1295387 九、發明說明: 【發明所屬之技術領域】 本發明有關一種可用於製造染色隱形眼鏡之方 法。本發明尤其提供一種藉著將用以製造鏡片之模具 加熱,而幫助單體擴散至著色劑内之方法。 【先前技術】 使用染色隱形眼鏡以改變虹膜之自然顏色的方式 係眾所周知。用以製造染色隱形眼鏡之著色劑通常包 含鍵結性聚合物及顏料。製造染色隱形眼鏡之一方法 (例如代理人文件編號VTN-571,美國申請案序號 10/027,579所描述及申請,以提及方式併入本文)中, 著色劑係施加於未固化之鏡片材料中,隨之進行固 化,使著色劑自模具表面輪送至鏡片材料。此種製邊 =鏡之^法的缺點在於該鏡片材料可能無法 化之刚適當地擴散至該著色劑内。導致在固化鎖 片加工的水合步驟期 4間,有殘留、未鍵結之聚合物闹 者於鏡片表面。 局了克服此項缺莖μ 可進行較長之時間。、;1試增長固化時間’使 鏡片模具之變形,導W而,此種方法之問題在於 種不會對於形成之铲欵邊緣缺陷增加。因此,需 的方法。 、兄片產生負面影響而可改善擔 【發明内容】 本發明提供〜# 万法、及該方法所製造之隱形眼 ㈣387 表面粗S鏡=表面上殘留、未鍵結之聚合物及鏡片 隱形眼具體實例中’本發明提供一種製造 之模制表 / ,其基本上包括下列步驟:a)於模具 劑;b)蔣:的至少一部分上施加染色有效量之著色 迅速力;量,鏡片材料分配至該模具内;C) 以上;〜、至該者色劑之玻璃態化溫度或該溫度 度或更古ί使該模具溫度保持於該著色劑玻璃態化溫 ί e)隨使該鏡片材料擴散至該著色劑内; 内之於H J k ;形成染色隱形眼鏡之條件下,使模具 種夢匕。另一具體實例中,本發明提供-喱猎由该方法製得之鏡片。 【實施方式】 性光方f:第-步驟中’著色劑係施加於熱塑 表面上,該光學模具係自任何適當 脂不限於)聚丙婦樹脂、聚苯乙稀樹 咅扑用^r,與其组合物。本發明中,,,模製表面” -才曰用於形成鏡片表面之模具表面。 模製=效量,劑施加於該模具之所有或部分 、兄片覆现使用者虹膜之部分的表面上。,,旦” 二色劑係為足以使製得之鏡片具有所需色度之>量里。 ^吊,母片鏡片使關㈠亳克絲4.0毫克之著色 方便方式進行。該 軋印法進行為佳。 A稽田 1295387 將鏡片形成量之鏡片材料分配於該模具内。”鏡片 形成量,,係意指足以製得具有所需尺寸及厚度之鏡片 的量。一般,使用約10至約75(以約50至爾75毫克 為佳)鏡片材料。”鏡片材料,,係意指在固化時形成鏡片 之早體或早體專。該鏡片材料可包括各種添加劑中之 任一種’包括(但不限於)起始劑、紫外線吸收劑、及 其類者,及其組合物。 該模具隨之迅速加熱,幫助鏡片材料擴散至該著 色劑中。本發明發現藉著迅速將模具加熱至該著色劑 之玻璃態化溫度(“Tg”)或更高溫度,可增加該鏡片單 體混合物擴散至該著色劑之程度。然而,加熱之迅速 程度需不致導致該鏡片模具變形,該變形會於固化鏡 片中導致邊緣缺陷。該模具以於約28秒内自約室溫加 熱至Tg為佳,於約1〇秒内為佳,而於約4秒内最佳。 該溫度隨之於鏡片材料開始固化之前保持一段時間 使^擴散進行至所需之程度。該擴散以進行歷經足 使著色劑潤脹成為其乾燥厚度之約丨至約4倍的時 為佳。模具保持於Tg或更高溫度的㈣係視該著色; 之組成及所選擇之鏡片材料而定。該時間以由約45 約75秒為佳,約65至 · 秒最佳。 5至、々75衫L 65至約: 熱該模具可藉任何簡便 較佳方法中’使用多個具有約丨至约::二 ^95387 具燈’ Μ速加熱該模具。該燈可I置於該模 桓的特定點上。在進行擴散時保持該 度模具溫度保持於該著色劑Tg或更高溫 尸猎〗何簡便加熱裝置進行。較佳具體實例中, :具ΐ度係藉由加熱環繞該模具之空氣而保持。因 Θ述具體g例中’在先迅速加熱至該著色劑Tg :炎’該模具移動通經該隧道中空氣已加熱(例如藉加 热裔)的部分。 在鏡片材料擴散至該著色劑内之後,該鏡片材料 者色劑係於適於形成染色鏡片的條件下進行固化。 用於固化之精確條件係依著色劑之成份及所選擇之鏡 2材料而定,且係熟習此項技術者可決定。較佳具體 貝例中,於室内空氣下且於約55至約70°c之高溫下 使用可見光固化。此具體實例中,固化係花費約乃至 約150秒。一旦完全固化,則該鏡片自模具脫離,且 可於經緩衝之鹽水溶液中達到平衡。 所使用之著色劑-般係包含一或多種顏料、 多種溶劑及-鍵結性聚合物。於本發明—較佳具體杏 例中,使用可與該鏡片材料形成互相貫穿之聚合物 絡的鍵結性聚合物。因此,於另—具體實例中私 明提供-種製造隱形眼鏡之方法,其基本上包括 : 驟· a)於模具之模製表面的至少—部分上施加 ^ 效量之著色劑,該著色劑基本上係包含或由一或 顏料、-❹種溶劑及鍵結性聚合物所組成 片形成量之鏡片材料分配至該模具内;c)迅速加熱二 1295387 至該著色劑之玻璃態化溫度或該溫度以上;d)在 保才寸^亥溫度下,使該鏡片材料擴散至該著色劑内; 及e)lk之於適於形成染色隱形眼鏡之條件下,使模具 =之鏡片材料固化,其中該鍵結性聚合物及該鏡片材 料形成一相互貫穿之聚合物網絡。 μ、本备明中,相互貫穿之聚合物網絡,,或”IpN,,係定 義為兩種或多種個別聚合物之組合物,其中一聚合物 =於另者存在下合成及/或交聯。因此,該網絡結構 產生邛刀耘度之相互貫穿。一般用以形成ιρΝ之個 別聚合物料網絡形式。其中腦—尤其是半 侧-係包含-或多種經交聯之聚合物,及一或多種 貝貝上未父聯之聚合物,如Sperling,L H於幻^瓜仲吒1295387 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method that can be used to manufacture dyed contact lenses. In particular, the present invention provides a method of assisting in the diffusion of monomer into a colorant by heating the mold used to make the lens. [Prior Art] The manner in which dyed contact lenses are used to change the natural color of the iris is well known. The colorant used to make the dyed contact lens typically contains a bonding polymer and a pigment. A method of making a dyed contact lens, such as the agent's document number VTN-571, described in U.S. Patent Application Serial No. 10/027,579, the entire disclosure of Curing is then carried out to transfer the colorant from the mold surface to the lens material. A disadvantage of such a method of forming a mirror is that the lens material may not be properly diffused into the colorant. This results in residual, unbonded polymer smearing on the lens surface during the hydration step of the curing lock process. Overcoming this lack of stem μ can be carried out for a longer period of time. The problem of the method is that the deformation of the lens mold is deformed, and the problem of this method is that the defect does not increase for the edge of the formed shovel. Therefore, the method needed. The invention provides a negative effect and can be improved. [Invention] The present invention provides a ~# 10,000 method, and a contact lens manufactured by the method (4) 387 surface rough S mirror = residual, unbonded polymer on the surface and lens contact lens In a specific example, the present invention provides a molded watch for manufacturing / which basically comprises the following steps: a) applying a dyeing effective amount of coloring force to at least a portion of the mold agent; b) Jiang: amount, lens material distribution To the mold; C) above; ~, to the glass transition temperature of the toner or the temperature or the temperature to keep the mold temperature at the glassing temperature of the colorant ί e) with the lens material Diffusion into the colorant; inside the HJ k; under the conditions of forming the dyed contact lens, the mold is a nightmare. In another embodiment, the invention provides a gel that is made by the method. [Embodiment] Sexual light side f: In the first