,且聚合引發之較 佳+法為可見光。最佳為雙(2,4,6-三甲基苯曱醯基)_笨基 氧化膦(Irgacure 819®)。 本發明進一步包括、包含及實質上包含以下所示之配方 之石夕氧烷水凝膠、生物醫學裝置、眼用裝置及隱形眼鏡: 經濟部智慧財產局員工消費合作杜印製 成分之重量% ------- lHMWHP SCM HM ~ l5"90 -------- 1-15,3-15 或 5-12 0 0 ~~~~~~~~~~ 10-80 --__1 1-15,3-15 或 5-12 0 〇 ~~- 20-50 ----- 1-15, 3-15 或 5-12 0 0 '~~ 5-90 1 1-15, 3-15 或 5-12 0-80, 5-60 或 0-70,^60^ ΤίδΟ --*--二 10-40 10-50 1-15,3-15 或 5-12 0-80, 5-60 或 〇-70,5^60^~ -27- 本紙張尺度適財㈣家標準(CNS)A4規格 (210x297 公釐) 1311580 A7 B7 五、發明說明(26: 10-40 10-50 20-50 1-15,3-15 或 5-12 0-80,5-60 或 10-40 0-70, 5-60 或 10-50 HFSCM為含羥基-官能化矽氧烷之單體 HMWHP為高分子量親水性聚合物 SCM為含矽氧烷單體 HM為親水性單體 以上之重量百分比為基於全部之反應成分為準。因此, 本發明包括具有表中所列各組成(其描述了 9〇値可.能之 組成範圍)之矽氧烷水凝膠、生物醫學裝置、眼用裝置及 隱形眼鏡。上列之各範圍以字詞“約”為開頭。前述範圍之 組合被呈現,前提是所列之成分及任何其他成分加總至 100重量%。 組合之含矽氧烷單體(含羥基-官能化矽氧烷及其他含 矽氧烷之單體)之較佳範圍為反應成分之約5至99重量 百分比,尤佳約15至90重量百分比,最佳約25至約80 重量百分比。含羥基-官能化矽氧烷之單體之較佳範圍為 約5至約90重量百分比,較佳約10至約80,且最佳約 20至約50重量百分比。親水性單體之較佳範圍為反應成 分之約0至約70重量百分比,尤佳約5至約60重量百分 比,最佳約10至約50重量百分比。高分子量親水」生聚合 物之較佳範圍為約1至約15重量百分比,尤佳約3至約 15重量百分比,最佳約5至約12重量百分比。所有之大 約重量百分比為基於反應成分之總重為準。稀釋劑之較佳 範圍基於反應混合物中之所有成分之重量為準為約0至約 70重量百分比,尤佳約0至約50重量百分比,更約0至 -28- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 訂 線 # 經濟部智慧財產局員工消費合作社印製 A7 B7 311580 五、發明說明(27 約40重量百分比且在一些具體例中,最佳為介於約10至 約30重量百分比之間。所需要之稀釋劑之量視反應成分 之性質及相對量而變動。 在一較佳具體例中,反應成分包含2-丙烯酸、2-甲基-、2-羥基-3-[3-[l,3,3,3-四曱基-1-[(三甲基曱矽烷基)氧基] 二矽氧烷基]丙氧基]丙酯“SiGMA”(反應成分之〜28重量 %) ; (8OO-tOO0 MW單甲基丙烯氧基丙基終端之單-正-丁基終端之聚二曱基矽氧烷“mPDMS”(〜31%重量); Ν,Ν-二甲基丙烯醯胺“DMA”(〜24%重量);2-羥基乙基 甲基丙烯酸酯“HEMA”(〜6%重量);四乙二醇二曱基丙 烯酸酯“TEGDMA”( ~1.5 %重量);聚乙烯吡咯啶酮“K-90.PVP”(〜7%重量);餘量包含小量之添加物和光引發 产、 劑。聚合反應最佳在約23% (組合之單體和稀釋劑摻合 物之重量%)之3,7-二曱基-3-辛醇稀釋劑的存在下進 行。 在其他較佳具體例中,反應成分包含下表所示者。所有 之量以字詞“約”開頭。 訂 線 經濟部智慧財產局員工消費合作杜印製 成分 重量% SiGMA 30 30 mPDMS 23 18 DMA 31 31 HEMA 7.5 9 EGDMA 0.75 0.8 PVP 6 6 -29- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 B7 五、發明說明( 28 物 上述配方之聚合較佳在以第三-戊醇作為稀釋劑的存在 下進行,其包含約29重量百分比之未固化之反應混合 加工 本發明之生物醫學裝置係藉將高分子量親水性聚合物、 3羥基-官能化矽氧烷之單體,加上一或多種下述者:含 其他矽氧烷之單體、親水性單體、添加物(“反應成分”) 及稀釋劑(“反應混合物”),與一種聚合引發劑混合,並 措適當條件固化以形成一種產物,其隨後可藉車床、切割 被开/成適當形狀。另外,反應混合物可被一中 隨後被固化成適當物體。 ,、中 經濟部智慧財產局員工消費合作社印製 在隱形眼鏡的製造中,處理反應混合物之各種方法為已 知,包括旋轉鑄造及靜電鑄造。旋轉鑄造法被揭示於美國 專利案3,4〇M29及3,660,545,而靜電鑄造法被揭示於 4,113,224及4,197,施巾。製造包含本發明聚合物之隱形 眼鏡之較佳方法為模塑魏財凝膠,其為轉的且精 確地控制水合鏡片的最終形狀。就此方法而言,反库甲人 置於—具有最終期望之⑪氧財_ (亦即^月^ ΛΚα )之形狀的模具巾’歧應齡物處於單體聚 =丄藉此產生—種呈最終期望產品形狀之聚合物/_ 物。然、後,以-溶劑處理此聚合物/稀釋劑混合物 以去除稀咖,最後將其以水置換,產生_具有最終大小 /狀之矽氧烧水凝朦,该形狀相當類似於原始模塑之聚 -30- 本纸張尺度適用中國國家標準(CNS)A4規格(2丨〇 X 297公复) !311580 五、發明說明(29 合物/稀釋劑物體之大小和形狀。此方法可被用來 形眼鏡且進-步被描述於美國專利案4,495=隱 =,336、4,889,664 及 5,〇39 459 巾併人本文作 μ 固化 ^發明之又—特徵為—種固対魏水凝膠配方 曰進之濕難之料。現已發財魏錢膠之凝= 可被用來選擇可提供濕潤之眼用裝置(特別是一_ = 潤 鏡)的固化條件。凝膝時間為交聯之聚合物網絡开Μ的日^ 間’其導致固化反應混合物的黏度接近無限大,及庵 混合物變成非液體。凝膠點係在-特定之轉化程度發生了 與反應條件無關,因此可被用作反應速率之指標。現 現’就給(之反應混合物而言,凝膠時間可被用來決a 與期望之鋪度之固化條件。因此,在本發明之製法= 反應混合物係在可提供待使用之所得裝置之改良的渴 度’或尤佳充分之濕潤度的凝膠時間或以上予以固化’了 須親水性塗覆物或表面處理(“最小凝膠時間,,)。1無 地’改良之濕潤度為前進動態接觸角相較於無高分^佳 合物之配方而言’減少至少職。愈長的凝膠時= 佳,因為彼等改良濕'潤度且增加加工撓性。 θ1愈 凝膠時間依不同之石夕氧烧水凝膠配方而異。固 影響凝膠㈣。例如,交_之漠度將景彡響㈣時間、件亦 加交聯劑之濃度會減少凝膠時間。增加輻射的強度(―增 •31- ^ 1311580 A7 ___ B7 五、發明說明(3〇 聚合而言)或溫度(就熱聚合而言引發 取、攻能(不論 藉選擇更有效之引發劑或照射範圍,或藉— ° 4里在選定之昭 射範圍内吸收更強之弓丨發劑)亦將減少凝膠時間。㈤‘… 稀釋劑種類及濃度亦以熟悉該項技術者所瞭解的二 凝膠時間。 、式影曰 最小凝膠時間可藉選擇一特定配方、改變上述因子之一 及測量I1膠時間及接觸角來決定。最小凝膠時間為在形成 之鏡片為通常濕潤之點以上。低於最小凝膠時間,鏡片通 常非為濕潤的。就—種隱形眼鏡而t,“通常濕潤的”為鏡 片顯示低於約80° ’較佳低於70。且尤佳低於約6〇。之前進 動態接觸角,或隱形眼鏡顯示淚膜崩潰時間等於或優於 ACUVUE®鏡片者。因此,熟悉該項技術者將明白本文上 述,義之最小嘁膠時間可為一範圍,考慮到統計上之實驗 變異。 ' 在某些利用可見光照射之具體例中,最小凝膠時間至少 約30秒,較佳至少約35秒,且尤佳大於約4〇秒業經發 現為有利的。 經濟部智慧財產局員工消費合作社印製 將包含反應混合物之模具曝露於離子化或光化輻射,例 如電子束、X射線、UV或可見光,亦即具有波^約丨5(] 至約800奈米範圍之電磁輻射或粒子輻射中。較佳地,輕 射源為UV或具有約250至約700奈米波長之可見光。適 當之輻射源包括UV燈及日光。在UV吸收化合物被含括 於組成物中(例如作為一種UV阻斷劑)的具體例中,固 化係藉除了 UV照射以外(諸如藉可見光或熱)的方式來 -32- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) [311580 A7 B7 五、發明說明(31 經濟部智慧財產局員工消費合作社印製 進行。在一較佳具體例中,輻射源係選自低強度之UVA (約315-約400奈米)、UVB (約280-約315)或可見光 (約400-約450奈米)。在另一較佳具體例中,反應混 合物包括一種UV吸收化合物,利用可見光及低強度予以 固化。當於本文中使用時,“低強度”意表介於約0.1毫瓦 /平方公分至約6毫瓦/平方公分之間,較佳介於約0.2 毫瓦/平方公分和3毫瓦/平方公分之-間〇固化時間很 長,通常高於約1分鐘,較佳介於約1至約60分鐘,更 佳介於約1及約30分鐘之間。此緩慢、低強度之固化為 提供可顯示持續活體内耐蛋白質沉積性之相容眼用裝置的 關鍵。 反應混合物之固化的時間亦為重要的。當溫度增加高於 室溫時,形成之聚合物的霧度降低。有效降低霧度之溫度 包括形成鏡片之霧度相較於在25°C下所製造之相同組成 物之鏡片降低至少約20%之溫度。因此,適合之固化溫 度包括那些大於約25°C者,較佳為那些介於約25°C和70 °C之間者,尤佳為那些介於約40°C和70°C之間者。固化 條件(溫度、強度及時間)之精確設定將視所選擇之鏡片 材料的成分而定且為在熟悉該項技術之人參照本之教不 可決定之範圍内。固化可在一或多個固化區間中進行。 固化時間必須足以由反應混合物形成一種聚合物網絡。 形成之聚合物網絡以稀釋劑膨脹且模穴之形狀。 去枯連 -33- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 訂 線 鬌 1311580 A7V. Description of the invention (23 2-nonanol, 3-octanol, hypotenol, etc. Examples of useful tertiary alcohols include *He Leyi alcohol, third brewing, 2-methyl-2_e Alcohol, -pentane and methylhexanol, 2-methyl-2-ol wide" two; methyl-3-butanol, methylcyclopropanol, monoheptanol, hydrazine: octyl 2-methyl-2 Sterol, 3-C, η-methyl I decyl alcohol, • 4′^-yl-3-hexanol, 3-methyl-3-heptanol, 4-mercapto-4-heptanol, 3-methyl- 3-octanol, 4 and 4 m. K-methyl-4-octanol, 3-methyl-3-nonanol~ 4-methyl-4-nonanol, 3-methyl-Q-li, " Octanol, 3-ethyl-3-hexanol, 3-mercapto-3-heptanol, 4-ethyl-4-glyoxime. ^. Antiallergic, 4-propyl-4-heptanol, 4 _isopropyl_4_heptanol, 2,4-dimethyl-2-pentanol, j-1 methyl hydrazine, 1-ethylcyclopentanol, 1-ethyl i-pentanol, 3 -hydroxy_3_methyl-3-mercapto-1-butene, 4-hydroxy-4-methyl-1-indenyl-2-propanol, 2-methoxy-2-methyl-2- Propanol, 2,3,4-dimethyl-3-pentanol, 3,7--methyl, ffy'-methyl-3-octanol, 2-phenyl-2-butanol, 2-mercapto -1-phenyl-2-propanol and 3-ethyl-3-butanol, etc. single alcohol or two or more A mixture of the above alcohols or two or more alcohols according to the above structure can be used as a diluent for the production of the polymer of the present invention. In one embodiment, the preferred alcohol diluent is a grade t having at least * charcoal. And tertiary alcohols. More preferred alcohol diluents include tert-butanol, third pentanol: 2: butanol, 2-methyl-2, pentanol, 2,3-dimercapto-2-butanol, !_曱基_ 3-pentanol, 3-ethyl_3_pentanol, 3,7-dimethyl_3_octanol. ~ The current best diluent is hexanol, heptanol, octanol , sterol, sterol, tert-butanol, 3-methyl-3-pentanol, isopropanol, third pentanol, lactic acid ethyl acetate, methyl lactate, isopropyl lactate, 3 dimethyl _3^Dimethylmethaneamine, dimethylacetamide, dimethylpropanamine, N-methylpyridin-25- ordering line 1 t Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed paper scale applicable China National Standard (CNS) A4 Specification (7f〇χ 297 public) Α7 !31158〇五, invention description (24) rancidinone and mixtures thereof. Other diluents which can be used in the present invention are described in the US patent Case 6,020,445, which is incorporated herein as a reference In one embodiment of the invention, the diluent is water-soluble under processing conditions and is readily washable by water from the lens in a short period of time. Suitable water-soluble diluents include Κethoxy 2 _propanol, 1-mercapto-2-propanol 'third, sterol, tripropylene glycol methyl ether, isopropanol, 1-methyl-2-pyrrolidone, 'team-mercaptopropane SI amine, lactic acid Ethyl vinegar, dipropyl ketone, bismuth oxime, methyl ether and mixtures thereof. The use of a water-reducible diluent allows the horizontal molding process to be carried out using only water or an aqueous solution containing water as a substantial component. In one embodiment, the diluent is typically present in an amount of less than about 5% by weight of the reaction mixture and preferably less than about 4,000%, more preferably between about 10 and about 3%. ·- Strict! · The diluent can also contain other ingredients, such as excipients. A suitable release agent is i to bath and help the lens to deblocking. The Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives, printing polymerization initiators include compounds such as lauryl peroxide, benzoquinone pervaporate, isopropyl carbonate, azobisisobutyl carbonitrile, etc. Lower free radicals are produced, as well as photoinitiator systems such as & hydroxy = oxime, oxime ethoxybenzoin, acetophenone, acetamyl oxidized scale, and: amine plus diketone, mixtures thereof, and the like. The description of the photoinitiator is based on the cyclohexyl ketone, 2-carbyl-2-methylphenyl-propyl-(tetra), bis((dimethoxybenzophenone)-2,4-4 -trimethylpentyloxyphosphonium _BAP0), bis(2,4,6-trimethylbenzylidene)-stupyloxy (1st _ 819) ' 2,4,6_trimethyl fresh base II Phenylphosphine oxide and dimethyl benzophenone diphenylphosphine oxide, benzoin A and camphor and ^ -26- This paper scale applies to China National Standard (CNS) A4 specifications (21〇χ297 public Chu)- ~~ ~—— _ A7 1311580 V. DESCRIPTION OF THE INVENTION (25) A composition of 4-(N,N-didecylamino)benzoate. Commercially available visible light initiator systems include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (all from Steam Batt Chemicals) and Lucirin TPO Initiator (available from BASF). Commercially available UV photoinitiators include Darocur 1173 and Darocur 2959 (Steam Bart Chemicals). The initiator is used in the reaction mixture in an amount effective to effect photopolymerization of the mixture, e.g., from 1 to about 2 parts by weight per 1 part of the reaction monomer. The polymerization of the reaction mixture can be initiated by suitably selecting heat or visible light or ultraviolet light or other methods depending on the polymerization initiator used. Alternatively, the priming can be carried out using, for example, an electron beam, without a photoinitiator. However, when a photoinitiator is used, preferred initiators are 1-nonylcyclohexylbenzophenone and bis(2,6-dimethoxybenzylidene)-2,4-4-trimethylpentene. A composition of phosphine oxide (DMBAPO), and the preferred method of polymerization initiation is visible light. Most preferred is bis(2,4,6-trimethylphenylhydrazinyl)-phenylphosphine oxide (Irgacure 819®). The present invention further comprises, consists of, and substantially comprises a formulation of the following shown as a hydrocele, a biomedical device, an ophthalmic device, and a contact lens: The Ministry of Economic Affairs, the Intellectual Property Office, the employee's consumption cooperation, the weight of the printed product ------- lHMWHP SCM HM ~ l5"90 -------- 1-15,3-15 or 5-12 0 0 ~~~~~~~~~~ 10-80 -- __1 1-15,3-15 or 5-12 0 〇~~- 20-50 ----- 1-15, 3-15 or 5-12 0 0 '~~ 5-90 1 1-15, 3 -15 or 5-12 0-80, 5-60 or 0-70, ^60^ ΤίδΟ --*--two 10-40 10-50 1-15,3-15 or 5-12 0-80, 5 -60 or 〇-70,5^60^~ -27- The paper scale is suitable for money (4) Household standard (CNS) A4 specification (210x297 mm) 1311580 A7 B7 V. Invention description (26: 10-40 10-50 20 -50 1-15,3-15 or 5-12 0-80,5-60 or 10-40 0-70, 5-60 or 10-50 HFSCM is a hydroxyl-functionalized alkane-containing monomer HMWHP The high molecular weight hydrophilic polymer SCM is a oxosiloxane-containing monomer HM which is a hydrophilic monomer or more by weight based on all the reaction components. Therefore, the present invention includes the components listed in the table (which describes 9 〇値可. The composition of energy Perfluoroalkane hydrogels, biomedical devices, ophthalmic devices, and contact lenses. Each of the above ranges begins with the word "about." The combination of the foregoing ranges is presented, provided that the ingredients listed are The other ingredients are added up to 100% by weight. The preferred range of the combined methoxyxane-containing monomer (hydroxy-functionalized decane and other oxo-containing monomers) is from about 5 to 99 weight percent of the reaction component. More preferably, it is from about 15 to 90 weight percent, most preferably from about 25 to about 80 weight percent. The preferred range of the hydroxyl-functionalized alkane-containing monomer is from about 5 to about 90 weight percent, preferably from about 10 to about 10 weight percent. 80, and most preferably from about 20 to about 50 weight percent. The preferred range of hydrophilic monomer is from about 0 to about 70 weight percent of the reaction component, particularly preferably from about 5 to about 60 weight percent, most preferably from about 10 to about 50 percent. The weight percent. high molecular weight hydrophilic "green polymer" preferably ranges from about 1 to about 15 weight percent, particularly preferably from about 3 to about 15 weight percent, most preferably from about 5 to about 12 weight percent. All about weight percent is based on The total weight of the reaction components is the standard. Preferably, the range is from about 0 to about 70 weight percent, based on the weight of all ingredients in the reaction mixture, particularly preferably from about 0 to about 50 weight percent, more preferably from about 0 to -28 - the paper scale applies to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) Ordering line #Ministry of Economics Intellectual Property Bureau Staff Consumer Cooperatives Printing A7 B7 311580 V. Invention Description (27 about 40 weight percent and in some specific examples, the best is between about 10 to about Between 30 weight percent. The amount of diluent required will vary depending on the nature and relative amount of the reaction components. In a preferred embodiment, the reaction component comprises 2-acrylic acid, 2-methyl-, 2-hydroxy-3-[3-[l,3,3,3-tetradecyl-1-[(trimethyl)曱矽alkyl)oxy]dioxaxyalkyl]propoxy]propyl ester "SiGMA" (~28% by weight of the reaction component); (8OO-tOO0 MW monomethacryloxypropyl terminal single-positive -butyl terminated polydioxanoxane "mPDMS" (~31% by weight); hydrazine, hydrazine-dimethyl methacrylamide "DMA" (~24% by weight); 2-hydroxyethyl methacrylic acid Ester "HEMA" (~6% by weight); tetraethylene glycol dimercapto acrylate "TEGDMA" (~1.5% by weight); polyvinylpyrrolidone "K-90.PVP" (~7% by weight); The amount contains a small amount of additives and a photoinitiator. The polymerization is preferably diluted at about 23% (by weight of the combined monomer and diluent blend) of 3,7-dimercapto-3-octanol. In other preferred embodiments, the reaction components include those shown in the table below. All amounts begin with the word "about." SiGMA 30 30 mPDMS 23 18 DMA 31 31 HEMA 7.5 9 EGDMA 0.75 0.8 PVP 6 6 -29- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 1311580 A7 B7 V. Invention Description (28 The polymerization of the above formula is preferably in the third - Pentanol is carried out as a diluent, comprising about 29% by weight of uncured reaction mixing process. The biomedical device of the present invention utilizes a high molecular weight hydrophilic polymer, a monomer of 3 hydroxy-functionalized decane. , plus one or more of the following: a monomer containing other oxoxane, a hydrophilic monomer, an additive ("reaction component"), and a diluent ("reaction mixture"), mixed with a polymerization initiator, and The product is cured under suitable conditions to form a product which can then be opened/formed into a suitable shape by lathe, cutting. In addition, the reaction mixture can be subsequently solidified into a suitable object in one, and the Ministry of Economy, Intellectual Property Office, Staff Consumer Cooperatives In the manufacture of contact lenses, various methods of treating the reaction mixture are known, including spin casting and electrostatic casting. Rotary casting is disclosed in U.S. Patent 3 4, M29 and 3, 660, 545, and the electrostatic casting method is disclosed in 4, 113, 224 and 4, 197. A preferred method of making a contact lens comprising the polymer of the present invention is molding Wei Cai gel, which is rotary and precise. Controlling the final shape of the hydrated lens. In this way, the anti-Kujia people are placed in a mold towel with the shape of the final desired 11 oo- _ (ie, ^ ^ ^ ΛΚ α ) = 丄 to produce a polymer / _ in the shape of the final desired product. Thereafter, the polymer/diluent mixture is treated with a solvent to remove the dilute coffee, and finally it is replaced with water to produce a helium-oxygen boiling water gel having a final size/shape which is quite similar to the original molding.聚聚-30- This paper scale is applicable to China National Standard (CNS) A4 specification (2丨〇X 297 public recovery)!311580 V. Invention description (29 compound/diluent object size and shape. This method can be Used to shape glasses and further steps are described in U.S. Patent No. 4,495=Hid=, 336, 4,889,664 and 5, 〇39 459, and this article is used for μ-curing, and the invention is characterized by a solid-state hydrogel formulation. Into the dampness of the material. Now the wealth of Wei Qianjiao = can be used to select the curing conditions that provide a moist eye device (especially a _ = lens). The knee time is the crosslinked polymer During the opening of the network, the viscosity of the curing reaction mixture is close to infinity, and the mixture becomes non-liquid. The degree of conversion of the gel point system is independent of the reaction conditions, so it can be used as the reaction rate. The indicator of the present For the compound, the gel time can be used to determine the curing conditions of a and the desired spread. Therefore, in the process of the present invention = the reaction mixture is in the improved thirst of the device to be used, or Good enough to wet the gel time or above to cure 'has to be hydrophilic coating or surface treatment ("minimum gel time,"). 1 no land 'improved wetness is forward dynamic contact angle compared to no In the formulation of high scores ^ good compound, 'reduced at least the job. The longer the gel, the better = because they improve the wetness and increase the processing flexibility. The θ1 gel time varies according to the different times. The hydrogel formula varies. Solid effect gel (4). For example, the indifference of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ - ^ 1311580 A7 ___ B7 V. Description of invention (for polymerization) or temperature (initiating extraction and attack energy in terms of thermal polymerization (whether by choosing a more effective initiator or range of irradiation, or by borrowing - ° 4 The stronger absorption of the bow hair styling agent in the selected range Reduce the gel time. (5) '... The type and concentration of the diluent are also known as the second gel time known to those skilled in the art. The minimum gel time can be selected by selecting a specific formula, changing one of the above factors and measuring I1 gel time and contact angle are determined. The minimum gel time is above the point where the formed lens is usually wet. Below the minimum gel time, the lens is usually not wet. Just a contact lens and t, "usually wet "Shows less than about 80° for the lens" is preferably less than 70. And preferably less than about 6 〇. Before entering the dynamic contact angle, or the contact lens shows that the tear film collapse time is equal to or better than ACUVUE® lens. Those familiar with the technology will understand the above-mentioned, the minimum gel time can be a range, taking into account the statistical variation of the experiment. In certain embodiments utilizing visible light illumination, a minimum gel time of at least about 30 seconds, preferably at least about 35 seconds, and especially preferably greater than about 4 seconds, has been found to be advantageous. The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, prints the mold containing the reaction mixture to ionized or actinic radiation, such as electron beam, X-ray, UV or visible light, that is, having a wave 丨5(] to about 800 奈Preferably, the light source is UV or visible light having a wavelength of from about 250 to about 700 nm. Suitable sources of radiation include UV lamps and daylight. The UV absorbing compounds are included in In a specific example of the composition (for example, as a UV blocker), curing is performed by means of UV irradiation (such as by means of visible light or heat) -32- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification ( 210x297 mm) [311580 A7 B7 V. Description of invention (31 Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printing. In a preferred embodiment, the radiation source is selected from low-intensity UVA (about 315-about 400 奈m), UVB (about 280 to about 315) or visible light (about 400 to about 450 nm). In another preferred embodiment, the reaction mixture comprises a UV absorbing compound which is cured by visible light and low strength. This article When used, the "low strength" means between about 0.1 milliwatts per square centimeter to about 6 milliwatts per square centimeter, preferably between about 0.2 milliwatts per square centimeter and 3 milliwatts per square centimeter. The time is very long, usually above about 1 minute, preferably from about 1 to about 60 minutes, more preferably between about 1 and about 30 minutes. This slow, low strength cure provides a display of sustained in vivo resistance to protein deposition. The key to compatible ophthalmic devices. The curing time of the reaction mixture is also important. When the temperature increases above room temperature, the haze of the formed polymer decreases. The effective temperature to reduce haze includes the formation of fog of the lens. The temperature is reduced by at least about 20% compared to lenses of the same composition made at 25 ° C. Thus, suitable curing temperatures include those greater than about 25 ° C, preferably those between about 25 ° C. And those between 70 ° C, especially those between about 40 ° C and 70 ° C. The exact setting of curing conditions (temperature, strength and time) will depend on the composition of the selected lens material and For those who are familiar with the technology, it is undecided to refer to this teaching. Within a certain range, curing can be carried out in one or more curing zones. The curing time must be sufficient to form a polymer network from the reaction mixture. The polymer network formed is expanded with a diluent and the shape of the cavity. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). Ordering line 1311580 A7

