TW311914B - - Google Patents
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- TW311914B TW311914B TW082106816A TW82106816A TW311914B TW 311914 B TW311914 B TW 311914B TW 082106816 A TW082106816 A TW 082106816A TW 82106816 A TW82106816 A TW 82106816A TW 311914 B TW311914 B TW 311914B
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A6 B6 SI1914 五、發明説明(/ ) (請先閲讀背面之注意事項再填寫本頁) 本發明傜有闢眼鏡,眼.鏡的製造方法及苯二甲酸二烯 丙基酯類寡合物(diallyl phthalate type oligomer)在 眼鏡中的使用。 最近,有機玻璃已開始取代無機玻璃用於光學元件, 例如窗、稜鏡、照相機、電視螢幕、望遠鏡、和眼鏡等之 中。眼鏡(ophthalmic lenses)之意包括矯治鏡片以及非 矯治鏡片,例如,太陽眼鏡。有機玻璃具有幾項有利的待 性,包括重量較輕且比無機玻璃更為安全。 傳統上,用於有機玻璃的材料包括聚苯乙烯樹脂,聚 甲基丙烯酸甲酯樹脂,和聚碩酸酯樹脂。不過,這些聚合 物各有其缺點。例如,聚甲基丙烯酸酯樹脂易於發生高吸 溼現象而改變其形狀和折射率。另外,聚苯乙烯樹脂和聚 碩酸酯樹脂具有下列缺陷:産生双折射,光散射,以及隨 時間發生之透明度損失等。再者,聚甲基丙烯酸甲酯和聚 苯乙烯兩者既不能抗刮擦也不能抗溶劑。 · 用多羥基醇類之聚碩酸烯丙基酯(PQlylallyl c a r b ο n a t e 〇 f ρ ο 1 y h y d r ο X y a 1 c ο Ιι ο 1 s )經由自由基聚合所 得産物製備成的有機玻璃也是已知者,例如,EP — A — 、 0 473163中所逑及者。這種聚合物不具上述問題 經濟部中央標準局工消費合作社印製 。不過,在將多羥基醇聚(5庚酸烯丙基酯)用於眼鏡中時 ,常發生另外兩種問題,亦即,著色失敗及在模子內預離 型(prerelease)等〇 著色眼鏡,包括矯治鏡和非矯治鏡(如,太陽眼鏡) -4- 本纸张又度遇用中0國家抒準(CNS)甲4说格(210 X 297公货) 82.6. 40,000 311914 A6 B6 經濟部中去標準局β工消費合作社印製 五、發明説明(1) 兩者,其製備幾乎完全是利.用表面浸染法,將眼鏡浸漬於 染料的水分散液中進行之。不過,用多羥基醇聚(碩酸烯 丙基酯,製成的眼鏡常顯示弧狀形式的表面著色不均勻現 象。這種在著色眼鏡中的著色失敗會因為不適合作為商業 産品而導致所製成的鏡片有大比例的退件。 在模中預離型或過早離型為澆鑲好的眼鏡在聚合中即 從模子表面鬆脱之現象。如此一來,會在鏡Η表面發生敗 麋而在未徑研磨及/或磨光之校正下,該鏡片卽不能使用 。於用多羥基醇類之碩酸烯丙基酯製造成品鏡片中,這種 預離型現象是一項特別顯著的問題。 成品鏡M (finished lens)是一種矯治鏡片,其最後 形狀決定於模子的尺寸。因此,於鏡片從模子内取出之後 ,即應具有正確的曲率和倍率而無需後續加工。由於没有 後缜加工步驟來校正鏡片的缺陷,因此,即要求成品鏡片 的聚合澆鑄産品需符合終端産品的規格。使用多羥基·醇聚 (磺酸烯丙基酯)製造成品鏡片時,因為其在聚合澆鑄中 所發生的預離型現象而致促成高達7 0%成品鏡片被退件 之情形。 雖然不希望被任何理論所限,不過仍認為是因為多羥 .基醇類之碳酸丙烯酯,常有的皺縮(shrinkage)導致發生 預離型。例如,碩酸二乙二醇二烯丙基酯(diethylene glycol diallyl carbonate在聚合中會皺縮14%,參看 Kirk Othaer,化學技術百科全書(Encyclopedia of (請先閏讀背面之注意事項再填寫本頁) •装· 訂. 本紙張尺度通用中S國家抒準(CIS-S:).甲4現烙(210 X 297公货〉 82.6. 40,000 經濟部中央標準局貝工消费合作社印製 的者基 羥和至W 1 成丙値.,有 ◦ L0 構 輝6劑含 1 . 所酸到始中於 1 物碩 2 起物少 到産之和基成量 ο 化類子由組含 5 固醇原自該其 . 之基碩種於 , 1 物羥値一在物 率成多 ο 少徵合 射組種 2 至特寡 折的一到的其類 有成少冇%,酯 具組至具 t 體基 種列的子W單丙 。一 下%分 ο 共烯 低關有 t 的 1 的二 減有具W醇 1% 酸 地 偽 由 9 基 1 t 甲 顯明慑 9 羥 oW二 明發其 I 多 .ο 苯 以本 -ο 該 ◦ 2 種 可 鏡 6 , . 1 一 率 眼:酯基 ο 少 A6 _B6_ 五、發明説明) G h e in i c a 1 T e c h η ο 1 〇 g y),第三販,J 〇 h n W i 1 e y & S ο n s, 1978, Vol.2,第1 1 2頁。此外,該皺縮也不是均勻地發 生者。因此,成品鏡片的預離型可能為聚合澆鑄中發生收 縮之結果。更特別者八因為成品鏡Η的厚度從邊緣到鏡Η 中心有廣大的差異,所以其皺縮量也有廣大的差別且因而 成品鏡片的預離型經常發生。因此,預離型問題必須解決 〇 一種防止過早離型的方法為在多羥基醇類之碩酸烯丙 基酯)中使用黏著促進劑(a d h e s i ο η p r 〇 m 〇 t 〇 r)。這類黏 著促進劑的例子有矽烷和,順丁烯一酸酐。不過,這種方 法無法明顯地減低預離型現象。再者,該黏著促進劑會增 加對玻璃模子的黏著而導致較高的模子損壞率。 综上所述,本發明的最初目標即為提出一種可均勻著 色的眼鏡。本發明的另一目標為提出一種可在最低預離型 之下製成的眼鏡,使得這種眼鏡,尤其是成品鏡片的退件 本紙张又度適用中國國家丨ί準(CNS)甲4规格(210 X四7公货) 82.6. 40,000 -----------------{------裝-------訂------{. (請先閲讀背面之注意事項再塡窝本頁) , A6 B6 經濟部t央標準局R工消费合作社印製 五、發明説明(屮) t% ;該苯二甲酸二烯丙基酯類寡合物偽具有化學式I者 0 0 ch2=ch-ch2-o-c-^ Vt-C-O- -CH2-CH=CH2 (I) 式中X為從具有2 _ 2 0値碩原子的二醇所衍生的二價烴 基,其視情況可部份為從具有3個以上磺原子和3_ 10 値羥基的多元醇衍生之基所取代;且η = 1 — 1 00 ;該 寡合物具有依據Wi j s法測出之碘價20— 1 00之不 飽和度。 _ 本發明的眼鏡偽可著色者,且無高著色失敗率。而且 ,本發明眼鏡,尤其是成品鏡片,因其在聚合澆鑄中的預 騰型現象減少,所以在生産中的退件率明顯地降低。 本發明的眼鏡需要有· 1 . 5 ◦到1 . 5 1的折射率。 更特別者,今日在製備多羥基醇類之碩酸烯丙基酯(折射 率=1. 498)眼鏡的工業中所用之模子只適合於可製 成具有相近折射率的眼鏡之組成物所用。折射率羑動時, 在採用相同的模子下,會導致鏡片倍率的變動,。要産生 高折射率鏡片時,其所用组成物必須採用不同的模子才能 得到具有相同倍率的眼鏡。所以,要經由導入某種寡體物 及視情況選用之共單體來改良鏡片性質時,沒有辦法在不 限制到所得鏡片的折射率以便不必改變模子的情況下完成 本纸張又度逋用中國國家惮芈(CNS)甲4规格(210 X 297公釐〉 82.ΰ· 40,000 (請先閲讀背面之注意事項再埸寫本頁)A6 B6 SI1914 V. Description of the invention (/) (Please read the precautions on the back before filling in this page) The present invention has the manufacturing methods of glasses, eyes, mirrors and diallyl phthalate oligomers (diallyl phthalate type oligomer) in glasses. Recently, plexiglass has begun to replace inorganic glass for optical components, such as windows, tinctures, cameras, TV screens, telescopes, and glasses. Ophthalmic lenses include corrective lenses as well as non-corrective lenses, for example, sunglasses. Plexiglass has several advantages, including lighter weight and safer than inorganic glass. Traditionally, materials used for organic glass include polystyrene resin, polymethyl methacrylate resin, and polyester resin. However, these polymers have their own disadvantages. For example, polymethacrylate resins are prone to high moisture absorption and change their shape and refractive index. In addition, polystyrene resins and polyester resins