step, the coloring agent is applied to a thermoplastic surface, which is not limited to any suitable fat, and the polyacrylonitrile resin and the polystyrene tree are used. And its composition. In the present invention, the molding surface is used to form the surface of the mold on the surface of the lens. Molding = effect, the agent is applied to all or part of the mold, and the surface of the part of the iris that the user iris is exposed on the surface of the user's iris The dichroic dye is in an amount sufficient to provide the desired color of the lens produced. ^ Hang, the master lens to close (a) 亳 丝 4.0 mg of coloring in a convenient way. This stamping method is preferred. A. The field 1295387 distributes the lens forming amount of lens material into the mold. "Lens formation amount," means an amount sufficient to produce a lens having a desired size and thickness. Typically, from about 10 to about 75 (preferably from about 50 to 75 mg) of lens material is used." Lens material, By means of an early or early body that forms a lens upon curing. The lens material can include any of a variety of additives including, but not limited to, initiators, UV absorbers, and the like, and combinations thereof. The mold is then heated rapidly to help the lens material diffuse into the colorant. The present inventors have discovered that by rapidly heating the mold to the glass transition temperature ("Tg") or higher of the colorant, the extent to which the lens monomer mixture diffuses to the colorant can be increased. However, the degree of rapid heating does not require deformation of the lens mold which can cause edge defects in the cured lens. Preferably, the mold is heated from about room temperature to about Tg in about 28 seconds, preferably in about 1 second, and most preferably in about 4 seconds. This temperature is then maintained for a period of time before the lens material begins to solidify to allow diffusion to proceed to the desired extent. The diffusion is preferably carried out when the colorant is allowed to swell to about 4 times its dry thickness. The mold maintained at Tg or higher (iv) depends on the coloration; the composition and the selected lens material. This time is preferably from about 45 to about 75 seconds, and most preferably from about 65 to about sec. 5 to, 々75 shirts L 65 to about: hot the mold can be heated in any convenient and convenient manner by using a plurality of lamps having a temperature of about : to about :: 2 ^ 95387 lamps. The lamp can be placed at a specific point of the die. The mold temperature is maintained at the Tg or higher temperature of the colorant during the diffusion. In a preferred embodiment, the degree of twist is maintained by heating the air surrounding the mold. The mold moves through the portion of the tunnel where the air has been heated (e.g., heated) by the rapid heating to the colorant Tg: inflammation in the specific g example. After the lens material has diffused into the colorant, the lens material lacquer is cured under conditions suitable for forming a dyed lens. The precise conditions for curing will depend on the composition of the colorant and the material selected for the lens 2 and will be determined by those skilled in the art. In a preferred embodiment, visible light curing is carried out under room air at a high temperature of from about 55 to about 70 °C. In this particular example, the cure system takes about or even about 150 seconds. Once fully cured, the lens is detached from the mold and is equilibrated in a buffered saline solution. The coloring agent used generally comprises one or more pigments, a plurality of solvents, and a bonding polymer. In the present invention, preferably a specific apricot, a bonding polymer which forms an interpenetrating polymer with the lens material is used. Thus, in another embodiment, a method of making a contact lens is provided, which basically comprises: a) applying an effective amount of a colorant to at least a portion of a molding surface of the mold, the colorant Basically comprising or consisting of a sheet material comprising a pigment, a solvent and a bonding polymer, into the mold; c) rapidly heating two 1295387 to the glass transition temperature of the colorant or Above the temperature; d) diffusing the lens material into the colorant at a temperature of 2,000 ° C; and e) lk to cure the lens material under conditions suitable for forming a dyed contact lens Wherein the bonding polymer and the lens material form a network of interpenetrating polymers. μ, in the present specification, interpenetrating polymer networks, or "IpN," is defined as a combination of two or more individual polymers, one of which = synthesized and/or crosslinked in the presence of the other Therefore, the network structure produces a cross-cutting of the knives. It is generally used to form a network of individual polymer materials, wherein the brain, especially the half-side, contains - or a plurality of cross-linked polymers, and one or A variety of polymers on the babe that are not parented, such as Sperling, LH in the illusion
