200817166 九、發明說明 【發明所屬之技術領域】 本發明係關於無光學斑之光學薄膜之製造方法。 【先前技術】 光學薄膜除了要求透明性等光學特性優，同時薄膜的 均勻，少光學斑也是重要的。製膜所用之樹脂如劣化，則 樹脂中產生膠體，於所得之薄膜表面產生點狀缺陷，成爲 光學斑之原因。因此，防止樹脂劣化之方法方面，提出有 使用特定氣體透過量·異物量之容器的方法、使與氧氣檢 測劑及/或水分檢測劑於密封容器中共存之方法等樹脂之 保存方法（參考專利文獻1及2 )。然而，近年伴隨著液 晶面板之大型化等，尋求產能高地製造寬1 m以上之薄膜 的方法，製作此般寬廣之光學薄膜時，寬範圍內不產生光 學斑的方法方面，以傳統製法係不足的。 〔專利文獻1〕特開平7— 206998號公報 〔專利文獻2〕特開200 1 — 1 92458號公報 【發明內容】 〔發明所欲解決之課題〕 本發明以提供在廣範圍不產生光學斑之光學薄膜之製 造方法爲課題。 〔解決課題之方法〕 -4- 200817166 本發明係關於將樹脂顆粒以氧濃度1 〇PPm以下之惰性 氣體爲媒介輸送至壓出機後，將該顆粒熔融壓出成形爲特 徵之光學薄膜之製造方法。 本發明中，以將封入箱中之樹脂顆粒輸送至乾燥機 後，由該乾燥機以氧濃度1 Oppm以下之惰性氣體爲媒介輸 送至壓出機爲佳。此情況以將封入箱中之樹脂顆粒以氧濃 度1 0 p p m以下之惰性氣體爲媒介輸送至乾燥機爲佳。 本發明中，惰性氣體以氮氣爲佳。 本發明中，樹脂顆粒爲具由來自下式（1 )所示之化 合物之構造單元之環狀烯烴系樹脂之顆粒爲佳。200817166 IX. Description of the Invention [Technical Field] The present invention relates to a method for producing an optical film without optical spots. [Prior Art] In addition to the optical characteristics such as transparency, the optical film is uniform, and the film is uniform, and less optical spots are also important. If the resin used for the film formation is deteriorated, a colloid is generated in the resin, and a dot defect is generated on the surface of the obtained film to cause optical spots. Therefore, in the method of preventing deterioration of the resin, a method of storing a container using a specific gas permeation amount and a foreign matter amount, and a method of preserving a resin such as a method of coexisting with an oxygen detecting agent and/or a moisture detecting agent in a sealed container have been proposed (refer to a patent) Documents 1 and 2). However, in recent years, with the increase in the size of liquid crystal panels, it has been sought to produce a film having a width of 1 m or more in a high-capacity manner. When a wide optical film is produced, a method of not generating an optical spot in a wide range is insufficient in the conventional method. of. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A method of producing an optical film is a problem. [Means for Solving the Problems] -4- 200817166 The present invention relates to the production of an optical film characterized in that the resin particles are transported to an extruder by using an inert gas having an oxygen concentration of 1 〇ppm or less as a medium, and the pellets are melt-extrusion molded. method. In the present invention, it is preferred that the resin particles enclosed in the tank are transported to the dryer by the inert gas having an oxygen concentration of 1 Oppm or less. In this case, it is preferred that the resin particles enclosed in the tank are transported to the dryer via an inert gas having an oxygen concentration of 10 p p or less. In the present invention, the inert gas is preferably nitrogen. In the present invention, the resin particles are preferably particles of a cyclic olefin-based resin having a structural unit derived from a compound represented by the following formula (1).
(式（1)中，R1〜R4爲氫原子，鹵原子，碳數1〜30之 烴基，或其他1價有機基，各自可爲相同或相異。又’ R1 〜R4之中任意2者可相互鍵結，形成單環或多環構造，m 爲〇或正整數，p爲0或正整數） 本發明亦可爲將該光學薄膜進一步延伸而成之光學薄 膜之製造方法。 〔發明效果〕 -5- 200817166 本發明可提供一種就算薄膜寬廣亦無光學斑之光學薄 膜之製造方法。又，如光學薄膜爲施加延伸之薄膜時，可 適用於相位差及光軸安定且無光學斑之薄膜而。本發明之 光學薄膜，爲光學斑少，薄膜產率佳，進一步在延伸薄膜 上霧値小而透明性優，於使用此之大畫面液晶顯示器等可 全面達成彎曲及不均少之高性能。 〔實施發明之最佳型態〕 《光學薄膜》 <樹脂> 本發明所用之樹脂方面，爲薄膜形狀，光線透過率爲 70%以上，以85%以上之者爲佳。具體上，以透明環氧樹 脂、聚酯樹脂、聚碳酸酯樹脂、聚醚颯樹脂、聚亞芳基樹 脂、環狀烯烴系樹脂、聚苯撐醚系樹脂、有機矽氧烷系樹 脂等之具有高透明性同時有優異耐熱性之樹脂爲佳。此等 中，由透明性及耐熱性優，以及吸濕（水）性低，所得之 特定構件之不易吸濕（水）變形點來看，以環狀烯烴系樹 脂、聚苯撐系樹脂及有機矽氧烷系樹脂爲佳，特別以具由 來自該式（1)所示之化合物之構造單元之環狀烯烴系樹 脂爲佳。 本發明之光學薄膜所用之環狀烯烴系樹脂方面，有如 下次之（共）聚物。 (1 )該式（1 )所示之特定單體之開環聚合物。 (2 )該式（1 )所示之特定單體與共聚合性單體之開 -6- 200817166 環共聚合物。 (3 )該（1 )或（2 )之開環（共）聚物之氯化 (共）聚物。又，（3 )中，該（1 )之開環聚合物之氫化 聚合物構造單元可以該式（2)表示。 (4 )該（1 )或（2 )之開環（共）聚物經Friedel-(In the formula (1), R1 to R4 are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, each of which may be the same or different. Further, any of 'R1 to R4' They may be bonded to each other to form a monocyclic or polycyclic structure, m is 〇 or a positive integer, and p is 0 or a positive integer. The present invention may also be a method for producing an optical film in which the optical film is further extended. [Effect of the Invention] -5- 200817166 The present invention can provide a method for producing an optical film which is thin and has no optical spots. Further, when the optical film is a film to which an extension is applied, it can be applied to a film having a phase difference and an optical axis stability without an optical spot. The optical film of the present invention has a small number of optical spots and a good film yield, and further has a small haze on the stretched film and excellent transparency, and a large-screen liquid crystal display or the like can be used to achieve high performance in bending and unevenness. [Best Mode of Carrying Out the Invention] "Optical Film" <Resin> The resin used in the present invention is in the form of a film, and the light transmittance is 70% or more, and preferably 85% or more. Specifically, a transparent epoxy resin, a polyester resin, a polycarbonate resin, a polyether oxime resin, a polyarylene resin, a cyclic olefin resin, a polyphenylene ether resin, an organic siloxane resin, or the like is used. A resin having high transparency and excellent heat resistance is preferred. Among these, the transparency and heat resistance are excellent, and the moisture absorption (water) property is low, and the obtained member is not easily moisture-absorbent (water) deformation point, and a cyclic olefin resin, a polyphenylene resin, and The organic oxyalkylene-based resin is preferred, and a cyclic olefin-based resin having a structural unit derived from the compound represented by the formula (1) is particularly preferred. The cyclic olefin resin used in the optical film of the present invention is, for example, the next (co)polymer. (1) A ring-opening polymer of a specific monomer represented by the formula (1). (2) The specific monomer represented by the formula (1) and the copolymerizable monomer are opened -6-200817166 ring copolymer. (3) A chlorinated (co)polymer of the ring-opening (co)polymer of (1) or (2). Further, in (3), the hydrogenated polymer structural unit of the ring-opening polymer of (1) may be represented by the formula (2). (4) The ring-opening (co)polymer of (1) or (2) via Friedel-
Crafts反應環化後，氫化之（共）聚物。 (5) 該式（1)所示之特定單體與含有不飽和雙鍵化 合物之飽和共聚合物。 (6) 由該式（1)所示之特定單體、乙烯系環狀烴系 單體及環戊二烯系單體選出之1種以上之單體加成型 (共）聚物及其氫化（共）聚物。 (7) 該式（1)所示之特定單體與丙烯酸酯之交互共 聚合物。 <特定單體> 該特定單體之具體例方面，有如下之化合物，但本發 明並不爲此等具體例所限定。 二環〔2.2.1〕庚—2 —烯， 三環〔4.3_0.12,5〕— 8 —癸烯， 三環〔4.4.0.12,5 〕一 3 —十一烯， 四環〔4·4·0·12,5.17，1()〕一 3—十二烯， 五環〔6·5·1·13,6·02,7.09，13〕— 4一十五烯， 5—甲基二環〔2.2.1〕庚—2—烯， 5 —乙基二環〔2.2.1〕庚—2 —烯， -7- 200817166 5—甲氧基簾基一環〔2.2.1〕庚一 2 —矯， 5—甲基一 5—甲氧基鑛基二環〔2.2.1〕庚一 2—烯， 5—氯基一環〔2.2.1〕庚一 2 —燃， 8 —甲氧基羰基四環〔4.4·0·12,5.Γ，1()〕一 3 —十二 烯， 8 —乙氧基羰基四環〔4·4·0.12,5·Γ，1()〕一 3 —十二 烯， 8 — η—丙氧基羰基四環〔4·4·0·12,5·Γ，1()〕一 3—十二 烯， 8 —異丙氧基羰基四環〔4·4·0·12’5.17’1()〕一 3 —十二 烯， 8 — η — 丁 氧基羰基四環〔4 · 4.0 · 1 2，5 · Γ，1G〕一 3 —十二 儲， 8 —甲基一 8 —甲氧基羰基四環〔4.4.0.12 ’5.17’1G〕— 3 一十二烯， 8—甲基一 8—乙氧基羰基四環〔4·4·0·12’5.Γ’1()〕— 3 一十二烯， 8 —甲基—8— η —丙氧基羰基四環〔4.4.0.12’5.17’1()〕 —3 —十一^嫌， 8 —甲基一 8 —異丙氧基羰基四環〔4·4.0.12’5·Γ’1()〕 —3 —十二烯， 8 —甲基一 8 — η—丁 氧基羰基四環〔4·4.0.12’5·Γ，1()〕 —3 -十二烯， 5 —亞乙基二環〔2.2.1〕庚—2 —烯， -8- 200817166 8 —亞乙基四環〔4.4.0.12,5.r，1G〕一3—十二烯， 5-苯基二環〔2.2.1〕庚—2 —烯， 8— 苯基四環〔4·4·0·12,5·17，1()〕— 3-十二烯， 5- 氟二環〔2.2.1〕庚—2-烯， 5—氟甲基二環〔2.2.1〕庚一 2—烯， 5 —三氟甲基二環〔2.2.1〕庚一2—烯， 5 —五氟乙基二環〔2.2.1〕庚一 2—烯， 5，5 —二氟二環〔2.2.1〕庚—2-烯， 5，6—二氟二環〔2.2.1〕庚—2—烯， 5，5—雙（三氟甲基）二環〔2.2.1〕庚一 2—烯， 5，6—雙（三氟甲基）二環〔2.2.1〕庚一 2—烯， 5 —甲基一 5 —三氟甲基二環〔2.2.1〕庚—2—烯， 5，5,6 — 三氟二環〔2.2.1〕庚一 2-烯， 5，5,6 —三（氟甲基）二環〔2.2.1〕庚一 2 —烯， 5,5，6,6 —四氟二環〔2.2.1〕庚一 2 —烯， 5，5,6,6 —四（三氟甲基）二環〔2.2.1〕庚一 2—烯， 5,5 —二氟一 6,6-雙（三氟甲基）二環〔2.2.1〕庚一 2 —少希’ 5,6-二氟—5,6 -雙（三氟甲基）二環〔2.2.1〕庚一 2 —矯’ 5，5,6 —三氟一 5 —三氟甲基二環〔2.2.1〕庚—2 — 嫌， 5 —氟—5 —五氟乙基一6,6—雙（二氟甲基）二環〔 2.2.1〕庚—2 —嫌， -9- 200817166 5，6 —二氟一 5 —五氟—iso —丙基一 6 -三氟甲基二環 〔2.2.1〕庚—2 —烯， 5 —氯一5,6,6 —二氟二環〔2.2.1〕庚—2- 儲， 5，6 — 二氯一 5,6 —雙（二氟甲基）二環〔2.2.1〕庚一 2 -儲’ 5.5.6 —三氟一 6 -三氟甲氧基二環〔2.2.1〕庚一 2 - 烯， 5.5.6 -三氟一 6 —五氟丙氧基二環〔2.2.1〕庚一 2- 烯， 8 —氟四環〔4·4·0.12,5·17，1()〕一 3 —十二烯， 8—氟甲基四環〔4·4·0·12,5·17，1()〕一 3—十二烯， 8—二氟甲基四環〔4·4.0·12’5·Γ，1()〕一 3—十二烯， 8 — 三氟甲基四環〔4·4·0·12,5·17，1()〕一 3—十二烯， 8 —五氟乙基四環〔4.4.0.12,5.17，1g〕一 3—十二烯， 8.8— 二氟四環〔4·4·0·12,5·17，1()〕— 3 —十二烯， 8.9— 二氟四環〔4·4·0.12,5·17，1()〕一 3—十二烯， 8,8— 雙（三氟甲基）四環〔4.4·0·12,5·ΐ7，1()〕一 3—十 二烯， 8，9 一雙（三氟甲基）四環〔4 · 4 · 0 · 1 2，5 · 1 7，1 G〕一 3 -十 二烯， 8 —甲基一8 —三氟甲基四環〔4.4.0.I2,5.Γ，10〕一 3 — 十二烯， 8,8,9一三氟四環〔4.4.0.12,5.17，1()〕一3—十二烯， 8,8,9 一三（三氟甲基）四環〔4·4.0·12,5·Γ，1()〕一3 — -10- 200817166 8,8,959—四氟四環〔4.4.0.12,5.17，1()〕一3—十二烯， 8,8,9,9—四（三氟甲基）四環〔4·4·0·12,5.Γ，1()〕一 3 一十二烯， 8.8 —二氟一 9,9 一雙（三氟甲基）四環 〔 4.4·0·12,5·Γ，1()〕— 3 —十二烯， 8.9 一二氟一 8,9 —雙（三氟甲基）四環〔 4·4·0·12,5.Γ，1()〕— 3 —十二烯， 8.8.9 一 三氟一 9 一 三氟甲基四環〔4·4·0·12,5·17，1()〕一 3 -十二烯， 8.8.9 一三氟一 9 一三氟甲氧基四環〔4·4·0·12,5·17，10〕 一 3 -十二烯， 8,8,9_三氟一 9 一五氟丙氧基四環〔4.4.0·12,5·17，10〕 一 3 -十二烯， 8 —氟一 8 —五氟乙基—9,9 —雙（三氟甲基）四環〔 4·4·0·12,5·17，1()〕一 3—十二烯， 8，9 一二氟一 8—五氟iso —丙基一 9 一三氟甲基四環〔 4.4.0.12,5 .17，1()〕— 3-十二烯， 8—氯一8,9,9一 三氟四環〔4·4·0·12,5·17，1()〕一 3—十 二烯， 8.9 一二氯一 8,9 —雙（三氟甲基）四環〔 4 · 4 · 0 · 1 2，5 · 17，1G〕— 3 —十二烯， 8 — （2,2,2—三氟乙氧基羰基）四環〔4·4·0·12,5·Γ，10 〕一 3 -十二烯， -11 - 200817166 8 —甲基一 8 — （2，2,2 —三氟乙氧基羰基）四環〔 4·4.0·12,5·17’1()〕一 3—十二烯等。 此等可1種單獨或2種以上倂用。 特定單體中較佳爲，該式（1)中，R1及R3爲氫原子 或碳數1〜10，較佳爲1〜4，更佳爲1〜2之烴基，R2及 R4爲氫原子或1價之有機基，R2及R4之至少1者爲具 有氫原子及烴基以外之極性之極性基，m爲0〜3之整 數，p爲0〜3之整數，較佳爲m+p=0〜4，爲0〜2更 佳，而m=l，p=0又更佳。m=l，p二0之特定單體，因 所得之環狀烯烴系樹脂之玻璃轉移溫度高且機械強度優而 適宜。 該特定單體之極性基方面，可舉出有羧基、羥基、烷 氧基羰基、烯丙氧基羰基、胺基、醯胺基、氰基等，此等 極性基爲經亞甲基等連結基鍵結亦可。又，羰基、醚基、 矽烷基醚基、硫醚基、亞胺基等具有極性之2價之有機基 爲連結基而鍵結之烴基等亦可作爲極性基。此等中，以羧 基、羥基、烷氧基羰基或烯丙氧基羰基爲佳，特別以烷氧 基羰基或烯丙氧基羰基爲佳。 另外，R2及R4之至少1者爲式-(CH2)nCOOR所示之 極性基單體，因所得之環狀烯烴系樹脂有高玻璃轉移溫度 與低吸濕性，與各種材料有優異之密著性而適合。該特定 極性基相關式中，R爲碳原子數1〜12，以1〜4更佳，特 別以1〜2之烴基更佳，以烷基爲佳。