^做15]化後 經濟部智慧財產局員工消費合作社印製 地,用於鏡片配方^由财中移除。不幸 難以由鏡片模具中釋出。元成”片、連,,且 劑)將其去枯連1種*劑(如有機溶 而,在本發明之持鏡片之工具中移除)。然 合物被添加至反㈣^ ’至少—種低分子量親水性聚 '物體,經於朴雜 ^應齡物被形成所期望之 表面活性劑的水溶液中=:、實質上包含或包含小量之 性聚合物可為任何 化及絲連。低分子量親水 但其分子量4 2 分子量聚合物所定義之結構, 咖之去==親水性聚合物在可幫助鏡片釋 40 000 道耳頓之間。此技蓺之專^,較佳介於低於約2〇,_ ' π f之專豕將知道前述之分子晋A ^且某量之具有分子量高於特定平均數之材料將 ?’只要平均分子量在特定範圍内即可。較佳地,低八; 夏親水《合物騎自水可溶聚醯胺、㈣乙刀_ = 及其混合物且尤佳為聚-乙㈣咬嗣、聚乙二醇乙= 乙基-2-十坐口林(可得自聚合物化學創新公司,丁咖⑽, AZ)、聚(甲基丙稀酸)、聚(1_乳酸)、聚己内醯胺—、聚己 内略、聚己内醋二醇1乙稀醇、聚㈣基甲基丙稀酸 唣)、聚(丙烯酸)、聚(1-曱基丙烯酸甘油酿)、聚(2_乙夷2 口等.林)、聚(2-輕基丙基甲基丙稀酸醋)、聚(2_乙稀:比啶 ,氡化物)、聚丙烯醯胺、聚曱基丙烯醯胺及其之混合物 等。^ Do 15] After the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed place, used for lens formula ^ removed from the money. Unfortunately, it is difficult to release from the lens mold. Yuan Cheng" tablets, even, and agents) will be dried up with a kind of * agent (such as organic solution, removed in the lens holding tool of the present invention). The compound is added to the anti (four) ^ ' at least a low molecular weight hydrophilic poly' object, which is formed into an aqueous solution of a desired surfactant by using an ageing substance =: substantially containing or containing a small amount of a polymer, which can be any and silky Low molecular weight hydrophilic but its molecular weight is 4 2 molecular weight polymer defined structure, the coffee == hydrophilic polymer can help the lens release 40 000 Dalton. This technology is better, preferably lower At about 2 〇, the specialization of _ ' π f will know the aforementioned molecular group A ^ and a certain amount of material having a molecular weight higher than a specific average will be as long as the average molecular weight is within a specific range. Preferably, Low eight; Xia Hydrophilic compound ride from water soluble polyamine, (four) E knife _ = and their mixture and especially good poly-B (four) bite, polyethylene glycol B = ethyl-2- ten sitting Lin (available from Polymer Chemical Innovation, Dinga (10), AZ), poly(methyl acrylate), poly (1 lactic acid), poly Indoleamine, polyhexene, polyhexyl vinegar diol 1 ethyl alcohol, poly(tetrakisylmethyl methacrylate), poly(acrylic acid), poly(1-mercapto glycerol glycerin), poly ( 2_Baiyi 2, etc. Lin), poly(2-light propyl methacrylate), poly(2_ethylene:bipyridine, telluride), polyacrylamide, polydecyl propylene Indoleamine and mixtures thereof, and the like.

-34- 本·我張尺度適用中國國家標準(CMS)A4規格(21〇 X 297公釐)-34- Ben·Zhang scale applies Chinese National Standard (CMS) A4 specification (21〇 X 297 mm)

1311580 A7 B7 五、發明說明(33) 低分子量親水性聚合物可被使用之量基於反應成分之總 重至多達約20重量% ’尤佳用量介於約5和約20重量% 之間。 適合之表面活性劑包括甜菜鹼、胺氧化物及其之組合物 等。適合之表面活性劑的實例包括TWEEN®(ICI)、DOE 120(Amerchol/Union Carbide)等。表面可被使用之量至多 達約10,000 ’較佳介於約25和約1500 ppm之間且~尤佳 介於約100 ppm和約1200 ppm之間。 適合之釋離劑為低分子量且包括丨_甲基_4_六氫吡啶 酮、3-嗎福咁-1,2-丙二醇、四氫_2H-哌喃-4-醇、甘油甲 醛、乙基_4·氧-1-六氫吡啶羧酸酯、13—二曱基_3,4,5,6_四 氫广2(iH)-嘧啶酮及1_(2_羥乙基)_2-吡咯啶酮。 由不具低分子量親水性聚合物之反應混合物所製得之鏡 片可於包含至少一種有機溶劑之水溶液中予以去軲連。 合之有機溶劑為疏水性,但可與水混溶。醇類、醚類等 適合的,尤其是一級醇且特佳為異丙醇、DPMa、τρΜ DPM、曱醇、乙醇、丙醇及彼等之混合物為適合之 適為 裴 计 線 例 實 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 適合之去粘連溫度範圍在約室溫至約1〇〇。匸,較枰人、 約70C和95°C之間,較高的溫度提供較快的去點遠^ 間。授拌(諸如藉聲波)亦可被用來減少絲連時間。日守 他此技藝中已知的方法,諸如真空喷嘴,亦可被 具中移除鏡片^ 目 其模 -35- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐 A7 B7 [311580 五、發明說明(34 稀釋劑之置換/水合 基本上,於固化反應混合物之後,將形成之聚合物以一 種溶劑予以處理以去除稀釋劑(若有使用)、未反應之成 分、副產物等,並水合聚合物以形成水凝膠。另外,視水 凝膠之成分之溶解度特性而定,起初使用之溶劑可為乙 醇、甲醇、異丙醇、TPM、DPM、PEGs、PPGs、甘油、 其之混合物,或一種一或多4貧此等有機液體與水之混合 物,接著以純水(或生理食鹽水)萃取。有機液體亦可被 用作一種“預-浸潤”。於脫模(由鏡片去除背曲面)之 後,鏡片可短暫地被浸潤(時間至多達約30分鐘,較佳 介於約5和約30分鐘之間)於有機液體或一種有機液體 與水之混合物中。於預-浸潤之後,可利用水萃取溶劑將 Γν 鏡片進一步水合。 在一些具體例中,較佳之方法使用一種主要為水(較佳 大於90%之水,尤佳大於97%的水)之萃取溶劑。其他 成分可包括鹽類,諸如氣化鈉、硼酸鈉硼酸、DPM、 ΤΡΜ、乙醇或異丙醇。鏡片通常由模具釋放於此萃取溶劑 中,視情況藉攪拌或連續流動萃取溶劑於鏡片上。此方法 可在由約2至約121°C,較佳由約20至約98°C4溫度下 進行。此方法可在高壓下進行,特別是當使用溫度超過約 100°C時,但較典型地為在大氣壓力下進行。亦可去粘連 鏡片於一種溶液中(例如包含一些釋離助劑),然後將彼 等轉移至另一種溶液(例如最後包裝溶液)中,但也可將 鏡片去粘連於彼等所包裝之相同溶液中。以此萃取溶劑處 -36- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 裝 訂 線 經濟部智慧財產局員工消費合作社印製 A7 1311580 五、發明說明(35) 理鏡片可進行約30秒至約3天,較佳介於約5和約%分 鐘之間。所選擇之水合溶液可另包含小量之添加劑,諸如 表面活性劑。適合之表面活性·括非離子係表面活性 劑,諸如甜菜鹼及氧化胺。特殊之表面活性劑包括 TWEEN 80 (可得自 Amerchol)、DOE 120 (可得自聯合 石厌化公司)、普若尼克(Plur〇nics)、曱基纖維素、其之混 一一合物f,且其可以介於約0.01重量%和約5重量%之間 的用罝(基於所使用之水合溶液的總重為準)被添加。 在一具體例中,鏡片可利用一種“逐漸減少,,法予以水 合,其中浴劑在水合過程中逐步被取代。適合之“逐漸減 少”法具有至少兩步驟’其中某百分比之溶劑被水取代。 於聚合物之水合之後,石夕氧烧水凝膠較佳包含石夕氧烧水 凝膠總重之約1G至約6G重量百分比之水,尤佳約2〇至 約55重量百分比之水,最佳約25至約%重量百分比之 水。製造石夕氧烧水凝膠隱形眼鏡之進一步細節被描述於美 國專利案 4,495,313、4,680,336、4,889,664 及 5,039,459 中’併入本文作為參考。 經濟部智慧財產局員工消費合作社印製 本發明之固化之眼用裝置無須塗覆物即展現優良之活體 内p才/亏^ 生&amp;生物醫學裝置為一種眼用裝置時,」耐生物 /了染性可於配戴期間藉測量鏡片之表面沉積物(其通常被 稱為“脂質沉積物,,)的量來測定。 鏡、片表面沉積物之測定如下:將鏡片放在人眼中並於 3〇分鐘及一週之配戴後利用狭縫燈予以評估。於評估期 間,患者被要求眨眼數次並財“推m區分沉積物與 -37- 本紙張尺度適用中國國(2丨〇χϋ幻--— 1311580 A7 B7 五、發明說明(π: ----- 經濟部智慧財產局員工消費合作社印製 背表面包陷之殘渣。前及背表面沉積物被言忍為是分離的 (亦即膠狀凸塊)或薄難。前表面沉積物给與光亮的反 射而背表面沉積物則否。纽眼或上推試驗期間,沉積物 可與背表面包陷之錢有所區別。沉積物會移動而背表面 包陷之殘渣則仍為靜止。基於受影響之鏡片表面的百分 比,將沉積物分級成五類:無(&lt;約1%),稍微(約i 至約5% ),輕微(約6%至約15% ),_中庚(約16%至 約25%)及嚴重(大於約25%),各類間1〇%差異被認 為是臨床上顯著的。 本發明之眼用裝置亦展現低霧度、良好濕潤度及模數。 霧度係藉將試驗鏡片置於一在黑色背景上之透明小室中 之生理食鹽水中,由下方以一纖維光學燈,以垂直於鏡片 小室66。之角度照光,並由上方以—攝影機捕捉鏡片之影 像。背景-減除之散射光影像藉對鏡片中央丨〇毫米之積分 予以定量分析,然後與一-1.00屈光度之CSI Thin Lens® (其被任,¾、设疋在100之霧度值)比較,無鏡片設定為ο 之霧度值。 濕潤度係藉以棚酸緩衝之食鹽水,利用Wilhelmy天平 測罝動態接觸角或DCA (基本上為在231下)一予以測 定。當樣品被浸入或拉出食鹽水時,介於鏡片表面及硼酸 緩衝之食鹽水之間的濕化力係利用Wilhelmy微天平予以 測量。使用下述之方程式: F = 2ypcos0 或㊀=cos·1 ( ργ2γρ ) 其中F為濕化力,γ為探針液體之表面張力,ρ為彎月形 -38- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 訂 線 # A7 1311580 B7 五、發明說明(37) 樣品之周邊且θ為接觸角。基本上,兩接觸角係由〜動雜 濕化試驗而獲得_前進接觸角和後退接觸角。前進I @胃 係由漁化試驗之部分獲得’其中樣品係被浸入探g # 中,這些數值被報告於本文中。測量各組成物之1 0 4 jgj 鏡片並以平均值報告。 經濟部智慧財產局員工消費合作社印製 然而,DCA通常不是一個眼中濕潤度之良好指標。前_ 鏡片淚膜非侵入-性崩潰時間(PLTF-NIBUT )為活體内或 “臨床”鏡片濕潤度之一種測量值。PLTF-NIBUT為利用狹 缝燈及一供淚膜之非侵入性觀察之圓形螢光淚鏡(Keeler Tearscope Plus)來測量。在眨眼之後眼睛張開和隱形眼 鏡前表面之淚膜内之第一個暗點出現之間的經過時間被記 錄為·ΡυΓΡ-ΝΙΒυΤ。PLTF-NIBUT於鏡片被放入眼中且於 一週後被測量30-分鐘。每次時間間隔進行三次測量並予 以平均成一個讀值。PLTF-NIBUT係測定兩眼,先右眼, 然後左眼。移動性係利用“上推”試驗測量^患者眼睛為在 最初凝視位置。上推試驗為利用下眼瞼溫和的向上指推鏡 片。判斷鏡片對向上移動之抵抗性並根據下列等級予以分 級:1(過度’不可接受之移動),2(中等,但可接受的移 動)’ 3(適度的移動)’ 4(最小,但可接受的移動),j(不足, 不可接受的移動)。 本發明之鏡片展現至少約3 〇碎/平方英叶,較佳介於 約30和約90磅/平方英吋之間,尤佳介於約40和約70 碎/平方英吋之間。模數係利用配設有被下降至最初軌距 高度之負載小室之定速移動型張力試驗機之十字頭來測 -39- 本紙張尺度適用中國ΐ家標準(CNS)A4規格γ21〇χ297公 '' 1311580 A7 B7 五、發明說明(π: 量。適當之試驗機包括Instron型1122。具有0.522 〇寸 長、0.276吋“耳”寬及0.213吋頸寬之狗骨形樣品裝在夾 具上並以2吋/分鐘之定速應變予以伸長直到斷裂。測量 樣品之最初軌距長度(Lo)和樣品之斷裂長度(Lf)。測量各 組成物之十二個樣本並記錄平均值。拉伸模數係以鹿力/ 應變曲線之最初線性部分所測得。 藉本發明所製備·之隱形眼鏡具有具於約40和約3〇〇巴 耳(barrer)之〇2Dk值(藉極譜儀法予以測量)。將鏡片放 在感應器上,然後以一網狀支撐物覆蓋上面。將鏡片曝露 於經濕化之2.1 % 〇2之氛圍中。利用由一 4毫米直徑金阶 極和一銀環陽極之極譜氧感應器測量擴散通過鏡片之氧。 對照值為那些利用此方法對隱形眼鏡商品所測量而得者。 得自Bausch &amp; Lomb之Balafilcon A鏡片給與一約79巴 耳之測量值,Etafilcon鏡片給與一約20至25巴耳之測量 值(1巴耳=立方公分氣體X平方公分)/(聚合物 之立方公分X秒X公分汞柱))。 經濟部智慧財產局員工消費合作社印製 凝膠時間係利用下列方法測定。光聚合反應係藉配設有 光固化辅助設備(其由具石英質底板和鋁質頂板之溫控電 池所組成)之ATS StressTech電流計及一配設帶通濾 波器之輻射傳送系統予以監視。由一配設有光圈和電腦控 制快門之Novacure汞派燈而來之輕射經由液體光導被傳 送到電流計之石英板上。濾光器為420奈米(20奈米 FWHM)之帶通濾光器,其模擬由TL03燈泡所發出之 光。輻射之強度(在石英窗之表面藉一 IL1400A輻射 -40- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公楚) A7 1311580 五、發明說明(39) '— 計,利用XRL140A感知器予以測定)藉光圈予以控制在 土0.02耄瓦/平方公分。溫度被控制在45±〇_i°c。在約1 cfe升之脫氣反應混合物被放在電流計之底板上之後,將 25毫米直把之頂板下降至於底板上方之〇 5〇〇 ± 〇 毫 米處,維持於該處直到反應達到凝膠點為止。在燈光圈^ 啟及反應開始之前,使樣品達到熱平衡(〜4分鐘,藉穩 定切變黏度之調平予以測定)。在樣品達到熱平衡時^期' 間,以速率4G0 scxm之氮氣吹拂樣品室。反應期間,電 流計持續監視由所施加之動態應力(快速振動模式)而來 之應變’其中少於-個完整循環之時間片段被用來計算在 所施加之程控應力下之應變。電腦計算動態切變模式 (G,)、,損失模數(G”)及黏度(v*),作為曝露時間之函數^ 隨^反應進行,切變模式由〈丨Pa增加至&gt;〇」Mpa,而 經濟部智慧財產局員工消費合作社印製 tan 5(=G”/G,)由接近無限大下降至低於1。就本文所進行 之測^而言,凝膠時間為tan δ等於i下之時間 G-G時之交又點)。在G,達到1〇〇 (於凝膠點後仿 短時^,移動對頂板之限制,使在頂板和底板之間的間 隙可隨著反應單體混合物於固化期間之收縮而改變。 應瞭解所有上述之試驗都具有某量之固有試驗誤差。因 本文所報導之結果並未被認為是一絕對數,但數字 基於特殊試驗之精確度定範圍。 ’、 下列實施例被包括以說明本發明。此等實施例並未限制 本發明。彼等僅係用來建議實施本發明之方法。那些在障 t眼鏡之學有專精者及其他專家可發現實施本發明之其他 -41- 本紙張尺度適用—中國國~^^^〇 x—297公爱1--- 1311580 A7 B7 五、發明說明(40) 方法。惟該等方法被視為在本發明之範脅内。 貫施例_ 以下之縮寫被用於以下之實施例中: SiGMA 2_丙烯酸,2·曱基-,2-羥基-3-[3-[l,3,3,3-四甲基_ 1-[(三曱基甲矽烷基)氧基]二矽氧烷基]丙氧基] 丙酯 DMA , N,N-二曱基丙烯醯胺1311580 A7 B7 V. INSTRUCTIONS (33) The low molecular weight hydrophilic polymer can be used in an amount of up to about 20% by weight based on the total weight of the reaction components, particularly preferably between about 5 and about 20% by weight. Suitable surfactants include betaines, amine oxides, combinations thereof, and the like. Examples of suitable surfactants include TWEEN® (ICI), DOE 120 (Amerchol/Union Carbide), and the like. The surface can be used in an amount up to about 10,000', preferably between about 25 and about 1500 ppm and more preferably between about 100 ppm and about 1200 ppm. Suitable excipients are low molecular weight and include 丨_methyl_4_hexahydropyridone, 3-fosfos-1,2-propanediol, tetrahydro-2H-pentan-4-ol, glycerol formaldehyde, B _4·oxy-1-hexahydropyridinecarboxylate, 13-dimercapto-3,4,5,6-tetrahydro 2 (iH)-pyrimidinone and 1_(2-hydroxyethyl)_2- Pyrrolidone. The lens obtained from the reaction mixture having no low molecular weight hydrophilic polymer can be deintercalated in an aqueous solution containing at least one organic solvent. The organic solvent is hydrophobic but miscible with water. Suitable alcohols, ethers, etc., especially primary alcohols, and particularly preferred are isopropanol, DPMa, τρΜ DPM, decyl alcohol, ethanol, propanol, and mixtures thereof, which are suitable for the Ministry of Economics. The Intellectual Property Office staff consumption cooperative prints a suitable debonding temperature range from about room temperature to about 1 〇〇. Hey, between the 70C and 95°C, the higher temperature provides a faster point to go. Mixing (such as sound waves) can also be used to reduce the silk connection time. The method known in the art, such as vacuum nozzles, can also be removed from the lens. The mold is used. -35- This paper size applies to the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm A7). B7 [311580 V. INSTRUCTIONS (34 Distillation/Hydration of Diluent Basically, after curing the reaction mixture, the formed polymer is treated with a solvent to remove the diluent (if used), unreacted components, and vice Products, etc., and hydrate the polymer to form a hydrogel. In addition, depending on the solubility characteristics of the components of the hydrogel, the solvent used initially may be ethanol, methanol, isopropanol, TPM, DPM, PEGs, PPGs, glycerin. , a mixture thereof, or a mixture of one or more of the organic liquid and water, followed by extraction with pure water (or physiological saline). The organic liquid can also be used as a "pre-wetting". After removal of the back curve by the lens, the lens can be briefly infiltrated (for up to about 30 minutes, preferably between about 5 and about 30 minutes) in an organic liquid or a mixture of an organic liquid and water. After infiltration, the Γν lens can be further hydrated with a water extraction solvent. In some embodiments, a preferred method uses an extraction solvent that is primarily water (preferably greater than 90% water, and particularly preferably greater than 97% water). Other ingredients may include salts such as sodium hydride, sodium borate boric acid, DPM, hydrazine, ethanol or isopropanol. The lenses are typically released from the mold by the mold, optionally with agitation or continuous flow of solvent extraction onto the lens. The process can be carried out at a temperature of from about 2 to about 121 ° C, preferably from about 20 to about 98 ° C. This process can be carried out under high pressure, especially when the use temperature exceeds about 100 ° C, but is more typical The ground is carried out under atmospheric pressure. It is also possible to stick the lens in a solution (for example, containing some excipients) and then transfer them to another solution (such as the final packaging solution), but the lens can also be removed. Adhere to the same solution packaged by them. Use this extraction solvent -36- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) Gutter Ministry of Economic Affairs Intellectual Property Bureau employees Co., Ltd. Printing A7 1311580 V. Invention Description (35) The lens can be carried out for about 30 seconds to about 3 days, preferably between about 5 and about % minutes. The selected hydration solution can additionally contain a small amount of additives. Such as surfactants. Suitable surface activity · including nonionic surfactants such as betaines and amine oxides. Special surfactants include TWEEN 80 (available from Amerchol), DOE 120 (available from joint stone anemia) Company), Plur〇nics, thiol cellulose, a mixture thereof f, and which may be between about 0.01% by weight and about 5% by weight (based on the use) The total weight of the hydration solution is accurate) is added. In one embodiment, the lens can be hydrated using a "gradual reduction," wherein the bath is gradually replaced during the hydration process. Suitable "gradual reduction" methods have at least two steps 'where a percentage of the solvent is replaced by water After the hydration of the polymer, the Shixi oxygen-fired hydrogel preferably comprises from about 1G to about 6G by weight of water, more preferably from about 2 〇 to about 55 weight percent, based on the total weight of the yoke oxygenated hydrogel. The water is preferably from about 25 to about 5% by weight of water. Further details of the manufacture of the diarrhea-hydrogel contact lens are described in U.S. Patent Nos. 4,495,313, 4, 680, 336, 4, 889, 664 and 5, 039, 459, incorporated herein by reference. The Ministry of Intellectual Property's employee consumption cooperative prints the cured ophthalmic device of the present invention without exhibiting a coating, which means that the living body is excellent in the body. The raw &amp; biomedical device is an ophthalmic device," Dyeability can be measured by measuring the amount of surface deposits of the lens (which is commonly referred to as "lipid deposits,") during wear. The surface and surface deposits of the mirror are determined as follows: The film was placed in the human eye and evaluated with a slit lamp after being worn for 3 minutes and a week. During the evaluation period, the patient was asked to blink several times and “make the difference between sediment and -37- this paper size applies to China. Country (2 丨〇χϋ - - 1311580 A7 B7 V. Invention Description (π: ----- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed on the back surface of the debris. The front and back surface sediments are said Tolerance is separate (ie, gel-like bumps) or thin. The front surface deposits give a bright reflection and the back surface deposits no. During the eye or push-up test, the deposit can be trapped with the back surface. The money is different. The sediment will move and the debris on the back surface will remain static. Based on the percentage of the affected lens surface, the sediment will be classified into five categories: none (about 1%), slightly ( From about i to about 5%), slight (about 6% to about 15%), _zhong Geng (about 16% to about 25%) and serious (greater than about 25%), the difference between 1% in each category is considered to be Clinically significant. The ophthalmic device of the present invention also exhibits low haze, good wettability, and modulus. The sheet is placed in a physiological saline solution in a transparent chamber on a black background, with a fiber optic lamp underneath, perpendicular to the lens chamber 66. The image of the lens is captured by the camera from above. Background-subtraction The scattered light image is quantified by integrating the center 丨〇 millimeter of the lens, and then compared to a CSI Thin Lens® of one-1.00 diopter (which is used, 3⁄4, set at a haze value of 100), no lens setting The value of haze is hum. The degree of wetness is determined by using a linoleic acid buffered saline solution, using a Wilhelmy balance to measure the dynamic contact angle or DCA (essentially at 231). When the sample is immersed or pulled out of saline solution The wetting force between the lens surface and the borate buffered saline was measured using a Wilhelmy microbalance. Use the following equation: F = 2ypcos0 or a = cos·1 ( ργ2γρ ) where F is the wetting force, γ is the surface tension of the probe liquid, and ρ is the meniscus -38- This paper scale applies to the Chinese national standard ( CNS) A4 size (210x297 mm) Setting line # A7 1311580 B7 V. Description of invention (37) The periphery of the sample and θ is the contact angle. Basically, the two contact angles were obtained by the ~hybridization test to obtain the advancing contact angle and the receding contact angle. Advance I @gastric system was obtained from the section of the fishery test' where the sample was immersed in the probe g# and these values are reported herein. The 1 0 4 jgj lenses of each composition were measured and reported as an average. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives However, DCA is usually not a good indicator of wetness in the eye. Pre-Lens Tear Film Non-Invasive-Sexual Crash Time (PLTF-NIBUT) is a measure of in vivo or "clinical" lens wetness. The PLTF-NIBUT is measured using a slit lamp and a Keeler Tearscope Plus for non-invasive observation of the tear film. The elapsed time between the opening of the eye after blinking and the appearance of the first dark spot in the tear film on the anterior surface of the contact lens was recorded as ΡυΓΡ-ΝΙΒυΤ. The PLTF-NIBUT was placed in the eye and was measured for 30-minutes after one week. Three measurements were taken at each time interval and averaged to one reading. The PLTF-NIBUT measures two eyes, first right eye and then left eye. The mobility system uses the "push up" test to measure the patient's eye at the initial gaze position. The push-up test is to use a gentle upward pointing of the lower eyelid to push the lens. Determine the resistance of the lens to upward movement and rank according to the following levels: 1 (excessive 'unacceptable movement'), 2 (medium but acceptable movement) '3 (moderate movement)' 4 (minimum, but acceptable Move), j (insufficient, unacceptable movement). The lenses of the present invention exhibit at least about 3 mins per square inch, preferably between about 30 and about 90 pounds per square inch, and more preferably between about 40 and about 70 pieces per square inch. The modulus is measured by a crosshead equipped with a fixed-speed mobile tension tester that is lowered to the load compartment of the initial gauge height. -39- This paper scale applies to the China National Standard (CNS) A4 specification γ21〇χ297 '' 1311580 A7 B7 V. INSTRUCTIONS (π: Quantities. Suitable testing machines include Instron Model 1122. Dog bone samples with 0.522 inch length, 0.276 inch "ear" width and 0.213 inch neck width are mounted on the fixture and The elongation was measured at a constant speed of 2 吋/min until the fracture was measured. The initial gauge length (Lo) of the sample and the fracture length (Lf) of the sample were measured. Twelve samples of each composition were measured and the average value was recorded. The number is measured as the initial linear portion of the deer force/strain curve. The contact lens prepared by the present invention has a 〇2Dk value of about 40 and about 3 barrer (by polarography) Measured. Place the lens on the sensor and cover it with a mesh support. Expose the lens to a humidified 2.1% 〇2 atmosphere. Use a 4 mm diameter gold step and a silver The polar anode oxygen sensor of the ring anode measures the diffusion through the lens Oxygen. Control values are those measured by contact lenses for this product. The Balafilcon A lens from Bausch &amp; Lomb gives a measurement of about 79 bar, and the Etafilcon lens gives about 20 to 25 bar. Measurement of the ear (1 bar = cubic centimeter gas X cm ^ 2 ) / (cubic centimeters of polymer x seconds X cm mercury column)). Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. The gel time is determined by the following methods. The photopolymerization reaction was monitored by an ATS StressTech galvanometer equipped with a photocuring auxiliary device consisting of a temperature-controlled battery having a quartz substrate and an aluminum top plate, and a radiation delivery system equipped with a band pass filter. A light shot from a Novacure Mercury lamp with an aperture and a computer-controlled shutter is transmitted via a liquid light guide to the quartz plate of the galvanometer. The filter is a 420 nm (20 nm FWHM) bandpass filter that simulates the light emitted by the TL03 bulb. Radiation intensity (by the IL1400A radiation on the surface of the quartz window -40 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210x297 public Chu) A7 1311580 V. Invention description (39) '-meter, using XRL140A sensor It is determined by the aperture to control 0.02 watts/cm 2 of soil. The temperature is controlled at 45 ± 〇 _i ° c. After the degassing reaction mixture of about 1 cfe is placed on the bottom plate of the ammeter, the top plate of the 25 mm straight handle is lowered to 5 〇〇 ± 〇 mm above the bottom plate, and maintained there until the reaction reaches the gel. So far. Allow the sample to reach thermal equilibrium (~4 minutes, measured by steady-state shear viscosity leveling) before the light circle starts and the reaction begins. The sample chamber was purged with nitrogen at a rate of 4 G0 scxm between the time the sample reached thermal equilibrium. During the reaction, the current meter continuously monitors the strain due to the applied dynamic stress (rapid vibration mode). The time segments of less than one complete cycle are used to calculate the strain under the applied programmed stress. The computer calculates the dynamic shear mode (G,), the loss modulus (G"), and the viscosity (v*) as a function of the exposure time ^ with the ^ reaction, and the shear mode is increased from <丨Pa to &gt;〇 Mpa, while the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed tan 5 (= G" / G,) decreased from near infinity to less than 1. For the test conducted in this paper, the gel time is tan δ equals The time under GG is the point of GG.) At G, it reaches 1〇〇 (after the gel point, it is short-lived ^, moving to the top plate, so that the gap between the top plate and the bottom plate can follow the reaction list. The bulk mixture changes during shrinkage during curing. It should be understood that all of the above tests have inherent test errors of a certain amount. As the results reported herein are not considered to be an absolute number, the numbers are based on the accuracy of the particular test. The following examples are included to illustrate the invention. These examples are not intended to limit the invention. They are merely intended to suggest a method of practicing the invention. Those skilled in the field of spectacles and other experts Other -41- paper rulers for implementing the present invention can be found Applicable—China Country~^^^〇x-297 Public Love 1--- 1311580 A7 B7 V. Inventive Note (40) Method, but these methods are considered to be within the scope of the present invention. The abbreviation is used in the following examples: SiGMA 2_acrylic acid, 2·indolyl-, 2-hydroxy-3-[3-[l,3,3,3-tetramethyl-1-system Methyl decyl)oxy]dioxaxyalkyl]propoxy]propyl DMA, N,N-dimercaptopropenylamine