Sperling^ Utracki Interpenetrating Polymer ^猜_994)第 3 至 6 頁的”lnterpenetrating P〇ly贿Sperling^ Utracki Interpenetrating Polymer ^ guess _994) "Lerterpenetrating P〇ly bribes on pages 3 to 6"
Networks·· An 〇verview,,中所揭示。本發明中,所使用 之相互貫穿?A合物網絡類型係為半侧。於—具 例中,該半_IPN係使用經㈣之則材料及實質上二 性聚合物形成。本發明中,實質未交聯係 思私“未父聯材料在與該鏡諸 ===或雜質)會產生有助於形成有° 1295387 該鍵結性聚合物具有與該鏡片材料相同之溶解度參 數。此等鍵結性聚合物可含有官能基,使該鍵結性聚 合物之聚合物及共聚物可彼此相互作用。該官能基需 使聚合物或共聚物之基團彼此相互作用,以增加相互 作用之密度,而幫助抑制該顏料粒子的移動性及/或截 留該顏料粒子。該官能基之間的相互作用可為極性、 分散性、或電荷轉移複合性。該官能基可位於該聚合 物或共聚物主鏈上或該主鏈之側鏈上。 例如,形成具有正電荷之聚合物的單體或單體混 合物可與形成具有負電荷之聚合物的單體或單體等結 合使用,以形成鍵結性聚合物。特定實例中,可使用 曱基丙烯酸(“MAA”)及甲基丙烯酸2-羥基乙酯 (“HEMA”)以提供MAA/HEMA共聚物,其隨之與 HEMA/3-(N,N-二甲基)丙基丙烯醯胺共聚物混合,以 形成鍵結性聚合物。 另一實例中,該鍵結性聚合物可包含經疏水性修 飾之單體,包括(但不限於)具有下式之醯胺及酯: ch3(ch2)x-l - cochr=ch2 其中L可為-NH或氧,X可為由2至24之整數, R可為q至06烷基或氳,以曱基或氫為佳。該醯胺及 酯之實例係包括(不限於)月桂基曱基丙烯醯胺及曱基 丙烯酸己酯。另一實例中,脂族鏈延伸碳酸酯與脲之 聚合物可用以形成該鍵結性聚合物。 較佳鍵結性聚合物係為HEMA、MAA、與甲基丙 烯酸月桂酯(“LMA”)之任意嵌段共聚物、HEMA與 1295387 ΜΑA或HEMA與LMA之任意嵌段共聚物、或HEMA 之均聚物。此等具體實例中,各成份以該鍵性聚合物 總重計之重量百分比係約93至約1〇〇重量百分比之 HEMA,約0至約2重量百分比之MAA,及約〇至約 5重量百分比之LMA。 該鍵結性聚合物之分子量需使得其可稍微溶解於 該鏡片材料中,而該鏡片材料可擴散於其中。然而, 該鍵結性聚合物之分子量同時不能高至影響到所印刷 之衫像的xm貝。該鍵結性聚合物之分子量以約7,〇⑻ 至約100,000 Mpeak(對應於SEc分析中最高峰的分子 量,=(MnxMw)1/2)為佳,約7,_至約4〇,_更佳,而 約17,000至約35,000最佳。 本發明中,該分子量係使用凝膠滲透層析以9〇。 光散射及折射率偵測器測定。使用兩管柱PW4〇〇〇及 PW2500 ,調整至50 mM氯化鈉之75/25 wt/wt甲醇- 水溶離物,及明確界定分子量由325,〇〇〇至194之聚 乙一醇與聚氧化乙烯分子的混合物。 熟習此項技術者可確認,藉著在製造鍵結性聚合 物時使用鏈轉移劑、藉由使用大量起始劑、藉由使用 活性聚合、藉由選擇適當之單體及起始劑濃度、藉由 選擇溶劑之用量及種類、或其組合,可得到所需^鍵 結性聚合物分子量。較佳係鏈轉移劑與起始劑結合使 用,更佳係與起始劑及一或多種溶劑結合使用,以達 到所需之分子量。或少量極高分子量鍵結性聚合物可 與大量溶劑結合使用,以保持該鍵結性聚合物所需之 11 1295387 4,〇〇〇 至 黏度。該鍵結性聚合物之黏度在2;rc下以約 約15,000厘泊為佳。 可用以形成該鍵結性聚合物的鍵轉移劑 約O.CH之鏈轉移常數值,以大於約7為佳/而大於約 25,000更佳。適當之該鏈轉移劑係已知,且包括(不限 於)通式R-SH之脂族硫醇(其中R係為仏至 基、ΐ基、環脂族基或CH3(CH2Vsh, ^二 Π苯、正丁基氣、正丁基漠,基乙醇 十一基石瓜醉、2-氯丁烷、丙酮、乙酸、氯仿 三乙胺、二-正丁基硫及二_正丁基_ 土胺 四漠化碳、及其類者、㈣且合四,化碳及 一長、、五口物。通常,使用以聚 ό物調配物總重計約〇至約7重量百分比。使用十二 烧硫醇、魏硫醇、钱硫醇或其組合 轉移 劑為佳。 可使用任何所需之起始劑,包括(不限於)紫外線、 可見光、熱起始劑及其類者,與其組合物。以使用熱 起始劑$佳,2,2_偶氮基雙異丁腈及2,2-偶氮基雙2-甲基丁腈更佳。起始劑之用量以該調配物之總重計係 約0·1至約5重量百分比。2,2-偶氮基雙2-甲基丁腈以 與十二烷硫醇一起使用為佳。 ^本發明鍵結性聚合物可藉任何簡便聚合方法製 :,包括(不限於)自由基鏈聚合、逐步聚合、乳化聚 ^、離子鏈聚合、開環、基目轉移聚合、原子轉移聚 f其類者。以使用熱-起始、自由基聚合為佳。進 行"亥本S之條件係屬熟習此項技術者之經驗範圍。 1295387 可用於製造該鍵結性聚合物的溶劑係為具有約 12(^及230°C之間的沸點之中沸點溶劑。所使用/之溶劑 的選擇係依欲製得之鍵結性聚合物的種類及其分子^ 而定。適當之溶劑係包括(不限於)雙丙g同醇、環刀己酮里 乳酸異丙酯、3-甲氧基卜丁醇、i乙氧基_2: 其類者。 可與該鍵結性聚合物一起使用之顏料有 形眼鏡之有機或無機顏料,或該顏料之組合物。該ς 3性可藉由改變所使用之顏料及不透明劑的濃^而 控制’較大量產生較大之*透明性。代表財機顏料 係包括(不限於)酜花青藍、酞花青綠、咔唑 春、 1;二ίΓ者’與其組合物。可使用之無機顏料的實 限於)氧化鐵黑、氧化鐵棕、氧化鐵黃、 、二氧化鈦、及其類者, =_之:卜,亦可使用可溶性及不可溶; =—顏:4、=一主之染料。可使用 二=:===子使, 覆可使用靜電、八體鍵結性聚合物中。該塗 表面。較佳信77政、或虱鍵力達成,以覆蓋該顏料 合物内。讀切力將顏料分散於該鍵結性聚 之混合者將姆合物及_分配於適當 之混合物二二 性聚合物中。G分鐘’而添加於該鍵結 叇>tb合物隨之可進料至高剪切磨機(諸如 13 1295387Networks·· An 〇verview,, as revealed in . In the present invention, the interpenetrating type used is a half side. In the example, the semi-IPN is formed using the material of (4) and a substantially amphoteric polymer. In the present invention, substantially unconnected thoughts "the unparent material is in contact with the mirror === or an impurity" may contribute to the formation of the temperature 1295387. The bonding polymer has the same solubility parameter as the lens material. The bonding polymer may contain a functional group such that the polymer and the copolymer of the bonding polymer may interact with each other. The functional group needs to cause groups of the polymer or copolymer to interact with each other to increase The density of the interaction helps to inhibit the mobility of the pigment particles and/or trap the pigment particles. The interaction between the functional groups can be polar, dispersive, or charge transfer complex. The functional group can be located in the polymerization. On the backbone of the article or copolymer or on the side chain of the backbone. For example, a monomer or monomer mixture forming a polymer having a positive charge can be used in combination with a monomer or monomer forming a polymer having a negative charge. To form a bonding polymer. In a specific example, methacrylic acid ("MAA") and 2-hydroxyethyl methacrylate ("HEMA") can be used to provide a MAA/HEMA copolymer, which is followed by HEMA. /3-(N,N- The dimethyl)propyl acrylamide