又，η通常爲〇〜 5，而η値愈小，所得之環狀烯烴系樹脂之玻璃轉移溫度 -12- 200817166 變高而爲適合，而η爲0之特定單體因其合成容易而適宜 使用。 又，該式（1)中，R1或R3以院基爲佳，係爲碳數1〜4 之烷基，以1〜2之烷基更佳，特別以甲基又更佳，特別 是此烷基爲該式-(CH2)nCOOR所示之特定極性基爲與鍵結 碳原子相同碳原子鍵結，所得之環狀烯烴系樹脂因可吸濕 性低而適用。 <共聚合性單體> 共聚合性單體之具體例方面，可舉例有環丁烯，環戊 烯，環庚烯，環辛烯，二環戊二烯等之環烯烴。 環烯烴之碳數方面，以4〜20爲佳，更佳爲5〜12。 此等可1種單獨或2種以上倂用。 特定單體/共聚合性單體之偏好使用範圍，重量比爲 100/0 〜50/50，更佳爲 100/0 〜60/40。 <開環聚合觸媒> 本發明中，（1 )特定單體之開環聚合物，及（2 )爲 得到特定單體與共聚合性單體之開環共聚合物之開環聚合 反應，爲在歧化觸媒存在下進行。 此歧化觸媒爲，（a)由W、Mo及Re化合物所選出 之至少1種，與（b ) Deming之週期表ία族元素（如 Li、Na、K 等）、ΠΑ 族元素（如、Mg、Ca 等）、ΠΒ 族 元素（如，Zn、Cd、Hg等）、ΠΙΑ族元素（如，B、A1 -13- 200817166 寺）、IVA S矢兀素（如’ Si、Sn、Pb等）、或IVB族元 素（如，Ti、Zr等）之化合物、具有至少1種含該元素一 碳鍵結或該元素-氫鍵結之者所選出之至少1種之組合所 成之觸媒。又，此場合爲提高觸媒活性亦可添加後述之 (c )添加劑。 (a )成分方面適當之 w、Mo或Re化合物之代表例 方面，有WC16、M〇Cl6、Re〇Cl3等特開平1— 132626號公 報第8頁左下欄第6行〜第8頁右上欄第1 7行之化合 物。 (b) 成分之具體例方面，有 n — C4H9Li、 (C2H5)3A1、（C2H5)2A1C1、（C2H5)15A1C115、（C2H5)A1C12 、甲基鋁氧烷、LiH等特開平1— 132626號公報第8頁右 上欄第1 8行〜第8頁右下欄第3行之化合物。 添加劑（c )成分之代表例方面，有醇類、醛類、酮 類、胺類等適宜使用，進一步可使用特開平1— 132626號 公報第8頁右下欄第16行〜第9頁左上攔第17行之化合 物。 歧化觸媒使用量方面，該（a)成分與特定單體之莫 耳比「（a)成分：特定單體」，通常爲1:5 00〜1: 50,000之範圍，以1:1，000〜1:10,000之範圍爲佳。 (a)成分與（b)成分之例，以金屬原子比（a)： (b)爲1: 1〜1: 50，以1: 2〜1: 30之範圍爲佳。 (a )成分與（c )成分之比例，以莫耳比（c ): (a)爲 0.005: 1〜15: 1，以 0.05: 1〜7: 1 之範圍爲 -14- 200817166 佳。 <聚合反應用溶劑> 開環聚合反應中所用之溶劑（構成分子量調節劑溶液 之溶劑、特定單體及/或歧化觸媒之溶劑）方面，如戊 烷、己烷、庚烷、辛烷、壬烷、癸烷等鏈烷類，環己烷、 環庚烷、環辛烷、萘烷、原菠烷等環鏈烷類，苯、甲苯、 二甲苯、乙基苯、異丙苯等芳香族烴，氯丁烷、溴己烷、 氯化甲烷、二氯乙烷、六亞甲基二溴、氯苯、氯仿、四氯 乙烯等鹵化鏈烷、鹵化芳基等化合物、酢酸乙酯、酢酸η 一丁酯、酢酸iso — 丁酯、丙酸甲酯、二甲氧基乙烷等飽 和羧酸酯類，二丁基醚、四氫呋喃、二甲氧基乙烷等醚類 等，此等可單獨或混合使用。此等中，以芳香族烴爲佳。 溶劑使用量方面，「溶劑：特定單體（重量比）」， 通常爲1: 1〜10: 1，以1: 1〜5: 1之量爲佳。 <分子量調節劑> 所得之開環（共）聚物之分子量調節，可依聚合溫 度，觸媒種類，溶劑種類而進行，本發明中，藉由與分子 量調節劑於反應系共存而調節。 在此，合適之分子量調節劑方面，如乙j：希、丙丨希、1 一 丁嫌、1一戊燒、1 一己嫌、1一庚燦、1 一辛燦、1 一壬 嫌、1 一癸烯等α -嫌烴類及苯乙烯，此等中，特別以i _ 丁嫌、1 一己嫌爲佳。 -15- 200817166 此等分子囊調節劑，可單獨或2種以上混合使用。 分子量調節劑使用量方面，相對於供應開環聚合反應 之^疋單體1莫耳，爲0.005〜〇·6莫耳，以〇·〇2〜0.5莫 耳爲佳。 爲彳守到（2 )開環共聚合物，於開環聚合工程中，使 特定單體與共聚合性單體進行開環共聚合即可，另外，在 聚丁 一烯’聚異丙烯等共軛雙烯化合物，苯乙烯一 丁二烯 共聚合物，乙烯一非共軛雙烯共聚合物，聚原菠烯等主鏈 中含2個以上碳一碳間雙鍵之不飽和烴系聚合物等存在下 令特定單體進行開環聚合亦佳。 以上般所得之開環（共）聚物，可直接使用，而將此 進一步氫化所得之（3 )氫化（共）聚物，可用作耐衝撃 性大之樹脂原料。 <氫化觸媒> 氫化反應，通常之方法，也就是於開環聚合物溶液中 添加氫化觸媒，在常壓〜300氣壓，以3〜200氣壓之氫氣 體爲佳，於〇〜200 °C進行，而以20〜18(TC使其作用爲 佳。 氫化觸媒方面，可使用在一般之烯烴性化合物氫化反 應所用者。此氫化觸媒方面，舉例有不均一系觸媒及均一 系觸媒。 不均一系觸媒方面，有銷、白金、鎳、錯、纟了等貴金 屬觸媒物質，其載負於碳、二氧化砂、氧化銘、欽等載體 -16- 200817166 之固體觸媒。又’均一系觸媒方面，有環烷酸鎳/三乙基 鋁、乙醯基丙酮鎳/三乙基鋁、辛烯酸鈷/ η 一丁基鋰、 Cp2ZrTiCl2/二乙基鋁單氯化物、酢酸铑、氯三（三苯基 膦）铑、二氯三（三苯基膦）釕、氯氫羰基三（三苯基 膦）釕、二氯羰基三（三苯基膦）釕等。觸媒形態可爲粉 末或粒狀。 此等氫化觸媒，使用開環（共）聚物：氫化觸媒（重 量比）爲1 : 1 X 1 〇 ·6〜1 : 2之比例。 如此，經氫化所得之氫化（共）聚物’成爲有優異之 熱安定性，成形加工時及作爲製品使用時就算加熱’其特 性亦不會劣化。在此，氫化率，通常爲50%以上，以70 %以上爲佳，更佳爲90%以上’ 99%以上又更佳。 又，氫化（共）聚物之氫化率’以500MHz，ΑΝ MR 測定 之値爲 50% 以上 ，以 90% 以上 爲佳， 更佳爲 98 %以上，99%以上又更佳。氫化率愈高’對熱或光之安定 性愈優異，使用作爲本發明波長板時’可得到經長期間仍 安定之特性。 又，作爲本發明之環狀烯烴系樹脂使用之氫化（共） 聚物，該氫化（共）聚物中所含膠體之含有量以5重量％ 以下爲佳，以1重量％以下更佳。 又，本發明之環狀烯烴系樹脂方面，（4 )將該（1 ) 或（2 )之開環（共）聚物經Friedel-Crafts反應環化 後，亦可使用已氫化之（共）聚物。 -17- 200817166 〈經 Friedel-Crafts 反應環化〉 將（1)或（2)之開環（共）聚物經 Friedel-Crafts 反應環化之方法並未特別限定，可用特開昭5 0 — 1 543 99 號公報之酸性化合物之公知方法。酸性化合物方面，具體 上，可用 A1C13 、 BF3 、 FeCl3 、 A1203 、 HC1 、 CH2C1C0 0H、沸石、活性白土等路易士酸、布氏酸。 環化之開環（共）聚物，可與（1 )或（2 )之開環 (共）聚物同樣地方法氫化。 另外，本發明之環狀烯烴系樹脂方面，亦可使用 (5)該特定單體與含有不飽和雙鍵化合物之飽和共聚合 物0 <含有不飽和雙鍵化合物> 含有不飽和雙鍵化合物方面，如乙烯、丙儲、丁烯 等’以碳數2〜12爲佳，更佳爲碳數2〜8之燒烴系化合 物。 特定單體/含有不飽和雙鍵化合物之偏好使用範圍， 以重量比爲90/10〜40/60，更佳爲85/15〜50/50。 本發明中，爲得到（5 )特定單體與含有不飽和雙鍵 化合物之飽和共聚合物，可使用一般之加成聚合法。 <加成聚合觸媒> 合成該（5)飽和共聚合物之觸媒方面，可使用由鈦 化合物、鉻化合物及釩化合物選出之至少一種，與作爲輔 -18- 200817166 助觸媒之有機鋁化合物。 於此，鈦化合物方面，有四氯化鈦、三氯化鈦等，而 锆化合物方面有雙（環戊二烯）鉻氯化物、雙（環戊二 烯）鉻二氯化物等。 另外，釩化合物方面，可使用如下式 VO(OR)aXb5 或 V(OR)cXd 〔但，R爲烴基，X爲鹵原子，〇Sa$3，0SbS3， (a+b) $3，0^c$4，0^d^4，3$ (c+d) ^ 4 ] 所示之釩化合物，或此等之電子供給加成物。 該電子供給體方面，有醇、苯酚類、酮、醛、羧酸、 有機酸或無機酸之酯、醚、酸醯胺、酸酐、烷氧基矽烷等 含氧電子供給體、氨、胺、腈、異氰酸酯等含氮電子供給 體等。 另外，輔助觸媒之有機鋁化合物方面，可使用由含至 少1個鋁-碳鍵結或鋁-氫鍵結之者選出之至少一種。 該等中，如使用釩化合物時，釩化合物與有機鋁化合 物之比率，相對於釩原子，鋁原子之比（A1 / V )爲2以 上，以2〜5 0爲佳，以3〜2 0之範圍更佳。 加成聚合中所使用之聚合反應用溶劑，可使用與開環 聚合反應中所使用之溶劑相同者。又，所得之（5 )飽和 共聚合物分子量之調節，通常，以氫進行。 另外，本發明之環狀烯烴系樹脂方面，亦可使用 -19- 200817166 (6)該特定單體’及乙嫌系環狀煙系單體或環戊二綠系 單體所選出之1種以上卓體之加成型共聚合物及宜氨化丑 聚合物。 <乙烯系環狀烴系單體> 乙烯系環狀烴系單體方面，如，4 一乙烯環戊丨希、2 — 甲基一 4 一異丙嫌基環戊等乙j：希環戊烯系單體、*一乙烯 環戊烷、4-異丙烯基環戊烷等乙烯環戊烷系單體等乙烯 化5員環烴系單體、4 一乙烯環己烯、4-異丙烯基環己 烯、1—甲基一 4 一異丙綠基環己烯、2 —甲基一 4 一乙儲環 己烯、2 -甲基- 4 -異丙烯基環己烯等乙烯環己烯系單 體、4 —乙烯環己烷、2—甲基一 4 —異丙烯基環己烷等乙 嫌環己院系單體、苯乙儲、α —甲基苯乙嫌、2 -甲基苯 乙烯、3 —甲基苯乙烯、4 一甲基苯乙烯、1 一乙烯萘、2_ 乙烯萘、4一苯基苯乙烯、ρ—甲氧基苯乙烯等苯乙烯系單 體、d —帖嫌、1 一蔽嫌、一·帖細、d-棒彳冡綠、1 一棒樣 烯、二戊烯等萜烯系單體、4 -乙烯環庚烯、4-異丙烯基 瓌庚烯等乙烯環庚烯系單體、4 -乙烯環庚烷、4 -異丙烯 基環庚院等乙燒環庚院系單體等。其中以苯乙稀、α -甲 基苯乙烯爲佳。此等可1種單獨或2種以上倂用。 C環戊二烯系單體> 本發明之（6)加成型共聚合物單體中所使用之環戊 二烯系單體方面，如環戊二烯、1—甲基環戊二烯、2—甲 -20- 200817166 基環戊二嫌、2-乙基環戊二嫌、5 -甲基環戊二嫌、5,5 -甲基環戊二烯等。以環戊二烯爲佳。此等可1種單獨或 2種以上倂用。 由該特定單體、乙烯系環狀烴系單體及環戊二烯系單 體所選出之1種以上之單體的加成型（共）聚物爲，可以 以與該（5)特定卓體與含有不飽和雙鍵化合物之飽和共 聚合物同樣之加成聚合法得到。 又，該加成型（共）聚物之氫化（共）聚物爲，可以 與該（3 )開環（共）聚物之氫化（共）聚物同樣之氫化 法得到。 另外，本發明之環狀烯烴系樹脂方面，亦可使用 (7)該特定單體與丙烯酸酯之交互共聚合物。 <丙烯酸酯> 本發明之（7)該特定單體與丙烯酸酯之交互共聚合 物之製造中所使用之丙烯酸酯方面，如，甲基丙烯酸酯、 2-乙基己基丙烯酸酯、環己基丙烯酸酯等碳原子數1〜20 之直鏈狀、分支狀或環狀烷基丙烯酸酯、縮水甘油基丙烯 酸酯、2-四氫糠基丙烯酸酯等碳原子數2〜20之含雜環 基之丙烯酸酯、具有苄基丙烯酸酯等碳原子數6〜20之含 芳香族環基丙烯酸酯、異冰片基丙烯酸酯、二環戊基丙烯 酸酯等之碳數7〜30之有多環構造之丙烯酸酯。 本發明中，爲得到（7 )該特定單體與丙烯酸酯之交 互共聚合物，在路易士酸存在下，使該特定單體與丙烯酸 -21 - 200817166 酯合計爲100莫耳時’通常，以該特定單體爲30〜70莫 耳，丙烯酸酯爲70〜30莫耳之比例，而以該特定單體爲 40〜60莫耳，丙烯酸酯爲60〜4〇莫耳之比例爲佳，又以 該特定單體爲45〜55莫耳，丙烯酸酯爲55〜45莫耳之比 例進行自由基聚合更佳。 爲得到（7)該特定單體與丙烯酸酯之交互共聚合物 所使用之路易士酸的量，相對於丙烯酸酯1 0 0莫耳，爲 0.001〜1莫耳之量。又，可使用公知之產生游離自由基之 有機過氧化物或偶氮雙系之自由基聚合起始劑，聚合反應 溫度，通常爲一2 0 °C〜8 0 °C，以 5 °C〜6 0 °C爲佳。又，聚 合反應用溶劑，可使用與開環聚合反應中所使用之溶劑相 同之者。 又，本發明之「交互共聚合物」爲，來自該特定單體 之構造單元爲不相連，也就是，指具有來自該特定單體之 構造單元旁必爲來自丙烯酸酯之構造單元之構造的共聚合 物，但來自丙烯酸酯之構造單元間相鄰存在之構造並不排 除。 本發明所用之環狀烯烴系樹脂之適宜分子量爲，在固 有黏度〔7?〕inh時爲0.2〜5dl/g，更佳爲〇·3〜3dl/g， 特別佳爲0.4〜1 . 5 d 1 / g ’溶解於四氫咲喃後以膠體滲透層 析法（GPC )測定之聚苯乙烯換算之數平均分子量（Mn ) 爲8,000〜100,000，更佳爲10,000〜80,000，特別佳爲 12,000〜50,000，重量平均分子量（Mw)爲20，000〜 300，〇〇〇，更佳爲 30, 〇〇〇 〜000 ’ 特別佳爲 000 〜 -22- 200817166 200,000之範圍者爲合適。又，分子量分布（Mn/Mw)， 以2.0〜4.0爲佳，更佳爲2.5〜3.7，又更佳爲2.8〜3·5。 固有黏度〔7?〕inh，藉由數平均分子量及重量平均分 子量在該範圍的話，環狀烯烴系樹脂之耐熱性、耐水性、 耐藥品性、機械的特性，以及作爲本發明之光學薄膜之成 形加工性良好。 本發明所用之環狀烯烴系樹脂之玻璃轉移溫度（Tg ) 方面，通常爲1 1 0 °C以上，以1 1 0〜3 5 0 °c爲佳，更佳爲 1 2 0〜2 5 0 °C，特別佳爲 1 2 0〜2 0 0 °C。T g未滿 1 1 0 °C時， 在高溫條件下之使用，或塗佈、印刷等二次加工時會變形 而不適宜。另一方面，Tg超過350 °C則成形加工變困難， 又因成形加工時提高加熱溫度是必要的，樹脂因熱劣化之 可能性變高。 以上之環狀烯烴系樹脂，於不損及本發明效果之範圍 下，可搭配如特開平9 - 22 1 5 77號公報、特開平 1 0 — 2 8 773 2號公報所記載之特定烴系樹脂、或公知之熱可 塑性樹脂、熱可塑性彈性體、橡膠質聚合物、有機微粒 子、無機微粒子等。 又，本發明所用之環狀烯烴系樹脂，於不損及本發明 效果之範圍下，可添加爲改善耐熱劣化性或耐光性之公知 之抗氧化劑或紫外線吸收劑等添加劑。如，將由下述苯酚 系化合物、硫醇系化合物、硫化物系化合物、二硫化物系 化合物、磷系化合物所成群中選出之至少1種化合物，相 對於本發明之環狀烯烴系樹脂1 0 0重量份，添加0.0 1〜1 〇 -23- 200817166 重量份，可提升耐熱劣化性。 苯酚系化合物： 苯酚系化合物方面，三乙二醇一雙〔3 — （3 - t 一丁 基—5 -甲基一 4一羥基苯基）丙酸酯〕、1，6-己烷二醇 一雙〔3 - （3,5 -二一 t 一丁基一 4 一羥基苯基）丙酸酯 〕、2,4 —雙—（η —辛基硫）一 6-（4 —羥基 一3,5- 二— t — 丁基苯胺基）一 3,5 -三嗪、季戊四醇一四〔3— (3,5 一二一 t 一丁基—4 —羥基苯基）丙酸酯〕、2，2—硫一二乙 撐雙〔3 - （3,5 -二一 t — 丁基—4 一羥基苯基）丙酸酯 〕、十八烷基一 3— (3,5-二一 t 一丁基一 4 —羥基苯基） 丙酸酯〕、N，N—六亞甲基雙（3,5—二一t一丁基 — 4一 羥基一氫桂皮醯胺）、1，3,5 -三甲基一 2,4,6-三（3,5 — 二一 t — 丁基—4一羥基苄基）苯、三—（3,5 -二—t 一丁 基一 4 一羥基苄基）一異氰脲酸酯、3,9 -雙〔2 - 〔3 - (3 - t — 丁基一 4一經基一 5—甲基苯基）丙釀氧基〕一 1，1 —二甲基乙基〕一 2,4,8, 10—四氧雜螺〔5.5〕十一烷等。 以十八烷基一 3 -（3,5 -二一 t — 丁基_4 一羥基苯基）丙 酸酯〕、1，3,5—三甲基一254,6—三（3,5—二一1一丁基一 4一羥基苄基）苯、季戊四醇—四〔3 — （3,5—二—t — 丁 基一 4 一羥基苯基）丙酸酯〕爲佳，特別佳爲，十八烷基 一 3-（3,5-二一 t — 丁基一 4 —羥基苯基）丙酸酯〕等。 硫醇系化合物： 硫醇系化合物方面，有t -十二烷基硫醇、己基硫醇 -24- 200817166 等烷基硫醇、2 -锍基苯並咪唑、2 -锍 味π坐、1 一甲基一 2 -（甲基疏基）苯並ϊ 一甲基苯並咪唑、2—锍基一 4 一甲基苯 一 5-甲基苯並咪唑、2-锍基—5,6 —二 一（甲基锍基）苯並咪唑、1—甲基一2-（ 唑、2 —锍基一 1，3 -二甲基苯並咪唑、锍 硫化物系化合物： 硫化物系化合物方面，有2，2 -硫 (3,5 -二一 t 一丁基一 4一羥基苯基）丙 雙（4 —甲基一 6 - t一丁基苯酚）、2,4一 基）一 6—甲基苯酚、雙十二烷基3,3’-十四烷基3,3’ -硫二丙酸酯、二硬酯基 酯、季戊四醇四（3 -十二烷基硫丙酸酯 3，3’ 一硫二丙酸酯等。 基一 6—甲基苯並 Μ坐、2 —锍基一 1 並咪唑、2 -锍基 甲基苯並咪唑、2 甲基锍基）苯並咪 基酢酸等。 一二乙撐雙〔3 — 酸酯〕、2,2 -硫 雙（η —辛基硫甲 硫二丙酸酯、雙 3，3 ’ 一硫二丙酸 )、雙十三烷基After the Crafts reaction is cyclized, the (co)polymer is hydrogenated. (5) A specific monomer represented by the formula (1) and a saturated copolymer containing an unsaturated double bond compound. (6) One or more monomer addition molding (co)polymers selected from the specific monomer represented by the formula (1), the ethylene cyclic hydrocarbon monomer, and the cyclopentadiene monomer, and hydrogenation thereof (co)polymer. (7) An interactive copolymer of a specific monomer and an acrylate represented by the formula (1). <Specific monomer> The specific examples of the specific monomer include the following compounds, but the present invention is not limited to such specific examples. Bicyclo[2.2.1]hept-2-ene, tricyclo[4.3_0.12,5]-8-decene, tricyclo[4.4.0.12,5]-3-epene, tetracyclic [4· 4·0·12, 5.17, 1()] 3- 3-dodecene, pentacyclo[6·5·1·13,6·02,7.09,13]—tetradecene, 5-methyldi Ring [2.2.1] hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, -7- 200817166 5-methoxyl-ring [2.2.1]g-2 Correction, 5-methyl-5-methoxy ore-bicyclo[2.2.1]heptan-2-ene, 5-chloro-a ring [2.2.1]g- 2 -flame, 8-methoxycarbonyl tetra Ring [4.4·0·12,5.Γ,1()]-3-dodecene, 8-ethoxycarbonyltetracyclo[4·4·0.12,5·Γ,1()]-3-10 Diene, 8-n-propoxycarbonyltetracyclo[4·4·0·12,5·Γ,1()]-3-dodoene, 8-isopropoxycarbonyltetracyclo[4·4 ·0·12'5.17'1()]-3-dodecene, 8-n-butoxycarbonyltetracyclo[4 · 4.0 · 1 2,5 · Γ, 1G]- 3 - 12 storage, 8 —methyl-8-methoxycarbonyltetracyclo[4.4.0.12 '5.17'1G]-3 Diene, 8-methyl-8-ethoxycarbonyltetracyclo[4·4·0·12'5.Γ'1()]-3 Tetradoene, 8-methyl-8-η-propyl Oxycarbonyl tetracyclo[4.4.0.12'5.17'1()] -3 -11^, 8-methyl-8-isopropoxycarbonyltetracycline [4.4.0.12'5·Γ'1 ()] -3 - dodecene, 8-methyl-8-n-butoxycarbonyltetracycline [4.4.0.12'5·Γ,1()]-3-butene, 5-Asia Ethyl bicyclo [2.2.1] hept-2-ene, -8- 200817166 8 - ethylene tetracyclo [4.4.0.12, 5.r, 1G] 3-dodecene, 5-phenyl bicyclo [2.2.1] Geng-2-ene, 8-phenyltetracycline [4·4·0·12,5·17,1()]-3-dodecene, 5-fluorobicyclo[2.2.1 ???hept-2-ene, 5-fluoromethylbicyclo[2.2.1]hept-2-ene, 5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-pentafluoroethyl Bicyclo[2.2.1]heptane-2-ene, 5,5-difluorobicyclo[2.2.1]hept-2-ene, 5,6-difluorobicyclo[2.2.1]hept-2-ene , 5,5-bis(trifluoromethyl)bicyclo[2.2.1]heptane-2-ene, 5,6-bis(trifluoromethyl Bicyclo [2.2.1] hept-2-ene, 5-methyl-5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5,5,6-trifluorobicyclo[2.2. 