HEMA mPDMS 經濟部智慧財產局員工消費合作社印製 5 ---1·*- 2-經乙基曱基丙烯酸醋 800-1000分子量(Mn)單甲基丙烯氧基丙基終端 之單-正-丁基終端之聚二甲基矽氧烷 2-(2’-羥基-5-曱基丙烯酸基氧基乙基笨基)_2H_ 苯並三唑 1:1(重量)之1-羥基環己基苯基酮和雙(2,6_二 甲氧基笨曱醯基)-2,4-4-三曱基戊基氧化膦之 摻合物 聚(N-乙烯吡咯啶酮)(κ值90) 藍ΗΕΜΑ反應性藍色4號及ΗΕΜΑ之反應產物,如於 美國專利案5,944,853之實施例4中所择述者 ΙΡΑ 異丙醇 D30 3,7-二甲基-3-辛醇 mPDMS-OH單-(3-甲基丙烯氧基-2-羥基丙基氧基)丙基終 端、單-丁基終端之聚二甲基矽氧烷(MW 1100) TEGDMA 四乙二醇二曱基丙烯酸酯 -42-HEMA mPDMS Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 5 ---1·*- 2-Ethyl Mercapto Acrylic Acid 800-1000 Molecular Weight (Mn) Monomethacryloxypropyl Terminal Single-Positive - Butyl terminal polydimethyl methoxy oxane 2-(2'-hydroxy-5-mercapto hydroxyethyl phenyl)_2H_ benzotriazole 1:1 (by weight) 1-hydroxycyclohexylbenzene a blend of ketone and bis(2,6-dimethoxyanthracenyl)-2,4-4-tridecylpentylphosphine oxide poly(N-vinylpyrrolidone) (κ value 90) The reaction product of the blue hydrazine reactive blue No. 4 and hydrazine, as described in Example 4 of U.S. Patent No. 5,944,853, isopropyl alcohol D30 3,7-dimethyl-3-octanol mPDMS-OH -(3-Methylpropoxy-2-hydroxypropyloxy)propyl terminal, mono-butyl terminal polydimethyl methoxy olefin (MW 1100) TEGDMA tetraethylene glycol dimercapto acrylate - 42-

Norbtoc CGI 1850Norbtoc CGI 1850

PVP 本纸張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 埤 訂 線 1311580 A7 B7 五、發明說明(4!PVP This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 埤 Ordering line 1311580 A7 B7 V. Invention description (4!

TrEGDMA三乙二醇二曱基丙烯酸酯 TRIS 3-甲基丙烯氧基丙基三(三甲基⑦氧基)石夕烧 MPD 3-曱基丙烯氧基丙基(五曱基二矽氧烷) MBM 3_甲基丙烯氧基丙基三(三甲基矽氧基)甲基矽TrEGDMA triethylene glycol dimercapto acrylate TRIS 3-methyl propylene oxypropyl tris(trimethyl 7 oxy) sulphuric acid MPD 3-mercapto propylene oxy propyl (pentamethoxy propylene oxide) MBM 3_Methacryloxypropyltris(trimethyldecyloxy)methylhydrazine

AcPDMS Triglide CGI 819 雙-3-甲基丙烯氧基_2-羥基丙基氧基丙基聚二 甲基矽氧烷 — 三丙二醇甲醚 雙(2,4,6-三甲基苯甲醯基)_苯基氧化膦 PVP低分子量聚(N-乙烯吡咯咬酮)(κ值π) 在貫施例中’強度係利用一種IL 1400Α輻射計利用一 XRL 140A感知器來測量。 實施例1-10 將列於表1中之反應成分及稀釋劑(D30) 在一· 祐 經濟部智慧財產局員工消費合作社印製 於約23 C下之搜拌或滾動至少約3小時,直到所有之成 分溶解為止。以所有反應成分之重量百分比報導反應成 分’而稀釋劑為最終反應混合物之重量百分比。將反應混 合物置於熱塑性隱形眼鏡模具(Topas®乙稀和原冰:片烯之 共聚物,獲自Ticona聚合物公司)並利用菲利浦tl 20W/03T螢光燈泡在45°C下於N2中輻照約20分鐘。打 開模具,將鏡片抽出於50:50 (重量)之IPA和H20之溶 液中並在室溫下浸泡於IPA中約15小時以去除殘餘之稀 -43- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 1311580 B7 五、發明說明(42) 釋劑及單體,將其放入去離子水中約30分鐘,然後在硼 酸鹽緩衝之食鹽水中平衡至少約24小時,並在122°C下 壓熱殺菌30分鐘。形成之鏡片的特性示於表1。 經濟部智慧財產局員工消費合作社印製 -44- 本纸張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 五、發明說明(43) A7 經濟部智慧財產局員工消費合作社印製 表 1 實施例# 1 2 3 4 5 6 7 8 9 10 組成物 SiGMA 28 30 28.6 28 31 32 29 39.4 20 68 PVP (K90) 7 10 7.1 7 7 7 6 6.7 3 7 DMA 23.5 17 24.5 23.5 20 20 24 16.4 37 22 MPDMS 31 32 0 31 31 34 31 29.8 15 0 TRIS 0 0 0 0 0 0 0 0 15 0 HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0 Norblo.c 2 2 0 2.0 2 2 2 1.9 0 0 CGI 1850 0.98 1 1.02 1 1 1 1 1 1 0 TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 0 2 TrEGDMA 0 0 0 0 0 0 0 0 1 0 藍 HEMA 0.02 0 0 0 0 0 0 0 0 0 mPDMS-OH - 0 0 31.6 0 0 0 0 0 0 0 Darocur 1173 0 0 0 0 0 0 0 0 0 1 D30 % 23 26 17 23 23 29 32 28 17 27 特性 %EWC' 36 33 39 40 36 37 39 25 48 29 模數(碎/平 方英吋) 68 78 112 61 67 50 66 92 43 173 %伸長度 301 250 147 294 281 308 245 258 364 283 DCA2 (前進) 62 55 58 64 72 65 61 55 92 72 (邊緣校正) 103 111 101 131 110 132 106 140 64 76 1.平衡水含量。 -45- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 1311580 五、發明說明(44) 2. 動態接觸角,利用Wilhehny天平藉生理硼酸緩衝之食 鹽水來測定。 3. 透氧性,邊緣校正過者,以巴耳計。 實施例1-10之結果顯示反應混合物成分及彼等之用量 實質上可變動,而仍提供具有優越機械特性及濕潤度平衡 之未塗覆鏡片。實施例9之接觸角(DCA)可能太高而不能 形成臨床上濕潤之鏡片’且模數可能比提供機械強固性之 鏡片所期望者為低。實施例9包含最低濃度之SiGMA (20%)。因為SiGMA已被降低,可添加較少之pvp至配 方中而仍提供-種相容之反應混合物。因此,此等實施例 顯示SiGMA在相容化PVP方面是有效的,且當充足之 SiG· A PW存在時,可在無任何形式之表面修飾下製 付具期望濕潤度及其他機械特性之鏡片。 實施例11 經濟部智慧財產局員工消費合作社印製 重製具有貫施例1之配方的鏡片,但不控制固化強度 。機械強度被報導於下表2。此等鏡片利用ACUVUE® 2 鏡片作為控制組予以臨床評估。由6位病患以每日配戴之 模式(晚上卸除)配戴鏡片一週的時間。在第一週, PLTF-NIBUT 為 3.6(±3_0)秒,相較之下 ACUVUE® 2 鏡片為 5.8( 士 2.5)秒。尤50%之§式驗及1〇〇%之控制組鏡片而言, 前表面沉積度被評等為無至稍微。試驗及控制組鏡片之移 動性為可接受的。 -46- ;ΰ ;本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Α7 !311580 五、發明說明(45) f施例12 重覆實施例11但降低固化強度至1.0毫瓦/平方公分 。機械強度被報導於下表2中。此等鏡片利用ACUYUE®2 鏡片作為控制組予以臨床評估。由15位病患以每日配戴 之模式(晚上卸除)配戴鏡片一週的時間。在第一週, PLTF-NIBUT 為 8.2(士 1·7)秒,相較之下 ACUVUE®2 鏡片 為6·9(±1·5)秒。就所有配戴試驗及控制組鏡片之病患而 言’前表面沉積度被評等為無至稍微。試驗及控制組鏡片 之移動性為可接受的。 表2 _^施例# 1 11 12 %EWC ------- 36 36 36 '模數(磅/平 —英吋) 68 74 87 Uijfe 度 301 315 223 -^dca 62 77 56 L_Dk 103 1 127 102 經濟部智慧財產局員工消費合作社印製 通常,實施例1、11及12之機械特性,就相同材料之 多次操作而言’有一致的結果。然而,實施例丨丨(未控 制之固化強度)及12 (低度受控制之固化強度)之臨床 結果為實質上不同的。實施例11之一週配戴後备眼中濕 潤度(依據PLTF-NIBUT所測定)比AcuVUE® 2鏡片為 差(3.6對5.8),且半數鏡片有高於稍微之表面沉積 度。實施例12之鏡(控制之低強度固化)展現明顯改良 之眼中濕潤度’其經測量優於ACUVUE® 2鏡片(8.2對 -47-1G2本纸張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 Λ7 B7 五、發明說明(46) 6.9 )且無表面沉積度。因此,利用低度、經控制之固化 可提供一種具有與傳統水凝膠鏡片相同或在許多情況中更 佳之眼中濕潤度之未塗覆鏡片。 實施例13-17 混合如表3所述且包含低量或不具含羥基-官能化矽氧 烷之單體(在此等實施例中為SiGMA)之反應混合物, 於室溫下穩定攪拌16小時。即使在16小時後,各反應混 合物仍為混濁且部分有沉殿。因此,此等反應混合物無法 被用來製造鏡片。 表3 實施例# 13 14 15 16 17 組成物 SiGMA 0 0 0 10 20 PVP ( K90 ) 12 12 10 8.0 8.0 DMA 10 10 8.3 19 19 MPDMS 37 37 30.8 35 28 TRIS 14 14 11.7 17 14 HEMA 25 25 37.5 8.0 8.0 TEGDMA 1.0 1.0 0.83 2.0 2.0 Darocur 1173 1.0 1.0 0.83 1.0 1.0 D30 % 23 31 31 27 一 27 經濟部智慧財產局員工消費合作社印製 實施例13至15顯示無任何含羥基-官能化矽氧烷之單 體(SiGMA或mPDMS-OH)之反應混合物為不相容的, 且不適合製造隱形眼鏡。實施例16及17顯示含羥基-官 -48- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1311580 A7 五 、發明說明( B7 經濟部智慧財產局員工消費合作社印製 =切氧燒之單體低於約2G重量%料足以相容化顯著 =向分子量PVP。惟,相較於實施17至實施例9,可 少量之高分子量PVP(3重量%)而仍可形成相容 之反應混合物。 18-25 將含1.00克之D30、1.00克之mPDMS和丨〇〇克之 ™s之溶液置於一小玻璃瓶中(實施例19)。當換合物 在約20至23 C下藉磁性攪拌子予以快速搜拌時,逐滴添 加含12份(重量)PVP (K90)和6〇份DMA之溶液直 到於3分鐘之攪拌後溶液仍為混濁為止。所添加之 dm^a/pvp摻合物之質量係被測定為克且被報導為“單體 相容性指數”。利用SiGMA(實施例18)、MBM(實施例 λ 20)、MPD(實施例 21)、acPDMS(其中 η=ι〇)(實施例 22)、 acPDMS(其中 η=20)(實施例 23)、iSiGMA-3Me (實施例 24) 及TRIS2-HOEOP2(實施例25)作為取代TRIS之試驗矽氧 烷單體,重覆此試驗。 -49- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1311580 Λ7 B7 五、發明說明(姑) 表4 實施 例# 試驗之含矽氧烷單 體 單體相容 性指數 Si:OH 18 SiGMA 1.8 3:1 19 TRIS 0.07 4:0 20 MBM 0.09 3:0 21 MPD 0.05 2:0 22 acPDMS (n= 10)* 1.9 11:2 23 acPDMS (n=20)* 1 21:2 24 · ISiMAA-3Me 0.15 4:0 25 TRIS2-HOEOP2 0.11 3:2 26 MPDMS-OH 0.64 〜11:1 acPDMS、iSiGMA-3Me 及 TRIS2-HOEOP2 之結構如下 所呆: acPDMS (η 平均 10 或 20) 經濟部智慧財產局員工消費合作社印製AcPDMS Triglide CGI 819 Bi-3-methylpropenyloxy-2-hydroxypropyloxypropylpolydimethyloxane - Tripropylene glycol methyl ether bis(2,4,6-trimethylbenzhydryl) _Phenylphosphine oxide PVP low molecular weight poly(N-vinylpyrrolidone) (κ value π) In the examples, the 'strength system was measured using an X 1400 Α radiometer using an XRL 140A perceptron. EXAMPLES 1-10 The reaction components and diluents (D30) listed in Table 1 are printed at about 23 C for at least about 3 hours at a trade association of the Intellectual Property Office of the Ministry of Economic Affairs. All ingredients are dissolved. The reaction component is reported as a weight percent of all reactive components and the diluent is the weight percent of the final reaction mixture. The reaction mixture was placed in a thermoplastic contact lens mold (Topas® Ethylene and Raw Ice: Copolymer of Phenene, available from Ticona Polymers) and utilized a Phillips tl 20W/03T fluorescent bulb at 45 ° C at N2 The irradiation is about 20 minutes. Open the mold, remove the lens from a 50:50 (by weight) solution of IPA and H20 and soak it in IPA for about 15 hours at room temperature to remove residual thinner -43- This paper scale applies to China National Standard (CNS) A4 size (210x297 mm) A7 1311580 B7 V. INSTRUCTIONS (42) Release and monomer, put it in deionized water for about 30 minutes, then equilibrate in borate buffered saline for at least 24 hours, and Autoclaved at 122 ° C for 30 minutes. The characteristics of the formed lens are shown in Table 1. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives-44- This paper scale applies the Chinese National Standard (CNS) A4 specification (210x297 mm) 1311580 V. Invention Description (43) A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Table 1 Example # 1 2 3 4 5 6 7 8 9 10 Composition SiGMA 28 30 28.6 28 31 32 29 39.4 20 68 PVP (K90) 7 10 7.1 7 7 7 6 6.7 3 7 DMA 23.5 17 24.5 23.5 20 20 24 16.4 37 22 MPDMS 31 32 0 31 31 34 31 29.8 15 0 TRIS 0 0 0 0 0 0 0 0 15 0 HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0 Norblo.c 2 2 0 2.0 2 2 2 1.9 0 0 CGI 1850 0.98 1 1.02 1 1 1 1 1 1 0 TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 0 2 TrEGDMA 0 0 0 0 0 0 0 0 1 0 Blue HEMA 0.02 0 0 0 0 0 0 0 0 0 mPDMS-OH - 0 0 31.6 0 0 0 0 0 0 0 Darocur 1173 0 0 0 0 0 0 0 0 0 1 D30 % 23 26 17 23 23 29 32 28 17 27 Characteristic %EWC' 36 33 39 40 36 37 39 25 48 29 Modulus ( Broken/square inch) 68 78 112 61 67 50 66 92 43 173 % elongation 301 250 147 294 281 308 245 258 364 283 DCA2 (forward) 62 55 58 64 72 65 61 55 92 72 (Edge Correction) 103 111 101 131 110 132 106 140 64 76 1. Balance the water content. -45- This paper size is applicable to China National Standard (CNS) A4 specification (210x297 mm). A7 1311580 V. INSTRUCTIONS (44) 2. Dynamic contact angle, measured by Wilhehny balance with physiological boric acid buffered saline. 3. Oxygen permeability, edge correction, measured in Barre. The results of Examples 1-10 show that the components of the reaction mixture and their amounts are substantially variable while still providing uncoated lenses having superior mechanical properties and wettability balance. The contact angle (DCA) of Example 9 may be too high to form a clinically wet lens&apos; and the modulus may be lower than would be expected for a lens that provides mechanical strength. Example 9 contained the lowest concentration of SiGMA (20%). Since SiGMA has been reduced, less pvp can be added to the formulation while still providing a compatible reaction mixture. Thus, these examples show that SiGMA is effective in compatibilizing PVP, and that when sufficient SiG·A PW is present, lenses with desired wettability and other mechanical properties can be produced without any form of surface modification. . Example 11 Printing by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives Remanufactured lenses with the formulation of Example 1, but did not control the curing strength. Mechanical strength is reported in Table 2 below. These lenses were evaluated clinically using ACUVUE® 2 lenses as a control group. The lens was worn by six patients in a daily wear mode (unloaded at night) for one week. In the first week, the PLTF-NIBUT was 3.6 (±3_0) seconds compared to 5.8 (2.5 seconds) for ACUVUE® 2 lenses. For the 50% § test and 1% control lens, the front surface deposition was rated as nothing. The mobility of the test and control group lenses is acceptable. -46- ; ΰ ; This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Α7 !311580 V. Invention description (45) f Example 12 Repeat Example 11 but reduce the curing strength to 1.0 Milliwatts per square centimeter. Mechanical strength is reported in Table 2 below. These lenses were clinically evaluated using ACUYUE® 2 lenses as a control group. The lens was worn by 15 patients in a daily wear mode (unloaded at night) for one week. In the first week, the PLTF-NIBUT was 8.2 (±1·7) seconds compared to 6.9 (±1·5) seconds for the ACUVUE®2 lens. For all patients wearing the test and control group lenses, the anterior surface deposition was rated as nothing. The mobility of the test and control group lenses is acceptable. Table 2 _^Example # 1 11 12 %EWC ------- 36 36 36 'Modulus (pounds/flats - inches) 68 74 87 Uijfe degrees 301 315 223 -^dca 62 77 56 L_Dk 103 1 127 102 Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperatives Printing Generally, the mechanical properties of Examples 1, 11 and 12 have consistent results for multiple operations of the same material. However, the clinical results of Example 丨丨 (uncontrolled cure strength) and 12 (low controlled compression strength) were substantially different. The wettability (measured by PLTF-NIBUT) of one of the Example 11 was lower than that of the AcuVUE® 2 lens (3.6 to 5.8), and half of the lenses had a higher surface deposition degree. The mirror of Example 12 (controlled low-intensity cure) exhibited a significantly improved wetness in the eye's measured better than ACUVUE® 2 lenses (8.2 pairs of -47-1G2 paper scales applicable to China National Standard (CNS) A4 specifications ( 210x297 mm) 1311580 Λ7 B7 V. Description of invention (46) 6.9) and no surface deposition. Thus, the use of low, controlled cure provides an uncoated lens having the same or in many cases better wetness in the eye as conventional hydrogel lenses. EXAMPLES 13-17 The reaction mixture of the monomers described in Table 3 and containing low or no hydroxyl-functionalized alkoxylated monomers (SiGMA in these examples) was mixed and stirred stably for 16 hours at room temperature. . Even after 16 hours, the reaction mixture was turbid and partially had a sink. Therefore, such reaction mixtures cannot be used to make lenses. Table 3 Example # 13 14 15 16 17 Composition SiGMA 0 0 0 10 20 PVP ( K90 ) 12 12 10 8.0 8.0 DMA 10 10 8.3 19 19 MPDMS 37 37 30.8 35 28 TRIS 14 14 11.7 17 14 HEMA 25 25 37.5 8.0 8.0 TEGDMA 1.0 1.0 0.83 2.0 2.0 Darocur 1173 1.0 1.0 0.83 1.0 1.0 D30 % 23 31 31 27 A 27 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Examples 13 to 15 show no hydroxy-functionalized alkane-containing singles The reaction mixture of the body (SiGMA or mPDMS-OH) is incompatible and is not suitable for the manufacture of contact lenses. Examples 16 and 17 show hydroxyl-containing---48- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1311580 A7 V. Invention Description (B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing = oxy-fired monomer less than about 2 G weight percent is sufficient to compatibilize significant = molecular weight PVP. However, compared to the implementation of 17 to Example 9, a small amount of high molecular weight PVP (3 wt%) can still be A compatible reaction mixture is formed. 18-25 A solution containing 1.00 gram of D30, 1.00 gram of mPDMS and gram of TMs is placed in a small glass vial (Example 19). When the compound is about 20 to 23 When the magnetic stirrer was used for rapid mixing, a solution containing 12 parts by weight of PVP (K90) and 6 parts of DMA was added dropwise until the solution remained turbid after stirring for 3 minutes. The added dm^ The mass of the a/pvp blend was determined to be grams and reported as the "monomer compatibility index." Using SiGMA (Example 18), MBM (Example λ 20), MPD (Example 21), acPDMS (where η = ι〇) (Example 22), acPDMS (where η = 20) (Example 23), iSiGMA-3Me (Example 24) and TR IS2-HOEOP2 (Example 25) was repeated as a test oxirane monomer in place of TRIS. -49- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1311580 Λ7 B7 , invention description (abbreviated) Table 4 Example # Test oxime-containing monomer monomer compatibility index Si: OH 18 SiGMA 1.8 3:1 19 TRIS 0.07 4:0 20 MBM 0.09 3:0 21 MPD 0.05 2 :0 22 acPDMS (n= 10)* 1.9 11:2 23 acPDMS (n=20)* 1 21:2 24 · ISiMAA-3Me 0.15 4:0 25 TRIS2-HOEOP2 0.11 3:2 26 MPDMS-OH 0.64 ~11 :1 The structure of acPDMS, iSiGMA-3Me and TRIS2-HOEOP2 is as follows: acPDMS (η average 10 or 20) Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