copolymer is mixed to form a bonding polymer. In another example, the bonding polymer may comprise a hydrophobically modified monomer including, but not limited to, having a lower Amidoxime and ester: ch3(ch2)xl - cochr=ch2 wherein L can be -NH or oxygen, X can be an integer from 2 to 24, R can be q to 06 alkyl or hydrazine, thiol or Hydrogen is preferred. Examples of the guanamine and ester include, without limitation, lauryl decyl acrylamide and hexyl methacrylate. In another example, a polymer of an aliphatic chain extension carbonate and urea can be used to form The bonding polymer is preferably HEMA, MAA, any block copolymer with lauryl methacrylate ("LMA"), HEMA and 1295387 ΜΑA or any block of HEMA and LMA. a copolymer, or a HEMA homopolymer. In these embodiments, the weight percent of each component based on the total weight of the bond polymer is from about 93 to about 1 weight percent HEMA, from about 0 to about 2 weight percent. MAA, and about 5% by weight of LMA. The molecular weight of the bonding polymer needs to be Slightly dissolved in the lens material, and the lens material can diffuse therein. However, the molecular weight of the bonding polymer cannot be so high as to affect the xm shell of the printed shirt image. The molecular weight of the bonding polymer Preferably, from about 7, 〇(8) to about 100,000 Mpeak (corresponding to the molecular weight of the highest peak in the SEc analysis, = (MnxMw) 1/2), about 7, _ to about 4 Å, more preferably, and about 17,000 to about 35,000 is the best. In the present invention, the molecular weight is determined by gel permeation chromatography at 9 Å. Light scattering and refractive index detector. Using two columns of PW4 〇〇〇 and PW2500, adjusted to 50 mM sodium chloride. 75/25 wt/wt methanol-water dissolvate, and a mixture of polyethylene glycol and polyethylene oxide molecules with a molecular weight defined from 325, 〇〇〇 to 194. Those skilled in the art will recognize that by using a chain transfer agent in the manufacture of the bonding polymer, by using a large amount of the initiator, by using living polymerization, by selecting an appropriate monomer and initiator concentration, The molecular weight of the desired polymer can be obtained by selecting the amount and type of the solvent, or a combination thereof. Preferably, the tether transfer agent is used in combination with an initiator, more preferably in combination with an initiator and one or more solvents to achieve the desired molecular weight. Or a small amount of very high molecular weight bonding polymer can be used in combination with a large amount of solvent to maintain the desired viscosity of the bonding polymer to 11 1295387 4 . The bonding polymer preferably has a viscosity of about 15,000 centipoise at 2; rc. The chain transfer agent used to form the bond polymer may have a chain transfer constant value of about O.CH, preferably greater than about 7 or more preferably greater than about 25,000. Suitable chain transfer agents are known and include, without limitation, aliphatic thiols of the formula R-SH (wherein R is fluorenyl, fluorenyl, cycloaliphatic or CH3 (CH2Vsh, ^ Π) Benzene, n-butyl, n-butyl, ketone eleven sulphate, 2-chlorobutane, acetone, acetic acid, chloroform triethylamine, di-n-butyl sulphide and di-n-butyl _ tertamine Four desertified carbons, and the like, (iv) and four, carbonized and one long, five mouths. Usually, the total weight of the polybenzate is about 7 to about 7 weight percent. Preferably, a thiol, a thiol, a thiol, or a combination thereof is used as the transfer agent. Any desired starter may be used including, but not limited to, ultraviolet light, visible light, hot starters, and the like, and combinations thereof. It is more preferable to use a hot initiator, preferably 2,2-azobisisobutyronitrile and 2,2-azobis 2-methylbutyronitrile. The amount of the initiator is based on the total weight of the formulation. The ratio is from about 0.1 to about 5 weight percent. 