1] Glyso-2-ene, 5,5,6-tris(fluoromethyl)bicyclo[2.2.1]gly-2-ene, 5,5,6,6-tetrafluorobicyclo[2.2.1] Gem-2-ene, 5,5,6,6-tetrakis(trifluoromethyl)bicyclo[2.2.1]gly-2-ene, 5,5-difluoro-6,6-bis(trifluoromethyl) Dibasic [2.2.1] Geng-2 - Shaoxi '5,6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]g- 2 -correction 5,5 ,6-trifluoro-5-trifluoromethylbicyclo[2.2.1]heptane-2, suspected, 5-fluoro-5-pentafluoroethyl-6,6-bis(difluoromethyl)bicyclo[ 2.2.1] Geng-2, suspected, -9- 200817166 5,6-difluoro-5-pentafluoro-iso-propyl-6-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-Chloro-5,6,6-difluorobicyclo[2.2.1]heptane-2-oxide, 5,6-dichloro-5,6-bis(difluoromethyl)bicyclo[2.2.1] Geng-2 -Accumulate 5.5.6-Trifluoro-6-trifluoromethoxybicyclo[2.2.1]heptan-2-ene, 5.5.6 -trifluoro-6-pentafluoropropoxybicyclo[2.2.1]heptan-2-ene, 8-fluorotetracyclo[4·4·0.12,5·17,1()]-3-dodoene , 8-fluoromethyltetracycline [4·4·0·12,5·17,1()]-3-dodecene, 8-difluoromethyltetracycline [4·4.0·12'5·Γ ,1()]-3-dodecene, 8-trifluoromethyltetracyclo[4·4·0·12,5·17,1()]-3-dodecene, 8-pentafluoroethyl Tetracycline [4.4.0.12, 5.17, 1g] 3- 3-dodecene, 8.8-difluorotetracycline [4·4·0·12,5·17,1()]-3 Tebutene, 8.9- Difluorotetracycline [4·4·0.12,5·17,1()]-3-dodoene, 8,8-bis(trifluoromethyl)tetracyclo[4.4·0·12,5·ΐ7, 1()]-3-dodecene, 8,9-bis(trifluoromethyl)tetracyclo[4 · 4 · 0 · 1 2,5 · 1 7,1 G]- 3 -dodecene, 8 —Methyl 8-octyl trifluoromethyltetracycline [4.4.0.I2,5.Γ,10]-3-indodiene, 8,8,9-trifluorotetracycline [4.4.0.12, 5.17,1 ()] 3- 3-dodecene, 8,8,9-tris(trifluoromethyl)tetracyclo[4·4.0·12,5·Γ,1()]-3 - -10- 200817166 8,8,959 —tetrafluorotetracycline [4.4. 0.12, 5.17, 1 ()] 3- 3-dodecene, 8,8,9,9-tetrakis(trifluoromethyl)tetracyclo[4·4·0·12,5.Γ,1()] 3-dodecene, 8.8-difluoro-9,9-bis(trifluoromethyl)tetracyclo[4.4.0·12,5·Γ,1()]-3-dodecene, 8.9-difluoro a 8,9-bis(trifluoromethyl)tetracyclo[4·4·0·12,5.Γ,1()]-3-dodoene, 8.8.9 trifluoro- 9-trifluoromethyl Tetracyclic ring [4·4·0·12,5·17,1()]-3-dodecene, 8.8.9 trifluoro- 9-trifluoromethoxytetracyclo[4·4·0· 12,5·17,10] 3- 3 - dodecene, 8,8,9-trifluoro- 9-pentafluoropropoxytetracycline [4.4.0·12,5·17,10] one 3 -10 Diene, 8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoromethyl)tetracyclo[4·4·0·12,5·17,1()]-3-dodecene , 8,9-difluoro- 8-pentafluoroiso-propyl- 9-trifluoromethyltetracycline [ 4.4.0.12,5 .17,1()]-3-dodecene, 8-chloro-8 ,9,9-trifluorotetracyclo[4·4·0·12,5·17,1()]-3-dodecene, 8.9-dichloro-8,9-bis(trifluoromethyl)tetra Ring [ 4 · 4 · 0 · 1 2, 5 · 17,1G]-3-dodecene, 8 —(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4·4·0·12,5·Γ,10]-3-dodecene , -11 - 200817166 8 —Methyl 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4·4.0·12,5·17'1()]-3-dodoene . These may be used alone or in combination of two or more. Preferably, in the specific monomer, R1 and R3 in the formula (1) are a hydrogen atom or a hydrocarbon number of 1 to 10, preferably 1 to 4, more preferably 1 to 2, and R2 and R4 are a hydrogen atom. Or a monovalent organic group, at least one of R2 and R4 is a polar group having a hydrogen atom and a polar group other than a hydrocarbon group, m is an integer of 0 to 3, and p is an integer of 0 to 3, preferably m+p= 0 to 4, preferably 0 to 2, and m = l, and p = 0 is even better. The specific monomer of m = l and p is 0, and the obtained cyclic olefin resin has a high glass transition temperature and is excellent in mechanical strength. Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amine group, a decylamino group, a cyano group, etc., and these polar groups are linked via a methylene group or the like. The base bond can also be used. Further, a hydrocarbon group or the like which has a polar valent organic group such as a carbonyl group, an ether group, a decyl ether group, a thioether group or an imine group and which is a linking group may be used as a polar group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferred, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferred. Further, at least one of R2 and R4 is a polar group monomer represented by the formula -(CH2)nCOOR, and the obtained cyclic olefin resin has high glass transition temperature and low hygroscopicity, and is excellent in adhesion to various materials. Sexual and suitable. In the specific polar group correlation formula, R is a carbon number of 1 to 12, more preferably 1 to 4, particularly preferably a hydrocarbon group of 1 to 2, more preferably an alkyl group. Further, η is usually 〇 5 5, and the smaller η , is, the glass transition temperature of the obtained cyclic olefin resin is higher, which is suitable, and the specific monomer having η of 0 is suitable for its synthesis. use. Further, in the formula (1), R1 or R3 is preferably a group, and is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2, particularly preferably a methyl group, particularly this. The alkyl group has a specific polar group represented by the formula -(CH2)nCOOR bonded to the same carbon atom as the bonded carbon atom, and the obtained cyclic olefin resin is suitable for low hygroscopicity. <Copolymerizable monomer> Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12. These may be used alone or in combination of two or more. The preferred range of use of the specific monomer/copolymerizable monomer is from 100/0 to 50/50, more preferably from 100/0 to 60/40. < Ring-opening polymerization catalyst> In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer The reaction is carried out in the presence of a disproportionation catalyst. The disproportionation catalyst is (a) at least one selected from W, Mo, and Re compounds, and (b) Deming's periodic table ία elements (such as Li, Na, K, etc.), lan elements (eg, Mg, Ca, etc.), lanthanum elements (eg, Zn, Cd, Hg, etc.), lanthanum elements (eg, B, A1 -13- 200817166 temple), IVA S sagittalin (eg 'Si, Sn, Pb, etc. a catalyst of a compound of a group IVB (e.g., Ti, Zr, etc.), a combination of at least one selected from the group consisting of at least one element containing one bond of the element or hydrogen bonding of the element. . Further, in this case, an additive (c) described later may be added to increase the activity of the catalyst. (a) In the case of a representative example of a suitable w, Mo or Re compound, there are WC16, M〇Cl6, Re〇Cl3, etc., JP-A No. 1-132626, page 8, left lower column, sixth line, eighth page, upper right column Compound of line 17. (b) Specific examples of the component include n-C4H9Li, (C2H5)3A1, (C2H5)2A1C1, (C2H5)15A1C115, (C2H5)A1C12, methylaluminoxane, LiH, etc., JP-A-132626 Compounds on the 8th line in the upper right column of page 8 to the third line in the lower right column of page 8. For the representative examples of the component (c), alcohols, aldehydes, ketones, amines, and the like are suitably used, and further, it can be used in the lower right column, line 16 to page 9 on the eighth page of the Japanese Patent Publication No. 1-132626. Block the compound of line 17. In terms of the amount of disproportionation catalyst used, the molar ratio of the component (a) to the specific monomer is "(a) component: specific monomer", usually in the range of 1:5 00 to 1:50,000, to 1:1,000. The range of ~1:10,000 is better. Examples of the component (a) and the component (b) are preferably a metal atomic ratio (a): (b) of 1:1 to 1:50, and a range of 1:2 to 1:30. The ratio of the component (a) to the component (c) is in the range of the molar ratio (c): (a) 0.005: 1 to 15: 1, and 0.05: 1 to 7: 1 is preferably -14 to 200817166. <Solvent for Polymerization> Solvents used in ring-opening polymerization (solvents forming a molecular weight modifier solution, a solvent of a specific monomer and/or a disproportionation catalyst), such as pentane, hexane, heptane, and octane Alkane such as alkane, decane or decane, cycloalkane such as cyclohexane, cycloheptane, cyclooctane, decalin, or porcine, benzene, toluene, xylene, ethylbenzene, cumene Aromatic hydrocarbons, compounds such as chlorobutane, bromohexane, chlorinated methane, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, etc., halogenated alkane, halogenated aryl, etc. Ester, butyl butyl citrate, isobutyl phthalate, saturated carboxylic acid esters such as methyl propionate, dimethoxyethane, ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane, etc. These can be used singly or in combination. Among these, aromatic hydrocarbons are preferred. In terms of the amount of solvent used, "solvent: specific monomer (weight ratio)" is usually 1:1 to 10:1, preferably 1:1 to 5:1. <Molecular weight modifier> The molecular weight of the obtained ring-opening (co)polymer can be adjusted depending on the polymerization temperature, the type of the catalyst, and the type of the solvent. In the present invention, it is adjusted by coexistence with the molecular weight modifier in the reaction system. . Here, suitable molecular weight regulators, such as B j: Xi, Bingxi, 1 Yi Ding, 1 Yi Bing, 1 Yi Yi, 1 Geng Can, 1 Xin Xin, 1 Yi Yi, 1 A-terminated hydrocarbons such as terpene and styrene. Among them, i _ □ s, especially one is preferred. -15- 200817166 These molecular capsule regulators may be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 〇6 mol per mol of the monomer 1 ring supplied for the ring-opening polymerization, preferably 〇·〇2 to 0.5 mol. In order to adhere to (2) a ring-opening copolymer, in a ring-opening polymerization process, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization, and in addition, polybutene-polypropylene, etc. Conjugated diene compound, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polyunspentene