-50- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 1311580 五、發明說明(4〇 iSiMAA3-Me 〇 /°Me 表4中所示之結果顯示siGMA、acpDMs (其中 及20)和mPDMs_〇H較之另一種含矽氧烷單體更易組合 ;稀釋劑另-種含⑦氧烧單體及高分子量聚合物 (PVP)之摻合物中。因此,具有相容性指數大於約0.5 之含相容切氧紅單體可祕相容化高分子量親水性聚 合物,像PVP ^ 實施例27-35 、' 經濟部智慧財產局員工消費合作社印製 利用實施例1之反應混合物配方製造鏡片。將塑膠之隱 形眼鏡模具(由獲自Ticona聚合物公司之Topas®之乙烯 和原冰片烯之共聚物所製造)於氮氣(&lt;〇 5% 〇2)中貯 存過夜。將每個模具按劑量裝入75微升之反應混合物。 封閉模具並利用於表5所示之時間及固化強度光固化鏡 片。藉利用可見光螢光燈輻照單體混合物形成鏡_片,在 45°C下固化。強度係藉使用可變光圈(baUast)或濾光器, 以兩步驟變動強度及固化時間予以改變。步驟2之時間係 選擇可提供各樣品相同之總輻照能量(約83〇毫焦耳/平 方公分)者。 利用IPA/水之60:40混合物將完工之鏡片脫模。將鏡 -51-ibb本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580-50- This paper size is applicable to China National Standard (CNS) A4 specification (210x297 mm) A7 1311580 V. Invention description (4〇iSiMAA3-Me 〇/°Me The results shown in Table 4 show siGMA, acpDMs (and 20) and mPDMs_〇H are easier to combine than another oxo-containing monomer; the diluent is further blended with a mixture of 7 oxy-fired monomers and high molecular weight polymer (PVP). A compatible high-molecular-weight hydrophilic polymer with a compatibility index of greater than about 0.5, such as PVP ^ Example 27-35, 'Industrial Intelligence Intellectual Property Bureau employee consumption cooperative printing use example 1 The reaction mixture was formulated to make lenses. A plastic contact lens mold (manufactured by a copolymer of ethylene and norbornene obtained from Topas® from Ticona Polymers) was stored in nitrogen (&lt; 5% 〇 2) overnight. Each mold was dosed into 75 microliters of the reaction mixture. The mold was closed and the lens was cured using the time and curing strength shown in Table 5. The mirror mixture was formed by irradiating the monomer mixture with a visible light fluorescent lamp. Cured at 45 ° C. Strength is used The variable aperture (baUast) or filter is changed in two steps of varying intensity and curing time. The time in step 2 is selected to provide the same total irradiation energy (about 83 〇mJ/cm 2 ) for each sample. The IPA/Water 60:40 mixture will release the finished lens. The mirror-51-ibb paper size is applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm) 1311580

片轉移至-包含克之1GG%異丙醇(IPA)之小罐 中。每2小時替換IPA 1〇小時,在約1〇小時之末,去掉 50%之IPA並以去離子水取代,轉動小罐2〇分鐘。於扣 分鐘後,去掉5〇%之IPA並以去離子水取代,轉動小罐 20分鐘。將鏡片轉移至包裝溶液中,轉動2()分鐘,然後 進行試驗。 ' 實施 例# 表 步驟1 強度(毫 瓦/平方 公分) 步驟1 時間(分: 秒) --- 步驟2 強度(毫 瓦/平方 公分) 步驟2 時間(分: 秒) 前進接 觸角 6:55 5.5 1:28 51 + 1 2:46 —1 —— 5.5 2:21 55 ± 2 11:03 ------- Π5.5 0:35 55 ± 1 6:30 -------- 5.5 0:35 50 ± 1 1:37 ~~ 5.5 2:21 55 + 1 4:04 ------ 5.5 1:28 54 ±2 2:52 —--— 5.5 1:28 62 ± 6 4:36 --------- 5.5 0:35 76 ± 9 1:09 ----- 5.5 0:35 78 ±6 貝施例27至32之接觸角並無顯著不同,表示低於約2 毫瓦/平方公分之步驟1之固化強度提供此鏡片 配方之改 良之制度’而不管步驟丄之固化時間。惟,熟悉該項技 術者將知道較短之步驟1之固化時間(諸如那些被用於實 施例28及31中者)容許有更短之整個固化循環。此外, 應注意即使實施例3 3至3 5之接觸角_量為高於實施例 -52- 本紙張尺度適用中國國- 27_ 28 29 30· 31 32 33 34 35 1. u_ \J_ 1.7 1.7 2.4 2.4 2.4 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 [311580 A7 B7 五、發明說明(51 27-32者,實施例33-35之鏡片仍可提供理想之眼中濕潤 度。 實施例36-41 訂 根據實施例1將將實施例1之反應成分與作為稀釋劑之 25%或40%D3O混合。將形成之反應混合物裝入塑膠隱 形眼鏡模具中(由獲自Ticona聚合物公司之Topas®之乙 烯和原冰片烯之共聚物所製造),並於一手套箱中及於氮 氣中,以約2.5毫瓦/平方公分之強度、約30分鐘及下 表6所示之溫度下予以固化。如實施例1所述,由模具中 去除鏡片、水合及壓熱殺菌。於水合後,測定鏡片之霧度 值.。結果示於表6中,其顯示霧度在較高溫度下被降低。 結果亦顯示稀釋劑之濃度減少,霧度亦降低。 線 經濟部智慧財產局員工消費合作社印製 表6 實施例# %D30 溫度(°C) %霧度 DCA(°) 36 25 25 3〇(6) 99 37 25 50-55 12(2) 100 38 25 60-65 14(0.2) 59 39 40 25 50(10) 68 40 40 50-55 40(9) 72 - 41 40 60-65 32(1) 66 +霧度(標準差) 表6之結果顯示藉增加固化溫度,霧度降低約20% (實施例41對實施例39)並至多達約65% (實施例37 對實施例36)。稀釋劑濃度由40減至25%,霧度降低介 -53- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) [311580 A7 B7 五、發明說明(52 於約40和75%之間。 實施例42-47 利用實施例1之程序由表7所示之配方製造鏡片,25°C 下之固化時間為30分鐘,強度約2.5毫瓦/平方公分。 測量百分比霧度並報導於表8。 經濟部智慧財產局員工消費合作社印製 表7 實施例# 42 43 44 45 46 47 SiGMA 28.0 28.0 28.0 28.0 28.0 28.0 mPDMS 31.0 31.0 28.0 28.0 28.0 28.0 acPDMS (n=10) 0.0 0.0 4.0 4.0 4.0 4.0 DMA 23.5 23.5 23.5 23.5 24.0 24.0 HEMA 6.0 6.0 5.0 5.0 6.0 6.0 TEGDMA 1.5 1.5 1.5 1.5 0.0 0.0 Norbloc 2.0 2.0 2.0 2.0 2.0 2.0 PVP (K-90) 7.0 7.0 7.0 7.0 7.0 7.0 CGI 1850 1.0 1.0 1.0 1.0 1.0 1.0 D30 25.0 40 25.0 40.0 25.0 40.0 特性 霧度 30 50 7.3 14 26 25 模數(磅/平 方英吋) 74 56 148 104 74 NT 伸長度(%) 326 395 188 251 312 NT EWC(%) 38 41 33 35 38 39 就具有同量之稀釋劑及TEGDMA或acPDMS之配方 (實施例42和46及實施例43和47)的結果比較顯示 -54- 裝 訂 線 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 B7 五、發明說明(《) acPDMS為有效之交聯劑且提供鏡片具有可比擬於以 TEGDMA用作交聯劑者之特性。實施例44和45包含兩 種交聯劑。此等實施例之霧度相較於由任一交聯劑所製得 之鏡片有實質地降低。然而,模數及伸長度為負面影響的 (可能是因為交聯劑之量太大)。 實施例48-54 一 利用表8所示之配方與所指示之稀釋劑製造反混合物。 將反應混合物置於熱塑性隱形眼鏡模具中並利用菲利浦 TL 20W/03T螢光燈泡在45°C、0.8毫瓦/平方公分輻照 約32分鐘。打開模具並將鏡片釋出於95°C之去離子水中 歷經20分鐘。將鏡片放入硼酸缓衝之食鹽水溶液中60分 鐘並在122°C下壓熱殺菌30分鐘。形成之鏡片的特性示 於表9。 經濟部智慧財產局員工消費合作社印製 表8 實施例# 48 49 50 51 52 53 54 成分 SiGMA 30 30 30 33 34 25 20 PVP 6 6 6 6 7 6 飞 DMA 31 31 31 30 30 31 31 MPDMS 19 22 23.5 16.5 19 25 28 AcPDMS (n=10) 2 0 0 3 0 0 0 HEMA 9.85 8.5 6.95 9 6 10.5 12.5 Norbloc 1.5 1.5 1.5 2 1.5 1.5 1.5 -55- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 B7 五、發明說明(Μ) CGI819 0.23 0.23 0.25 0.48 0 0.23 0.23 CGI 1850 0 0 0 0 1 0 0 EGDMA 0.4 0.75 0.8 0 0 0.75 0.75 TEGDMA 0 0 0 0 1.5 0 0 藍 HEMA 0.02 0.02 0 0 0 0.02 0.02 %稀釋劑^ 40 40 27.3 39.4 25.9 40 40 稀釋劑組 成物 A A B C D A A 特性 EWC (%) 45 45 47 49 47 49 50 DCA (前進) 52(2) 51(7) 74 (10) 108 75(6) 47(2) 56 (ID 模數(磅/平 方英-吋) 91 77 69 55 49 63 67 伸長度 NT 232 167 275 254 110 124 Dk 巴耳) 54 60 78 44 87 59 60 稀釋劑(重量份): A = 72_5% 第三-戊醇及 27.5PVP(Mw = 2500) B=第三-戍醇The tablets were transferred to a small can containing 1 g of isopropyl alcohol (IPA). Replace IPA for 1 hour every 2 hours. At the end of about 1 hour, remove 50% of IPA and replace with deionized water. Turn the canister for 2 minutes. After the deduction of the minute, remove 5% of the IPA and replace it with deionized water and turn the canister for 20 minutes. Transfer the lens to the packaging solution, rotate for 2 () minutes, and then test. 'Example# Table Step 1 Strength (milliwatts/cm 2 ) Step 1 Time (minutes: seconds) --- Step 2 Strength (milliwatts/cm 2 ) Step 2 Time (minutes: seconds) Advancing contact angle 6:55 5.5 1:28 51 + 1 2:46 —1 — 5.5 2:21 55 ± 2 11:03 ------- Π5.5 0:35 55 ± 1 6:30 ------- - 5.5 0:35 50 ± 1 1:37 ~~ 5.5 2:21 55 + 1 4:04 ------ 5.5 1:28 54 ±2 2:52 —--— 5.5 1:28 62 ± 6 4:36 --------- 5.5 0:35 76 ± 9 1:09 ----- 5.5 0:35 78 ±6 The contact angles of the examples 27 to 32 are not significantly different, indicating low The cure strength of step 1 at about 2 milliwatts per square centimeter provides an improved system for this lens formulation' regardless of the cure time of the step. However, those skilled in the art will recognize that the shorter cure times of step 1 (such as those used in Examples 28 and 31) allow for a shorter overall cure cycle. In addition, it should be noted that even the contact angle_amount of Examples 3 to 3 is higher than that of Example-52- This paper size is applicable to China - 27_ 28 29 30· 31 32 33 34 35 1. u_ \J_ 1.7 1.7 2.4 2.4 2.4 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing [311580 A7 B7 V. Inventions (51 27-32, the lenses of Examples 33-35 can still provide ideal intraocular moistness. Examples 36-41 Example 1 The reaction components of Example 1 were mixed with 25% or 40% D3O as a diluent. The resulting reaction mixture was loaded into a plastic contact lens mold (from ethylene and from Topas® from Ticona Polymers). The copolymer of norbornene was made and cured in a glove box and under nitrogen at a strength of about 2.5 mW/cm 2 , about 30 minutes, and the temperature shown in Table 6 below. According to 1, the lens, hydration and autoclaving were removed from the mold. After hydration, the haze value of the lens was measured. The results are shown in Table 6, which shows that the haze was lowered at a higher temperature. Reduced concentration of thinner and reduced haze Ministry of Finance, Intellectual Property Bureau, Staff and Consumers Cooperatives, Printed Table 6 Example # %D30 Temperature (°C) % Haze DCA(°) 36 25 25 3〇(6) 99 37 25 50-55 12(2) 100 38 25 60-65 14(0.2) 59 39 40 25 50(10) 68 40 40 50-55 40(9) 72 - 41 40 60-65 32(1) 66 + Haze (standard deviation) The results of Table 6 show By increasing the curing temperature, the haze is reduced by about 20% (Example 41 vs. Example 39) and up to about 65% (Example 37 vs. Example 36). The diluent concentration is reduced from 40 to 25%, and the haze is lowered. -53- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) [311580 A7 B7 V. Description of invention (52 between approximately 40 and 75%. Examples 42-47 Using Example 1 Procedures The lenses were made from the formulation shown in Table 7. The cure time was 30 minutes at 25 ° C and the strength was about 2.5 mW/cm 2 . The percent haze was measured and reported in Table 8. Ministry of Economic Affairs Intellectual Property Office Staff Cooperatives Printed Table 7 Example # 42 43 44 45 46 47 SiGMA 28.0 28.0 28.0 28.0 28.0 28.0 mPDMS 31.0 31.0 28.0 28.0 28.0 28.0 acPDMS (n=10) 0.0 0.0 4.0 4.0 4.0 4.0 DMA 23.5 23.5 23.5 23.5 24.0 24.0 HEMA 6.0 6.0 5.0 5.0 6.0 6.0 TEGDMA 1.5 1.5 1.5 1.5 0.0 0.0 Norbloc 2.0 2.0 2.0 2.0 2.0 2.0 PVP (K-90) 7.0 7.0 7.0 7.0 7.0 7.0 CGI 1850 1.0 1.0 1.0 1.0 1.0 1.0 D30 25.0 40 25.0 40.0 25.0 40.0 Characteristic haze 30 50 7.3 14 26 25 Modulus (pounds per square inch) 74 56 148 104 74 NT elongation (%) 326 395 188 251 312 NT EWC (%) 38 41 33 35 38 39 Comparison of the results of the same amount of diluent and TEGDMA or acPDMS (Examples 42 and 46 and Examples 43 and 47) shows that -54- gutter paper size applies to China National Standard (CNS) A4 specification (210x297 mm) 1311580 A7 B7 V. INSTRUCTIONS (") acPDMS is an effective cross-linking agent and provides lenses with characteristics comparable to those used as crosslinkers with TEGDMA. Examples 44 and 45 comprise two crosslinkers. The haze of these examples is substantially reduced compared to lenses made from either crosslinker. However, modulus and elongation are negatively affected (probably because the amount of crosslinker is too large). Examples 48-54 A counter-mix was made using the formulation shown in Table 8 with the indicated diluent. The reaction mixture was placed in a thermoplastic contact lens mold and irradiated with a Philips TL 20W/03T fluorescent bulb at 45 ° C, 0.8 mW/cm 2 for about 32 minutes. The mold was opened and the lens was released in deionized water at 95 ° C for 20 minutes. The lenses were placed in a boric acid buffered saline solution for 60 minutes and autoclaved at 122 ° C for 30 minutes. The characteristics of the formed lens are shown in Table 9. Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 8 Example # 48 49 50 51 52 53 54 Composition SiGMA 30 30 30 33 34 25 20 PVP 6 6 6 6 7 6 Flying DMA 31 31 31 30 30 31 31 MPDMS 19 22 23.5 16.5 19 25 28 AcPDMS (n=10) 2 0 0 3 0 0 0 HEMA 9.85 8.5 6.95 9 6 10.5 12.5 Norbloc 1.5 1.5 1.5 2 1.5 1.5 1.5 -55- This paper scale applies to the Chinese National Standard (CNS) A4 specification ( 210x297 mm) 1311580 A7 B7 V. Inventive Note (Μ) CGI819 0.23 0.23 0.25 0.48 0 0.23 0.23 CGI 1850 0 0 0 0 1 0 0 EGDMA 0.4 0.75 0.8 0 0 0.75 0.75 TEGDMA 0 0 0 0 1.5 0 0 Blue HEMA 0.02 0.02 0 0 0 0.02 0.02 % Thinner ^ 40 40 27.3 39.4 25.9 40 40 Thinner Composition AABCDAA Characteristics EWC (%) 45 45 47 49 47 49 50 DCA (Forward) 52(2) 51(7) 74 (10) 108 75(6) 47(2) 56 (ID Modulus (pounds per square inch - 吋) 91 77 69 55 49 63 67 Elongation NT 232 167 275 254 110 124 Dk Bar) 54 60 78 44 87 59 60 Dilution Agent (parts by weight): A = 72_5% third-pentanol and 27.5PVP (Mw = 2500) B = third-sterol