2,2-azobis 2-methylbutyronitrile is preferably used together with dodecyl mercaptan. ^The bonding polymer of the present invention can be used simply Aggregation method: package (not limited to) radical chain polymerization, stepwise polymerization, emulsion polymerization, ionic chain polymerization, ring opening, group transfer polymerization, atom transfer polymerization, etc. It is preferred to use heat-initiation or radical polymerization. "Heeben S conditions are within the skill of those skilled in the art. 1295387 The solvent that can be used to make the bonding polymer is a boiling point solvent having a boiling point between about 12 (and 230 ° C). The choice of the solvent to be used depends on the type of the bonding polymer to be prepared and the molecular weight thereof. Suitable solvent systems include, without limitation, dipropyl g-alcohol, cyclohexanone isopropyl lactate Ester, 3-methoxybutanol, i-ethoxy-2: An organic or inorganic pigment of a pigmented spectacles which can be used together with the bonding polymer, or a composition of the pigment. ς 3 properties can be controlled by changing the concentration of the pigments and opacifiers used to produce a larger amount of transparency. The representative pigments include (not limited to) phthalocyanine blue, phthalocyanine green, 咔Zolconchun, 1; Γ Γ ' ' and its composition. The use of inorganic pigments In the iron oxide black, iron oxide brown, iron oxide yellow, titanium dioxide, and the like, =_: Bu, can also be used soluble and insoluble; = - color: 4, = a main dye. Can be used Two =: = = = sub-sense, the coating can be used in static, eight-body bonded polymer. The coated surface is preferably 77 or 虱 bond force to cover the pigment composition. Dispersing the pigment in the bonding mixture, the compound and _ are dispensed into a suitable mixture of the di-dimer polymer. G minutes 'added to the bonding 叇> tb compound can then be fed High shear mill (such as 13 1295387
Eiger磨機)中,以將該顏 視需要進行重複之礙磨,以\砂該鍵結性聚合物内。 磨係進行至該顏料大小係為^完全分散。通常,碾 可使用任何適當之市售裝置t〇.2至約3微米。艰磨 切或球磨裝置。 運仃,包括(不限於)高剪 除了該顏料及鍵結性臂人此 色劑係含有-或多種溶^^物之外’本發明較佳著 表面上。期望(較佳)該著^助古於將該著色劑塗覆於 表面張力。此表面張力可^;、有低於約27涵如之 表面(例如模具表面)/處理欲施加該著色劑之 已知之方法進行,諸如°表面處理可藉由技術界 佳)藉由選擇該著色,中限於)電漿及電暈處理。或(較 表面張力。 使用之溶劑’而達成所需之 因此,可用於本發^日μ 或降低著色劑之黏声5明著色劑中之溶劑係為可增力 當之溶劑係包括(不^且幫助控制表面張力之溶劑。 甲氧-2-丙醇、^乙&限於)環戊酮、4-甲基-2-戊酮、1 與其組合物。以使用乳丙醇、乳酸異丙酯及其類者, 較佳且濟每在^虱基—2 -丙醇及乳酸異丙酯為佳 ^ '只心中’本發明著色劑中使用至少二泡 不同溶劑。此等溶劑 考⑸γ便用至〆一彩 以製造鍵結性聚^則兩者(皆為中彿點溶劑)係月 結性聚合物提除U。雖此等溶劑可在形成之後㈣ 1丙醇及乳酸異丙留為佳。該兩溶劑以卜乙摩 溶劑(意指炼點介“為7土°視需要使用另一種低沸累 低該著色劑之點度。、及約12GC之間的溶劑)則 適虽之低沸點溶劑係包括(不P] 1295387 .丙醇、及其類者,與其 於)2-丙醇、1_曱氧_2_丙醇、 組合物。以使用1-丙醇為佳 /溶劑之明確用量係視數·數而定。例如 =鍵結性聚合物之溶劑量係視所需鍵結性聚合物之 结性聚合物中所使用之成份(諸如單體 二、來物)而疋。低沸點溶劑之用量係视該著色劑所带 =度及表面張力而定。此外,若著色劑欲施加於ς /、且與鏡片材料一起固化,則 及模具使用之材料及模具材料是否已進;= 濕性之表面處理而定。溶劑之明確用量的決二;2 此項技術者之經驗範圍内。通常,所使用溶& 之…重係約40至約75重量百分比。 —般熟習此項技術者可確知所使用之各顏料备 於所選擇之溶劑具有臨界顏料體積。該臨界顏料^ =任何已知方式測定,通常料以溶劑及該鍵結^ 承口物懸浮該顏料粒子之效率而計的體積,例如, Patton, Temple C., Paint Fl〇w and Pigment Dispersion 2d ed·,pp 126-300 (1993)所揭示。 , 除了溶劑之外,可(較佳)添加增塑劑於該著色 以減少於著色劑及料模具零件乾燥期間之龜聲厂辦 向使用該著色劑製得之影像的最終品質,且促進^ 片材料對該著色劑之擴散及該著色劑之潤脹性传 ==劑的種類及用量係視所使用之鍵結性聚合物 置於在使用之前皆處於儲存狀態 〃、上的者色诏而s,亦視所需之適用期安定性而 15 1295387 定。可使用之增塑劑f包括(不限於)甘油、丙二醇、 二(丙二醇)、二(丙一醇)、聚乙二醇2〇〇、4〇〇或6〇〇、 及其類者,與其組δ物。以使用甘油為佳。增塑劑用 量以著色劑重量計通常係〇至約10重量百分比。 該著色劑之不透明性可藉由改變顏料濃度及所使 用之顏料粒徑而控制。或,可使用不透明劑。適當之 不透明劑(諸如例如一氧化鈦或氧化鋅)係為市售品。 本發明車父佳著色劑混合物中,使用約0.2至約25 重量百分比之顏料,約30至約45重量百分比之鍵結 性聚合物,約40至約70重量百分比之溶劑,約〇至 約25重量百分比之一氣化鈦,及約0·2至約7重量百 分比之增塑劑。該重量百分比係以著色劑混合物之總 重計。 該鍵結性聚合物可充填以著色劑重量計約0.2至 約25重量百分比之有機顏料,及約〇·2至約50重量 百分比之無機顏料。然而,高顏料濃度可能產生極暗 之色調。因此,以使用約〇·2至約7重量百分比之有 機顏料及約0至約20重量百分比之無機顏料為佳。可 視所需之顏色、色澤及色調依比例使用顏料之組合物。 一般熟習此項技術者確知本發明著色劑組成物可 包含前文所述以外之添加劑。適當之添加劑係包括(不 =二)有助於流動及勻平之添加劑、用以防止發泡之添 合物。用以修飾流變性之添加劑、及其類者,與其組 本發明# 色劑在該材料固化時變成包埋於該鏡片 16 1295387 二料中。因此’依著色劑所施加於 色劑可包埋於較接近該鏡片 〜、表面’该者 依任何次序施加-或多層著色2 = 2外,可 該著色劑可同時使用透明如士^另—具體貫例中, 本發明方法中,可在施加著:劑二物層。例如,在 聚合物可與該著色劑層所使該透明鍵結性 相異。若該透明鍵結性聚合物異合物相同或 =r:=:;::== 製1_含有縣1基、或*者之單體 取石s有'谷劑之聚合物諸如妙氧烧、水凝膠、 及其組合物製得更佳。可用於形成本 轉= 由大分子單體、單體及其組合物 適起始劑之摻合物進行反應而製得。 :生單體製得之聚㈣水凝膠。該聚石夕酮大 貫^係包括(不限於)經侧向親水性基團甲基丙稀酸化 之承一曱基矽氧烷,如美國專利編號4,259,467, =2⑼,725及4,261,875所述;具有可聚合之官能基的 汆一曱基矽烷氧大分子單體,如美國專利編號 4,136,250; 4,153,641; 4,189,546; 4,182,822; 1295387 4,343,927; 4,254,248; 4,355,147; 4,276,402; 4,327,203; 4,341,889; 4,486,577; 4,605,712; 4,543,398; 4,661,575; 4,703,097; 4,837,289; 4,954,586; 4,954,587; 5,346,946; 5,358,995; 5,387,632; 5,451,617; 5,486,579; 5,962,548; 5,981,615; 5,981,675;及 6,039,913 所述;及其組合 物。其亦可使用下列單體製得:摻有親水性單體之聚 矽氧烷大分子單體,諸如美國專利編號5,010,141; 5,057,578; 5,314,960; 5,371,147 及 5,336,797 所述;或 包含聚二曱基矽氧烷嵌段及聚醚嵌段之大分子單體, 諸如美國專利編號4,871,785及5,034,461所述。所列 之所有專利皆以提及方式完全併入本文中。 適當之材料亦可自歐西波爾(oxyperm)及伊諾波爾 (ionoperm)成份之組合物製得,諸如描述於美國專利編 號 5,760,100; 5,776,999; 5,789,461; 5,807,944; 5,965,631及5,958,440。親水性單體可摻入該共聚物 中,包括曱基丙浠酸2-羥基乙酯(“HEMA”)、丙烯酸 2-羥基乙酯、N,N-二甲基丙烯醯胺(“DMA”)、N-乙烯 基吼洛烧酮、2-乙稀基-4,4’·二甲基-2-崎0坐11 林-5-酮、曱 基丙烯酸、及2-羥乙基曱基丙烯醯胺。可摻入其他矽 氧烷單體,諸如曱基丙烯酸三(三甲基曱矽烷氧基)甲 矽烷基丙酯、或矽氧烷單體,如美國專利編號5,998,498; 3,808,178; 4,139,513; 5,070,215; 5,710,302; 5?7149557 及5,908,906所述。其亦可包括各種增韌劑、UV阻斷 劑及潤濕劑。其可使用稀釋劑諸如一級醇、或三級或 三級醇製得,如美國專利編號6,020,445所述。所列之 18 1295387 所有專利皆以提及方式完全併入本文。 用以製造隱形眼鏡之材料係眾所周知且係市售產 品。所用材料較佳係為以HEMA為主之水凝膠,伊塔弗 康A(etafilconA)更佳’該鍵結性聚合物係自MAA、 HEMA及曱基丙烯酸月桂酯(“LMA”)之線性任意嵌段 共聚物;MAA及HEMA之線性任意嵌段共聚物; HEMA及LMA之線性任意嵌段共聚物;或HEMA均 聚物所形成。