have the following defects: birefringence, light scattering, and loss of transparency over time. Furthermore, both polymethyl methacrylate and polystyrene are neither scratch resistant nor solvent resistant. · Plexylallyl carb ο nate 〇f ρ ο 1 yhydr ο X ya 1 c ο Ιι ο 1 s prepared by radical polymerization of organic glass products are also known For example, those mentioned in EP — A —, 0 473163. This polymer does not have the above problems. It is printed by the Industrial and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. However, when polyhydric alcohol poly (5heptanoate) is used in eyeglasses, two other problems often occur, namely, coloring failure and prerelease in the mold. Coloring glasses, Including corrective mirrors and non-corrective mirrors (eg, sunglasses) -4- This paper is used again in the 0 national express (CNS) A 4 standard (210 X 297 public goods) 82.6. 40,000 311914 A6 B6 in the Ministry of Economy Printed by the β Bureau of Standards and Consumers Cooperatives of the Bureau of Standards 5. Description of the invention (1) Both of them are almost entirely advantageous in preparation. The surface dip dyeing method is used to immerse the glasses in the aqueous dispersion of the dye. However, glasses made with polyhydric alcohol poly (allyl monoester) often exhibit uneven surface coloration in the form of an arc. This coloring failure in colored glasses can be caused by being unsuitable as a commercial product. The finished lens has a large proportion of retreat. Pre-release or pre-release in the mold is the phenomenon that the poured glasses loosen from the surface of the mold during polymerization. In this way, the failure will occur on the surface of the lens This lens can't be used without correction by grinding and / or polishing. This pre-release phenomenon is particularly noticeable in the production of finished lenses with polyhydric alcohol allyl esters The finished lens M (finished lens) is a corrective lens whose final shape depends on the size of the mold. Therefore, after the lens is taken out of the mold, it should have the correct curvature and magnification without subsequent processing. Because there is no post Rigorous processing steps to correct the defects of the lens, therefore, it is required that the polymer casting product of the finished lens must meet the specifications of the end product. The polyhydroxy · alcohol (allyl sulfonate) is used to manufacture the finished lens At the time, because of the pre-release phenomenon that occurred in the polymerization casting, it led to the situation that up to 70% of the finished lens was returned. Although not wanting to be bound by any theory, it is still believed to be due to polyhydroxy alcohol The common shrinkage of propylene carbonate leads to pre-release. For example, diethylene glycol diallyl carbonate (diethylene glycol diallyl carbonate) shrinks by 14% during polymerization, see Kirk Othaer, Encyclopedia of Chemical Technology (Encyclopedia of (please read the precautions on the back before filling in this page) • Binding and Ordering. This paper is common in S countries (CIS-S :). A 4 is now branded (210 X 297 Public goods> 82.6. 40,000 The base hydroxyl group printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs and W 1 becomes propyl. ◦L0 Gonhui 6 agent contains 1. The acid is up to the middle of 1 Wushu 2 The amount of starting material is as low as the total amount of production. The chemical species contains 5 sterols originally from the group. The basic species is that, 1 substance has a high hydroxyl value in the material rate. There are a few percent of those who have come to the fore, and the ester group has the sub-group W with single-substance W single C. One % Points ο low in the common ene with t 1 of the two minus the alcohol with 1% acidic pseudosynthesis by 9 bases 1 t A was obviously deterred 9 hydroxy oW diming made its I more. Ο Benz Yiben -ο The ◦ 2 Kind of mirror 6.. 