C= 15/38/38% TMP/2M2P/PVP (Mw = 2500) D = 57/43 2M2P/TMP 經濟部智慧財產局員工消費合作社印製 NT -未試驗 因此,實施例48及51顯示包含親水性(EGDMA或 TEGDMA)及疏水性交聯劑(acPDMS)之配方提供展現 優越特性平衡(包括良好的水含量、適度之Dk、濕潤 度、模數及伸長度)之矽氧烷水凝膠組成物。 -56- 本紙張尺度適用巾_家彳iJ^CNS)A4規f(21G撕公爱了 1311580 A7 B7 五、發明說明(55 實施例55 臨床評估實施例48之鏡片。由18位病患以每日配戴 之模式(晚上卸除)配戴鏡片一週的時間。在第一週, PLTF-NIBUT 為 8·4(±2·9)秒,相較之下 ACUVUE®2 鏡片 為7.0(±1.3)秒。就97%具試驗鏡片之病患而言,前表面 不連續沉積度被評等為無至稍微,而控制組為89%。試 驗及控制組鏡片之移動性為可接受的。- 實施例56 臨床評估實施例49之鏡片。由18位病患以每日配戴 之模式(晚上卸除)配戴鏡片一週的時間。在第一週, ?1^忾1^1丑11丁為8.4(士2.9)秒,相較之下八0;\〇]£@2鏡片 為7.0(±1.3)秒。就95%具試驗鏡片之病患而言,前表面 不連續沉積度被評等為無至稍微,而控制組為89%。試 驗及控制組鏡片之移動性為可接受的。 實施例57 臨床評估實施例51之鏡片。由13位病患以每日配戴 之模式(晚上卸除)配戴鏡片一週的時間。在第二週, PL·ΓF-NIBUT為4.3(±1.9)秒,相較之下ACUVUE®2鏡片 為9.6(±2,1)秒。就70%具試驗鏡片之病患而言,前表面 不連續沉積度被評等為無至稍微,而控制組為92%。試 驗及控制組鏡片之移動性為可接受的。因此,在接觸角測 量值(實施例51之108°相對於實施例48之52°)和依 -57- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 訂 線 經濟部智慧財產局員工消費合作社印製 1311580 A7 五、發明說明(56) PLTF-NIBUT所測量之臨床濕潤度(實施例sl之ο秒 相對於實施例48之W秒)係。 實施例58-60 利用表9中所列之成分(以重量份表示)及下列程序製 造矽氧烷水凝膠鏡片。 於小罐中將成分混合形成反應混合物。將包含反應混 合物之小罐置於一车T _v、两換± 虹式壓榨輥上並滾動過夜。 =,,一=置於—真空乾燥器並藉施加真空分 ==氣回填乾燥器。於-手套箱中,藉添加約 :克:::鏡片材料至τ〇ρΑρ (乙浠和原冰片烯之此 ί :咖聚合物公司)模穴之前曲凹面並吹;; 眼鏡。以聚丙歸凸底曲面半模封閉模具。 聚合,並藉利用20瓦具TL_035碟之 所產生之5亳瓦/平方公分之可見光予以光引發。於45 °C下固化25分鐘之徭,杆鬥扠^ ' 45 里之後打開抵具。於表H)所示之條件下 “度及TWeen之用量),將鏡片之前曲凹面部八 經濟部智慧財產局員工消費合作社印製 放入一含有去離子水之音波浴中Uquasonic 75D型)刀 鏡片去枯連時間示於表1G。鏡片為透明的且為_眼产 之適合形狀。 -58- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公复) 1311580 A7 B7 五、發明說明(57 表9 實施例 58 實施例 59 實施例 60 實施例 61 SiGMA 3.05 3.2 3.2 3.0 mPDMS 1.7 1.7 1.7 1.7 DMA 3.2 3.0 3.1 3.2 PVP 0.6 0.6 0.6 0.6 HEMA 1.0 0.8 0.8 1.0 TEGDMA 0.2 0.4 0.3 0.2 Norblock 0.15 0.2 0.2 0.2 CGI 1850 0.1 0.1 0.3 0.3 Triglide 1.5 1.5 1.5 2M2P 2.5 2.5 2.5 2.5 PVP低分子量 0.5 1.5 1.5 0.5 裝 訂 表10 實施 例# 配方實 施例# [Tween] (ppm) 溫度fc) 去粘連時間 (分鐘) 62 58 850 75 10 63 58 10,000 70 10-15 64 58 0 75 20-22 65 58 850 22 10-15 66 59 850 85 3 67 60 850 85 6 68 61 850 75 T8 實施例69 於65°C下將在實施例66中被去粘連之實施例59之鏡 片進一步於去離子水中水合20分鐘。然後將鏡片轉移至 -59- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 線 經濟部智慧財產局員工消費合作社印製 A7 1311580 B7 五、發明說明(5〇 硼酸緩衝之食鹽水溶液中,使其平衡至少約24小時。鏡 片為透明的且為隱形眼鏡之適合形狀。鏡片具有43%之 水含量、87磅/平方英吋之模數、175%之伸長度及61巴 耳之Dk。鏡片據發現具有57度之前進接觸角。此顯示鏡 片表面實質上沒有可濾取之疏水性材料。 實施例70 於約75t下,將由實施例61而來之鏡片模具的前曲凹 面部分置於包含約5%DOE-120於去離子水中之音波浴 (Aquasonic 75D型)中。於18分鐘内將鏡片由框架中 去粘連。 卢·· 實施例71 (使用有機溶劑) 於約75°C下,將由實施例61而來之鏡片模具的前曲凹 面部分置於包含約1〇%2-丙醇於去離子水中之音波浴 (Aquasonic 75D型)中。於15分鐘内將鏡片由框架中 去枯連。當使用Tween作為添加劑(實施例68)時,去 粘連時間為18分鐘。因此,本實施例顯示有機溶劑亦可 被用來去粘連包含低分子量親水性聚合物之鏡片。__ 實施例72 (不含低分子量PVP). 利用實施例58之配方及程序,但無任何低分子量PVP 來製造矽氧烷水凝膠鏡片。下列程序被用來去粘連鏡片。 於約65°C下,將鏡片模具的前曲凹面部分置於包含約 -60- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 訂 線 經濟部智慧財產局員工消費合作社印製 A7 1311580 B7 五、發明說明(59) 850 ppm之Tween於去離子水中之音波浴(Aquasonic 75D型)中。鏡片並未由模具中釋出。在類似之去粘連條 件下(實施例62-850ppm Tween及75°C ),包含低分子 量親水性聚合物(實施例58配方)之配方的去粘連時間 為10分鐘。因此,本實施例顯示去粘連不能僅在水中, 在配方中未包括低分子量親水性聚合物之配方中完成。 .實施例73 於約75°C下,將由實施例72而來之鏡片模具的前曲凹 面部分置於包含約1〇%2-丙醇有機溶劑於去離子水中之 音波浴(Aquasonic 75D型)中。於20至25分鐘内將鏡 片由框架中去钻連。因此,本發明不含低分子量親水性聚 合物之鏡片可利用包含有機溶劑之水溶液予以去钻連。 實施例74-76 經濟部智慧財產局員工消費合作社印製 根據實施例49製造配方及鏡片,但改變光引發劑之用 量( 0.23,0.38或0.5重量% ),在45°C下以菲利浦TL 20W/03T螢光燈泡(其緊密地配合用來測定凝膠時間之 可見光之光譜輸出),以2.0毫瓦/平方公分照射摸具進 行固化。形成之鏡片之前進接觸角示於表11。 -61- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1311580 A7 B7 五、發明說明(60) 表11 實施例# 重量% 前進DCA 凝膠時間 (秒) 74 0.23 59⑷ 65 75 0.38 62(6) 57 76 0.5 80(7) 51 實施例77-79 % 在45°C下,以1.0, 2.5及5·0毫瓦/平方公分測量實施 例1配方之凝膠時間。結果示於表12。 表12 實施例# 強度(毫瓦/ 平方公分) 凝膠時間 (秒) 77 1 52 78 2.5 38 79 5 34 5 線 經濟部智慧財產局員工消費合作社印製 實施例74至76及77至79之結果,與實施例27-35相 較之下顯示凝膠時間增加,濕潤度改良。因此,凝膠點, 配合接觸角之測良,可被用來決定給定聚合物配方及光引 發劑系統之適合之固化條件。 實施例79-83 利用表14所示反應性成分及以29% (基於所有反應性 成分及稀釋劑為基準)之第三-戊醇作為稀釋劑及11% PVP 2,500 (基於反應性成分為基準)來製造反應混合 -62- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) A7 B7 經濟部智慧財產局員工消費合作社印製 1311580 五、發明說明(6i 物。所示之量為以100%之反應成分為準。將反應混合物 置於熱塑性隱形眼鏡模具中並在60°c及氮氣下利用菲利 浦TL 20W/03T螢光燈泡,以0.8毫瓦/平方公分照射約 30分鐘。打開模具並在95°C下釋出於去離子水中經過15 分鐘。然後將鏡片置於删酸鹽缓衝食鹽水溶液中60分鐘 並在122°C下壓熱殺菌30分鐘。形成鏡片之特性示於表 13 〇 ‘ - 表13 實施例# 79 80 81 82 83 成分 SiGMA 30 30 30 30 30 PVP 0 1 3 6 8 DMA 37 36 34 31 29 MPDMS 22 22 22 22 22 HEMA 8.5 8.5 8.5 8.5 8.5 Norbloc 1.5 1 1.5 1.5 1.5 1.5 CGI 819 0.25 0.25 0.25 0.25 0.25 EGDMA 0.75 0.75 0.75 0.75 0.75 特性 DCA (前進) 122(8) 112(6) 66(13) 58(8) 54(3) 霧度 18⑷ 11(1) 13(1) 14(2) 12⑴ 表12顯示PVP之添加顯著降低接觸角。低至1%降低 動態接觸角約10%且低至3%降低動態接觸角約50%。 實施例84-86 -63- 訂 線 本紙張尺度適用中國國家標準(CNS)A4規格(2丨〇χ297公楚) A7 經濟部智慧財產局員工消費合作社印製 1311580 五、發明說明(ω) 利用表14所列之成分及下列程序製造矽氧烷水凝膠鏡 片: 在室溫下將反應性成分與稀釋劑一起混合於一小罐中。 將包含反應混合物之小罐置於一缸式壓榨輥上並滾動過 夜。 將反應混合物置於一真空乾燥器並藉施加真空40分鐘 去除氧氣。以氮氣回填乾燥器。於一手套箱中,藉添加約 ' 0.10克之脫氣鏡片材料至TOPAS®模穴之前曲凹面並吹以 氮氣以形成隱形眼鏡。以聚丙烯凸底曲面半模封閉模具。 在吹氮下進行聚合,並藉利用20瓦具TL-03磷之螢光所 產生之1.0毫瓦/平方公分之可見光予以光引發。於45 t下固化15分鐘之後,打開模具。將鏡片模具之前曲凹 面部分放入95-100°C之去離子水中。鏡片去粘連時間示 Λ 於表14。鏡片為透明的且為隱形眼鏡之適合形狀。 表14 實施例# 84 85 86 成分 SiGMA 30 30 30 PVP 6 6 6 DMA 31 31 31 MPDMS 21 21 21 AcPDMS (n=10) 0 0 0 HEMA 9.25 9.25 9.25 Norbloc 1.5 1.5 1.5 CGI 819 0.25 0.25 0.25 CGI 1850 0 0 0 -64- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 ____B7 五、發明說明(《)C= 15/38/38% TMP/2M2P/PVP (Mw = 2500) D = 57/43 2M2P/TMP Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed NT - Not tested Therefore, Examples 48 and 51 show that they contain hydrophilic Formulation of EGDMA or TEGDMA and hydrophobic crosslinker (acPDMS) provides a hydroxane hydrogel composition that exhibits a superior balance of properties including good water content, moderate Dk, wettability, modulus and elongation. . -56- This paper size is suitable for the towel _ 彳 J iJ ^ CNS) A4 regulation f (21G tearing public love 1311580 A7 B7 V, invention description (55 Example 55 clinical evaluation of the lens of Example 48. By 18 patients Daily wear mode (night unloading) wears the lens for one week. In the first week, the PLTF-NIBUT is 8·4 (±2·9) seconds, compared to 7.0 for the ACUVUE® 2 lens. 1.3) Seconds. For 97% of patients with test lenses, the opaque deposition of the anterior surface was rated as insignificant, compared with 89% in the control group. The mobility of the lenses in the test and control groups was acceptable. - Example 56 Clinical evaluation of the lens of Example 49. The lens was worn by 18 patients in a daily wear mode (unloaded at night) for one week. In the first week, ?1^忾1^1 ugly 11 Ding is 8.4 (±2.9) seconds, compared to 8.0; \〇] £@2 lenses are 7.0 (±1.3) seconds. For 95% of patients with test lenses, the front surface discontinuous deposition is The rating was no, and the control group was 89%. The mobility of the test and control group lenses was acceptable. Example 57 Clinical evaluation The lenses of Example 51 were worn daily by 13 patients. Mode (night dismount) wears the lens for one week. In the second week, PL·ΓF-NIBUT is 4.3 (±1.9) seconds compared to 9.6 (±2,1) seconds for ACUVUE® 2 lenses. For 70% of patients with test lenses, the degree of discontinuous deposition on the anterior surface was rated as insignificant, compared with 92% in the control group. The mobility of the lenses in the test and control groups was acceptable. Therefore, at the contact angle Measured values (108° of Example 51 vs. 52° of Example 48) and y-57- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). Consumer Cooperatives Printed 1311580 A7 V. INSTRUCTIONS (56) The clinical wetness measured by PLTF-NIBUT (the sec of Example sl vs. W seconds of Example 48) is used in Examples 9-60. The components of the column (expressed in parts by weight) and the following procedure for the manufacture of a helium oxide hydrogel lens. The ingredients are mixed in a small tank to form a reaction mixture. The small can containing the reaction mixture is placed in a car T_v, two exchanges ± rainbow Press on the press roll and roll overnight. =,, one = placed in - vacuum dryer and applied vacuum == gas backfill dryer. In the - glove box, add about: gram::: lens material to τ〇ρΑρ (this ί of 浠 and borneol): concave and blow before the cavity ;; glasses. The mold is closed with a polypropylene to the convex bottom curved mold. Polymerization, and light-induced by using visible light of 5 watts/cm 2 produced by a 20 watt TL_035 disc. Curing at 45 ° C for 25 minutes.徭, the bucket fork ^ 'After 45, open the abutment. Under the conditions shown in Table H), the amount of TWeen is used to print the Uquasonic 75D type knife in a sonic bath containing deionized water. The lens removal time is shown in Table 1G. The lens is transparent and is suitable for the shape of the eye. -58- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210x297). 1311580 A7 B7 V. (57) Table 9 Example 58 Example 59 Example 60 Example 61 SiGMA 3.05 3.2 3.2 3.0 mPDMS 1.7 1.7 1.7 1.7 DMA 3.2 3.0 3.1 3.2 PVP 0.6 0.6 0.6 0.6 HEMA 1.0 0.8 0.8 1.0 TEGDMA 0.2 0.4 0.3 0.2 Norblock 0.15 0.2 0.2 0.2 CGI 1850 0.1 0.1 0.3 0.3 Triglide 1.5 1.5 1.5 2M2P 2.5 2.5 2.5 2.5 PVP Low Molecular Weight 0.5 1.5 1.5 0.5 Binding Table 10 Example # Formulation Example # [Tween] (ppm) Temperature fc) Deblocking time (minutes) 62 58 850 75 10 63 58 10,000 70 10-15 64 58 0 75 20-22 65 58 850 22 10-15 66 59 850 85 3 67 60 850 85 6 68 61 850 75 T8 Example 69 will be implemented at 65 ° C Example 66 The lens of Example 59 was further hydrated in deionized water for 20 minutes. Then the lens was transferred to -59- This paper scale was applicable to China National Standard (CNS) A4 specification (210x297 mm). Ministry of Economy, Intellectual Property Bureau, Staff Consumption Cooperative Printed A7 1311580 B7 V. INSTRUCTIONS (5 in boric acid buffered saline solution to equilibrate for at least 24 hours. The lens is transparent and suitable for contact lenses. The lens has a water content of 43%, 87 lbs. The square inch modulus, 175% elongation and 61 bar Dk. The lens was found to have a 57 degree forward contact angle. This shows that the lens surface is substantially free of leachable hydrophobic material. Example 70 At 75t, the front curved concave portion of the lens mold from Example 61 was placed in a sonic bath (Aquasonic Model 75D) containing about 5% DOE-120 in deionized water. The lens was placed in the frame within 18 minutes. Sticky. Lu. Example 71 (Using an organic solvent) The front curved concave portion of the lens mold of Example 61 was placed in a sonic bath containing about 1% 2-propanol in deionized water at about 75 °C. (Aquasonic 75D type). The lens was removed from the frame within 15 minutes. When Tween was used as an additive (Example 68), the deblocking time was 18 minutes. Therefore, this example shows that an organic solvent can also be used to debond a lens comprising a low molecular weight hydrophilic polymer. __ Example 72 (without low molecular weight PVP). The decane hydrogel lens was made using the formulation and procedure of Example 58, but without any low molecular weight PVP. The following procedure was used to debond the lens. At about 65 ° C, the front concave concave portion of the lens mold is placed to contain about -60- the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Co-operative printing A7 1311580 B7 V. INSTRUCTIONS (59) 850 ppm Tween in a sonic bath in deionized water (Aquasonic 75D). The lens is not released from the mold. Under a similar debonding condition (Examples 62-850 ppm Tween and 75 ° C), the formulation containing the low molecular weight hydrophilic polymer (Example 58 formulation) had a deblocking time of 10 minutes. Thus, this example shows that deblocking cannot be accomplished in water only in formulations that do not include low molecular weight hydrophilic polymers in the formulation. Example 73 The front curved concave portion of the lens mold of Example 72 was placed in a sonic bath (Aquasonic Model 75D) containing about 1% 2-propanol organic solvent in deionized water at about 75 °C. in. The lens is drilled from the frame in 20 to 25 minutes. Therefore, the lens of the present invention which does not contain a low molecular weight hydrophilic polymer can be drilled by using an aqueous solution containing an organic solvent. Examples 74-76 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Formulations and lenses according to Example 49, but varying the amount of photoinitiator (0.23, 0.38 or 0.5% by weight), at Philippe at 45 °C The TL 20W/03T fluorescent bulb (which closely matches the spectral output of the visible light used to determine the gel time) was cured with a 2.0 mW/cm 2 irradiation. The contact angles of the formed lenses are shown in Table 11. -61- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1311580 A7 B7 V. Invention description (60) Table 11 Example #% by weight Advance DCA Gel time (seconds) 74 0.23 59(4) 65 75 0.38 62(6) 57 76 0.5 80(7) 51 Example 77-79 % The gel time of the formulation of Example 1 was measured at 45 ° C at 1.0, 2.5 and 5.0 mm/cm 2 . The results are shown in Table 12. Table 12 Example # Strength (milliwatts / cm ^ 2) Gel time (seconds) 77 1 52 78 2.5 38 79 5 34 5 Line Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Print Examples 74 to 76 and 77 to 79 As a result, it was revealed that the gel time was increased and the wettability was improved as compared with Examples 27 to 35. Therefore, the gel point, in conjunction with the good contact angle, can be used to determine the appropriate curing conditions for a given polymer formulation and photoinitiator system. Examples 79-83 Using the reactive components shown in Table 14 and 29% (based on all reactive components and diluents) of third-pentanol as diluent and 11% PVP 2,500 (based on reactive components) ) to manufacture reaction mix-62- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 1311580 V. Invention description (6i object. In order to be 100% of the reaction components, the reaction mixture was placed in a thermoplastic contact lens mold and irradiated with a Philips TL 20W/03T fluorescent bulb at 60 ° C under nitrogen for about 30 mW/cm 2 . Minutes. The mold was opened and released in deionized water for 15 minutes at 95 ° C. The lens was then placed in a salt buffered saline solution for 60 minutes and autoclaved at 122 ° C for 30 minutes. The characteristics are shown in Table 13 〇' - Table 13 Example # 79 80 81 82 83 Composition SiGMA 30 30 30 30 30 PVP 0 1 3 6 8 DMA 37 36 34 31 29 MPDMS 22 22 22 22 22 HEMA 8.5 8.5 8.5 8.5 8.5 Norbloc 1.5 1 1.5 1.5 1.5 1.5 CGI 8 19 0.25 0.25 0.25 0.25 0.25 EGDMA 0.75 0.75 0.75 0.75 0.75 Characteristic DCA (forward) 122(8) 112(6) 66(13) 58(8) 54(3) Haze 18(4) 11(1) 13(1) 14( 2) 12(1) Table 12 shows that the addition of PVP significantly reduces the contact angle. As low as 1%, the dynamic contact angle is reduced by about 10% and as low as 3%, the dynamic contact angle is reduced by about 50%. Example 84-86 -63- Bonding paper The scale applies to China National Standard (CNS) A4 specification (2丨〇χ297 public Chu) A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 1311580 V. Invention description (ω) Use the ingredients listed in Table 14 and the following procedures to manufacture oxygen Alkane hydrogel lenses: The reactive components are mixed with a diluent in a small pot at room temperature. A small can containing the reaction mixture is placed on a one-cylinder press roll and rolled overnight. The vacuum dryer was used to remove oxygen by applying vacuum for 40 minutes. The dryer was backfilled with nitrogen. In a glove box, about '0.10 grams of degassed lens material was added to the TOPAS® cavity before the concave surface and nitrogen was blown to form a contact lens. The mold is closed with a polypropylene convex bottom curved mold. Polymerization was carried out under nitrogen, and by using the generated fluorescence of 20 watts with phosphorus TL-03 1.0 mW / cm2 of visible light to be initiated. After curing at 45 t for 15 minutes, the mold was opened. The front concave portion of the lens mold was placed in deionized water at 95-100 °C. The lens debonding time is shown in Table 14. The lens is transparent and is a suitable shape for the contact lens. Table 14 Example # 84 85 86 Composition SiGMA 30 30 30 PVP 6 6 6 DMA 31 31 31 MPDMS 21 21 21 AcPDMS (n=10) 0 0 0 HEMA 9.25 9.25 9.25 Norbloc 1.5 1.5 1.5 CGI 819 0.25 0.25 0.25 CGI 1850 0 0 0 -64- This paper size is applicable to China National Standard (CNS) A4 specification (210x297 mm) 1311580 A7 ____B7 V. Invention description (")

EGDMA 1.0 1.0 1.0 TEGDMA 0 0 0 藍 HEMA 0 0 0 40.0 40.0 40.0 稀釋劑成分 Ε F G DCA (前進) 53(3) 55(3) 56(9) 霧度 丄.,~~-- 15(3) 22(2) 16(2) 去粘.連時間 (分鐘) — 3 5 8 稀釋劑(稀釋劑之重量份): E = 62·5%第三-戊醇和 37.5% PVP(MW = 2500) F = 62:5%第三-戊醇和37·5% 1,3-二曱基-3,4,5,6-四氫-2(出)-嘧 啶酮 G ='62,S%第三-戊醇和37.5%乙基_4_氧-1-六氫吡啶羧酸 鹽 因此’實施例84-86顯示許多釋離劑可用於改良去粘 連。 實施例 利用表15所示反應性成分及以42% (基於所有—反應性 成分及稀釋劑為基準)之第三-戊醇作為稀釋劑來製造反 應混合物。將反應混合物置於熱塑性隱形眼鏡模具中並在 50C及氡氣下利用菲利浦TL 20W/03T螢光燈泡,以〇8 毫瓦/平方公分照射約30分鐘。打開模具並於室溫下釋 -65- 本紙張尺度適用中國^&quot;Si(CNS)A4規格(21G X 297公釐) 1311580 A7 B7 五、發明說明(64) 出鏡片於去離子水中經過15分鐘。然後將鏡片置於硼酸 鹽緩衝食鹽水溶液中60分鐘並在122°C下壓熱殺菌30分 鐘。形成鏡片之特性示於表12。 表12 實施例# 87 成分 SiGMA 0 PVP 7 DMA 25 MPDMS 48.6 AcPDMS 5 HEMA 12.25 Norbloc 1.5 CGI 819 0.25 TEGDMA 0.4 訂 線 經濟部智慧財產局員工消費合作杜印製 實施例88 mPDMS-OH (用於實施例3)之製備 混合96克Gelest MCR-E11 (單-(2,3-環氧丙基)-丙醚終 端之聚二甲基矽氧烷(1000 MW))、11.6克甲基丙烯酸、 0.10克三乙胺和0.02克氫醌單曱醚並以氣泡機 &gt; 熱至 140°C並攪拌2.5小時。以飽和含水NaHC03及CH2C12.萃 取產物。將CH2C12層通過Na2S04乾燥並予以蒸發,獲得 94克產物。HPLC/MS與所期望之結構一致。 -66- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 1311580 A7 B7 八八 10-15 經濟部智慧財產局員工消費合作社印製 五、發明說明(65 0EGDMA 1.0 1.0 1.0 TEGDMA 0 0 0 Blue HEMA 0 0 0 40.0 40.0 40.0 Thinner Composition Ε FG DCA (Forward) 53(3) 55(3) 56(9) Haze 丄.,~~-- 15(3) 22(2) 16(2) Debonding. Connecting time (minutes) — 3 5 8 Thinner (parts by weight of diluent): E = 62.5% third-pentanol and 37.5% PVP (MW = 2500) F = 62: 5% tri-pentanol and 37.5% 1,3-dimercapto-3,4,5,6-tetrahydro-2(out)-pyrimidinone G = '62, S% third - Pentanol and 37.5% ethyl-4-oxo-1-hexahydropyridine carboxylate Thus 'Examples 84-86 show that many excipients can be used to improve deblocking. EXAMPLES Reaction mixtures were prepared using the reactive components shown in Table 15 and 42% (based on all-reactive components and diluents) of third-pentanol as a diluent. The reaction mixture was placed in a thermoplastic contact lens mold and irradiated with Phillips TL 20W/03T fluorescent bulb at 50 C and helium for about 30 minutes at 〇 8 mW/cm 2 . Open the mold and release it at room temperature-65- This paper size is applicable to China^&quot;Si(CNS)A4 specification (21G X 297 mm) 1311580 A7 B7 V. Invention description (64) The lens is in deionized water after 15 minute. The lenses were then placed in a borate buffered saline solution for 60 minutes and autoclaved at 122 °C for 30 minutes. The characteristics of forming the lens are shown in Table 12. Table 12 Example # 87 Ingredient SiGMA 0 PVP 7 DMA 25 MPDMS 48.6 AcPDMS 5 HEMA 12.25 Norbloc 1.5 CGI 819 0.25 TEGDMA 0.4 Customs Department of Intellectual Property Office Consumer Cooperation Duplicate Example 88 mPDMS-OH (for example 3) Preparation of 96 g of Gelest MCR-E11 (mono-(2,3-epoxypropyl)-propyl ether terminal polydimethyl methoxy oxane (1000 MW)), 11.6 g methacrylic acid, 0.10 g Triethylamine and 0.02 g of hydroquinone monoterpene ether were heated to 140 ° C with a bubble machine and stirred for 2.5 hours. The product was extracted with saturated aqueous NaHC03 and CH2C12. The CH2C12 layer was dried over Na.sub.2SO.sub.4 and evaporated. HPLC/MS is consistent with the desired structure. -66- This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) 1311580 A7 B7 Eighty-eight 10-15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (65 0

OH ·6 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)OH ·6 This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm)

Claims (1)