美國專利編號4,680,336及4,495,313(以In the Eiger mill, it is necessary to repeat the rubbing of the pigment to sand the bonding polymer. The mill is carried out until the pigment size is completely dispersed. Generally, milling can be carried out using any suitable commercially available apparatus from 2 to about 3 microns. Difficult to cut or ball mill. The present invention includes, but is not limited to, high shear except that the pigment and the bonding arm are in addition to - or a plurality of solvents. It is desirable (preferably) to apply the colorant to the surface tension. This surface tension can be achieved by a known method of applying a surface of less than about 27 culverts (e.g., a mold surface), such as a surface treatment to be applied by the art, by selecting the coloration. , limited to) plasma and corona treatment. Or (relative to the surface tension. Solvent used) to achieve the desired, therefore, can be used in the present day or reduce the viscosity of the colorant 5, the solvent in the colorant is a force can be added when the solvent system includes (not And a solvent that helps control the surface tension. Methoxy-2-propanol, Ethyl & is limited to cyclopentanone, 4-methyl-2-pentanone, 1 and its combination to use lactitol, lactate For propyl esters and the like, it is preferred to use at least two bubbles of different solvents in the colorant of the present invention for each of the pigments of the present invention. (5) γ It is used to make a bond to make a bonding polymer (both in the solvent) to remove U from the monthly polymer. Although these solvents can be formed after the formation of (IV) 1 propanol and isopropyl lactate It is better to leave the solvent in the solvent (meaning that it is 7 soils, depending on the need to use another low boiling low coloring agent, and a solvent between about 12 GC). Although the low boiling point solvent includes (not P) 1295387. propanol, and the like, with 2-propanol, 1_oxo-2-propanol, a composition. The preferred amount of the alcohol/solvent is determined by the number of the number. For example, the amount of the solvent of the bonding polymer depends on the component used in the binding polymer of the desired bonding polymer (such as monomer 2). The amount of the low-boiling solvent depends on the degree of the colorant and the surface tension. Further, if the coloring agent is to be applied to ς / and cured together with the lens material, the mold is used. Whether the material and the mold material have been advanced; = the surface treatment of the wetness. The exact amount of the solvent is determined; 2 The range of experience of the skilled person. Usually, the solution used is about 40 to about 75 weight percent. As is well known to those skilled in the art, it is known that each of the pigments used is prepared in a solvent having a critical pigment volume. The critical pigment is determined by any known means, usually by solvent and bonding. The volume of the efficiency of the suspension of the pigment particles, for example, Patton, Temple C., Paint Fl〇w and Pigment Dispersion 2d ed., pp 126-300 (1993). In addition to the solvent, Preferably) adding a plasticizer to the coloring to reduce During the drying of the colorant and the mold part, the turtle sounds the final quality of the image obtained by using the coloring agent, and promotes the diffusion of the coloring agent to the coloring agent and the swellability of the coloring agent. The type and amount of the bonding polymer used depends on the color of the bonding polymer used in the storage state before use, and it is also determined according to the required pot life stability, which is 15 1295387. The plasticizer f includes, without limitation, glycerin, propylene glycol, di(propylene glycol), di(propanol), polyethylene glycol 2, 4 or 6 fluorene, and the like, and its group delta. It is preferred to use glycerin. The plasticizer is typically used in an amount of up to about 10 weight percent based on the weight of the colorant. The opacity of the colorant can be controlled by varying the pigment concentration and the particle size of the pigment used. Alternatively, an opacifier can be used. Suitable opacifying agents, such as, for example, titanium oxide or zinc oxide, are commercially available. In the present invention, from about 0.2 to about 25 weight percent of the pigment, from about 30 to about 45 weight percent of the bonding polymer, from about 40 to about 70 weight percent of the solvent, from about 5% to about 25. One percent by weight of titanium oxide, and from about 0.2 to