and other unsaturated hydrocarbons containing more than two carbon-carbon double bonds in the main chain It is also preferred that the specific monomer is subjected to ring-opening polymerization in the presence of a polymer or the like. The ring-opening (co)polymer obtained in the above manner can be used as it is, and the (3) hydrogenated (co)polymer obtained by further hydrogenation can be used as a resin material having high impact resistance. <Hydrogenation Catalyst> Hydrogenation reaction, a usual method, that is, adding a hydrogenation catalyst to a ring-opening polymer solution, preferably at a pressure of 300 to 300 atmospheres, and a hydrogen gas of 3 to 200 atmospheres, preferably 〇~200 It is carried out at ° C, and it is preferably 20 to 18 (TC is preferred. For the hydrogenation catalyst, it can be used in the hydrogenation reaction of a general olefinic compound. Examples of the hydrogenation catalyst include heterogeneous catalyst and uniformity. Catalysts. Inhomogeneous catalysts, there are precious metal catalysts such as pin, platinum, nickel, wrong, and sputum, which are loaded with carbon, silica sand, oxidized Ming, Qin and other carriers-16-200817166 Catalyst. Also, 'homogeneous catalysts are nickel naphthenate/triethylaluminum, nickel acetoxyacetate/triethylaluminum, cobalt octylate/η-butyllithium, Cp2ZrTiCl2/diethylaluminum Monochloride, bismuth ruthenate, chlorotris(triphenylphosphine) ruthenium, dichlorotris(triphenylphosphine) ruthenium, chlorohydrocarbonyltris(triphenylphosphine) ruthenium, dichlorocarbonyltris(triphenylphosphine)触, etc. The catalyst form can be powder or granule. For these hydrogenation catalysts, use a ring-opening (co)polymer: hydrogenation The medium (weight ratio) is a ratio of 1: 1 X 1 〇·6 to 1: 2. Thus, the hydrogenated (co)polymer obtained by hydrogenation has excellent thermal stability, during molding, and when used as a product. The heating rate does not deteriorate even if it is heated. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, and 99% or more. Further, hydrogenation (co)polymerization The hydrogenation rate of the product is 500% or more, and the enthalpy of MR is 50% or more, preferably 90% or more, more preferably 98% or more, and 99% or more. The higher the hydrogenation rate, the stability to heat or light. It is excellent in the properties, and when it is used as the wavelength plate of the present invention, it is characterized in that it is stable over a long period of time. Further, it is a hydrogenated (co)polymer used as the cyclic olefin resin of the present invention, and the hydrogenated (co)polymer is used. The content of the colloid contained is preferably 5% by weight or less, more preferably 1% by weight or less. Further, in the case of the cyclic olefin resin of the present invention, (4) the ring opening of (1) or (2) ( The hydrogenated (co)polymer can also be used after the homopolymer has been cyclized by the Friedel-Crafts reaction. -17- 200817166 <Circularization by Friedel-Crafts Reaction> The method of cyclizing the ring-opening (co)polymer of (1) or (2) by Friedel-Crafts reaction is not particularly limited, and it can be used. A known method of the acidic compound of the publication No. 1 543, 99. In terms of the acidic compound, specifically, Lewis acid or Brinell such as A1C13, BF3, FeCl3, A1203, HC1, CH2C1C0 0H, zeolite, activated clay, etc. The ring (co)polymer can be hydrogenated in the same manner as the ring-opening (co)polymer of (1) or (2). Further, in the case of the cyclic olefin resin of the present invention, (5) the specific monomer and the saturated copolymer having an unsaturated double bond compound may be used. <A compound containing an unsaturated double bond> contains an unsaturated double bond. In terms of the compound, such as ethylene, propylene, butene, etc., the carbon number is preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. The preferred range of use of the specific monomer/containing unsaturated double bond compound is 90/10 to 40/60, more preferably 85/15 to 50/50 by weight. In the present invention, in order to obtain (5) a specific monomer and a saturated copolymer containing an unsaturated double bond compound, a general addition polymerization method can be used. <Addition polymerization catalyst> In synthesizing the catalyst of the (5) saturated copolymer, at least one selected from the group consisting of a titanium compound, a chromium compound and a vanadium compound can be used as a co-catalyst as auxiliary -18-200817166 Organoaluminum compound. Here, as the titanium compound, there may be mentioned titanium tetrachloride or titanium trichloride, and the zirconium compound may be bis(cyclopentadienyl)chromium chloride or bis(cyclopentadienyl)chromium dichloride. Further, as the vanadium compound, the following formula VO(OR)aXb5 or V(OR)cXd can be used [However, R is a hydrocarbon group, X is a halogen atom, 〇Sa$3, 0SbS3, (a+b) $3,0^c$4 , 0^d^4, 3$ (c+d) ^ 4 ] The vanadium compound shown, or the electron supply adduct of these. The electron donor includes an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an ester of an organic or inorganic acid, an ether, an acid anhydride, an acid anhydride, an alkoxysilane, or the like, an oxygen-containing electron donor, ammonia, an amine, A nitrogen-containing electron donor such as a nitrile or an isocyanate. Further, as the organoaluminum compound of the auxiliary catalyst, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond may be used. In the case of using a vanadium compound, the ratio of the vanadium compound to the organoaluminum compound is 2 or more with respect to the vanadium atom and the ratio of aluminum atoms (A1 / V), preferably 2 to 50, and 3 to 2 0. The range is better. The solvent for the polymerization reaction used in the addition polymerization can be the same as the solvent used in the ring-opening polymerization reaction. Further, the adjustment of the molecular weight of the obtained (5) saturated copolymer is usually carried out with hydrogen. Further, in the case of the cyclic olefin-based resin of the present invention, it is also possible to use -19-200817166 (6) one selected from the specific monomer' and the bivalent ring-shaped tobacco monomer or the cyclopentadiethylene monomer. Addition of the above-mentioned compound to the copolymer and ammonia ugly polymer. <Ethylene-based cyclic hydrocarbon-based monomer> Examples of the ethylene-based cyclic hydrocarbon-based monomer, such as 4-vinylcyclopentanyl, 2-methyl-tetra-isopropanylcyclopentene, etc. An ethylene-based 5-membered cyclic hydrocarbon monomer such as a cyclopentene monomer, an ethylene cyclopentane monomer such as an ethylene vinylcyclopentane or a 4-isopropenylcyclopentane, or a 4-vinylcyclohexene, 4- Ethylene isopropenyl cyclohexene, 1-methyl-4-isopropanylcyclohexene, 2-methyl-4-tetraethylcyclohexene, 2-methyl-4-isopropenylcyclohexene Cyclohexene monomer, 4-vinylcyclohexane, 2-methyl-4-isopropenylcyclohexane, etc., such as phenylene ring monomer, phenyl b, α-methyl benzene, 2 - styrene monomer such as methyl styrene, 3-methyl styrene, 4-methyl styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-phenyl styrene, ρ-methoxy styrene, d — suspicion, 1 suspicion, 1 帖 fine, d-rod 彳冡 green, 1 barene, dipentene and other terpene monomers, 4-vinylcycloheptene, 4-isopropenyl Ethylene cycloheptene monomer such as azetene, 4-vinylcycloheptane, 4-isopropene Cyclohexyl acetate and other hospital departments monomers burning cycloheptyl. Among them, styrene and α-methylstyrene are preferred. These may be used alone or in combination of two or more. C cyclopentadiene monomer> The cyclopentadiene monomer used in the (6) addition molding polymer monomer of the present invention, such as cyclopentadiene or 1-methylcyclopentadiene 2, A-20-200817166 Cyclopentane, 2-ethylcyclopentane, 5-methylcyclopentane, 5,5-methylcyclopentadiene, etc. It is preferred to use cyclopentadiene. These may be used alone or in combination of two or more. The addition (co)polymer of one or more monomers selected from the specific monomer, the ethylene-based cyclic hydrocarbon monomer, and the cyclopentadiene monomer may be specific to the (5) The body is obtained by the same addition polymerization method as the saturated copolymer containing an unsaturated double bond compound. Further, the hydrogenated (co)polymer of the addition (co)polymer can be obtained by the same hydrogenation method as the hydrogenation (co)polymer of the (3) ring-opening (co)polymer. Further, in the case of the cyclic olefin resin of the present invention, (7) an interactive copolymer of the specific monomer and the acrylate may be used. <Acrylate> The acrylate aspect used in the production of the interactive copolymer of the specific monomer and acrylate of the present invention (e.g., methacrylate, 2-ethylhexyl acrylate, ring) a heterocyclic ring having 2 to 20 carbon atoms such as a linear, branched or cyclic alkyl acrylate, glycidyl acrylate or 2-tetrahydrofurfuryl acrylate having 1 to 20 carbon atoms such as hexyl acrylate a polycyclic structure having a carbon number of 7 to 30, such as an acrylate having an aromatic cyclic acrylate, an isobornyl acrylate or a dicyclopentyl acrylate having 6 to 20 carbon atoms such as a benzyl acrylate. Acrylate. In the present invention, in order to obtain (7) an interactive copolymer of the specific monomer and the acrylate, in the presence of Lewis acid, the specific monomer and the acrylic acid-21 - 200817166 ester are combined to be 100 moles. The specific monomer is 30 to 70 moles, the acrylate is 70 to 30 moles, and the specific monomer is 40 to 60 moles, and the acrylate is preferably 60 to 4 moles. Further, radical polymerization is preferably carried out in a ratio of 45 to 55 moles of the specific monomer and a ratio of 55 to 45 moles of the acrylate. The amount of the Lewis acid used to obtain (7) the interactive copolymer of the specific monomer and the acrylate is 0.001 to 1 mole per 100 moles of the acrylate. Further, an organic peroxide or a azobis-based radical polymerization initiator which generates a free radical can be used, and the polymerization temperature is usually from 20 ° C to 80 ° C to 5 ° C. 60 ° C is preferred. Further, as the solvent for the polymerization reaction, the same solvent as that used in the ring-opening polymerization reaction can be used. Further, the "inter-copolymer" of the present invention is such that the structural unit derived from the specific monomer is not connected, that is, the structure having the structural unit derived from the acrylate adjacent to the structural unit derived from the specific monomer. Copolymers, but structures that exist adjacent to each other from the structural units of the acrylate are not excluded. The suitable molecular weight of the cyclic olefin resin used in the present invention is 0.2 to 5 dl/g, more preferably 〇3 to 3 dl/g, particularly preferably 0.4 to 1. 