131158011^ 今月 、申睛專利範圍 2. 3. 4. 5. 6. 專利申請案第91120935號 ^ -r ^ ^.R?C Patent Appln. No.91120935 修正5無鲆夸之ΐ請#利範圍中文本一附件(三、 1n-chinese - Rncl (τττ) (民國^ 11月19曰送呈) (Submitted on November 19,2008) 種生物醫學裝置,其係由一種包含高分子量親 水性聚合物和有效量之含羥基-官能化矽氧烷之單 體之反應混合物所形成。 根據申請專利範圍第1項之生物醫學裝置,其中 =效量之含羥基-官能化矽氧烷之單體為5%至、9〇 根據申請專利範圍第1項之生物醫學裝置 裝置為矽氧烧水凝膠隱形眼鏡。 根據申請專利範圍第1項之生物醫學裝置 含至15%之高分子量親水性聚合物。 根據申請專利範圍第2項之生物醫學裝置,立 有效量之含羥基-官能化矽氧烷之單體為ι〇% 80% 〇 根據申請專利範圍第1項之生物醫學裝置,其丁 :含羥基·官能化矽氧烷之單體為式〗或η之ς: R1 r2 r7一R6-C-R8—Si-R3 R5心. 4 其中 其包 其中 至 中 消 製 68- 本紙張尺度適財關家標準(CNS)A4規格(210 x 297公爱) A8 B8 C8 D8 311580 六、申請專利範圍 R1 R2 R2 R5 R7— R6- C - R8- Si- [OSi]n- R8-C - R6- R7 II 其中: n為介於3和3 5之間的整數; R1為氫、Cu烷基; R2,R3及R4互相獨立地為Cw烷基、三Cw烷基 矽氧基、苯基、萘基、經取代之Cu烷基、經 取代之苯基或經取代之蓁基, 其中烷基取代基係選自一或多個由Cw烷氧羰 基、Cw烧基、Ci-6烧氧基、臨胺基、1¾素、 羥基、羧基、Cw烷基羰基及曱醯所組成之組 群的成員,且 其中芳香族取代基係選自一或多個由Cw烷氧羰 基、Ch6烧基、c 1-6烧氧基、醯胺基、鹵素、 羥基、羧基、Cw烷基羰基及甲醯所組成之組 群的成員, 經濟部智慧財產局員工消費合作社印製 R為經基、一包含一或多個經基之烧基;或 (CH2(CR9 R10)y〇)x)-R&quot;,其中 y 為 1 至 5,X 為1至100之整數;W-R11互相獨立地選自 Η、具有至多達1〇個碳原子之烷基及至多達 1 〇個碳原子且經至少一個極性官能基取代之 烷基, -69- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) n131158011^ This month, the scope of the patent application 2. 3. 4. 5. 6. Patent application No. 91120935 ^ -r ^ ^.R?C Patent Appln. No.91120935 Correction 5 innocent praise please #利范围Chinese Annex 1 (3, 1n-chinese - Rncl (τττ) (Represented on November 19, 2008) (Submitted on November 19, 2008) A biomedical device consisting of a high molecular weight hydrophilic polymer and effective The biomedical device of the first aspect of the invention, wherein the hydroxy-functionalized oxane-containing monomer is 5% by weight. The biomedical device device according to claim 1 is a xenon-fired hydrogel contact lens. The biomedical device according to claim 1 of the patent scope contains 15% of a high molecular weight hydrophilic polymer. In the biomedical device of claim 2, the effective amount of the hydroxyl-functionalized azide-containing monomer is ι〇% 80%. According to the biomedical device of claim 1, the butyl group contains a hydroxyl group. ·The functionalized siloxane monomer is Or η ς: R1 r2 r7-R6-C-R8-Si-R3 R5 heart. 4 Among them, the package to the middle of the elimination of 68- the paper size of the standard (CNS) A4 specifications (210 x 297 public Love) A8 B8 C8 D8 311580 VI. Patent Application R1 R2 R2 R5 R7- R6- C - R8- Si- [OSi]n- R8-C - R6- R7 II where: n is between 3 and 3 5 Integer integer; R1 is hydrogen, Cu alkyl; R2, R3 and R4 are each independently Cw alkyl, tri Cw alkyl decyloxy, phenyl, naphthyl, substituted Cu alkyl, substituted benzene a substituted or substituted fluorenyl group, wherein the alkyl substituent is selected from one or more selected from the group consisting of Cw alkoxycarbonyl, Cw alkyl, Ci-6 alkoxy, arylamino, 1,3-hydroxy, hydroxy, carboxy, Cw alkane a member of a group consisting of a carbonyl group and a hydrazine, wherein the aromatic substituent is selected from one or more selected from the group consisting of Cw alkoxycarbonyl, Ch6 alkyl, c1-6 alkoxy, amidino, halogen, A member of a group consisting of a hydroxyl group, a carboxyl group, a Cw alkylcarbonyl group, and a formazan, and the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative prints R as a base group, a base containing one or more warp groups; or (CH2 ( CR9 R10) 〇)) x)-R&quot;, where y is from 1 to 5, and X is an integer from 1 to 100; W-R11 is independently selected from fluorene, an alkyl group having up to 1 carbon atom, and up to 1 〇 An alkyl group substituted with at least one polar functional group, -69- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) n R為包含至多達20個碳原子之碳原子之二價基 團; R 可進行自由基及/或陽離子性聚合且包含至 $多20個碳原子之單價基團; _ ^包合至多2〇個碳原子之二價或三價基團。 據申請專利範圍帛6項之生物醫學裝置,其中 y為1至3。 ' 8. 根據申請專利範圍第6項之生物醫學裝置,其中 X為2至90。 、 9. 根據申請專利範圍帛8項之生物醫學裝置,其中 x為10至25。 10. 根據申請專利範圍帛i項之生物醫學裝置,其中 忒3羥基-官能化矽氧烷之單體係選自由2_丙烯 酸、2-曱基_2_經基冬[3_[u,3,3_四曱基]七三甲 基甲矽烷基)氧基]二矽氧烷基]丙氧基]丙酯、(3_ f基丙烯氧基-2-羥基丙基氧基)丙基三(三甲基矽 氧基)矽烷、(2-甲基丙烯氧基_3_羥基丙基氧基)丙 經濟部智慧財產局員工消費合作社印制衣 基三(三甲基矽氧基)甲基矽烷及其之混合物所組 成之組群中。 11. 根據申請專利範圍第10項之生物醫學裝置,其 中有效量之含羥基-官能化矽氧烷之單體為20% 至 50%。 12. 根據申請專利範圍第i 〇項之生物醫學裝置,進 一步包含10%至40%之含其他矽氧烷之單體、 -70- 1311580 二---.六、申請專利範圍 經濟部智慧財產局員工消費合作社印製 川为主50%親水性單雕 水性單體。 至15%高分子量親 根據申請專利範圍第 w ^闺弟12項之生物醫學裝置,Α 中滅置為-種軟性隱形眼鏡。 、 14. 根據申請專利範圍第 人〜Α Α 固弟1項之生物醫學裝置,其中 έ經基_ g月芑化石夕氧餘&gt;μ a ^ 相容性指數。 之早體具有大於°.5之單體 15. 根據巾請專利範圍帛1項之生物醫學裝置,並中 ^刀子置親水性聚合物為聚I乙•比0酮。、 :種製備生物醫學裝置的方法’其包括混合 =子量親水性聚合物和有效量之含幾基官能化 矽氧烷之單體以形成一绣 ^机逯明洛液亚固化該溶液而 成。 -種石夕氧烧水凝膠’係由一種包含高分子量親水 性聚合物和有效量之含羥基—官能化矽氧烷之單體 之反混合物所形成。 18·根據申請專利範圍帛17項之石夕氧燒水凝膠,其 中該親水性聚合物係選自由聚醯胺、聚内酯、聚 醯亞胺、聚内醯胺、官能化聚醯胺、官能化聚内 酯、官能化聚醯亞胺、官能化聚内醯胺及其混合 物所組成之組群中。 19.根據申請專利範圍第17項之矽氡烷水凝膠,其 中該親水性單體係選自由聚_Ν_乙烯吡咯啶酮、 聚-Ν-乙烯-2-六氫吡啶酮、聚_Ν_乙烯_2_己内酿 16. 17. -71 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)R is a divalent group containing up to 20 carbon atoms; R can undergo free radical and/or cationic polymerization and contains a monovalent group of up to 20 carbon atoms; _ ^ inclusion up to 2 〇 A divalent or trivalent group of carbon atoms. According to the biomedical device with 6 patent applications, y is 1 to 3. 8. A biomedical device according to item 6 of the patent application, wherein X is 2 to 90. 9. According to the biomedical device with 8 patent applications, x is 10 to 25. 10. The biomedical device according to the scope of patent application ,i, wherein the single system of 忒3 hydroxy-functional oxirane is selected from the group consisting of 2-acrylic acid, 2-mercapto-2-_2 via JI [3_[u, 3 ,3_tetradecyl]heptamethylmethylmethylalkyl)oxy]dimethoxyalkyl]propoxy]propyl, (3-f-propenyloxy-2-hydroxypropyloxy)propyl (Trimethyl decyloxy) decane, (2-methyl propyleneoxy _3 hydroxypropyloxy) propylene Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed clothing tris (trimethyl decyloxy) A a group consisting of decane and mixtures thereof. 11. The biomedical device according to claim 10, wherein an effective amount of the hydroxyl-functionalized alkane-containing monomer is from 20% to 50%. 12. According to the biomedical device of the scope of patent application, further comprising 10% to 40% of other monomers containing other oxane, -70- 1311580 bis---. Bureau employees' consumption cooperatives printed 50% hydrophilic single-water-based monomer. Up to 15% high molecular weight pro According to the patent application scope w ^ 闺 12 12 biomedical devices, Α 灭 为 - - 。 soft soft contact lenses. 14. According to the patent application scope of the first person ~ Α 固 Gudi 1 biomedical device, which is έ 基 _ g 芑 芑 芑 芑 夕 夕 氧 & & μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ The early body has a monomer larger than °. 5. 15. According to the scope of the patent application, the biomedical device of the first paragraph, and the hydrophilic polymer of the knife is a poly-I-B. A method of preparing a biomedical device comprising mixing a sub-amount of a hydrophilic polymer and an effective amount of a monomer containing a polyfunctional siloxane to form an embroidering solution. The seed oxy-hydrogel is formed from a reverse mixture comprising a high molecular weight hydrophilic polymer and an effective amount of a monomer comprising a hydroxy-functional oxoxane. 18. The invention according to claim 17 of the present invention, wherein the hydrophilic polymer is selected from the group consisting of polyamines, polylactones, polyamidiamines, polyendammines, and functionalized polyamines. a group of functionalized polylactones, functionalized polyimines, functionalized polyendammines, and mixtures thereof. 19. The decane hydrogel according to item 17 of the patent application, wherein the hydrophilic single system is selected from the group consisting of poly-indole vinylpyrrolidone, poly-fluorene-ethylene-2-hexahydropyridone, poly_ Ν_Ethylene_2_内内 16. 17. -71 This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) 1311580 六、申請專利範圍 A8 B8 C8 D8 水-乙烯_3-甲基-2-己内醯胺 經濟部智慧財產局員工消費合作社印制衣 3-甲基-2-六氫吡啶酮、聚_N_乙烯_4_甲基_2_六氫 ^疋嗣承-N-乙稀_4_甲基_2_己内醯胺、聚-乙 稀-3-乙基_2-吼略咬_及聚_N_乙稀_4,5_二甲基 ^各咬_、聚乙㈣唾、聚_N_N_二f基丙㈣ 、?炎乙烯醇、聚丙烯酸、聚氧化乙烯、聚2乙 基今㈣、肝素多糖、多糖、其之混合物及共聚 物所組成之組群中。 20.根據申請專利範圍帛17項之石夕氧烧水凝膠,其 中该親水性聚合物包含聚-N-乙烯吼略咬酮。 21 ·根據申請專利範圍黛, 月号π乾固第17項之矽氧烷水凝膠,包 3 1至15 之高分子量親水性單體。 22·根據申請專利範圍第 .^ /項之矽軋烷水凝膠,包 3 3至15$量%之高分子量親水性單體。 23·根據申請專利範圍第1 * c 矛7項之矽氧烷水凝膠,包 3 5至12重量%之高分子量親水性單體。 24·根據申請專利範圍第17項之 Φ诗人^甘一所W項之矽氧烷水凝膠,其 合物 S能切氧燒之單體為式I或η之化 R1 R2 R6'9~R8*~Si-R3R5 ^ -72 本紙張尺度適財_家標準(CNS)A4規格(2心297以1311580 VI. Patent application scope A8 B8 C8 D8 Water-ethylene _3-methyl-2-caprolactam Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed clothing 3-methyl-2-hexahydropyridone, poly_ N_ethylene_4_methyl_2_hexahydro^疋嗣承-N-ethylene _4_methyl_2_hexylamine, poly-ethylene-3-ethyl_2-吼 slightly bite _ and poly_N_ethyl _4,5_ dimethyl ^ each bite _, polyethyl (tetra) saliva, poly _N_N_ bis f-propyl (tetra), inflammatory vinyl alcohol, polyacrylic acid, polyethylene oxide, poly 2 Ethyl (4), heparin polysaccharide, polysaccharide, mixtures thereof and copolymers. 20. The oxime oxygen-fired hydrogel according to claim 17, wherein the hydrophilic polymer comprises poly-N-vinyl ketone. 21 · According to the scope of application of the patent, the date number π dry solid 17th alkane hydrogel, containing high molecular weight hydrophilic monomers of 3 1 to 15. 22. A high molecular weight hydrophilic monomer in an amount of from 3 to 15% by weight based on the oxime hydrogel of the scope of the patent application. 23. A high molecular weight hydrophilic monomer comprising from 5 to 12% by weight of a hydroxane hydrogel according to the scope of the patent application 1*c spear. 24. According to the 17th article of the patent application scope, the Φ poet ^ Gan Yi's W-based alkane hydrogel, the compound S can be oxidized and the monomer is the formula I or η R1 R2 R6'9~ R8*~Si-R3R5 ^ -72 This paper scale is suitable for the standard _ home standard (CNS) A4 specifications (2 hearts 297 Αδ Β8 C8 D8 1311580 六、申請專利範圍 R 6R 5 一 1 RICIR - 8 R - R2lsi—^4 [0 2 .'-4 RISIR I 8 R 1 - 5 RICIR - 6 R I I 其中: η為介於3和35之間的整數; R為氯、Ci.6烧基; R2,R3及R4互相獨立地為Cw烷基、三Cw烷基 矽氧基、苯基、萘基、經取代之Cu烷基、經 取代之苯基或經取代之萘基, 其中烷基取代基係選自一或多個由Cw烷氧羰 基、Cw烷基、CN6烷氧基、醯胺基、函素、 羥基、羧基、Cw烷基羰基及甲醯所組成之組 群的成員,且 其中芳香族取代基係選自一或多個由(^_6燒氧幾 基、Cl _6烧基、Cl 烧氧基、酿胺基、函素、 羥基、羧基、Cw烷基羰基及曱醯所組成之組 群的成貝’ 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 R5為經基、一包含一或多個經基之烧基;或 (CH2(CR9 R10)yO)x)-Rn ’ 其中 y 為 1 至 5,X 為1至100之整數;R9-R&quot;互相獨立地選自 Η、具有至多達1〇個碳原子之烷基及至多達 10個碳原子且經至少一個極性官能基取代之 烷基, 73-Αδ Β8 C8 D8 1311580 VI. Patent application scope R 6R 5 -1 RICIR - 8 R - R2lsi-^4 [0 2 .'-4 RISIR I 8 R 1 - 5 RICIR - 6 RII where: η is between 3 and An integer between 35; R is chloro, Ci.6 alkyl; R2, R3 and R4 are, independently of each other, Cw alkyl, tri Cw alkyl decyloxy, phenyl, naphthyl, substituted Cu alkyl, a substituted phenyl or substituted naphthyl group, wherein the alkyl substituent is selected from one or more selected from the group consisting of Cw alkoxycarbonyl, Cw alkyl, CN6 alkoxy, decylamine, hydroxyl, hydroxy, carboxy, a member of a group consisting of Cw alkylcarbonyl and formamidine, and wherein the aromatic substituent is selected from one or more of (^_6 anthracene, Cl-6, alkoxy, aramidyl) , a group consisting of a group consisting of a hydroxyl group, a hydroxyl group, a carboxyl group, a Cw alkylcarbonyl group and a hydrazine. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, prints R5 as a radical, and contains one or more bases. Or (CH2(CR9 R10)yO)x)-Rn ' where y is 1 to 5, X is an integer from 1 to 100; R9-R&quot; is independently selected from Η, up to 1 〇 Until alkyl atoms up to 10 carbon atoms and substituted with at least one of the polar functional group, 73- A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 1311580 六、申請專利範圍 為G 3至多達2〇個碳原子之碳原子之二價基 團; ' R為可進行自由基及/或陽離子性聚合且包含至 多20個碳原子之單價基團; R為包含至多20個碳原子之二價或三價基團。 根射請專利_第24項之料垸— 水凝膠,其 中y為1至3。 26·根射請專利範圍第24項之錢料凝膠,其 中X為2至90。 2入根據巾請翻範圍第26項之石凝膠,其 中X為10至25。 28.根據巧專利範圍第17項之錢烧水凝膠,其 中有效1之含羥基-官能化矽氧烷之單體為20% 至 50%。 29·根據申請專利範圍第24項之石夕氧炫水凝膠,其 中忒3羥基-官能化矽氧烷之單體係選自由L丙烯 酸、2-甲基-2-羥基-叩,,^3_四甲基小[(三甲 基甲矽烷基)氧基]二矽氧烷基]丙氧基]丙酯、(3_ 曱基丙烯氧基-2-羥基丙基氧基)丙基三(三甲基矽 氧基)矽烷、(2-甲基丙烯氧基_3_羥基丙基氧基)丙 基三(三甲基矽氧基)甲基矽烷及其之混合物所組 成之組群中。 30.根據申請專利範圍第17項之矽氧烷水凝膠,進 一步包含至少一種含其他矽氧烷之單體。 —------Ί上 本紙張尺度翻t 麟(21G X 297公复)A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1311580 VI. The patent application range is from C 3 to a divalent group of carbon atoms up to 2 carbon atoms; ' R is a free radical and / or cation A monovalent group which polymerizes and contains up to 20 carbon atoms; R is a divalent or trivalent group containing up to 20 carbon atoms. The root shot is patented _24 item 垸 - hydrogel, where y is 1 to 3. 26. Root shots require a money gel of item 24 of the patent range, where X is 2 to 90. 2 Enter the stone gel according to item 26 according to the towel, where X is 10 to 25. 28. A hydrogel according to the item 17 of the patent specification, wherein the hydroxy-functionalized alkane-containing monomer of the effective 1 is from 20% to 50%. 29. The invention according to claim 24, wherein the single system of 忒3 hydroxy-functional siloxane is selected from the group consisting of L acryl, 2-methyl-2-hydroxy-hydrazine, ^ 3_Tetramethyl-small [(trimethylcarbinyl)oxy]dioxaxyalkyl]propoxy]propyl ester, (3-decylpropenyloxy-2-hydroxypropyloxy)propyl a group consisting of (trimethyldecyloxy)decane, (2-methylpropenyloxy-3-hydroxypropyloxy)propyltris(trimethyldecyloxy)methylnonane, and mixtures thereof in. 30. A decane hydrogel according to item 17 of the patent application, further comprising at least one monomer containing other oxane. —------ Ί上 This paper scale turns t Lin (21G X 297 public) 1311580 B8 C8 I &quot; D8 六、申請專利範圍 — 3L根射請專利範㈣3Q項之♦氧烧水凝谬,其 中該含其他矽氧烷之單體係選自由3_甲基丙烯氧 基丙基三(三甲基矽氧基)矽烷之醯胺類似物;矽 I烷乙烯胺基f酸酯類似物、矽氧烷乙烯碳酸酯 !貞似物及含錢垸單體 '其之組合物及低聚物。 32.根據申請專利範圍第%項之⑦氧烧水凝膠,其 中該含其他矽氧烷之單體係選自由 3-甲基丙烯氧基丙基三(三甲基矽氧基)矽烷, 單甲基丙稀氧基丙基終端之聚二甲基矽氧烷, 聚二甲基矽氧烷, 3-甲基丙烯氧基丙基雙(三甲基石夕氧基)甲基石夕烧 甲基丙稀氧基丙基五甲基二石夕氧燒及其組合物所 組成之組群中。 33.根據申請專利範圍第3〇項之石夕氧烧水凝膠,其 中°亥含其他矽氧烷之單體為以0至80重量%之 用量存在。 34. 根據申印專利範圍第3〇項之矽氡烷水凝膠,其 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 杜 印 中忒含其他矽氧烷之單體為以5至6〇重量%之 用量存在。 35. 根據申請專利範圍帛3〇項之石夕氧烧水凝膠,其 中該含其他矽氧烷之單體為以1〇至4〇重量%之 用量存在。 36. 根據申請專利範圍f 17項之石夕氡烧水凝膠,進 一步包含至少一種親水性單體。 ___ -75- Ϊ紙張尺度適用中國國家標準(CNS)A4規格:X297 — 311580 六、申請專利 A8 B8 C8 D8 範圍 37 •根據申請專利範圍第36項之矽氧烷水凝膠,其 中該至少一種親水性單體包含至少一種丙烯酸 基、乙浠基或其之組合物。 38 4 39 •根據申請專利範圍第37項之矽氧烷水凝膠,其 中該丙烯酸基具有式CH2=CRCOX,其中R為氫 或Cl-6烷基且X為〇或N。 根據申請專利範圍第36項之矽氧烷水凝膠,其 中該至少一種親水性單體係選自由Ν,ν-二曱基丙 烯醯胺、2-羥基乙基甲基丙烯酸酯、單曱基丙烯 酸甘油酯、2-羥基乙基曱基丙烯醯胺、聚伸乙基 單甲基丙烯酸甘油酯、曱基丙烯酸、丙烯酸、Ν_ 乙烯吡咯啶酮、Ν-乙烯-Ν-甲基乙醯胺、Ν_乙蝉_ 乙基乙醯胺、Ν-乙烯-Ν-乙基甲醯胺、Ν_乙烯 曱醯胺、親水性乙烯碳酸酯單體、乙烯胺基曱酸 酯單體、親水性呤唑咁酮單體、聚葡萄糖及其之 共聚物及組合物所組成之組群中。 經濟部智慧財產局員工消費合作社印製 4〇.根據申請專利範圍帛36項之石夕氧垸水凝膠,其 中該至少一種親水性單體包含至少一種具有一或 多個經含有可聚合雙鍵之官能基取代之終端羥基 之來氧伸乙基多元醇。 41.根據申請專利範圍第4〇項之矽氧烷水凝膠,其 中該至少一種親水性單體係選自由聚乙二醇、/乙 氧基化烧基糖苷、及具有一或多個被鍵結至聚乙 二醇之終端可聚合烯烴基團之聚乙二醇所組成之 -76- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) Αδ Β8 C8 D8 圍 1311580 —— /'、申請專利範 m群中。 42_根據申請專利範圍第36項之矽氧烷水凝膠,其 中該至少一種親水性單體係選自由Ν,Ν—二曱基丙 稀酿胺、2-羥基乙基甲基丙烯酸酯、曱基丙烯酸 甘油酿、2_經基乙基甲基丙烯醯胺、N-乙烯吡咯 疋嗣I伸乙基單甲基丙烯酸甘油@旨、曱基丙烯 酸、丙烯酸及其之組合物所成之組群中。 43. 根據申請專利範圍第36項之矽氧烷水凝膠,其 中忒至少一種親水性單體包含n,n_二曱基丙烯醯 胺。 44. 根據申請專利範圍第%項之矽氧烷水凝膠,其 中該至少一種親水性單體係以0至70重量%之 用量存在。 45·根據申請專利範圍第%項之矽氧烷水凝膠,其 中该至少一種親水性單體係以5至60重量%之 用量存在。 46.根據申請專利範圍第30項之石夕氧院水凝膠,其 霞濟部智慧財產局員工消費合作社印製 中έ亥至少一種親水性單體係以丨〇至重量%之 用量存在。 47·根據申請專利範圍第17項之石夕氧烧水凝膠,其 包含1至15重量%之高分子量親水性聚合物和5 至90重量%之含羥基_官能化矽氧烷之單體。 钒根據申請專利範圍第17項之石夕氧燒水凝膠,其 匕3 3至15重量%之高分子量親水性聚合物和 -77- 私紙張尺度適用t國國家標準(CNS)A4規格(21〇 X 297公釐) ΐ3Π58〇 、申清專利 Α8 Β8 C8 D8 範圍 1 ο $ 49柜 8〇重量%之含羥基-官能化秒氧烧之單體。 .艮據申請專利範圍第17項之矽氧烷水凝膠,其 5至12重量%之高分子量親水性聚合物和 5〇 至50重量%之含羥基-官能化矽氧烷之單體。 .二據申請專利範圍第η項之矽氧烷水凝膠,進 步包含0至8〇重量%之至少一種其他含矽氧 烷之單體。 51,才p '申凊專利範圍第17項之矽氧烷水凝膠,進 步包含0至70重量%之至少_種親水性 體。 干 52 .=據申請專利範圍第50項之矽氧烷水凝膠,包 έ 5至6〇重量%之該至少一種其他含矽氧燒 單體。 53_ =據申請專利範圍第50項之矽氧烷水凝膠,包 含10至40重量%之該至少一種其他含矽氧烷之 單體。 經濟部智慧財產局員工消費合作社印制衣 54·根據申請專利範圍第51項之矽氧烷水凝膠,包 含5至60重量%之該至少一種親水性單體。 55. 根據申請專利範圍第51項之矽氧烷水凝膠,包 含10至5〇重量%之該至少一種親水性單體。 56. 根據申請專利範圍第17項之矽氧烷水凝膠,包 δ 1/6至15%之南分子1親水性聚合物;$至9〇 重量%之含羥基-官能化矽氧烷之單體;5至6〇 重量%之其他含矽氧烷之單體及5至60重量% -78- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ297公爱) 之親水性單體。 57.:據二:專利範圍第17項之秒氧規水凝膠,包 二二1,分子量親水性聚合物;1。至 里〇之3羥基-官能化矽氧烷 5至 :;重量%之其他含石夕氧貌之單體及二重量 %之親水性單體。 58. 根據申清專利範圍第1 7 寸W乾固弟Π項之矽氧烷水凝膠,包 3 〇至12%之高分子量親水性聚合物;20至 5〇重量%之含經基_官能切氧垸之單體;5至 6〇重量%之其他含石夕氧烧之單體及50至60重量 %之親水性單體。 设根據申請專利範圍第n項之石夕氧烧水凝膠,包 含5'至12%之高分子量親水性聚合物;20至 重畺%之§羥基-官能化矽氧燒之單體;1〇至 4〇重量%之其他含石夕氧院之單體及1〇至5〇重量 %之親水性單體。 6〇.根據申請專利範圍筮,7 tS + τ^ 月寸〜尊已国弟17項之矽氧烷水凝膠,其 中該親水性聚合物具有至少1〇,_道耳頓之重 量平均分子量。 61.根據申請專利範圍f 17項之石夕氧院水凝膠,其 中該親水性聚合物沿著該親水性聚合物之骨架部 分包含至少一個環狀部分。 62_根據申請專利範圍第n項之石夕氧燒水凝膠,其 中5亥親水性聚合物係選自由包含環狀醯胺、環狀 -79- 131158〇 、申請專利範圍 A8 B8 C8 D8 亞胺及其之組合物所組成之組群中。 .種眼用裝置’其包含根據申請專利範圍第17 項之矽氧烷水凝膠。 64. 根據申請專利範圍帛63項之眼用裝置,進一步 包含低於70。之前進動態接觸角。 65. 根據申請專利範圍帛63項之眼用裝置,進一步 包含低於60。之前進動態接觸角。 66·根據申請專利範圍第63項之眼用裝置,進一步 包含於約一週之配戴後,至少7秒之淚膜崩潰時 間及至少50巴耳之透氧度。 7.根據申請專利範圍第64項之眼用裝置,進一步 包含低於90磅/平方英吋之模數。 68. 根據申請專利範圍第64項之眼用裝置,進一步 包含介於10和60%之間的水含量。 69. 根據申請專利範圍第64項之眼用裝置,進一步 包含介於20和55%之間的水含量。 經濟部智慧財產局員工消費合作社印制衣 7〇.根據申請專利範圍第64項之眼用裴置,進—步 包含介於25和40%之間的水含量。 71.根據申請專利範圍第66項之眼用裝置,其中於7 天之配戴後,該淚膜崩潰時間為至少7秒。 72二種形成生物醫學裝置之方法,其包括步驟⑷混 合包含至少一種高分子量親水性聚合物和有效量 之至少一種含羥基-官能化矽氧烷之單體之反應 性成分及(b)固化步驟(&amp;)之產物以形成一種生物 本...氏張尺度適用中國國家標準(cns)A4規格d撕公 1311580 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 範圍 六、申請專利 醫學裝置。 73 •根據申請專利範圍第72項之方法,其中該生物 74遽學裝置包含一種眼用裝置。 ’根據申請專利範圍第73項之方法,其中該眼用 裳置為一種矽氧烷水凝膠隱形眼鏡。 75·根據申請專利範圍第73項之方法,其中該反應 生成分係在稀釋劑的存在下被混合以形成一種反 應混合物。 76·根據申請專利範圍第75項之方法,其中該稀釋 劑係選自由醚類、酯類、烷類、鹵化烷類、矽烷 大貝、S&amp;胺類、醇類及其之混合物所組成之組群 中。 77. 根據申請專利範圍第75項之方法,其中該稀釋 劑係選自由醯胺類、醇類及其之混合物所組成之 組群中。 78. 根據申請專利範圍第乃項之方法,其中該稀釋 劑係選自由二級及三級醇類及其之混合物^組 之組群中。 '' 79. 根據申請專利範圍帛75項之方法,其中該 劑係選自四氫呋喃、乙酸乙酯、乳酸甲鲳:乳萨 異丙酯、氯乙烯、八甲基環四矽氧烷 :夂 酿胺、二甲基乙醯胺、二甲基丙醯胺: 咯啶酮、其之混合物及任何前述與至少—二 混合物所組成之組群中。 種醇之 81 - 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐)1311580 B8 C8 I &quot; D8 VI. Scope of Application for Patent - 3L Radiation Requesting Patent (4) 3Q ♦ Oxygen boiling water coagulation, wherein the single system containing other oxane is selected from 3 - methacryloxy A decylamine analog of a tris(trimethyldecyloxy)decane; a hydrazine I alkylvinylamine f-ester analog, a decyl alkane ethylene carbonate, a hydrazine, and a hydrazine-containing monomer And oligomers. 