about 7 weight percent plasticizer. The weight percentage is based on the total weight of the colorant mixture. The bonding polymer may be filled with from about 0.2 to about 25 weight percent of the organic pigment by weight of the colorant, and from about 2 to about 50 weight percent of the inorganic pigment. However, high pigment concentrations can produce very dark tones. Accordingly, it is preferred to use from about 2 to about 7 weight percent of the organic pigment and from about 0 to about 20 weight percent of the inorganic pigment. The composition of the pigment can be used in proportion to the desired color, color and hue. It is well known to those skilled in the art that the colorant compositions of the present invention may comprise additives other than those previously described. Suitable additives include (not = two) additives which aid in flow and leveling, and additives to prevent foaming. The additive for modifying rheology, and the like, and the group thereof, the colorant becomes embedded in the lens 16 1295387 when the material is cured. Therefore, depending on whether the colorant can be embedded in the lens closer to the lens, the surface is applied in any order - or the multi-layer coloring is 2 = 2, the coloring agent can be used at the same time as transparent. In a specific example, in the method of the present invention, a two-layer layer of the agent may be applied. For example, the polymer may be rendered different from the colorant layer by the colorant layer. If the transparent bonding polymer is the same or =r:=:;::== 1_ contains the monomer of the county 1 or the monomer of the stone s. The hydrogel, and combinations thereof are preferably made. It can be used to form a reaction = a reaction of a blend of a macromonomer, a monomer, and a composition thereof as a suitable initiator. : Poly(tetra) hydrogel prepared from raw monomers. The polyoxanthene group includes, without limitation, a fluorenyl group which is methylated by a laterally hydrophilic group, as described in U.S. Patent Nos. 4,259,467, = 2 (9), 725 and 4,261,875. a fluorenyl decyloxy macromonomer having a polymerizable functional group such as U.S. Patent Nos. 4,136,250; 4,153,641; 4,189,546; 4,182,822; 1295387 4,343,927; 4,254,248; 4,355,147; 4,276,402; 4, 486, 577; 4, 486, 577; 4, 605, 712; 4, 543, 398; 4, 661, 575; 4, 703, 097; 4, 837, 289; 4, 954, 586; 4, 954, 587; 5, 346, 946; 5, 358, 995; 5, 387, 632; 5, 451, 617; 5, 486, 579; 5, 962, 548; 5, 981, 615; 5, 981, 675; ; and its composition. It can also be prepared using the following monomers: a polyoxyalkylene macromonomer incorporating a hydrophilic monomer, such as described in U.S. Patent Nos. 5,010,141; 5,057,578; 5,314,960; 5,371,147 and 5,336,797; The mercapto oxyalkylene block and the polyether block macromonomer are described in U.S. Patent Nos. 4,871,785 and 5,034,461. All of the patents listed are fully incorporated herein by reference. Suitable materials can also be prepared from compositions of oxyperm and ionoperm compositions, such as those described in U.S. Patent Nos. 5,760,100; 5,776,999; 5,789,461; 5,807,944; 5,965,631 and 5,958,440. Hydrophilic monomers can be incorporated into the copolymer, including 2-hydroxyethyl mercaptopropionate ("HEMA"), 2-hydroxyethyl acrylate, N,N-dimethyl decylamine ("DMA") ), N-vinyl fluorenone, 2-ethylene-4,4'. dimethyl-2-sodium 0 sitting 11 lin-5-ketone, methacrylic acid, and 2-hydroxyethyl fluorenyl Acrylamide. Other oxoxane monomers may be incorporated, such as tris(trimethyldecyloxy)methyl propyl propyl methacrylate, or a decyl siloxane monomer, such as U.S. Patent Nos. 5,998,498; 3,808,178; 4,139,513; 5,070,215; 5,710,302 ; 5?7149557 and 5,908,906. It may also include various toughening agents, UV blockers, and wetting agents. It can be prepared using a diluent such as a primary alcohol, or a tertiary or tertiary alcohol, as described in U.S. Patent No. 6,020,445. All of the listed 18 1295387 patents are hereby incorporated by reference in their entirety. The materials used to make contact lenses are well known and commercially available. The material used is preferably a HEMA-based hydrogel, and etafilcon A is better. The bonding polymer is linear from MAA, HEMA and lauryl methacrylate ("LMA"). Any block copolymer; linear arbitrary block copolymer of MAA and HEMA; linear arbitrary block copolymer of HEMA and LMA; or HEMA homopolymer. US Patent Nos. 4,680,336 and 4,495,313