1 first-rate eye: ester group ο less A6 _B6_ V. Description of the invention) G he in ica 1 T ech η 1 〇gy), the third vendor, J 〇hn W i 1 ey & S ο ns, 1978, Vol. 2, p. 112. In addition, the shrinkage does not occur uniformly. Therefore, the pre-release of the finished lens may be the result of shrinkage during polymerization casting. More specifically, because the thickness of the finished mirror H varies widely from the edge to the center of the mirror H, the amount of shrinkage also varies widely and thus pre-release of the finished lens often occurs. Therefore, the problem of pre-release must be solved. One method to prevent premature release is to use an adhesion promoter (adhe s i ο η p r 〇 m 〇 t 〇 r) in polyhydric alcohols such as allyl oleate. Examples of such adhesion promoters are silane and maleic anhydride. However, this method cannot significantly reduce the pre-release phenomenon. Furthermore, the adhesion promoter will increase the adhesion to the glass mold, resulting in a higher mold damage rate. In summary, the initial goal of the present invention is to propose a pair of glasses that can be colored evenly. Another object of the present invention is to propose a pair of glasses that can be made under the lowest pre-release type, so that the glasses, especially the returned lenses of the finished lenses, are again applicable to China National Standard (CNS) A4 (210 X 4.7 public goods) 82.6. 40,000 ----------------- {------ installed ------- order ------ {. (Please read the precautions on the back before reading this page), A6 B6 Printed by the R and Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (屮) t%; the diallyl phthalate Oligomeric compounds with the chemical formula I 0 0 ch2 = ch-ch2-oc- ^ Vt-CO- -CH2-CH = CH2 (I) where X is derived from a diol with 2 _ 2 0 tremendous atoms The divalent hydrocarbon group may be partially substituted by a group derived from a polyol having more than 3 sulfonic atoms and 3-10 hydroxyl groups; and η = 1 — 1 00; the oligomer has a Wi js method for measurement The unsaturation of the iodine value of 20-100. _ The glasses of the present invention are pseudo-colorable and have no high coloring failure rate. Moreover, the eyeglasses of the present invention, especially the finished lenses, have a reduced premature phenomenon during polymerization casting, so the rejection rate in production is significantly reduced. The glasses of the present invention need to have a refractive index of 1.5 to 1.51. More particularly, the molds used in the industry of preparing allyl alcohol esters of polyhydric alcohols (refractive index = 1.498) today are only suitable for compositions that can produce glasses with similar refractive indices. When the index of refraction is moved, the same model will be used, which will cause the lens magnification to change. To produce high-refractive-index lenses, the composition used must use different molds to obtain glasses with the same magnification. Therefore, there is no way to improve the properties of the lens by introducing a certain oligomeric substance and optionally selected comonomers without limiting the refractive index of the resulting lens so as not to change the mold. China National Trust (CNS) A 4 specifications (210 X 297 mm> 82.ΰ · 40,000 (Please read the precautions on the back before writing this page)
J _裝· 訂. 311914 A6 B6 五、發明説明(了) 〇 ‘ 曰本專利申請第03199218號掲示一種可固化 的組成物,含有至少1 〇w t%的苯二甲酸二烯丙基酯類 寡合物,一種乙烯基共單體,例如二乙二醇二烯丙基碩酸 酯,和自由基起始劑。該组成物可以用於光學元件,例如 ,高折射率透鏡之中。根據其説明部份,只以二乙二醇二 烯丙基碩酸酯為基質的固化組成物具有太低的折射率,導 致産生厚鏡片而需大幅校正。此外,含有少於10wt% 的苯二甲酸二烯丙基酯類寡合物之固化组成物也具有不良 的抗衝擊性與不良的耐熱性。再者,該申請案也未提及具 有改良著色性或減低嘵鏵時預離型現象等優點。所以,本 發明並未為該JPO 1 3992 1 8所掲示到。另外從該 專利的掲示内容來看,諳於此技者絶不會選用含有少於1 Ow t%苯二甲酸二烯丙基酯類寡合物的組成物來製造鏡 片之事實而論,該申請案所述甚至於有異於本發明。 經濟部中央標準局A工消費合作社印製 日本專利申請第03054213號掲示一種類似9 於JP03199218號的組成物。該組成物可用於塗 料,填縫料,油漆,黏著割,和光學元件等之中。該日本 專利公開從未提及眼鏡或成品鏡片。此外,也未掲示到發 .明所具改良箸色性或澆鑲中減低預離型現象等優點。綜上 所述,該日本專利申請亦未渉及本發明。 歐洲專利申請第0 4 7 3 1 6 3號掲示一種液體組成 物,含有多羥基醇類之碩酸烯丙基酯和〇· 01 — lwt -8- 82.6. 40,000 (請先閲讀背面之注意事項再璜寫本頁) 本紙張又度適用中囷囷家愫準(CNS)甲4現格^210 X 297 ^¾) > A6 _B6_ 五、發明説明(4 ) %的脂醇以改良該液體組成物所製鏡片之著色性。另外, 也可含有選用之單體,例如,苯二甲酸二烯丙基酯,其量 高達50wt%。如其所述,透過使用化學式I苯二甲酸 二烯丙基酯類寡合物而非經由添加多元醇達到著性之改良 並非該掲示的一部份。此外,該專利申請未提及用多羥基 醇類之碩酸烯丙基酯製造眼鏡,特別是成品鏡片之中有關 模子内過早離型之問題。 多羥基醇聚(碩酸烯丙基酯)可由單體或寡合物任一 種形式來使用。其單體通常是用氯甲酸酯製成。在該方式 中,可以用二(氯甲酸)二乙二醇酯〔diethylene glycol bis (chlarof ormate)]與丙烯醇在鹼存在下反應 而製得二乙二醇二烯丙基,磺酸酯,如Kirk-Othmer,化學 技術百科全書,第三販,J 〇 h n W i 1 e y & S ο n s , 1 9 7 8 , V ο 1, 2 P.ll中所述者。多羥基醇聚(碩酸烯丙基酯)的單體和 寡體物也可以經由碩酸二烯丙基酯.