32. The oxyhydrogenated hydrogel according to item 5% of the patent application, wherein the single system containing other oxane is selected from the group consisting of 3-methacryloxypropyltris(trimethyldecyloxy)decane. Monomethyl propyloxypropyl terminal polydimethyl methoxy oxane, polydimethyl methoxy oxane, 3-methyl propylene oxy propyl bis (trimethyl sulphate ) methyl sulphur A group consisting of acryloxypropylpentamethyl pentoxide and its composition. 33. A Xixi oxygen-fired hydrogel according to the third aspect of the patent application, wherein the monomer containing other oxoxane is present in an amount of from 0 to 80% by weight. 34. According to the decane hydrogel of the third paragraph of the scope of the patent application, the Ministry of Economic Affairs, the Intellectual Property Office, the employee's consumption cooperation, the printing of the monomer containing other oxoxane in the amount of 5 to 6 〇% by weight presence. 35. The invention according to claim 3, wherein the other alkoxysilane-containing monomer is present in an amount of from 1 to 4% by weight. 36. Further comprising at least one hydrophilic monomer according to the Si Xizhuo hydrogel of claim 17 of the patent application. ___ -75- Ϊ Paper scale applicable to China National Standard (CNS) A4 Specification: X297 - 311580 VI. Application for patent A8 B8 C8 D8 Scope 37 • A paraxane hydrogel according to Article 36 of the patent application scope, at least one of which The hydrophilic monomer comprises at least one acrylic group, ethyl fluorenyl group or a combination thereof. 38 4 39. The alkane hydrogel according to claim 37, wherein the acrylic group has the formula CH2=CRCOX, wherein R is hydrogen or Cl-6 alkyl and X is deuterium or N. The alkane hydrogel according to claim 36, wherein the at least one hydrophilic single system is selected from the group consisting of ruthenium, ν-dimercaptopropenylamine, 2-hydroxyethyl methacrylate, and monodecyl. Glyceryl acrylate, 2-hydroxyethyl decyl acrylamide, polyethyl methacrylate, methacrylic acid, acrylic acid, hydrazine-vinyl pyrrolidone, hydrazine-ethylene-hydrazine-methyl acetamide, Ν_乙蝉_ethylacetamide, Ν-ethylene-Ν-ethylformamide, Ν_vinylamine, hydrophilic ethylene carbonate monomer, vinyl phthalate monomer, hydrophilic 呤A group consisting of oxazolone monomer, polydextrose, copolymers and compositions thereof. The Ministry of Economic Affairs, the Intellectual Property Office, and the Employees' Cooperatives Co., Ltd. 4, which is based on the patent application 帛36, wherein the at least one hydrophilic monomer comprises at least one of having one or more polymerizable doubles. The functional group of the bond is substituted with the terminal hydroxyl group to form an ethyl alcohol. 41. The alkane hydrogel of claim 4, wherein the at least one hydrophilic single system is selected from the group consisting of polyethylene glycol, /ethoxylated alkyl glycoside, and having one or more -76- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) Αδ Β8 C8 D8 circumference 1311580 —— / ', apply for a patent in the m group. 42. The alkane hydrogel according to claim 36, wherein the at least one hydrophilic single system is selected from the group consisting of hydrazine, hydrazine-dimercaptopropene, 2-hydroxyethyl methacrylate, Group of methacrylic acid glycerin, 2_ mercaptoethyl methacrylamide, N-vinylpyrrole I extended ethyl monomethacrylic acid glycerin, thioglycolic acid, acrylic acid and the like In the group. 43. The alkane hydrogel of claim 36, wherein at least one of the hydrophilic monomers comprises n,n-dimercaptopropeneamine. 44. A decane hydrogel according to item % of the patent application, wherein the at least one hydrophilic single system is present in an amount of from 0 to 70% by weight. 45. A decane hydrogel according to item 5% of the patent application, wherein the at least one hydrophilic single system is present in an amount of from 5 to 60% by weight. 46. According to the scope of patent application No. 30, Shixia Oxygen Hydrogel is printed by Xiahai Department of Intellectual Property Bureau employee consumption cooperative. At least one hydrophilic single system exists in the amount of 丨〇 to weight%. 47. The oxime oxygen-fired hydrogel according to claim 17 which comprises 1 to 15% by weight of a high molecular weight hydrophilic polymer and 5 to 90% by weight of a monomer having a hydroxy-functional siloxane. . Vanadium according to the scope of application of the scope of the 17th oxime oxygenated hydrogel, its 匕 33 to 15% by weight of high molecular weight hydrophilic polymer and -77- private paper scale applicable to national standard (CNS) A4 specifications ( 21〇X 297 mm) ΐ3Π58〇, Shenqing Patent Α8 Β8 C8 D8 Range 1 ο $49 Cabinet 8 〇% by weight of hydroxyl-functionalized oxy-burning monomer. The alkane hydrogel according to claim 17 of the patent application, which is 5 to 12% by weight of a high molecular weight hydrophilic polymer and 5 to 50% by weight of a monomer having a hydroxyl group-functionalized alkane. 2. The alkane hydrogel according to item η of the patent application, further comprising 0 to 8% by weight of at least one other halogen-containing monomer. 51. The helium a hydrogel of claim 17 of the patent application scope further comprises from 0 to 70% by weight of at least one hydrophilic body. Dry 52. = a decane hydrogel according to claim 50 of the patent application, comprising 5 to 6 重量% of the at least one other oxo-containing monomer. 53_ = a decane hydrogel according to claim 50 of the patent application, comprising 10 to 40% by weight of the at least one other oxene-containing monomer. Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printed Clothing 54. The decane hydrogel according to claim 51 of the patent application contains 5 to 60% by weight of the at least one hydrophilic monomer. 55. The alkane hydrogel according to item 51 of the patent application, comprising 10 to 5 % by weight of the at least one hydrophilic monomer. 56. A hydroxane hydrogel according to item 17 of the scope of the patent application, comprising δ 1/6 to 15% of the South molecule 1 hydrophilic polymer; from 9% to 9% by weight of the hydroxyl-functionalized oxirane Monomer; 5 to 6 重量% of other siloxane-containing monomers and 5 to 60% by weight -78- This paper scale applies to Chinese National Standard (CNS) A4 (210 χ 297 gong) hydrophilic monomer . 57.: According to the second: the scope of the scope of the 17th oxygen oximeter hydrogel, package 22, 1, molecular weight hydrophilic polymer; 3 hydroxy-functionalized oxirane to 〇 5 to :; % by weight of other monomers containing a sulphuric oxide and 2% by weight of a hydrophilic monomer. 58. According to the patent scope of the patent, the 17th inch of the dry silicone hydrogel, from 3 〇 to 12% of high molecular weight hydrophilic polymer; 20 to 5% by weight of the containing ketone _ a monomer having a functional oxoquinone; 5 to 6 重量% by weight of other anthracene-containing monomer and 50 to 60% by weight of a hydrophilic monomer. The invention provides a high-molecular-weight hydrophilic polymer of 5' to 12% according to the nth item of the patent application scope; 20 to 5% by weight of the hydroxy-functionalized oxime-burning monomer; 〇 to 4% by weight of other monomers containing a ceramsite and 1 〇 to 5% by weight of a hydrophilic monomer. 6〇. According to the scope of the patent application, 7 tS + τ ^ 寸 〜 尊 尊 尊 尊 国 国 17 17 17 17 17 17 17 17 尊 尊 尊 尊 尊 尊 , , , , , , , , , , , , , , , , , , . 61. The yoke oxygen hydrogel according to claim 17, wherein the hydrophilic polymer comprises at least one annular portion along a skeleton portion of the hydrophilic polymer. 62_ According to the patent application scope nth, the Xiyang oxygenated hydrogel, wherein the 5 HAI hydrophilic polymer is selected from the group consisting of cyclic guanamine, cyclic -79-131158 〇, patent application range A8 B8 C8 D8 A group consisting of amines and combinations thereof. An ophthalmic device which comprises a hydroxane hydrogel according to item 17 of the patent application. 64. The ophthalmic device according to application No. 63 of the patent application further contains less than 70. Enter the dynamic contact angle before. 65. The ophthalmic device according to application No. 63 of the patent application further contains less than 60. Enter the dynamic contact angle before. 66. The ophthalmic device of claim 63, further comprising a tear film collapse time of at least 7 seconds and an oxygen permeability of at least 50 bar after wearing for about one week. 7. An ophthalmic device according to claim 64, further comprising a modulus of less than 90 psi. 68. The ophthalmic device according to claim 64, further comprising a water content of between 10 and 60%. 69. The ophthalmic device according to claim 64, further comprising a water content of between 20 and 55%. Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing and Printing Co., Ltd. 7〇. According to the eye treatment of Article 64 of the patent application, the step further includes a water content between 25 and 40%. 71. The ophthalmic device of claim 66, wherein the tear film collapse time is at least 7 seconds after 7 days of wearing. 72. A method of forming a biomedical device comprising the steps of (4) mixing a reactive component comprising at least one high molecular weight hydrophilic polymer and an effective amount of at least one hydroxyl-functionalized siloxane containing monomer and (b) curing The product of the step (&amp;) to form a biological one... The Chinese standard (cns) A4 specification d tear public 1311580 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A8 B8 C8 D8 Scope six, apply for patent Medical device. 73. The method according to claim 72, wherein the biological 74 drop-out device comprises an ophthalmic device. The method of claim 73, wherein the ophthalmic coating is a decane hydrogel contact lens. 75. The method according to claim 73, wherein the reaction-generating fraction is mixed in the presence of a diluent to form a reaction mixture. 76. The method of claim 75, wherein the diluent is selected from the group consisting of ethers, esters, alkanes, halogenated alkanes, decane, shellfish, amines, alcohols, and mixtures thereof In the group. 77. The method of claim 75, wherein the diluent is selected from the group consisting of guanamines, alcohols, and mixtures thereof. 78. The method of claim 5, wherein the diluent is selected from the group consisting of secondary and tertiary alcohols and mixtures thereof. '' 79. According to the method of claim 75, wherein the agent is selected from the group consisting of tetrahydrofuran, ethyl acetate, methyl lactate: lactam isopropyl ester, vinyl chloride, octamethylcyclotetraoxane: brewing Amine, dimethylacetamide, dimethylpropanamine: a flavonone, a mixture thereof, and any of the foregoing and at least two mixtures. 81 - This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 1311580 A8 B8 C8 D8 六、申請專利範圍 80_根據申請專利範圍第77 劑包含至少一種具有至少 81 _根據申請專利範圍第 劑包含至少一種具有至少 82. 根據申請專利範圍第75 劑為惰性且易以水置換。 83. 根據申請專利範圍第75 劑包含至少一種醇,選 醇、2- 丁醇、2-甲基 項之方法,其中該稀釋 5個碳原子之醇。 項之方法,其中該稀釋 6個碳原子之醇。 項之方法,其中該稀釋 項之方法,其中該稀釋 自由第三丁醇、第三戊 戊醇、2,3-二甲基_2· 丁 經 濟 部 智 慧 財 產 局 員 工 消 費 合 社 印 製 醇、3-甲基-3-戊醇、3_乙基_3_戊醇、3,7_二甲基 3-辛醇及其之混合物所組成之組群中。 84.根據申請專利範圍第75項之方法,其 劑係選自由己醇、庚醇、辛醇、壬醇、癸醇、 三丁醇、3-甲基戊醇、異丙醇、第三戊醇 酸乙酯、乳酸曱酯、乳酸異丙酯、3,7_二甲美3 辛醇、二曱基曱醯胺、二甲基乙醯胺、二甲 醯胺、Ν-甲基吡咯啶酮及彼等之混合物所組^ 組群中。 85·根據申清專利乾圍第75項之方法,与中、 劑係遙自由1-乙氧基_2_丙醇、甲義 一 土、、丙醇、 第三-戊醇、三丙二醇甲醚、異丙醇、^甲其2 吡咯啶酮、乳酸乙酯、Ν,Ν-二曱基丙醯胺、二_2 一醇甲謎及其混合物所組成之組群中。 86.根據申請專利範圍第75項之方法,波办 /、肀該稀 第乳 丙 之 釋 丙 釋 -82- 本紙張尺度適用中關家標準(CNS)A4規格(21〇 X现公复) 13 11580 、申請專利範圍 A8 B8 C8 D8 劑係以低於50重量% (基於反應混合物為準) 之用量存在。 I根據申請專利_ 75項之方法,其中該稀釋 月J係以低於40重量% (基於反應混合物為準) 之用量存在。 88.根據申請專利範圍第75項之方法,其中該稀釋 劑係以介於1〇和3〇重量% (基於反應混合物為 準)之間的用量存在。 89 根據申請專利範圍第75項之方法,其中該稀釋 劑在加工條件下為水可溶且該方法進一步包含(c) 由忒鏡片被固化所在之模具中移除該鏡片及(d)水 t該鏡片,其中步驟(c)和(d)係在包含水作為實 質成分之水溶液中進行。 9〇.根據申請專利範圍帛75項之方法,其中該反應 混合物進一步包含至少一種引發劑。 91. 根據申請專利範圍第90項之方法,其中該固化 係藉由熱、曝露至輻射或其之組合來進行。 經濟部智慧財產局員工消費合作社印制衣 92. 根據申請專利範圍第9〇項之方法其中該固化 係藉由包含離子化及/或光化光輕射之照射及包 含至少一種光引發劑之該引發劑來進行。 93·根據申請專利範圍第92項之方法,其中該輻射 包含具有波長200至500奈米之光且該引發劑係 選自由芳香族α-羥基酮、烷氧基氧基安息香、苯 乙酮、乙醯基氧化膦、第三胺與二_之混合物, -83 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) B8 C8 D8 1311580 、申請專利範圍 及其之混合物所組成之組群中。 94.根據申請專利範圍第92項之方法,其中該引發 劑係選自由1 -羥基環己基苯酮、2_羥基_2_曱基-1-苯基-丙-1-酮、雙(2,6_二甲氧基苯甲醯基)_2,4_ 4-二甲基戊基氧化膦、雙(2,4,6-三曱基苯甲醯 基l·苯基氧化膦、2,4,6-三甲基苄基二苯基氧化膦 和2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香 甲酯、樟腦醌和乙基4_(N,N_二曱基胺基)苯曱酸 酉旨之組合物所組成之組群中。 95_根據申請專利範圍第9〇項之方法,其中該引發 劑係以可有效引發反應混合物之聚合之用量存在 於反應混合物中。 96. 根據申請專利範圍第9〇項之方法其中該引發 劑係以基於該反應性成分為準由〇1至2重量百 分比的用量存在於反應混合物中。 97. 根據申請專利範圍第92項之方法,其中該固化 係藉由可見光照射來進行。 經濟部智慧財產局員Η消費合作社印製 98. 根據申請專利範圍第9〇項之方法,其中該引發 劑包含1-羥基環己基苯酮、雙(2,6_二曱氧基苯曱 醯基)-2,4-4-二甲基戊基氧化膦及其之混合物。 99. 根據申請專利範圍第98項之方法,其中該引發 劑包含雙(2,6-二甲氧基苯曱醯基)_2,心心三甲基戊 基氧化膦。 根據申請專利範圍帛99項之方法,其中該 -84- 1311580 B8 C8 ___D8____ 六、申睛專利範圍 性成分進—步包含至少一種uv吸收化合物。 101.根據申請專利範圍第97項之方法,其中該固化 步驟係在介於0.1和6毫瓦/平方公分之間的固 化強度下進行。 1〇2·根據申请專利範圍第97項之方法,其中該固化 步驟係在介於0.2毫瓦/平方公分至3毫瓦/平 方公分之間的固化強度下進行。 103·根據申請專利範圍第101項之方法,其中該固化 步驟進一步包含至少1分鐘之固化時間。 104. 根據申請專利範圍第1〇1項之方法,其中該固化 步驟進一步包含介於i和60分鐘之間的固化時 間。 105. 根據申請專利範圍第101項之方法,其中該固化 步驟進一步包含介於丨和30分鐘之間的固化時 間。 106. 根據申請專利範圍第1〇3項之方法,其中該固化 步驟下係在大於25。(:之溫度下進行。 107. 根據申請專利範圍第103項之方法,其中該固化 經濟部智慧財產局員工消費合作社印製 步驟下係在介於25°C和70X:之間的溫度下進 行。 108. 根據申請專利範圍第103項之方法,其中該固化 步驟下係在介於40。(:和7(TC之間的溫度下進 行。 109. 根據申請專利範圍第75項之方法,其中該反废、 -85- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公麓) — [311580 申請專利範圍 A8 B8 C8 D8 混合物係在一模具中被固化且該方法進一 :::用裝置由該模具中去枯連之步驟。〜 no.根據申tf專利範㈣⑽項之方法, 混合物進一步包含至少 :中5亥反應 物。 7裡低刀子夏親水性聚合 hi·根據中請專利範圍帛110項之方法, 子量親水性聚合物具有低於4〇,_道:之: 目平均分子量。 今顿之數 112.根據巾請專利範㈣11G項之方法,㈠ 子量親水性聚合物具有低於20,咖 頓之二 目平均分子量。 斗貝之數 ⑴.根^請專利範圍f 110項之方法,其中該低分 ^置親水性聚合物係選自由水可溶聚醯胺、_ 胺及聚乙二醇及其之混合物所組成之組群中。 114_根:申請專利範圍帛110項之方法,其中該低分 f量親水性聚合物係選自由聚_乙烯吡咯啶酮、 及乙一醇、聚2乙基_呤唑咁及其之混合物所組 成之組群中。 ' 經濟部智慧財產局員工消費合作社印製 115. 根據申請專利範圍第11〇項之方法,其中該低分 子1E親水性聚合物係以基於反應混合物為準至多 達20重量%的用量存在。 116. 根據申請專利範圍第11〇項之方法,其中該低分 子昼親水性聚合物係以基於反應混合物為準介於 5和20重量%的用量存在。 本紙張尺度適財_家標準(CNS)A4規格⑽χ 297公楚) 1311580 、申請專利範圍 B8 C8 D8 i _根據申請專利範圍第109項之方法,其中該去柏 連係利用一種水溶液來進行。 118. 根據申請專利範圍第1〇9項之方法,其中該水溶 液另包含至少一種表面活性劑。 119, 根據申請專利範圍第118項之方法,其中該表面 活性劑包含至少一種非離子性表面活性劑。 12〇.根據申請專利範圍第lls項之方法,其中該表面 活性劑包含TWEEN®或DOE120。 121. 根據申請專利範圍第118項之方法,其中該表面 活性劑係以至多達10,000 ppm之用量存在。 122. 根據申請專利範圍第118項之方法,其中該表面 /舌性劑係以介於500 PPm和1500 ppm之間的用 量存在。 123. 根據申請專利範圍第118項之方法,其中該表面 活性劑係以介於1〇〇和12〇〇 ppm之間的用^存 在。 Π4.根據申請專利範圍第1〇9項之方法,其中該水溶 液包含至少一種有機溶劑。 人 ^ 經濟部智慧財產局員工消費合作社印制衣 125.根據申請專利範圍第1〇9項之方法,其中該去枯 連係在介於室温和1〇〇。(:之間的溫度下進行I , 126_根據申請專利範圍第1〇9項之方法,其中I 連係在介於70t和95°C之間的溫度下進行4去钻 127.根據申請專利範圍第1〇9項之方法,其 連係利用攪拌進行。 °亥去枯 -87 本紙張尺度適用中國國家標準(CNS)A4規格(210 297公釐) '—^ 1311580 六、申請專利範圍 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 128·=請專利範圍第109項之方法,其中該擾拌 包含音波震盪。 129. ^形成可濕潤之生物醫學裝置之方法,其包括 二:(a)此合包含一種高分子量親水性聚合物和有 交置之—種含㈣官能化錢烧之單體之反應 成刀及(b)在表小凝膠時間下或以上固化步驟(a) 之產物以形成一種可濕潤之生物醫學裝置。 130. 根據中請專利範圍帛129項之方法,^中該裝置 為眼用鏡片。 131. 根據中請專利範圍f 129項之方法,其中該裝置 為隱形眼鏡。 132. 根據申請專利範圍帛131項之方法,其中該濕潤 度包含一種70。或更低之前進動態接觸角。 133. 根據申請專利範圍第131項之方法,其中該濕 度包含一種00。或更低之前進動態接觸角。 134·根據申請專利範圍第131項之方法,其中該濕 度包含一種至少7秒之淚膜崩潰時間。 135. 根據申請專利範圍第13 1項之方法,其中該反 性成分進一步包含至少一種引發劑。 136. 根據申請專利範圍第135項之方法,其中該固〜 係藉由照射及該包含一引發劑濃度和有效提供該 隶小凝膠日^間之固化時間之條件下進行。 137. 根據申請專利範圍第135項之方法,其中該引發 劑係以基於所有反應性成分為準至多1%之用 潤 潤 應 化 量 -88 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Αδ Β8 C8 D81311580 A8 B8 C8 D8 VI. Patent application scope 80_ According to the patent application scope, the 77th agent contains at least one of having at least 81 _ according to the scope of the patent application, the agent contains at least one of which has at least 82. According to the scope of the patent application, the 75th agent is inert and easy Replace with water. 83. A method of selecting at least one alcohol, alcohol, 2-butanol, 2-methyl term according to the scope of the patent application, wherein the alcohol having 5 carbon atoms is diluted. A method of diluting an alcohol having 6 carbon atoms. The method of the item, wherein the method of diluting the product, wherein the dilution is free of third butanol, third pentanol, 2,3-dimethyl-2, Ding, Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption, co-operative printing of alcohol, A group consisting of 3-methyl-3-pentanol, 3-ethyl-3-butanol, 3,7-dimethyl 3-octanol, and mixtures thereof. 84. The method according to claim 75, wherein the agent is selected from the group consisting of hexanol, heptanol, octanol, decyl alcohol, decyl alcohol, tributyl alcohol, 3-methylpentanol, isopropanol, and third pentane. Ethyl alkylate, decyl lactate, isopropyl lactate, 3,7-dimethyl octanol, dimethyl decylamine, dimethyl acetamide, dimethyl hydrazine, hydrazine-methyl pyrrolidine The ketones and their mixtures are grouped into groups. 85. According to the method of the 75th patent of Shenqing Patent, and the medium and the agent are free of 1-ethoxy-2-propanol, ketone, propanol, tri-pentanol and tripropylene glycol methyl ether. A group consisting of isopropanol, keto-2-pyrrolidone, ethyl lactate, hydrazine, hydrazine-dimercaptopropionamide, dioxopropanol, and mixtures thereof. 86. According to the method of applying for the scope of patents, item 75, Boss/, 肀 稀 第 - 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本13 11580, Patent Application A8 B8 C8 D8 The agent is present in an amount of less than 50% by weight, based on the reaction mixture. I. The method according to claim 76, wherein the dilution month J is present in an amount of less than 40% by weight, based on the reaction mixture. 88. The method of claim 75, wherein the diluent is present in an amount between 1 and 3% by weight, based on the reaction mixture. 89. The method of claim 75, wherein the diluent is water soluble under processing conditions and the method further comprises (c) removing the lens and (d) water from a mold in which the lens is cured. The lens wherein steps (c) and (d) are carried out in an aqueous solution containing water as a substantial component. 