提及方式完全併入本文)所揭示之伊塔弗康 A ^&出〇〇11八)通常係為100重量份數〇^,,)1^]\4八、約 1.5至約2.5 pbw MAA、約0.3至約1 ·3 pbw之乙二醇 二甲基丙烯酸酯、約0.05至約1.5pbw之1,1,1_三經甲 基丙烷三甲基丙烯酸酯、及約0.017至約0.024 pbw之 可見度著色物(visibility tint)之調配物。較佳伊塔弗康 A (etafilcon A)係與 MAA、HEMA 及 LMA(比例為 〇·47 ΜAA比100 HEMA比4.14 LMA)之線性任意喪段共聚 物或與HEMA及MAA(比例為99.9 HEMA及〇· 1 MAA 至99.5HEMA及0.5MAA)之線性任意嵌段共聚物一起 使用。 、 染色鏡片之較佳製造方法係如下使用軋印法進 行。金屬板(以自鋼材製得為佳,自不銹鋼製得更佳) 覆以可在固化時變成不溶於水之光阻材料。選擇或設 計該著色劑之圖案’之後使用數種技術(諸如微影術) 中之任-雜小輯需尺寸,放£_金屬板上,使 該光阻材料固化。進行圖案_之條件係—般熟習此 19 1295387 項技術者之經驗範圍。 圖案化之後,該板以水溶液洗滌,形成之影像蝕 刻至板内到達適當之深度,例如約2〇微米。隨之於該 圖Ϊ上沉積著色劑,以著色劑充填凹陷。將具有適當 之,何形狀及不同硬度(通常約丨至約10蕭氏人硬^ =單位)+之矽墊壓向位於該板上之影像,以移除該著ί 釗二该著色劑隨之藉由蒸發溶劑而稍微乾燥。該墊隨 ,壓向光學模具之模製表面,使著色劑乾燥。模具脫 乳,最少約8小時’以移除過量之溶劑及氧,之後 具内充填鏡片形成量之鏡片材料。使用互補半模 f完全,模具組合體,在擴散期(該鏡片單體擴散至所 f7刷之衫像内)之後,模具組合體曝露於適合固化所使 用之鏡片•材料的條件下。 藉以下非限制實施例進一步闡明本發明。 實施你丄 允1含有鍵結性聚合物(曱基丙烯酸月桂酯、曱基丙烯 酉欠罗工乙^曰及甲基丙烯酸)、顏料及乳酸異丙酯、ι_乙氧 “丙醇及u丙醇之著色劑組成物軋印於聚笨乙烯光學 核具之刖方模製曲面上。該模具脫氣至少8小時,以 溶劑及氧’之後於該模具充填鏡片形成量之 體Metamc°nA)。之後使用互補半模完成該 該模具組合體放置於通經固化隧道之皮帶上,隧 道内部置有4組2個(並排)位在陵道起點的短波^ 20 1295387 燈。該模具組合體於此隧道内通過該it燈泡下方,加 熱至該著色劑之Tg。各燈泡之強度控制係藉由以微處 理器為主之溫度控制器保持。該模具組合體隨之進入 沒有燈泡的黑暗區,但加熱將其中空氣加熱至55及 75°C之間,以保持模具溫度處於或高於該著色劑Tg。 該模具通經該隧道之IR燈泡及黑暗區的速度係於此 區中保持約75秒,期間藉由偵測模具溫度之連續回饋 系統保持Tg溫度。該模具隨之離開此區,起始且完成 鏡片材料之固化。一旦完全固化,該鏡片脫離模具, 於經緩衝之鹽水溶液中達到平衡。 21The manner in which it is referred to fully incorporated herein is based on the fact that it is usually 100 parts by weight ,^,,) 1^]\4 VIII, about 1.5 to about 2.5 pbw. MAA, from about 0.3 to about 1.3 pbw of ethylene glycol dimethacrylate, from about 0.05 to about 1.5 pbw of 1,1,1-trimethylpropane trimethacrylate, and from about 0.017 to about 0.024 A formulation of pbw visibility tint. Preferably, etafilcon A is linear with any MAA, HEMA and LMA (ratio of 47 ΜAA to 100 HEMA to 4.14 LMA) or with HEMA and MAA (99.9 HEMA and A linear arbitrary block copolymer of 〇·1 MAA to 99.5HEMA and 0.5MAA) is used together. The preferred method of producing the dyed lens is as follows using a stamping method. A metal plate (preferably made of steel, preferably made of stainless steel) is coated with a photoresist material that becomes insoluble in water upon curing. After selecting or designing the pattern of the colorant, a size of any of a number of techniques (such as lithography) is used, and the sheet is placed on a metal plate to cure the photoresist. The conditions for the pattern _ are familiar to the general experience of 19 1295387. After patterning, the plate is washed with an aqueous solution and the resulting image is etched into the panel to a suitable depth, such as about 2 microns. A colorant is then deposited on the image to fill the depression with a colorant. Pressing the appropriate pad, the shape and the different hardness (usually about 丨 to about 10 萧人^^^)+ the pad is pressed against the image on the plate to remove the 着色 钊It is slightly dried by evaporating the solvent. The pad is pressed against the molding surface of the optical mold to dry the colorant. The mold is de-milked for a minimum of about 8 hours to remove excess solvent and oxygen, followed by a lens material filled with lens forming amount. Using a complementary mold half f, the mold assembly, after the diffusion period (the lens monomer is diffused into the image of the f7 brush), the mold assembly is exposed to the lens material used for curing. The invention is further illustrated by the following non-limiting examples. Implementation of your 11 contains a bonding polymer (lauryl methacrylate, decyl propylene oxime) and pigment isopropyl acrylate, ι_ ethoxy "propanol and u The propanol coloring agent composition is imprinted on the square molded surface of the polystyrene optical fixture. The mold is degassed for at least 8 hours, and the solvent and oxygen are added to the mold to form a lens forming body Metacc°nA. Then, the mold assembly is placed on the belt passing through the curing tunnel by using a complementary mold half. The tunnel is internally provided with 4 sets of 2 (side by side) short wave ^ 20 1295387 lamps located at the beginning of the mausoleum. In this tunnel, under the it bulb, it is heated to the Tg of the colorant. The intensity control of each bulb is maintained by a microprocessor-based temperature controller. The mold assembly then enters the dark area without the bulb. But heating heats the air to between 55 and 75 ° C to maintain the mold temperature at or above the colorant Tg. The speed of the mold through the tunnel's IR bulb and dark zone is maintained in this zone. 75 seconds, during the detection mode Continuous feedback system to maintain the temperature of the Tg. The mold will leave the area, and following completion of the curing of the lens material. Once fully cured, the lens removed from the mold, in an aqueous solution buffered by salts of equilibrium. 21