5 d at an intrinsic viscosity [7?] inh. The average molecular weight (Mn) in terms of polystyrene measured by colloidal permeation chromatography (GPC) after dissolving in tetrahydrofuran is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000. 50,000, weight average molecular weight (Mw) is 20,000~300, 〇〇〇, more preferably 30, 〇〇〇~000 'Specially good for 000 ～ -22- 200817166 200,000 range is suitable. Further, the molecular weight distribution (Mn/Mw) is preferably from 2.0 to 4.0, more preferably from 2.5 to 3.7, still more preferably from 2.8 to 3.5. Intrinsic viscosity [7?]inh, when the number average molecular weight and the weight average molecular weight are within this range, the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin, and the optical film of the present invention Good formability. The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 110 ° C or more, preferably 1 1 0 to 3 50 ° C, more preferably 1 2 0 to 2 5 0. °C, especially preferably 1 2 0~2 0 0 °C. When T g is less than 1 1 0 °C, it may not be deformed when it is used under high temperature conditions or during secondary processing such as coating or printing. On the other hand, when the Tg exceeds 350 °C, the forming process becomes difficult, and it is necessary to increase the heating temperature during the forming process, and the possibility of deterioration of the resin due to heat is high. The above-mentioned cyclic olefin-based resin can be used in combination with the specific hydrocarbon system described in JP-A-H09-A 2,773,277, and JP-A No. Hei. A resin, or a known thermoplastic resin, a thermoplastic elastomer, a rubbery polymer, organic fine particles, inorganic fine particles, or the like. Further, the cyclic olefin-based resin to be used in the present invention may be added as an additive such as an antioxidant or an ultraviolet absorber which is known to improve heat deterioration resistance or light resistance without departing from the effects of the present invention. For example, at least one compound selected from the group consisting of a phenol-based compound, a thiol-based compound, a sulfide-based compound, a disulfide-based compound, and a phosphorus-based compound is used in the cyclic olefin-based resin 1 of the present invention. 0 0 parts by weight, adding 0.01 1 to 1 〇-23- 200817166 parts by weight to improve heat deterioration resistance. Phenol compound: In terms of a phenol compound, triethylene glycol mono-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol a pair of [3 - (3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(η-octylsulfo)-6-(4-hydroxyl-3 ,5-di-t-butylanilino)-3,5-triazine, pentaerythritol-tetra-[3-(3,5-di-di-butyl-4-hydroxyphenyl)propionate], 2 , 2-sulfo-diethylene bis[3-(3,5-di-t-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t Monobutyl- 4-hydroxyphenyl)propionate], N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyl-hydrocinnamate), 1,3, 5-trimethyl- 2,4,6-tris(3,5-di-t-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxyl Benzyl)-isocyanurate, 3,9-bis[2-[3-(3-t-butyl-4-yl-yl-5-methylphenyl)propanyloxy]-1,1 — Dimethyl b A] 2,4,8, 10-tetraoxa-spiro [5.5] undecane. Octadecyl-3-(3,5-di-t-butyl-4-ylhydroxyphenyl)propionate], 1,3,5-trimethyl-254,6-three (3,5 —1—1-butyl-4-hydroxybenzyl)benzene, pentaerythritol—tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] is preferred, particularly preferably , octadecyl-3-(3,5-di-t-t-butyl-4-hydroxyphenyl)propionate] and the like. Thiol-based compounds: In terms of thiol-based compounds, there are t-dodecyl mercaptan, alkyl mercaptan such as hexyl mercaptan-24-200817166, 2-mercaptobenzimidazole, 2-anthracene π sitting, 1 Monomethyl-2-(methylbenzyl)benzopyrene monomethylbenzimidazole, 2-indenyl-4-methylphenyl-5-methylbenzimidazole, 2-mercapto-5,6 — Di-(methylmercapto)benzimidazole, 1-methyl-2-benzoxazole, 2-mercapto-1,3-dimethylbenzimidazole, sulfonium sulfide compound: sulfide compound, There are 2,2-sulfur (3,5-di-t-butyl-4-hydroxyphenyl)propane (4-methyl-6-t-butylphenol), 2,4-yl)-6- Methylphenol, dodecyl 3,3'-tetradecyl 3,3'-thiodipropionate, distearyl ester, pentaerythritol tetrakis(3-dodecylthiopropionate 3, 3'-monodipropionate, etc., keto-6-methylbenzoindole, 2-mercapto- 1-imidazole, 2-nonylmethylbenzimidazole, 2-methylindenyl)benzimidyl Tannic acid, etc. 1-diethylene bis[3-acidate], 2,2-sulfuric bis(η-octylthiomethane dipropionate, bis 3,3 ′ thiodipropionic acid), ditridecyl
二硫化物系化合物方面，有雙（4 -物、雙（2—氯苯基）二硫化物、雙（2, 硫化物、雙（2,4,6-三氯苯基）二硫化: 苯基）二硫化物、2,2’ 一二硫二安息香酸 醯基苯基）二硫化物、雙（4 一胺甲醯 物、1，1 ’ 一二萘基二硫化物、2，2 ’ 一二萘 2’ 一二萘基二硫化物、2,2’ 一雙（1 一氯 氯苯基）二硫化 5 -二氯苯基）二 樹、雙（2 -硝基 乙基、雙（4—乙 基苯基）二硫化 基二硫化物、1， 二萘基）二硫化 -25- 200817166 物、1，1，一雙（2-氯萘基）二硫化物、2,2, 一雙（1 一氰 基萘基）二硫化物、2,2, 一雙（1 一乙醯基萘基）二硫化 物、雙十二烷基一 3，3, 一硫二丙酸酯等。 隣系化合物： 磷系化合物方面，有三（4 —甲氣基一 3,5 —二苯基） 磷酸酯、三（壬基苯基）磷酸酯、三（2,4 一二一 t 一丁基 苯基）磷酸酯、雙（2，6-二一 t 一丁基一 4 一甲基苯基） 季戊四醇二磷酸酯、雙（2,4 一二—t 一丁基苯基）季戊四 醇二磷酸酯等。 另外，將2,4 —二羥基苯並苯酮、2 —羥基一 4 一甲氧 基苯並苯酮等苯並苯酮系化合物、N -（苄氧基羰氧基）苯 並三唑等苯並三唑系化合物、或2—乙基乙二醯苯胺、2-乙基一 2, 一乙氧基乙二醯苯胺等乙二醯苯胺系化合物，相 對於環狀烯烴系樹脂100重量份，藉由添加0.01〜3重量 份，又以0.0 5〜2重量份爲佳，可提升耐光性。 又，本發明之環狀烯烴系樹脂，藉由溶融壓出成形爲 薄膜等時，爲防止溶融壓出時之熱經歷而使該樹脂熱劣 化，亦可添加抗氧化劑。 該抗氧化劑之具體例方面，如，1 ,3，5 -三甲基一 2,4,6 —三（3,5 —二—t — 丁基—4 —羥基苄基）苯、N，N， 一六亞甲基雙（3，5 -二一 t一 丁基一 4一趨基一氫化肉桂醯 fl女）、二一（3,5 -二—t 一丁基—4 一經基节基）一異氯酸 酯、三（2，4 一二一 t 一丁基苯基）亞磷酸酯等，本發明並不 -26- 200817166 爲此等所限定，又，關於此等，有因溶融壓出之環狀烯烴 系樹脂之Tg而不適合的狀況。又，在不損及本發明之效 果範圍內，此等可組合使用，或單獨使用。 此等抗氧化劑之添加量，相對於環狀烯烴系樹脂100 重量份，通常爲0.01〜5重量份，以0.05〜4重量份爲 佳，更佳爲0.1〜1.5重量份。抗氧化劑添加量未滿0.01 重量份時，於壓出加工時於樹脂易產生膠體，因此，於所 得之薄膜上發生缺陷而不適用。另一方面，添加劑量，超 過5重量份則於加工時會招致產生沈積物，此沈積物因會 成爲分模線、薄膜上之魚眼、燒焦等原因而不適用。 相關抗氧化劑，可於製造環狀烯烴系樹脂時添加，或 於溶融壓出時與環狀烯烴系樹脂顆粒一同搭配。 又’將本發明之環狀烯烴系樹脂經溶融壓出成形時， 在不損及本發明效果之範圍內，可使用滑劑、紫外線吸收 劑、染料或顔料等該抗氧化劑以外之添加劑。當然在此狀 況，爲具有融點之添加劑的情況時，其融點以在本發明之 必須抗氧化劑融點之範圍內爲佳。 <薄膜成形> 本發明光學薄膜之成形方法爲溶融壓出法，將樹脂顆 粒，以氧濃度1 〇ppm以下之惰性氣體爲媒介輸送至壓出 機，將該顆粒溶融壓出成形。具體上，將封入箱中之樹脂 顆粒輸送至乾燥機，由該乾燥機以氧濃度10ppm以下，較 佳爲8PPm以下，更佳爲6ppm以下惰性氣體爲媒介輸送 -27- 200817166 至壓出機。具體上，如圖1所示般，將封入箱中之樹脂顆 粒’以氧濃度lOppm以下之惰性氣體爲媒介輸送至乾燥 機’進行乾燥處理後，以使用藉由先前之輸送於乾燥機所 充塡之惰性氣體將該顆粒輸送至壓出機爲佳。 該箱爲具有將顆粒封入之儲存槽與將顆粒取出之取出 管以及於上部下部有將顆粒取出用之設備之者即可。箱内 部爲以清潔狀態將顆粒封入爲必要的，又，顆粒封入後， 使異物無法由外部侵入而被遮蔽是必要的。 該乾燥機，通常，於將樹脂顆粒投入壓出機前，以將 該樹脂所含之水分、氣體（氧等）、殘留溶劑等預先除去 爲目的，爲於該樹脂Tg以下之適當溫度，進行樹脂乾燥 所使用。以使用惰性氣體循環式乾燥機、真空乾燥機爲 佳。 樹脂顆粒，通常經由箱與乾燥機間所設置之吸引送料 斗（以下，也單稱「送料斗」）輸送至乾燥機。輸送時， 將送料斗減壓，藉由從箱所配備之閥將該惰性氣體輸送， 使樹脂顆粒於乾燥機中空轉。又，爲抑制送料斗内之吸濕 及氧之吸收，偏好之方法有將送料斗以氮或氬等惰性氣體 封閉，或使用可保持減壓狀態之真空送料斗。 經乾燥之樹脂顆粒，經壓出機上部所設置之送料斗運 送至壓出機。與至乾燥機之輸送相同地，輸送時將送料斗 減壓，於乾燥機内所充塡之惰性氣體與樹脂顆粒被輸送至 乾燥機。又，由外部更進一步持續導入惰性氣體亦可。 本發明所用之惰性氣體方面，只要與樹脂顆粒不反應 -28- 200817166 之氣體即可並未特別限定，如氮、二氧化碳、氬等’以使 用氮爲佳。又，運送樹脂顆粒時，氮氣流量，因乾燥機及 壓出機之尺寸而異，通常爲100〜8001/ min，以120〜 6001/min 爲佳。 經溶融壓出法得到之環狀烯烴系樹脂薄膜之方法方 面，並未特別限定，使用公知之方法即可。如，有由壓出 機所配置之模頭將溶融狀態之環狀烯烴系樹脂壓出，使該 樹脂於鏡面輥表面壓著，之後，冷卻後剝離後進行薄片化 之方法。 將環狀烯烴系樹脂溶融之方法方面，以經壓出機將樹 脂溶融之方法爲佳，將該溶融樹脂以齒輪泵定量供給，將 此以金屬過濾器等過濾除去不純物後，以模頭邊賦予薄膜 形狀邊壓出之方法爲佳。 將由模頭壓出之薄膜冷卻進行薄膜化之方法方面，有 夾輪方式、施加靜電方式、氣刀方式、壓延方式、單面帶 方式、雙面帶方式、3本輥方式等，製造光學斑少之薄膜 時，以使用單面帶式，其中稱套管式之薄膜製造裝置、施 加靜電方式等爲佳。如，於模頭吐出口下方配置鏡面輥與 金屬帶，設置與該鏡面輥並排之剝離輥之薄膜製造裝置。 該金屬帶，藉由與其内面相接所設置之2個保持輥，保持 張力作用狀態。由吐出口所吐出之樹脂，經該鏡面輥與金 屬帶間之挾壓，轉印至鏡面輥，冷卻後，由剝離輥剝離而 薄膜化。又，於所吐出之薄膜兩端之位置，配置爲與模頭 吐出口下方之鏡面輥相對，由帶電電極，將薄膜貼附於鏡 -29- 200817166 面輥側’得到無光學斑、薄膜表面性良好之方法等亦爲適 用之方法。 壓出機方面，可使用單軸、雙軸、遊星式、融混練機 等任一皆可，以使用單軸壓出機爲佳。又，壓出機之螺桿 形狀方面，有通氣孔型、副螺桿型（sub-flight screw )、 先端達魯曼基（Dulmadge)型、全程螺桿型等，有壓縮比 大的、小的，壓縮部之長度爲長緩壓縮、長度爲短急壓縮 型等’因氧混入及壓出機内部之剪斷發熱，使樹脂中易產 生膠體。因爲此膠體會成爲薄膜中稱爲魚眼之點狀缺陷及 燒焦之原因，以可壓抑氧溶解、剪斷發熱之螺紋形狀·壓 縮型之者爲佳，以壓縮比爲1 . 5〜4 · 5爲佳，特別佳爲1 . 8 〜3 · 6。樹脂計量中所使用之齒輪泵，使用内部潤滑式， 或外部潤滑式任一皆可，其中以外部潤滑方式爲佳。 關於異物過濾所使用之過濾器，有葉片圓盤型、燭狀 過濾器型、葉片型、篩網等。其中，使樹脂滞留時間分布 變小爲目的，以葉片圓盤型最佳，指過濾器之網孔大小習 稱網目，以20 // m以下，偏好爲1 0 // m以下，更佳爲5 //m以下。最好爲3/zm以下。習稱之網目，比20//m大 時，要除去肉眼可見之異物外，除去膠體等爲困難的，故 不宜用作製作光學薄膜用之過濾器。 模頭方面，使模頭内部樹脂流動均一爲必須的，爲保 持薄膜厚度均一性，在模頭出口附近之模頭内部壓力分布 於寬度方向保持一定是必須的。爲滿足此般條件，可使用 分歧管模頭、魚尾式模頭、衣架式模頭等，此等中，以衣 -30- 200817166 架式模頭爲佳。又模頭之流量調整，以彎曲唇型爲佳。 又，以附設經熱栓方式自動控制進行厚薄調整機能的模頭 更佳。爲調整流量設置之扼流桿、爲調整厚度而設置之支 撐墊塊，於設置部分產生高低差、設置部分之隙間等，混 入空氣等，而可能成爲燒焦之發生原因、模頭線之原因而 不適用。模頭吐出口，以塗佈鎢碳化合物等超硬塗佈等爲 佳。又，模頭材質方面，有 SCM系之鋼鐵、SUS等不繡 鋼材等、但並不限制於此等。又，可使用有於表面鍍上 絡、鎮、欽等之者，經 PVD ( Physical Vapor Deposition )法等，形成 T iN、T i A IN、T i C、C rN、D L C (金鋼石狀碳）等被膜之者，被其他陶瓷熔射者、表面被 氮化處理之者等。此般模頭，表面硬度高，與樹脂之摩擦 小，故於所得之透明樹脂薄膜，可防止燒焦雜質等混入且 防止模頭線產生，故爲適用。 鏡面輥，以具有内部加熱方法及冷卻方法者爲佳，其 表面粗度爲0.5 // m以下，特別以〇 · 3 // m以下爲佳。鏡面 輥方面，使用於金屬輥施加鍍敷者爲佳，以施加鉻鍍敷、 無電解鎳鍍敷等者更佳。 鏡面輥之加熱方法，以被覆式油調溫方式、介電加熱 方式等方法爲佳。輥之加熱方法並未特別限制，以輥溫度 於薄膜製膜範圍下，無溫度差爲佳，所容許之輥寬度方向 之溫度差以厂C以内爲佳，更佳爲厂C以内。 於單面帶式裝置或套管式取出裝置中使用之金屬帶方 面’以使用無接合處之無端帶爲佳。構成金屬帶之材料方 -31 - 200817166 面，可用不繡鋼、鎳等。