和·多羥基醇之間的轉醋 ------------------^------裝--:---·1 訂 (請先閲讀背面之注意事項再填寫衣頁) . 經濟部中央標準局貝工消费合作社印4i 。單酯類酯基 其 者到基醇基丙 於 述得丙基丙烯 醇 所以烯羥烯酸 基 中可二 多酸碩 羥 4例酸合碩之 多 ofcb磺混之類 的 3 的由到類醇 用 5 醇經得醇基 所 3 基 ,以基羥 酯 ο 羥外可羥多 基 ο 多此應多以 丙 P 對 。反合仍 。烯 E 酯物化混 ,中酸 如基合酯類過明磺 ,物混轉這不發之 得烯的以 。 。本類 製丙物物} 中於醇 地二 合合基明用基 當酸寡混丙發適羥 適碳與醇烯本較多 而依體基酸在體備 應,單羥磺括單製 反 中或多 ί .包的 化其體與之也酯 82.6. 40,000 本纸張又度通用中國國家样準(CNS)甲4现格(210 X 297公货) 經濟部中央律準局S工消贲合作社印11 A6 B6 五、發明説明(q ) 分子中含冇到2 0個磺原子和2到6個運基。這類醇的例 子有:乙二醇,二乙二醇,三乙二醇,四乙二醇,1,3 一二醇,1,4 — 丁二醇,1,6 一己二醇,新戊二醇, 2,2,4 —三甲基一 1, 3-丙二醇,1,4-二甲醇J _ 装 · 定. 311914 A6 B6 V. Description of the invention (to) 〇 'Japanese Patent Application No. 03199218 shows a curable composition containing at least 10% by weight of diallyl phthalate oligomers Substance, a vinyl comonomer, such as diethylene glycol diallyl master ester, and a free radical initiator. The composition can be used in optical components such as high-refractive-index lenses. According to its description, the cured composition based solely on diethylene glycol diallyl master ester has a too low refractive index, resulting in thick lenses that require significant correction. In addition, cured compositions containing less than 10% by weight of diallyl phthalate oligomers also have poor impact resistance and poor heat resistance. Furthermore, the application does not mention the advantages of improving color rendering or reducing the pre-release phenomenon of the wax. Therefore, the present invention is not disclosed by the JPO 1 3992 18. In addition, judging from the content of the patent, the skilled person would never choose a composition containing less than 1 Ow t% of diallyl phthalate oligomers to manufacture lenses, the application The case even differs from the present invention. Printed by the A-Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Japanese Patent Application No. 03054213 shows a composition similar to 9 in JP03199218. The composition can be used in coatings, caulk, paint, adhesive cutting, and optical components. This Japanese patent publication never mentions glasses or finished lenses. In addition, it has not been shown that it has the advantages of improving the color and reducing the pre-release phenomenon during pouring. In summary, this Japanese patent application does not involve the present invention. European Patent Application No. 0 4 7 3 1 6 3 shows a liquid composition containing polyhydroxy alcohols of allyl carboxylate and 〇.01 — lwt -8- 82.6. 40,000 (please read the notes on the back first Re-write this page) This paper is again applicable to the Zhongjiaojia Family Standard (CNS) A4 present format ^ 210 X 297 ^ ¾) > A6 _B6_ V. Description of the invention (4)% fatty alcohol to improve the liquid The color rendering of the lens made of the composition. In addition, it may also contain optional monomers, such as diallyl phthalate, in amounts up to 50% by weight. As described in it, the improvement of the performance achieved by using the diallyl oligomer of the chemical formula I rather than by adding a polyol is not part of the description. In addition, the patent application does not mention the use of allyl polyalcohols to produce eyeglasses, especially the problem of premature mold release in finished lenses. The polyhydric alcohol poly (allyl monoester) can be used in any form of monomers or oligomers. Its monomer is usually made of chloroformate. In this way, diethylene glycol bis (chloroformate) diethylene glycol ester [diethylene glycol bis (chlarof ormate)] can be reacted with propylene alcohol in the presence of a base to produce diethylene glycol diallyl, sulfonate, As described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Dealer, J Ohn Wie ey & S ο ns, 1 9 7 8, V ο 1, 2 P.ll. The monomers and oligomers of polyhydric alcohol poly (allyl monoester) can also pass through the diallyl ester of polyhydric alcohol. -------- ^ ------ Outfit-: --- · 1 Order (please read the precautions on the back before filling in the clothes page). Printed 4i, Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs . Monoester ester ester group which is based on the alcohol group propylene propylene alcohol, so the hydroxy-acrylic acid group can be diacidic hydroxy group 4 cases of acid synthesis of many