9. The method of claim 75, wherein the reaction mixture further comprises at least one initiator. 91. The method of claim 90, wherein the curing is performed by heat, exposure to radiation, or a combination thereof. The Ministry of Economic Affairs, Intellectual Property Office, Employees' Cooperatives, Printing and Garment 92. The method of claim 9 wherein the curing is by irradiation with ionizing and/or actinic light and comprising at least one photoinitiator. The initiator is carried out. The method according to claim 92, wherein the radiation comprises light having a wavelength of 200 to 500 nm and the initiator is selected from the group consisting of an aromatic α-hydroxy ketone, an alkoxy benzoin, acetophenone, Ethyl phosphine oxide, a mixture of a third amine and a second, -83 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm) B8 C8 D8 1311580, the scope of patent application and its mixture In the group consisting of. 94. The method of claim 92, wherein the initiator is selected from the group consisting of 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-indolyl-1-phenyl-propan-1-one, and bis (2) ,6-dimethoxybenzylidene)_2,4- 4-dimethylpentylphosphine oxide, bis(2,4,6-trimercaptobenzylidene l-phenylphosphine oxide, 2,4 ,6-trimethylbenzyldiphenylphosphine oxide and 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, benzoin methyl ester, camphorquinone and ethyl 4_(N,N_dioxin The method of claim 9, wherein the initiator is present in the reaction in an amount effective to initiate polymerization of the reaction mixture. 96. The method of claim 9 wherein the initiator is present in the reaction mixture in an amount of from 1 to 2 weight percent based on the reactive component. The method of item 92, wherein the curing is carried out by visible light irradiation. The Intellectual Property Department of the Ministry of Economic Affairs and the Consumer Cooperatives print 98. According to the scope of the patent application No. 9 The method wherein the initiator comprises 1-hydroxycyclohexyl benzophenone, bis(2,6-dimethoxyphenylphenyl)-2,4-4-dimethylpentyl phosphine oxide, and mixtures thereof. According to the method of claim 98, wherein the initiator comprises bis(2,6-dimethoxyphenylhydrazinyl)-2, cardiotrimethylpentylphosphine oxide. According to the scope of the patent application 帛99 The method, wherein the -84- 1311580 B8 C8 ___D8____, the sizing of the sizing component comprises at least one uv absorbing compound. 101. The method according to claim 97, wherein the curing step is between 0.1 And the curing strength between 6 mW / cm ^ 2. 1 〇 2 · according to the method of claim 97, wherein the curing step is between 0.2 mW / cm ^ 2 to 3 mW / cm ^ 2 The method of claim 101, wherein the curing step further comprises a curing time of at least 1 minute. 104. The method according to claim 1, wherein the curing Step further includes The curing time between i and 60 minutes. The method of claim 101, wherein the curing step further comprises a curing time between 丨 and 30 minutes. 106. According to the scope of the patent application. The method of claim 3, wherein the curing step is carried out at a temperature greater than 25. (: at a temperature of 107. 107. According to the method of claim 103, wherein the curing economics department intellectual property bureau employee consumption cooperative printing step is It is carried out at a temperature between 25 ° C and 70X:. 108. The method of claim 103, wherein the curing step is between 40. (: and 7 (the temperature between TC. 109. According to the method of claim 75, where the anti-waste, -85- this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public)麓) — [311580 Patent Application A8 B8 C8 D8 The mixture is cured in a mold and the method is advanced::: The step of removing the device from the mold by using the device. ~ no. According to the application of the patent (4) (10) The method further comprises at least: a medium-reacting reactant. 7 liters of low-knife summer hydrophilic polymerization hi. According to the method of the patent scope 帛110, the amount of hydrophilic polymer has less than 4 〇, _: : The average molecular weight of the target. The number of the current number 112. According to the method of the patent (4) 11G of the towel, (1) The amount of the hydrophilic polymer has an average molecular weight of less than 20, the color of the binocular of the coffee. The number of buckets (1). The method of claim 110, wherein the low-partition hydrophilic polymer is selected from the group consisting of water-soluble polyamines, amides, and polyethylene glycols, and mixtures thereof. A method of applying for a patent scope of 110, wherein The low-part f-weight hydrophilic polymer is selected from the group consisting of poly-vinylpyrrolidone, and ethyl alcohol, polyethyl 2-carbazole, and mixtures thereof. 'Ministry of Commerce, Intellectual Property Office, Staff Consumption Cooperative The method of claim 11, wherein the low molecular weight 1E hydrophilic polymer is present in an amount of up to 20% by weight based on the reaction mixture. 116. According to the scope of claim 11 The method wherein the low molecular weight hydrophilic polymer is present in an amount of 5 and 20% by weight based on the reaction mixture. The paper scale is suitable for the standard (CNS) A4 specification (10) 297 297 public Chu 1311580, Patent Application No. B8 C8 D8 i _ The method according to claim 109, wherein the borax is carried out using an aqueous solution. 118. The method of claim 1, wherein the aqueous solution further comprises at least one The method of claim 118, wherein the surfactant comprises at least one nonionic surfactant. The method of claim lls, wherein the surfactant comprises TWEEN® or DOE 120. 121. The method according to claim 118, wherein the surfactant is present in an amount up to 10,000 ppm. The method of claim 118, wherein the surface/tongue agent is present in an amount between 500 ppm and 1500 ppm. 123. The method of claim 118, wherein the surfactant is There is a presence between 1〇〇 and 12〇〇ppm. The method of claim 1, wherein the aqueous solution comprises at least one organic solvent. Person ^ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing clothing 125. According to the method of claim 1, paragraph 1, which is between room temperature and 1 〇〇. (: between the temperatures I, 126_ according to the method of claim 1, paragraph 1, wherein the I connection is carried out at a temperature between 70t and 95 ° C. 4 to drill 127. According to the scope of patent application The method of item 1〇9, the connection is carried out by stirring. °Hai-dry-87 This paper scale is applicable to China National Standard (CNS) A4 specification (210 297 mm) '—^ 1311580 VI. Patent application scope A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed 128·=Please refer to the method of Section 109 of the patent, wherein the disturbance contains sound waves. 129. ^ A method of forming a wettable biomedical device, comprising two: (a The combination comprises a high molecular weight hydrophilic polymer and a reaction comprising a (four) functionalized calcined monomer and (b) at a small gel time or a curing step (a) The product is formed into a wettable biomedical device. 130. The device is an ophthalmic lens according to the method of claim 129 of the patent application. 131. The method according to claim 129, wherein the device is Contact lenses. 132. According to the application The method of claim 131, wherein the wetness comprises a dynamic contact angle of 70 or less. 133. The method according to claim 131, wherein the humidity comprises a 00 or lower advance dynamic 134. The method of claim 131, wherein the humidity comprises a tear film collapse time of at least 7 seconds. 135. The method of claim 13 wherein the counter component further comprises at least An initiator according to the method of claim 135, wherein the solid is carried out by irradiation and the concentration of the initiator and the curing time of the gel. 137. According to the method of claim 135, wherein the initiator is used in an amount of up to 1% based on all reactive components - 88 sheets of paper are applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) Αδ Β8 C8 D8 申請專利範圍 [311580 存在。 138.根據申請專利範圚篦1 μ τΕ 輪… 項之方法,其中該引發 六、&amp; ;所有反應性成分為準低於〇_5%之用 量存在。 &lt;用 139_:據申請專利範圍f 136項之方法,其中該固化 ’、猎低於5鼋瓦/平方公分之強度照射下 行。 M〇t據中請專利範圍帛⑼項之方法,其中該凝膠 時間為至少30秒。 14=據中請專利範圍帛129項之方法,其中該凝膠 時間為至少3 5秒。 142、種眼用裝置,其包含至少一種含羥基-官能化矽 乳貌之單體和-足以提供該裝置在無表面處理下 具有低於80。之前進動態接觸角用量之高分子量 親水性聚合物。 經濟部智慧財產局員工消費合作社印製 143·,種眼用裝置,其包含至少一種含羥基-官能化矽 氧燒之單體和一足以提供該裝置在無表面處理下 具有前進動態接觸角至少較之不含該親水性聚合 物之眼用裝置之前進動態接觸角低至少10%之用 置之高分子量親水性聚合物。 144_ 一種眼用裝置,其包含至少一種含羥基-官能化矽 氧烧之單體和一足以提供該裝置在無表面處理 下’於一天之配戴至少7秒之後’具有淚膜崩潰 日τ間用量之南分子量親水性聚合物。 -89- 木纸張尺度適财關家標準(CNS)A4規格(21G x 297公 A8 B8 C8 D8 [311580 六、申請專利範圍 145.根據中請專利範圍帛142項之眼用裝置,其中該 裝置為矽氧烷水凝隱形眼鏡。 Λ Η6.根據中請專利範圍帛ΐ42項之眼用裝置,其中含 煙基-官能化石夕氧貌之單體係以相容化有效量: 在。 147. 根據中請專利範圍帛142項之眼用装置,其中該 含羥基-官能化矽氧烷之單體係以介於5%至_ %之用量存在。 148. 根據中請專利範圍帛142項之眼用裝置,其包含 1至15%之高分子量親水性聚合物。 Η9·根據中請專利範圍第142項之眼用裝置,另包含 〇至80重之至少一種含其他石夕氧烧之單體。 150·根據申請專利範圍第142項之眼用裝置,另包含 〇至70重量%之至少一種親水性單體。 151. 根據申請專利範圍第142項之眼用裝置,其包含 經濟部智慧財產局員工消費合作社印製 1 ^至15%之高分子量親水性聚合物;5至90重 里%之含羥基-官能化矽氧烷之單體;〇至80重 里%之含其他矽氧烷之單體及〇至7〇重量%之 親水性單體。 152. 根據申請專利範圍第丨42項之眼用裝置,另包含 低於100之霧度值。 153. 根據申請專利範圍第丨42項之眼用裝置,另包含 低於50之霧度值。 154. 根據申請專利範圍第56項之矽氧烷水凝膠,其 -90- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇χ297公釐) 1311580 B8 C8 六、申請專利範圍 ~ &quot;一~' 〜 中該含羥基-官能化矽氧烷之單體包含2_丙歸 酸、2-甲基_,2_經基甲基小[(三 曱基曱矽烷基)氧基]二矽氧烷基]丙氧基]丙酯, «亥親水性聚合物包含聚乙烯吡咯啶酮;該含其他 矽氧烷之單體包含單甲基丙烯氧基丙基終端之 單'正•丁基終端之聚二甲基矽氧烷及該親水性單 體包含2-經基乙基甲基丙烯酸酯及N,N_二甲基 丙浠醯胺。 155·根據申請專利範圍第丨54項之矽氧烷水凝膠,其 包含28重量%之2-丙烯酸、2-曱基-、2-羥基-3_ [3-[1,3,3,3-四甲基_1_[(三甲基曱矽烷基)氧基]二 石夕氧烧基]丙氧基]丙酯、31重量%之單甲基丙稀 氧基丙基終端之單-正-丁基終端之聚二甲基矽氧 烷;24重量%之n,N-二曱基丙烯醯胺;6重量% 之2-羥基乙基甲基丙烯酸酯;ι.5重量%之四乙 二醇二甲基丙稀酸酯;7重量%之聚乙烯吡洛n定 酉同及至多達1重量%之光引發劑之反應產物。 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 156.根據申請專利範圍第丨54項之石夕氧烧水凝朦,其 包含30重量%之2-丙烯酸、2-甲基-、2-羥基-3-[3-[1,3,3,3-四甲基-1_[(三甲基甲矽烷基)氧基]二 矽氧烷基]丙氧基]丙酯、23重量%之單甲基丙烯 氧基丙基終端之單-正-丁基終端之聚二曱基矽氧 烷;31重量%之N,N-二甲基丙烯醯胺;7.5重量 %之2-羥基乙基甲基丙烯酸酯;〇·75重量%之四 -91 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X297公髮) 1311580 B8 __JD8____ 六、申請專利範圍 —~ 乙二酵二甲基丙烯酸酯;6重量%之聚乙烯吡咯 啶酮及至多達1重量%之光引發劑。 157. 根據申請專利範圍第154項之矽氧烷水凝膠,包 含30重量%之2-丙烯酸、2-曱基…2_羥基_3_[3_ [1,3,3,3-四甲基-1-[(三甲基曱矽烷基)氧基]二矽氧 烷基]丙氧基]丙酯、18重量%之單甲基丙烯氧基 丙基終端之單-正-丁基終端之聚二甲基石夕氧燒; 31重量%之N,N-二甲基丙烯醯胺;9重量%之 2-羥基乙基甲基丙烯酸酯;〇 8%重量之四乙二醇 二甲基丙烯酸酯;6%重量之聚乙烯吡咯啶_及 低於1重量%之光引發劑。 158. —種改良由一種反應混合物所形成之眼用裝置之 濕潤度的方法,其包含混合至少一種高分子量親 水性聚合物及有效量之至少一種含羥基_官能化 矽氧烷單體至該反應混合物中。 159. 根據申請專利範圍第1S8項之方法,其中該相容 化單體具有大於0.5之相容性指數。 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 16〇_根據申請專利範圍第158項之方法,其中該相容 化單體具有大於1之相容性指數。 161.根據申請專利範圍第158項之方法,其中該相容 化單體具有低於15:1之Si對0H比例。 16Z根據申請專利範圍第158項之方法,其中該相容 化單體具有介於1:1至1〇:1之Si對〇H比例。 | 163.根據申請專利範圍第Π1項之方法,其中該濕潤 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公爱) 經濟部智慧財產局員工消費合作社印製 Αδ 1311580 cs _D8_ 六、申請專利範圍 劑包含一 80°或更低之接觸角。 3 9 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Patent application scope [311580 exists. 138. The method of claim 1, wherein the initiating agent is present in a quantity of less than 5% 5%. &lt;Use 139_: According to the method of claim 136, wherein the curing is performed under the intensity of less than 5 watts/cm 2 . The method of claim 帛 (9), wherein the gel time is at least 30 seconds. 14 = The method of claim 129, wherein the gel time is at least 35 seconds. 142. An ophthalmic device comprising at least one monomer having a hydroxyl-functionalized hydrazine emulsion and - sufficient to provide the device having less than 80 without surface treatment. A high molecular weight hydrophilic polymer that has previously been used in dynamic contact angles. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, 143. An ophthalmic device comprising at least one hydroxyl-functionalized xenon-burning monomer and one sufficient to provide the device with at least a forward dynamic contact angle without surface treatment. A high molecular weight hydrophilic polymer disposed at least 10% lower than the dynamic contact angle prior to the ophthalmic device without the hydrophilic polymer. 144_ An ophthalmic device comprising at least one hydroxyl-functionalized xenon-burning monomer and one sufficient to provide the device with a tear film collapse day after being worn for at least 7 seconds in a day without surface treatment Amount of south molecular weight hydrophilic polymer. -89- Wood paper scale suitable for financial standards (CNS) A4 specifications (21G x 297 A8 B8 C8 D8 [311580 VI. Patent application scope 145. According to the patent application scope 142 items of ophthalmic devices, which The device is a decane hydrogel contact lens. Λ Η 6. The ophthalmic device according to the scope of the patent application 帛ΐ42, wherein the single system containing the ketone-functional fossil oxime is used to compatibilize the effective amount: 147 The ophthalmic device according to the scope of the patent application 142, wherein the single system containing hydroxyl-functionalized alkane is present in an amount of from 5% to _%. 148. According to the scope of the patent application 帛 142 An ophthalmic device comprising 1 to 15% of a high molecular weight hydrophilic polymer. Η9. According to the ophthalmic device of claim 142, further comprising at least one of 〇 to 80 重量150. The ophthalmic device according to claim 142, further comprising 〇 to 70% by weight of at least one hydrophilic monomer. 151. The ophthalmic device according to claim 142 of the patent application, comprising an economic department Intellectual Property Bureau employee consumption cooperative printed 1 ^ to 15% a hydrophilic polymer; 5 to 90% by weight of a monomer containing a hydroxyl group-functionalized alkane; 〇 to 80% by weight of a monomer containing another oxime and a hydrophilicity of 〇 to 7% by weight 152. The ophthalmic device according to item 42 of the patent application, further comprising a haze value below 100. 153. The ophthalmic device according to item 42 of the patent application, further comprising a haze of less than 50 154. According to the 56th item of the patent application, the -90- paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇χ297 mm) 1311580 B8 C8 VI. ~ &quot;一~'~ The monomer containing hydroxyl-functionalized alkoxysilane contains 2-propanoid acid, 2-methyl-, 2-di-methyl-methyl [[tridecylfluorenyl)oxy (dioxaoxyalkyl)propoxy]propyl ester, «Hei hydrophilic polymer comprises polyvinylpyrrolidone; the monomer containing other alkoxysilanes comprises a single monomethacryloxypropyl terminal' a polybutyl methoxide of the n-butyl terminal and the hydrophilic monomer comprising 2-carbylethyl methacrylate and N,N-dimethylpropane 155. The alkane hydrogel according to claim 54 of the patent application, which comprises 28% by weight of 2-acrylic acid, 2-mercapto-, 2-hydroxy-3_[3-[1,3,3 , 3-tetramethyl_1_[(trimethyldecyl)oxy] diazepine]propoxy]propyl ester, 31% by weight of monomethyl propyloxypropyl terminal - n-butyl terminal polydimethyl methoxy oxane; 24% by weight of n, N-dimercapto acrylamide; 6% by weight of 2-hydroxyethyl methacrylate; ι. 5 wt% Tetraethylene glycol dimethyl acrylate; 7% by weight of polyvinylpyrrolidine and up to 1% by weight of the photoinitiator reaction product. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consortium 156. According to the scope of application No. 54 of the patent application, it consists of 30% by weight of 2-acrylic acid, 2-methyl-, 2-hydroxy-3. -[3-[1,3,3,3-Tetramethyl-1_[(trimethylmethylalkyl)oxy]dioxaxyalkyl]propoxy]propyl ester, 23% by weight of monomethyl a mono-n-butyl terminated polydioxanoxane terminated by a propyleneoxypropyl group; 31% by weight of N,N-dimethylpropenylamine; 7.5% by weight of 2-hydroxyethylmethacrylic acid Ester; 〇·75% by weight of 4-91 - This paper scale applies to China National Standard (CNS) A4 specification (210 X297 public hair) 1311580 B8 __JD8____ VI. Patent application scope - ~ Ethylene dimethacrylate; % by weight of polyvinylpyrrolidone and up to 1% by weight of photoinitiator. 157. A hydroxane hydrogel according to claim 154 of the patent application, comprising 30% by weight of 2-acrylic acid, 2-mercapto... 2_hydroxy_3_[3_[1,3,3,3-tetramethyl 1-[(Trimethyldecyl)oxy]dioxaxyalkyl]propoxy]propyl ester, 18% by weight of monomethacryloxypropyl terminated mono-n-butyl terminal Polydimethyl oxazepine; 31% by weight of N,N-dimethyl acrylamide; 9% by weight of 2-hydroxyethyl methacrylate; 8% by weight of tetraethylene glycol dimethyl Acrylate; 6% by weight of polyvinylpyrrolidine _ and less than 1% by weight of photoinitiator. 158. A method of improving the wettability of an ophthalmic device formed from a reaction mixture comprising mixing at least one high molecular weight hydrophilic polymer and an effective amount of at least one hydroxyl-containing functionalized oxoxane monomer to the In the reaction mixture. 159. The method of claim 1 , wherein the compatibilizing monomer has a compatibility index greater than 0.5. Printed by the Ministry of Economic Affairs, the Ministry of Finance, and the Consumers' Union. 16 _ According to the method of claim 158, wherein the compatibilizing monomer has a compatibility index greater than 1. 161. The method of claim 158, wherein the compatibilizing monomer has a Si to 0H ratio of less than 15:1. 16Z. The method according to claim 158, wherein the compatibilizing monomer has a Si to 〇H ratio of from 1:1 to 1〇:1. 163. According to the method of claim 1, the wet paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 public interest) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Α δ 1311580 cs _D8_ VI. Application The patented range contains a contact angle of 80° or less. 3 9 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)
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