又，固定金屬帶之保持輥，以其 表面經有矽酮橡膠或其他具耐熱性彈性體等所被覆爲佳。 金屬帶厚度，以〇·1〜〇.4mm爲佳，未滿0.1mm則彎曲 大，會立刻損傷帶而不宜。另一方面，比〇.4mm厚則加工 時不隨薄膜變形而不適合。 藉由該裝置，如下製造薄膜。 壓出機滾筒，爲防止溶融壓出中樹脂氧化產生膠體 等，以經氮或氬等惰性氣體密封爲佳。 經壓出機溶融之環狀烯烴系樹脂，由模頭吐出口向垂 直方向之下方壓出成薄膜狀。模頭出口之溫度分布，爲使 樹脂溶融黏度差少，控制在± 1 °C以下爲佳。 之後，所壓出之樹脂，經鏡面輥與金屬帶挾壓，冷 卻。接著，轉印至鏡面輥表面之樹脂，經剝離用輥由鏡面 輥表面剝離，製造薄膜狀之薄膜。 本發明中，樹脂加工溫度，也就是壓出機及模頭之設 定溫度，由可將流動性均一之溶融狀態樹脂從模頭吐出， 抑制樹脂劣化觀點，爲樹脂之Tg + 100°C以上、Tg + 200 °C以下爲佳。 又，經鏡面輥與金屬帶將樹脂挾壓時，也就是，將樹 脂轉印於鏡面輥時之壓力，以面壓爲〇.〇1〜0.8 MPa爲 佳，特別佳爲0.1〜0.6MPa。以0.15〜0.45MPa又更佳。 此時，以鏡面輥與金屬帶之周速度相近爲佳。偏好範 圍方面，當鏡面輥周速度爲1.00時，金屬帶之周速度爲 0.95〜1.05，特別佳爲0.99〜1.01。 -32- 200817166 另外，薄膜剝離時之條件，剝離溫度Tt ( °c )，剝離 應力 TF(MPa)時，各自以 Tg— 3(TCSTtSTg+5°C， 0.01MPa$TF$5MPa 之範圍爲佳。 於此，冷卻輥之鏡面輥溫度，通常爲Tg — 80〜Tg + l〇°C，以 Tg — 60 〜Tg — 2°C 爲佳。 本發明模頭之流路之水平部分與模頭出口之先端部分 相接觸，此先端水平部分稱模口平面。模口平面之長度爲 10〜50mm，以11〜40mm爲佳。 <薄膜延伸加工> 本發明之光學薄膜，可將如此所得之光學薄膜，進一 步延伸。其延伸加工方法方面，具體上，有公知之單軸延 伸法或雙軸延伸法。也就是，可使用經拉幅法之横單軸延 伸法、輥間壓縮延伸法、利用圓周相異之二組輥之縱單軸 延伸法等’或組合橫單軸與縱單軸之雙軸延伸法、經吹製 法之延伸法等。 單軸延伸法之狀況，延伸速度通常爲1〜5,000 % / 分，以50〜1，000% /分爲佳，更佳爲1〇〇〜1，〇〇〇%/ 分，特別佳爲1〇〇〜500 %/分。 雙軸延伸法之狀況，有同時於2方向進行延伸或單軸 延伸後於與最初延伸方向相異方向進行延伸處理之情況。 此時，爲控制延伸後薄膜之折射率橢圓體形狀之2延伸軸 相交角度’依所期望特性而決定並不特別限定，通常爲 120〜60度之範圍。又，延伸速度在各延伸方向相同也 -33- 200817166 可，相異亦可，通常爲1〜5,000%/分，以5(^1000% /分爲佳，更佳爲1〇〇〜1，〇〇〇%/分，特別佳爲1〇〇〜 5 0 0 % / 分。 延伸加工溫度，並未特別限定，以本發明之樹脂的玻 璃轉移溫度Tg爲基準，通常爲Tg±30°C，以Tg±15t：爲 佳’更佳爲Tg— 5°C〜Tg+15°C之範圍。在該範圍内，可 抑制相位差不均發生’又，控制折射率橢圓體變得容易所 以適合。 延伸倍率，依所期望特性而決定並不特別限定，通常 爲1.01〜10倍，以1.03〜5倍爲佳，更佳爲1·03〜3倍。 延伸倍率在1 0倍以上則有相位差之控制變得困難之情 形。 經延伸之薄膜，可直接冷卻，或於Tg — 20°c〜Tg之 溫度環境下保持至少1 0秒以上，較佳爲3 0秒〜6 0分鐘， 更佳爲1分〜6 0分鐘進行熱接合。藉由此，可得到透過光 相位差之經時變化少且安定之相位差薄膜。 不施加延伸加工情況之本發明之光學用薄膜之經加熱 的尺寸收縮率，在1〇〇 °C進行加熱5 00小時時，通常爲5 %以下，較佳爲3%以下，更佳爲1%以下，特別佳爲0.5 %以下。 又，本發明之相位差薄膜之經加熱之尺寸收縮率，在 100°c進行加熱5 00小時時，通常爲10%以下，較佳爲5 %以下，更佳爲3 %以下’特別佳爲1 %以下。 爲使尺寸收縮率在該範圍内’除本發明之樹脂原料之 -34- 200817166 單體A、B之選擇外，可藉由鑄模方法或延伸方法來控 制。 此般延伸之薄膜，經延伸而分子配向、賦予透過光相 位差，此相位差，可藉由延伸倍率、延伸溫度或薄膜厚度 等控制。如，延伸前薄膜厚度相同時，延伸倍率愈大之薄 膜透過光相位差之絕對値有變大之傾向，藉由變更延伸倍 率可得到賦予透過光所期望之相位差之相位差薄膜。另一 方面，延伸倍率相同時，延伸前薄膜厚度愈厚過光相位差 之絕對値有變大之傾向，故藉由變更延伸前薄膜厚度可得 到賦予透過光所期望之相位差之相位差薄膜。又，於該延 伸加工溫度範圍，延伸溫度愈低透過光相位差之絕對値有 變大之傾向，故藉由變更延伸溫度可得到賦予透過光所期 望之相位差之相位差薄膜。 如此延伸所得之相位差薄膜厚度，通常爲1 〇〇 // m以 下，較佳爲100〜20//m，更佳爲 80〜20//m。藉由使厚 度變薄則相位差薄膜可因應所使用之領域之製品的小型 化、薄膜化。於此，爲控制相位差薄膜之厚度，可由控制 延伸前光學薄膜之厚度、控制延伸倍率而得到。如，藉由 使延伸前之光學薄膜變薄，使延伸倍率變比較大，可進一 步使相位差薄膜之厚度變薄。 <薄膜特性> 如上述般所得之本發明之光學薄膜（溶融壓出薄膜’ 延伸薄膜），其特徵爲於薄膜表面，直徑3 0 // m以上之點 -35- 200817166 狀缺卩曰爲3個/ m以下，較佳爲1個/ m2以下。點狀缺 陷’爲於薄膜表面存在之點狀或略圓形狀之凹凸，該缺陷 之原因之一，爲於樹脂中存在之膠體等異物所造成。該點 狀缺陷，爲成爲光學斑之一大原因。 又’本發明之延伸的光學薄膜，因表面平滑性優，以 ASTM D1003標準測定之厚度於3mm下霧値爲1%以下， 較佳爲0 · 8 %以下。 又’薄膜之平均粗糙度Ra爲0.2 // m以下，較佳爲 0.15//m以下，更佳爲o.ivm以下。 《偏光板》 本發明之偏光板，於PVA系薄膜等所成之偏光子之 至少一面，將本發明之光學薄膜，以PVA樹脂爲主體之 水溶液所成之水系接著劑、含有極性基黏接著劑、光硬化 性接著劑等進行貼合，依必要將其加熱或曝光、壓著，可 藉由將偏光子與光學薄膜接著（積層）而製造。 《液晶面板》 本發明之液晶面板，可於2枚玻璃基板間挾持液晶所 成之液晶顯示元件之至少一面，貼合本發明之偏光板，可 經使液晶顯示元件與偏光板接著（積層）而製造。 【實施方式】 〔實施例〕 -36- 200817166 以下，具體說明關於本發明之實施例，但本發明並不 爲此等實施例所限定。又，以下，「份」，「％」，無特 別指示下係指「重量份」，「重量％」。 又’以下實施例中，各種評估經下述方法測定。 〔玻璃轉移溫度（Tg )〕 使用 Seiko Instruments Inc.製之示差掃瞄熱量計 (DSC)，氮環境下以昇溫速度2 0 °C /分之條件，測定玻 璃轉移溫度。 〔點狀缺陷測定〕 將光學薄膜卷起l〇m2放置於黑紙上，在100w螢光燈 下確認反射光之搖動。反射光搖動處爲點狀缺陷，將其做 記號。之後，以5 0倍光學顯微鏡觀察薄膜表面，計算直 徑3 0 // m以上點狀缺陷之個數。 〔全光線透過率，霧値〕 使用村上色彩技術硏究所製之霧値計「HM - 1 5 0 型」，測定全光線透過率及霧値。 〔透過光之面内相位差（R〇 )〕 使用王子計測機器（股）製之「KOBRA— 2 1ADH」， 將於薄膜垂直之光入射時之面内相位差（R 〇 )，在波長 5 5 0 n m進行測定。 -37- 200817166 〔偏光板之透過率及偏光度〕 使用大塚電子（股）製之「RETS」’測定偏光板之 透過率及偏光度。測定波長爲5 5 0nm。 〔薄膜厚度分布〕 使用薄膜厚度分布測定裝置（MOCON )，於薄膜長 度方向進行測定。 <調製例1 > 於由丙烯酸丁酯94.8份、丙烯酸5份、2-羥基乙基甲 基丙烯酸酯0.2份所成之重量平均分子量（Mw) 120萬， 重量平均分子量與數平均分子量（Μη)比（Mw/ Μη)爲 3·9之丙烯酸系聚合物之酢酸乙酯溶液中添加甲苯稀釋， 成爲丙烯酸系聚合物之1 3 %甲苯溶液，將添加異氰酸酯交 聯劑〔CORONA TEL (日本聚尿烷社製）〕2.0份攪拌後之 溶液塗佈於離型薄膜上，令其不發泡，以60 °C X5分鐘， 1 0 0 °C X 5分鐘之2階段進行乾燥後，進一步將輕剝離型之 離型薄膜暫時層合於黏著劑面，製作乾燥後黏著劑厚度 (平均値）爲25 // m之非支持薄膜。 〔實施例1〕 樹脂方面，使用環狀烯烴系樹脂（J S R股份公司製： 商品名「ARTON D45 3 1」，玻璃轉移溫度1 3 0 °C )之封入 -38- 200817166 8 00 k g箱中之樹脂顆粒，於以氧濃度〇.lppm之氮2001 / min的氮循環式乾燥機（曰水加工股份公司製：型號NS —200 )中輸送，在氮環境下，乾燥溫度i〇0°C下進行180 分鐘之除濕乾燥。之後，使該樹脂導入於使用氧濃度 O.lppm 之氮 2001/min 的壓出機（GM ENGINEERING CO.， LTD·製：GM— 90)，以 26(TC溶融，以齒輪泵定量送 液，使用5 // m葉片圓盤過濾器將異物除去，從經設定 2 5 0°C之鋁鑄加熱器所加熱之T模頭進行壓出。此時T模 頭之開口爲0.5mm，T模頭出口與冷卻輥之薄膜的壓著點 間之距離爲65mm時，使壓著於25 0mm φ之冷卻輥。冷卻 車毘之溫度爲1 2 0 °c，於其下方側設置2 5 0 m m φ之冷卻輥 2，於更下方側設置25 0mm φ之剝離輥。個別輥之溫度爲 1 15°C、n〇°c，在薄膜表面溫度l〇8t下由剝離輥剝離膜 厚1 00 // m之薄膜，得到原菠烯系樹脂薄膜。 確認所得之光學薄膜之點狀缺陷個數爲〇·3個/m2。 又，該光學薄膜之全光線透過率爲93% ’霧値爲0.2%。 〔比較例1〕 由箱輸送至乾燥機，以及由乾燥機輸送至壓出機在相 同空氣環境下進行，以外與實施例1相同’得到光學薄膜 (b- 1 )。確認光學薄膜點狀缺陷個數爲3·2個/m2。又， 該光學薄膜輥（b - 1)之全光線透過率爲93%，霧値爲 0.3%。 -39- 200817166 〔實施例2〕 使用於實施例1得到之光學薄膜（a - 1 )，1 3 〇 t 下，使用輥夾輪式縱單軸延伸機延伸1.2倍後，1 3 0。(：下 使用拉幅式之横延伸機延伸1.4倍後得到厚70 // m之延伸 光學薄膜（a — 2)。該光學薄膜（a - 2)之相位差爲薄膜 面内相位差（R0)爲60nm。又，該光學薄膜（a — 2)之 全光線透過率爲93%，霧値爲0.1%。 另外，確認該光學薄膜（a - 2 )之點狀缺陷數爲〇 . i 個 / m2。 〔比較例2〕 使用光學薄膜（b - 1 )以外與實施例2相同，得到延 伸之光學薄膜（b - 2 )。本薄膜之相位差爲薄膜面内相位 差（R0)爲63nm。又，全光線透過率爲 93%，霧値爲 0.2%。 另外，確認該光學薄膜（b - 2 )點狀缺陷數爲3 .5個 / m2 〇 〔實施例3〕 將厚5 0 // m之聚乙烯醇薄膜邊浸漬於碘5 g、碘化鉀 250g、硼酸l〇g、水i〇〇〇g所成之40°C浴中約5分鐘，邊 單軸延伸至4倍得到偏光膜。於此偏光膜表面，使用調整 例1所得之黏著劑，將實施例1製作之光學薄膜（a - 1 ) 與實施例2製作之光學薄膜（a 一 2 )各自於偏光膜單面連 -40- 200817166 續接著得到偏光板（a )。測定此偏光板（a )之透過率與 偏光度，各自爲43%、99.99%。又，使該偏光板（a)2 片呈正交偏光狀態，由一面以輝度10 〇〇〇cd之背光照射 時，由另一面觀察時，確認並無點狀缺陷引起之光漏。 〔比較例3〕 除使用光學薄膜（b - 2 )與（c 一 1 )以外與實施例3 相同樣，得到偏光板（b )。測定此偏光板（b )之透過率 及偏光度，各自爲42%、99.87%。又，使該偏光板（b) 在光學薄膜輥（b - 2 )爲内側，2片呈正交偏光狀態，由 一面以輝度1 0000 cd之背光照射時，由另一面觀察時，確 認到點狀缺陷引起之光漏爲3.0個/ m2。 〔産業上利用可能性〕 本發明之光學薄膜，不於光學薄膜表面產生點狀缺 陷，不產生光學斑。因此，由本發明之光學薄膜輥所得之 光學薄膜，可用於如行動電話、數位資訊終端、呼叫器、 衛星導航、車用液晶顯示器、液晶螢幕、液晶電視、調光 面板、OA機器用顯不器、AV機器用顯示器等各種液晶顯 示元件及電致發光顯示元件或觸控面板等。又，亦可用作 CD、CD — R、MD、MO、DVD等光碟之記錄·再生裝置中 之波長板。 【圖式簡單說明】 -41 - 200817166 〔圖1〕本發明之光學薄膜之製造方法中偏好使用之 樹脂顆粒輸送路徑示意圖。 -42-In terms of disulfide-based compounds, there are bis(4-, bis(2-chlorophenyl) disulfide, bis(2, sulfide, bis(2,4,6-trichlorophenyl) disulfide: benzene Disulfide, 2,2'-dithiobisbenzoic acid nonylphenyl) disulfide, bis(4-aminoformamidine, 1,1'-di-naphthyl disulfide, 2,2' Di-naphthalene 2'-di-naphthyl disulfide, 2,2'-bis(1-chlorochlorophenyl)disulfide 5-dichlorophenyl)di-tree, bis(2-nitroethyl, bis( 4-ethylphenyl) disulfide disulfide, 1, dinaphthyl) disulfide-25- 200817166, 1,1, bis(2-chloronaphthyl) disulfide, 2, 2, one Bis(1-cyanonaphthyl) disulfide, 2,2, mono-(1-ethylindolyl) disulfide, dodecyl-1,3, monothiodipropionate, and the like. Neighbor compounds: In terms of phosphorus compounds, there are tris(4-carbazyl-1,5-diphenyl)phosphate, tris(nonylphenyl)phosphate, and tris(2,41-2 di-butyl) Phenyl) phosphate, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphate Wait. Further, a benzophenone compound such as 2,4-dihydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone, N-(benzyloxycarbonyloxy)benzotriazole, or the like a benzotriazole-based compound or an oxadiphenylaniline compound such as 2-ethylglyoximine, 2-ethyl-2, monoethoxyglyoximine, and 100 parts by weight of the cyclic olefin resin. The light resistance can be improved by adding 0.01 to 3 parts by weight and preferably 0.05 to 2 parts by weight. Further, when the cyclic olefin resin of the present invention is formed into a film or the like by melt extrusion, the resin may be thermally deteriorated in order to prevent thermal history during melt extrusion, and an antioxidant may be added. Specific examples of the antioxidant are, for example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, N, N , hexamethylene bis (3,5-di-t-butyl- 4-a-radical-hydrogenated cinnamium fluorene), two-one (3,5-di-t-butyl- 4- aryl group An isochlorite, tris(2,4,2-di-t-butylphenyl)phosphite, etc., the present invention is not limited to -26-200817166, and, in connection with this, there is a cause of melting The Tg of the extruded cyclic olefin resin is not suitable. Further, these may be used in combination or alone without departing from the effects of the present invention. The amount of the antioxidant added is usually 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the cyclic olefin resin. When the amount of the antioxidant added is less than 0.01 part by weight, the resin is liable to be formed in the resin at the time of extrusion processing, and thus defects are not formed in the obtained film. On the other hand, if the amount of the additive exceeds 5 parts by weight, deposits may be generated during processing, and the deposit is not suitable for reasons such as a parting line, fish eyes on the film, charring, and the like. The related antioxidant can be added at the time of producing a cyclic olefin resin, or can be blended together with the cyclic olefin resin particles at the time of melt extrusion. Further, when the cyclic olefin resin of the present invention is subjected to melt extrusion molding, an additive other than the antioxidant such as a slip agent, an ultraviolet absorber, a dye or a pigment can be used as long as the effects of the present invention are not impaired. Of course, in this case, in the case of an additive having a melting point, the melting point is preferably in the range of the essential antioxidant melting point of the present invention. <Film Forming> The method for forming an optical film of the present invention is a melt extrusion method in which resin particles are transported to an extruder under an inert gas having an oxygen concentration of 1 〇 ppm or less, and the pellets are melt-molded and extruded. Specifically, the resin pellets enclosed in the tank are transported to a dryer, and the dryer is transported at an oxygen concentration of 10 ppm or less, preferably 8 ppm or less, more preferably 6 ppm or less, as an intermediate medium -27-200817166 to an extruder. Specifically, as shown in FIG. 1 , the resin particles enclosed in the box are transported to the dryer by using an inert gas having an oxygen concentration of 10 ppm or less as a medium for drying treatment, and then used for charging by using the previously transported dryer. It is preferred that the inert gas of the crucible is conveyed to the