ofcb sulfonate and the like from 3 to the class Alcohol can be obtained by using 5 alcohols to obtain 3 groups of alcohol groups, based on hydroxy esters, hydroxy exohydroxy poly groups, and more should be paired with propylene P. Anti-heavy. Ethylene E esters are chemically mixed, and intermediate acids such as base esters are too sulfonated. . This class of propylene-based compounds} in the alcohol-based two-in-synthetic base oligomer mixed propionate hydroxy-adaptable carbon-alcohol and alcohol is more and the body-based acid should be prepared in the body. Anti-center or multi-liquid. The package of its body and its ester is also 82.6. 40,000 This paper is once again universal Chinese National Standards (CNS) A 4 cash (210 X 297 public goods) Ministry of Economic Affairs Central Law Bureau S Engineering Xiao Ben Cooperative Seal 11 A6 B6 V. Description of the invention (q) The molecule contains no more than 20 sulfonic atoms and 2 to 6 transport groups. Examples of such alcohols are: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3 monodiol, 1,4-butanediol, 1,6 monohexanediol, neopentyl glycol Glycol, 2,2,4-trimethyl-1,3-propanediol, 1,4-dimethanol
基環己烷,4, 8 —二(羥乙基)參環(5,2, 1,D 26)癸烷,cx, a,一二甲苯二醇,1,4 -二(羥乙 基)甲苯,2,2 — (二(4 一羥乙基)苯基)丙烷,季 戊四醇,三甲醇丙烷,二季戊四醇,二(三甲醇基丙烷) ,和三一(羥乙基)異三聚氡酸酯等。其中以下多羥基醇 為較佳:二乙二醇,1, 4_甲醇基環己烷,朵季戊四醇 ,和三(羥乙基)異二聚氡酸酯等。 鄰苯二甲酸二烯丙基酯寡合物及其製備皆可參看美國 專利第4, 959, 451號,該專利併於本文供參考。 該鄰苯二甲酸二烯丙基寡合物可用幾種方法製備成,例如 ,用對苯二甲酸二烯丙基酯與二醇在酯交換觸媒存下反應 ,經由蒸餾脱除丙烯醇而製得;或用對苯二甲酸二甲酯( 或二乙酯),二醇,和丙烯醇等在交換觸媒存在之下反應 ,經由蒸餾脫除甲醇或乙醇而製得等方法。當部份體X被, 多元醇殘基所部份取代時,可以用二醇與多元醇組合而合 :成該寡合物,或用化學式I寡合物對應的多元醇在酯交換 媒存在之下加熱合成該寡合物。間苯二甲酸二烯丙基酯寡 體物,化學式I中的次苯基為1, 2 —取代者之寡合物, 或化學式I苯二甲酸二烯丙基酯類寡合物的共寡合物( -10- 本紙張尺度通用中國國家样準(CNS)甲4说格(210 X 297公货) 82.6. 40,000 (請先閲讀背面之注意事項再埸寫本頁) -裝. 訂. 311914 > A6Cyclocyclohexane, 4, 8-bis (hydroxyethyl) cyclic (5, 2, 1, D 26) decane, cx, a, xylene glycol, 1,4-di (hydroxyethyl) Toluene, 2,2- (bis (4-hydroxyethyl) phenyl) propane, pentaerythritol, trimethanol propane, dipentaerythritol, bis (trimethanol propane), and tris (hydroxyethyl) isotrimeric radon acid Ester etc. Among them, the following polyhydric alcohols are preferred: diethylene glycol, 1,4-methanolcyclohexane, dopentaerythritol, and tris (hydroxyethyl) isodipoly radonate. For diallyl phthalate oligomers and their preparation, see U.S. Patent No. 4,959,451, which is incorporated herein by reference. The diallyl phthalate oligomer can be prepared by several methods, for example, by reacting diallyl terephthalate with diol in the presence of a transesterification catalyst and removing allyl alcohol by distillation Obtained; or by using dimethyl terephthalate (or diethyl ester), diol, and propylene alcohol in the presence of exchange catalyst reaction, through distillation to remove methanol or ethanol and other methods. When the partial body X is partially substituted with a polyhydric alcohol residue, a diol can be combined with the polyhydric alcohol to form the oligomer, or a polyhydric alcohol corresponding to the oligomeric compound of formula I in the presence of a transesterification medium This oligomer was synthesized by heating. The diallyl isophthalate oligomer, the phenylene group in Chemical Formula I is an oligomer of 1, 2-substituted, or the co-oligomer of the diallyl oligomer of Chemical Formula I ( -10- This paper standard is universal Chinese National Standard (CNS) A4 said (210 X 297 public goods) 82.6. 40,000 (please read the precautions on the back before writing this page)-installed. Ordered. 311914 > A6
五、發明説明(》)V. Description of Invention (》)
Co-olQgomer)等皆可用類似的方式製備成。其中以對苯二 甲酸二烯丙基酯寡聚物較適用於本發明。 上述二醇的例子包括乙二醇,1, 2 —丙二醇,1, 4 一 丁二醇,1,6 —己醇,1,4 —二甲醇基環己烷, ,3 —戊二醇,1, 2 — 戊二醇,2,3 —戊二醇,2, 4 一戊二醇,1, 5 —己二醇,1, 4 一 己二醇,1, 3 一己二醇,1, 2 — 己二醇,2, 3 —己二醇,2, 4 — 己二醇,2, 5 —己二醇,和3, 4 —己醇等。 多元醇的例子包括脂族三羥基醇,例如甘油和三甲醇 基丙烷;及脂族多羥基醇,如,季戊四醇和山梨糖醇等。 該固化型組成物也可視情況含有高達2 Ow 的共 單髏。這類共單髏可為烯基条,乙烯基糸或烯丙基糸等共 單體。其例子包括丙烯酸甲酯,甲基丙烯酸甲酯,甲基丙 烯酸苯酯,乙酸乙烯酯,苯甲酸乙烯酯,間苯二甲酸二烯 丙基酯,對苯二甲酸二烯丙基酯,己二酸二烯丙基酯,和 三聚氰酸二烯丙基酯等。 -----------------^------装!------tr------产- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局WC工消費合作社印製 到之産氣異酯明 1 含內過 二酸發 ο 所圍機酸磺本 , 物範有磺二以 ο 成度括二 氣 。 為組溫包氧過等 量的 υ 子過基酯 其化 ο 例為丁丁 , 固 ◦性者二 二 劑要 1 制別第第 始於約限特二酸 起溶到非-酯甲 合可 Ρ 些劑酸苯 聚須 ο 一始碩過 有必 3 的起二和 含劑在劑之氣 , 也始夠始類過基 物起能起等基醯 成該要種酯己甲 組 。