extruder. The tank may be a storage tank having a pellet enclosed therein and a take-out tube for taking out the particles, and a device for taking out the particles at the upper portion of the upper portion. It is necessary to enclose the granules in a clean state in the inside of the tank, and it is necessary to block the foreign matter from being invaded by the outside after the granules are sealed. In the drying machine, before the resin pellets are put into the extruder, the water, the gas (oxygen, etc.), the residual solvent, and the like contained in the resin are removed in advance, and the resin is subjected to an appropriate temperature of Tg or less. The resin is used for drying. It is preferred to use an inert gas circulation dryer or a vacuum dryer. The resin pellets are usually conveyed to a dryer via a suction hopper (hereinafter also referred to as "feed hopper") provided between the tank and the dryer. At the time of conveyance, the hopper is decompressed, and the inert gas is conveyed from the valve provided in the tank to circulate the resin pellets in the dryer. Further, in order to suppress moisture absorption and oxygen absorption in the hopper, a preferred method is to seal the hopper with an inert gas such as nitrogen or argon, or to use a vacuum hopper that can maintain a reduced pressure state. The dried resin pellets are transported to the extruder through a hopper provided on the upper portion of the extruder. In the same manner as the transfer to the dryer, the hopper is depressurized during transportation, and the inert gas and resin particles charged in the dryer are sent to the dryer. Further, it is also possible to continuously introduce an inert gas from the outside. The inert gas used in the present invention is not particularly limited as long as it does not react with the resin particles. For example, nitrogen, carbon dioxide, argon or the like is preferably used. Further, when the resin particles are transported, the flow rate of nitrogen varies depending on the size of the dryer and the extruder, and is usually 100 to 8001/min, preferably 120 to 6001/min. The method of the cyclic olefin resin film obtained by the melt extrusion method is not particularly limited, and a known method may be used. For example, there is a method in which a cyclic olefin-based resin in a molten state is extruded from a die disposed by an extruder, and the resin is pressed against the surface of the mirror roll, and then cooled, peeled off, and then flaky. In the method of melting the cyclic olefin resin, it is preferred to melt the resin by an extruder, and the molten resin is quantitatively supplied by a gear pump, and the impurities are removed by filtration using a metal filter or the like, and then the die side is used. It is preferred to impart a film shape while pressing it out. In the method of cooling and thinning the film extruded by the die, there are a pin wheel method, an electrostatic application method, an air knife method, a rolling method, a single-sided tape method, a double-sided tape method, and a three-roll method, etc., to manufacture an optical spot. In the case of a small film, a single-sided tape type, in which a sleeve type film manufacturing apparatus, an electrostatic application method, or the like is preferable. For example, a mirror roll and a metal strip are disposed under the die discharge port, and a film manufacturing apparatus for a peeling roll which is arranged in parallel with the mirror roll is provided. The metal strip is held in tension by two holding rolls provided in contact with the inner surface thereof. The resin discharged from the discharge port is transferred to the mirror roll by rolling between the mirror roll and the metal belt, and after cooling, it is peeled off by a peeling roll to form a film. Further, at the positions of both ends of the film to be ejected, the film is placed opposite to the mirror roll under the die discharge port, and the film is attached to the mirror side by the charged electrode to obtain the optical spot and the film surface. A method of good sex is also applicable. For the extruder, a single-axis, a double-axis, a star-type, a melt-mixing machine, or the like can be used, and a single-axis extruder is preferred. Further, the shape of the screw of the extruder includes a vent type, a sub-flight screw, a Dulmadge type, a full-screw type, etc., and has a large compression ratio and a small compression ratio. The length of the part is long-slow compression, and the length is short-short compression type. The oxygen is mixed into the extruder and the heat is cut inside the extruder, so that the resin is prone to colloid. 5〜4, because the colloid is a cause of the spot-like defect and the scorching of the fish eye, and the shape of the thread that can suppress the oxygen dissolution and shear heat is preferably compressed, and the compression ratio is 1. 5~4 · 5 is better, especially preferably 1. 8 ~ 3 · 6. The gear pump used in the resin metering can be either an internal lubrication type or an external lubrication type, and external lubrication is preferred. Regarding the filter used for foreign matter filtration, there are a vane disc type, a candle type filter type, a vane type, a screen, and the like. Among them, the purpose of reducing the residence time of the resin is small, and the blade disc type is the best, and the mesh size of the filter is referred to as the mesh size, which is 20 // m or less, and the preference is 1 0 // m or less, more preferably 5 //m or less. It is preferably 3/zm or less. When the mesh is called a larger size than 20/m, it is difficult to remove the colloid and the like, and it is not suitable for use as a filter for producing an optical film. In terms of the die, it is necessary to make the resin flow inside the die uniform. In order to maintain the film thickness uniformity, it is necessary to maintain the pressure inside the die near the exit of the die in the width direction. In order to satisfy such conditions, a manifold die, a fishtail die, a hanger die, etc. can be used, and in this case, a -30-200817166 frame die is preferred. The flow rate of the die is also adjusted, and the curved lip shape is preferred. Further, it is more preferable to provide a die which is automatically controlled by a hot plug to perform a thickness adjustment function. In order to adjust the flow setting, the choke rod and the support pad set to adjust the thickness cause a height difference, a gap between the set parts, and the like, and air is mixed in, which may become a cause of scorching, a cause of the die line. Not applicable. The die discharge port is preferably coated with a super hard coat such as a tungsten carbon compound. In addition, there are SCM-based steels, SUS and other non-embroidered steel materials, but they are not limited thereto. In addition, it is possible to form T iN, T i A IN, T i C, C rN, DLC (gold-steel) by PVD (Physical Vapor Deposition) method or the like on the surface plating. A film such as carbon) is used by other ceramics, and the surface is nitrided. Since the surface hardness is high and the friction with the resin is small, the obtained transparent resin film can prevent the incorporation of scorched impurities and the like and prevent the generation of the die line. The mirror roll is preferably one having an internal heating method and a cooling method, and has a surface roughness of 0.5 // m or less, particularly preferably 〇 · 3 // m or less. As the mirror roll, it is preferable to apply a plating to a metal roll, and it is preferable to apply chrome plating or electroless nickel plating. The method of heating the mirror roll is preferably a method such as a covered oil temperature adjustment method or a dielectric heating method. The heating method of the roll is not particularly limited. The roll temperature is preferably in the film forming range, and the temperature difference is not preferable. The temperature difference in the width direction of the roll is preferably within the range of the factory C, and more preferably within the factory C. It is preferable to use a metal belt surface for use in a one-side belt type device or a sleeve type take-up device to use an endless belt having no joint. The material constituting the metal strip -31 - 200817166, can be made of stainless steel, nickel, etc. Further, it is preferable that the holding roller for fixing the metal tape is coated with an anthrone rubber or other heat-resistant elastic body. The thickness of the metal strip is preferably 〇·1~〇.4mm, and if it is less than 0.1mm, the bending is large, and the belt is immediately damaged. On the other hand, it is not suitable for deformation of the film when it is thicker than 〇.4mm. With this apparatus, a film was produced as follows. The extruder roller is preferably sealed with an inert gas such as nitrogen or argon to prevent colloidal oxidation of the resin during melt-extrusion. The cyclic olefin resin which was melted by the extruder was extruded into a film shape from the die discharge port in the vertical direction. The temperature distribution at the outlet of the die is preferably such that the viscosity of the resin is less than ± 1 °C. Thereafter, the pressed resin is pressed by a mirror roll and a metal belt to be cooled. Then, the resin transferred to the surface of the mirror roll was peeled off from the surface of the mirror roll by a peeling roll to produce a film-like film. In the present invention, the resin processing temperature, that is, the set temperature of the extruder and the die, is such that the resin having a uniform fluidity is