且這酸環苯 明%内 。磺 二酸 發 t 份基過 ,化 本W成由和酯氣 ο 他自' 物基過 1 其生化丙 , 本纸張尺度適用中國國家樣準(CNS)甲4現格(210 X 297公:^ ) 82.6. 40.000 A6 B6 經濟部中夹標準马Α工消費合作社印5i 五、發明説明(7 ) 目的而言,組合物的聚合起,始劑含量較佳者為1到8w t%。 本發明組合物也可含有其量不高於1 w t %的一種或 多種慣用添加劑,例如,紫外光吸收劑,離g劑,染料, 色素,红外光吸收劑等。 較佳者,該眼鏡為含有0.1—9. 9wt%苯二甲 酸二烯丙基酯類寡合物的組成物之固化産品。更佳者,該 組成物含有2 — 8w t%的苯二甲酸二烯丙基酯類寡合物 〇 本發明也有關一種製備具有1. 50到1. 51折射 率的眼鏡之方法,包括將上述組成物予以聚合澆鏵而成。 該聚合方法傜經由自由基起始劑在通常為30它到1 ◦0 C的操作溫度下分解産生的自由基所起始者。在這些條件 下,完全聚合所需的時間為0. 5到100小時。 另外,本發明也有關至少一種具上述化學式I的苯二 甲酸二烯丙基酯類寡合物在眼鏡製造中之用途,該眼鏡傺 由具有下列組成的組成物固化所得之産品:至少一種多羥 基醇類之碳酸烯丙基酯,該多羥基醇在分子内具有2到2 0痼碩原子和2到6痼羥基;自由基起始劑,及,選用之 共單體等以改良眼鏡的著色性及減少眼鏡製造中的退件率 Ο 本發明將用下面的實施例績予閭述,這些實施例不可 視為對本發明有任何方面的限制。本發明的範圍偽由後附 -12- (請先閲讀背面之注意事項再填寫本頁) 4 -装. 訂·Co-ol Qgomer) can be prepared in a similar manner. Among them, diallyl terephthalate oligomer is more suitable for the present invention. Examples of the above diols include ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanol, 1,4-dimethanolcyclohexane,, 3-pentanediol, 1 , 2 — pentanediol, 2, 3-pentanediol, 2, 4 monopentanediol, 1, 5-hexanediol, 1, 4 monohexanediol, 1, 3 monohexanediol, 1, 2 — hexane Glycol, 2, 3-hexanediol, 2, 4-hexanediol, 2, 5-hexanediol, and 3, 4-hexanol, etc. Examples of polyhydric alcohols include aliphatic trihydric alcohols such as glycerin and trimethylolpropane; and aliphatic polyhydric alcohols such as pentaerythritol and sorbitol. The cured composition may also contain a total of up to 2 Ow, as the case may be. Such co-monomers may be comonomers such as alkenyl strips, vinyl or allyl. Examples include methyl acrylate, methyl methacrylate, phenyl methacrylate, vinyl acetate, vinyl benzoate, diallyl isophthalate, diallyl terephthalate, hexane di Diallyl acid, and diallyl cyanurate. ----------------- ^ ------ install! ------ tr ------ Production- (Please read the precautions on the back before filling in this page) The gas-producing isoester produced by the WC Industrial and Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs contains 1 Diacid hair ο The surrounding organic acid sulphur, the physical range of sulphur two with ο 2 degrees including two gas. It is a group of oxygen-contained oxygen equal amount of υ subperyl ester. The example is butyl butadiene, the solid one should be two or two agents. The first starts from the restriction of the special acid and dissolves to the non-ester methyl ester. Ρ These agents acid benzene poly whiskers ο first of all, must have the first three and the content of the agent in the agent, it can also be used as a base material can be used as a base compound into the essential ester group. And this acid cyclic benzene Ming%. Sulphuric acid has t parts of base, chemical base and ester gas. It has a base of 1 base and its biochemical base. This paper scale is applicable to China National Standards (CNS) A4 (210 X 297 : ^) 82.6. 40.000 A6 B6 Printed by the Ministry of Economic Affairs Standard Ma A Consumer Consultation Co., Ltd. 5i V. Description of Invention (7) For the purpose of polymerization of the composition, the content of the starting agent is preferably 1 to 8 wt%. The composition of the present invention may also contain one or more conventional additives in an amount of not more than 1 wt%, for example, ultraviolet light absorbers, ionizing agents, dyes, pigments, infrared light absorbers, and the like. Preferably, the spectacles are cured products of a composition containing 0.1-9. 9 wt% diallyl phthalate oligomer. More preferably, the composition contains 2-8 wt% of diallyl phthalate oligomer. The present invention also relates to a method for preparing glasses having a refractive index of 1.50 to 1.51, including the above The composition is polymerized and poured. The polymerization method is initiated by free radicals generated by the decomposition of free radical initiators at an operating temperature of usually 30 to 1 ° C. Under these conditions, the time required for complete polymerization is 0.5 to 100 hours. In addition, the present invention also relates to the use of at least one diallyl phthalate oligomer having the above chemical formula I in the manufacture of eyeglasses, which is a product obtained by curing a composition having the following composition: at least one polyhydroxyl Allyl carbonate of alcohols, the polyhydric alcohol has 2 to 20 atoms and 2 to 6 hydroxyl groups in the molecule; free radical initiators, and, selected comonomers to improve the color of the glasses And reduce the rejection rate in the manufacture of eyeglasses. The present invention will be described in the following examples. These examples should not be considered as limiting the invention in any way. The scope of the present invention is attached to -12- (please read the precautions on the back before filling this page) 4-Install. Order ·
衣紙张又度遑用中®國家標準(CNS)甲4¾格(210 X 297 'aD 82.6. 40,000 > A6 _B6_ 五、發明説明((ΰ ) 之申請專利範圍所決定。. 實施例For clothing and paper, the Chinese® National Standard (CNS) Grade A 4¾ (210 X 297 'aD 82.6. 40,000 & A6 _B6_ V. Invention description ((ΰ)) is determined by the scope of patent application .. Examples
實施例1和比較例A — D '將一条列5 0個眼鏡依照傳統方法予以著色,用以澆 鑄眼鏡的组成物含有二乙二醇二烯丙基碩酸酯(IPO) 和,適當的添加劑。表I列出所聚合的組成物,其所製成 的眼鏡之Barco 1硬度(BH),其折射率(RI) ,及因着色失敗被退件的鏡Η百分比等。折射率傜用Ze i s s折射計在2 0 t:測得者。 表 1 鏡片 添’加劑 IPP (%) RI BH 著色娜率 A 2.9 1.499 31 38% B 5% Uvithane® 893 2.9 1.498 31 28% C 3.6% TAC 2.6 1.502 30 26% D 40 ppm Ortholeum® 162 2.9 1.499 31 23% 1 5% ΑΕ0 .. 2.9 1.502 32 4%Example 1 and Comparative Examples A to D 'A row of 50 glasses are colored according to the traditional method, and the composition used to cast the glasses contains diethylene glycol diallyl master ester (IPO) and appropriate additives . Table I lists the polymerized composition, the Barco 1 hardness (BH), the refractive index (RI) of the eyeglasses made by it, and the percentage of mirror H that was rejected due to coloring failure. The refractive index is measured by Ze i s s refractometer at 20 t: measured. Table 1 Lens Additive IPP (%) RI BH Coloring Rate A 2.9 1.499 31 38% B 5% Uvithane® 893 2.9 1.498 31 28% C 3.6% TAC 2.6 1.502 30 26% D 40 ppm Ortholeum® 162 2.9 1.499 31 23% 1 5% ΑΕ0 .. 2.9 1.502 32 4%
Uvithane 8 9 3 =二丙烯酸尿烷酯寡合物,偽M 〇 r t ο ηUvithane 8 9 3 = urethane diacrylate oligomer, pseudo M 〇 r t ο η
International的産品 TAC =三聚氰酸三烯丙基酯 緩濟部中失標準局Λ工消費合作钍印裝 ,Ortholeum 1 6 2 =混合烷基酸式正磷酸酯,D u Ρ ο n t的産品 AE0=對苯二甲酸二烯丙基酯,Showa Denko的産品,為聚 〔氧(甲基一1, 2 —乙二基)氧羧基1, 4 —次苯 基羰基〕c(一 〔4 一 (2 —丙烯氣基)羰基)苯甲 82.6. 40,000 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中0國家撣準(CNS)甲4 4見烙(210 X 297公) A6 B6 五、發明説明(U ) 醯基〕W — ( 2 —丙,稀氧基),亦即,化學式I寡 合物,式中X為甲基一 1, 2 —乙二基 c Η 3 C Η 3 或 | —CH-CH2 — -CH2 - CH- 在鏡Η的著色方面,由表1所示結果可以看出用傳統材料 製成的鏡Η仍因為著色失敗而有高退件率。而本發明的眼 鏡則顯示有近乎100%的成功率。 實施例2 — 3和比較例Ε - Ν 以下列方式製備倍率為負4 (直徑6 5毫米)之成品 鏡Κ。將二乙醇二烯丙基碳酸酯,二異丙基過氣二碳酸酯. (I Ρ Ρ )和適當的添加劑等混合得到透明均勻溶液。將 該溶液置於約2 0毫巴下除氣約.1- 5分鏡直到氣體的冒出 停止為止。然後,用該混合物充镇玻璃模子組合體。將其 置於拱箱內,於溫度呈指教方式從45t:上升到801C之 條件下,以2 1小時之聚合週期進行聚合。 經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再璜寫本頁) 表2列出所聚合的組成物,其所製成的鏡片之Barcol 硬度,其折射率,及過早離型百分比,亦即,因為在模子 内預離型而不能用為成品鏡片的産品之百分比等,。 表2 -1 4 - 本纸Λ尺度通用中國國家棵準(CNS)甲4規格(210 X 297 H ) 82.6· 40,000 311914 Α7 Β7 五、發明説明() 鏡片 添加劑 IPP (%) RI BH 過早離型率 Ε 2.7 1.499 29 70% F ___ 3.25 1.499 34 66% G 5% TAC ' 2.65 1.503 27 73% Η 5% TAC 3.00 1.503 35 83% I 10% MMA 3.00 1.499 35 100% J 0.3% DBP 3.00 1.499 30 67% Κ 6.8¾ 0ΑΙΡ 2.7 1.505 30 58¾ L 10% OATP 2.7 1.510 33 64% Μ 25 ppm矽烷 3.25 1.499 33 60% Ν 0.5% MA 3.25 1.499 30 90% 2 5% AEO 2;7 1.502 30 40% 3 9.9% AEO 2.7 1.505 31 30% (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 TAC=三聚氰酸二烯丙基酯 MMA=甲基丙烯酸甲酯 DBP=苯二甲酸二酯 DA I P=間苯二甲酸二烯丙基酯 DATP=對苯二甲酸二烯丙基酯 Μ A =順丁烯二酸酐 表2所列结果顯示用傳統組成物製備成品鏡片時具有 非常高的退件百分比。這種情形甚至於發生在含有^售黏 著促進劑,例如矽烷或順丁烯二酸酐(比較例Μ和N)等 的姐成物之情況中。不過,本發明成品鏡片所具退件百分 率則明顯地較比較例產品更為低。 -15- 本纸張尺度適用中國國家標準(CNS ) Α4規格(210 X 297公釐) 訂 線International's products TAC = triallyl cyanurate, Ministry of Economic Relief, Bureau of Standards, and Consumer Cooperation, Thorium Printing, Ortholeum 1 6 2 = mixed alkyl acid orthophosphate, Du Ρ ο nt products AE0 = diallyl terephthalate, a product of Showa Denko, which is poly [oxy (methyl-1,2-ethylenediyl) oxycarboxyl 1,4-phenylenecarbonyl] c (one [4 one (2-Propylene) carbonyl) benzyl 82.6. 40,000 (please read the precautions on the back before filling in this page) This paper size is applicable to 0 national Shan Zhun (CNS) A 4 4 see the brand (210 X 297 ) A6 B6 V. Description of the invention (U) Acetyl] W — (2-Propyl, dilute oxy), that is, the oligomer of Chemical Formula I, where X is methyl-1,2-ethanediyl c Η 3 C Η 3 or | —CH—CH2 — —CH2 — CH— In terms of the coloring of the mirror Η, from the results shown in Table 1, it can be seen that the mirror Η made of traditional materials still has a high rejection rate due to coloring failure. The eyeglasses of the present invention show a nearly 100% success rate. Examples 2-3 and Comparative Examples Ε-Ν A finished mirror K with a negative magnification of 4 (65 mm diameter) was prepared in the following manner. Mix diethanol diallyl carbonate, diisopropyl peroxydicarbonate. (I Ρ Ρ) and appropriate additives, etc. to obtain a transparent homogeneous solution. The solution was placed at about 20 mbar and degassed for about .1-5 split mirrors until gas evolution ceased. Then, the glass mold assembly is filled with the mixture. It was placed in an arch box, and the polymerization was carried out in a polymerization cycle of 2 hours under the condition that the temperature rose from 45t: 801C in a teaching manner. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before writing this page). Table 2 lists the polymerized components, the Barcol hardness of the lenses produced, the refractive index, and The percentage of premature release, that is, the percentage of products that cannot be used as finished lenses due to pre-release in the mold. Table 2 -1 4-Λ size of this paper is common to China National Standard (CNS) Grade 4 (210 X 297 H) 82.6 · 40,000 311914 Α7 Β7 5. Description of invention () Lens additive IPP (%) RI BH premature departure Type rate E 2.7 1.499 29 70% F ___ 3.25 1.499 34 66% G 5% TAC '2.65 1.503 27 73% Η 5% TAC 3.00 1.503 35 83% I 10% MMA 3.00 1.499 35 100% J 0.3% DBP 3.00 1.499 30 67% Κ 6.8¾ 0ΑΙΡ 2.7 1.505 30 58¾ L 10% OATP 2.7 1.510 33 64% Μ 25 ppm Silane 3.25 1.499 33 60% Ν 0.5% MA 3.25 1.499 30 90% 2 5% AEO 2; 7 1.502 30 40% 3 9.9 % AEO 2.7 1.505 31 30% (Please read the precautions on the back before filling in this page) Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative TAC = diallyl cyanurate MMA = methyl methacrylate DBP = Phthalic acid diester DA IP = diallyl isophthalate DATP = diallyl terephthalate M A = maleic anhydride The results listed in Table 2 show that when the finished lenses are prepared with traditional compositions Has a very high percentage of returned items. This situation even occurs in cases where the product contains an adhesion promoter such as silane or maleic anhydride (Comparative Examples M and N). However, the percentage of returned parts of the finished lens of the present invention is significantly lower than that of the comparative example. -15- This paper scale is applicable to China National Standard (CNS) Α4 specification (210 X 297 mm)
At >,.-.- ;c] ..j'·..i A7 B7 五、發明説明( 表2 b 鏡片 添加劑 IPP ⑴ RI BH 過早離型率 4 5UE0 + 5XDAIP 2.7 1.506 30 38¾At >,.-.-; c] ..j '· ..i A7 B7 V. Description of the invention (Table 2 b Lens Additive IPP ⑴ RI BH Premature release rate 4 5UE0 + 5XDAIP 2.7 1.506 30 38¾
K上數據明白顯示A E 0可有效地降低含共軍體之眼 用鏡片聚合组成物之過早離型率(相較於對照實例Κ和L ...... II 1 - - I - - - : I : ------ -- --- ---- ----iI 士 - -- - - ! j Hi I -I - ii.i ! - - - 一 V ---- n ------ I— n^i Dll (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 -16 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)The data on K clearly shows that AE 0 can effectively reduce the premature release rate of the ophthalmic lens polymer composition containing the common military (compared to the control examples K and L ... II 1--I-- -: I: ---------- ---- ---- iI taxi----! J Hi I -I-ii.i!---One V ---- n ------ I— n ^ i Dll (Please read the precautions on the back before filling out this page) Printed by Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -16 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X 297mm)
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP93202480 | 1993-08-24 | ||
IN605MA1993 IN181576B (en) | 1993-08-26 | 1993-08-26 |
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TW311914B true TW311914B (en) | 1997-08-01 |
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TW082106816A TW311914B (en) | 1993-08-24 | 1993-08-24 |
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1993
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