discharged from the die and suppressing deterioration of the resin, and the resin has a Tg + 100 ° C or higher. Tg + 200 ° C or less is preferred. Further, when the resin is pressed by the mirror roll and the metal belt, that is, the pressure at which the resin is transferred to the mirror roll is preferably 面1 to 0.8 MPa, particularly preferably 0.1 to 0.6 MPa. It is preferably 0.15 to 0.45 MPa. At this time, it is preferable that the peripheral speed of the mirror roll and the metal strip are similar. In terms of the preference range, when the mirror roll peripheral speed is 1.00, the circumferential speed of the metal strip is 0.95 to 1.05, particularly preferably 0.99 to 1.01. -32- 200817166 In addition, when the film is peeled off, the peeling temperature Tt (°c), and the peeling stress TF (MPa) are preferably in the range of Tg-3 (TCSTtSTg+5°C, 0.01MPa$TF$5MPa). Here, the mirror roll temperature of the cooling roll is usually Tg - 80 to Tg + l 〇 ° C, preferably Tg - 60 〜 Tg - 2 ° C. The horizontal portion and the die of the flow path of the die of the present invention The leading end portion of the outlet is in contact with each other, and the horizontal portion of the leading end is referred to as a plane of the die. The length of the die plane is 10 to 50 mm, preferably 11 to 40 mm. <Film stretching processing> The optical film of the present invention can be obtained as such The optical film is further extended. In terms of the stretching processing method, specifically, there is a known uniaxial stretching method or a biaxial stretching method. That is, a transverse uniaxial stretching method by a tenter method and a compression stretching method between rolls can be used. The longitudinal uniaxial stretching method of the two sets of rolls having different circumferential directions, or the biaxial stretching method of combining the horizontal single axis and the vertical single axis, the stretching method by the blowing method, etc. The condition of the uniaxial stretching method, the extension speed is usually 1 to 5,000 % / min, preferably 50 to 1,000% /, preferably 1 〇~1, 〇〇〇%/min, especially preferably 1〇〇~500%/min. The condition of the biaxial stretching method is that it extends in two directions at the same time or uniaxially extends in a direction different from the initial extending direction. In this case, the angle of intersection of the two extension axes of the refractive index ellipsoid shape of the film after the extension is determined is not particularly limited depending on the desired characteristics, and is usually in the range of 120 to 60 degrees. The speed is the same in all directions of extension -33- 200817166 Yes, it can be different, usually 1~5,000%/min, preferably 5 (^1000%/minor, more preferably 1〇〇~1,〇〇〇 % / min, particularly preferably from 1 〇〇 to 500% / min. The elongation processing temperature is not particularly limited, and is based on the glass transition temperature Tg of the resin of the present invention, usually Tg ± 30 ° C, in Tg ±15t: Preferably, it is preferably in the range of Tg - 5 ° C to Tg + 15 ° C. In this range, the occurrence of unevenness in phase difference can be suppressed, and it is suitable to control the refractive index ellipsoid. The magnification is not particularly limited depending on the desired characteristics, and is usually 1.01 to 10 times, preferably 1.03 to 5 times. Preferably, it is 1·03~3 times. If the stretching ratio is more than 10 times, the control of the phase difference becomes difficult. The stretched film can be directly cooled, or in a temperature environment of Tg-20°c~Tg. The bonding is carried out for at least 10 seconds, preferably from 30 seconds to 60 minutes, more preferably from 1 minute to 60 minutes, whereby a phase change with a phase change of the transmitted light is small and stable. The differential film shrinkage ratio of the optical film of the present invention which is not subjected to the stretching process is usually 5% or less, preferably 3% or less, when heated at 100 ° C for 5 00 hours, more preferably Preferably, it is 1% or less, and particularly preferably 0.5% or less. Further, when the temperature shrinkage ratio of the retardation film of the present invention is heated at 100 ° C for 500 hours, it is usually 10% or less, preferably 5% or less, more preferably 3% or less, which is particularly preferable. 1% or less. In order to make the dimensional shrinkage ratio within this range, in addition to the selection of the monomers A and B of the resin raw material of the present invention, it can be controlled by a molding method or an extension method. Such a stretched film is extended to molecularly align and impart a phase difference in transmitted light, which can be controlled by stretching ratio, stretching temperature or film thickness. For example, when the thickness of the film before stretching is the same, the film having a larger stretching ratio tends to have a larger absolute difference in the transmission phase difference, and by changing the stretching ratio, a phase difference film which imparts a desired phase difference to the transmitted light can be obtained. On the other hand, when the stretching ratio is the same, the thicker the film thickness before stretching, the greater the absolute difference in the optical phase difference tends to be, so that the retardation film which gives the desired phase difference of the transmitted light can be obtained by changing the thickness of the film before stretching. . Further, in the extended processing temperature range, the lower the extension temperature, the higher the absolute phase of the transmitted light phase difference tends to be, so that the retardation film which gives the phase difference desired for the transmitted light can be obtained by changing the stretching temperature. The thickness of the retardation film thus obtained is usually 1 〇〇 / m or less, preferably 100 to 20 / / m, more preferably 80 to 20 / / m. By making the thickness thin, the retardation film can be made smaller and thinner in accordance with the product in the field to be used. Here, in order to control the thickness of the retardation film, it can be obtained by controlling the thickness of the optical film before stretching and controlling the stretching ratio. For example, by making the optical film before stretching thinner and making the stretching ratio larger, the thickness of the retardation film can be further reduced. <Film Characteristics> The optical film (thropressed and extruded film 'stretched film) of the present invention obtained as described above is characterized in that it has a diameter of 3 0 // m or more at the surface of the film - 35 - 200817166 It is 3 / m or less, preferably 1 / m2 or less. The dot-like defect is a point or a slightly rounded shape of the surface of the film, and one of the causes of the defect is caused by a foreign matter such as a colloid present in the resin. This point defect is one of the major causes of becoming an optical spot. Further, the optical film of the present invention has an excellent surface smoothness, and the smog measured at a thickness of 3 mm measured by ASTM D1003 is 1% or less, preferably 0. 8 % or less. Further, the average roughness Ra of the film is 0.2 / m or less, preferably 0.15 / / m or less, more preferably 0. ivm or less. <<Polarizing Plate>> The polarizing plate of the present invention is a water-based adhesive comprising an aqueous solution mainly composed of a PVA resin and having a polar group adhered to at least one surface of a polarizer formed by a PVA-based film or the like. The agent, the photocurable adhesive, and the like are bonded together, and if necessary, they are heated, exposed, and pressed, and can be produced by laminating a polarizer and an optical film (layering). <<Liquid Crystal Panel>> The liquid crystal panel of the present invention can hold at least one surface of a liquid crystal display element formed by liquid crystal between two glass substrates, and can be bonded to the polarizing plate of the present invention, and the liquid crystal display element and the polarizing plate can be laminated (layered) And manufacturing. [Embodiment] [Embodiment] - 36 - 200817166 Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the embodiments. In addition, the following, "parts", "%", unless otherwise specified, means "parts by weight" and "% by weight". Further, in the following examples, various evaluations were carried out by the following methods. [Glass transfer temperature (Tg)] Using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc., the glass transition temperature was measured under a nitrogen atmosphere at a temperature increase rate of 20 °C /min. [Measurement of spot defects] The optical film was wound up on a black paper, and the shaking of the reflected light was confirmed under a 100 W fluorescent lamp. The reflected light is punctured as a point defect, which is marked. Thereafter, the surface of the film was observed with a 50x optical microscope, and the number of point defects having a diameter of 3 0 // m or more was calculated. [Full light transmittance, smog] The haze meter "HM - 150 type" manufactured by Murakami Color Technology Co., Ltd. was used to measure the total light transmittance and haze. [Intra-plane phase difference (R〇)] The "KOBRA-2 1ADH" manufactured by Oji Scientific Instruments Co., Ltd. is used to make the in-plane phase difference (R 〇) at the incident of the film perpendicular to the light, at wavelength 5 The measurement was carried out at 50 nm. -37- 200817166 [Transmission and Polarization of Polarizer] The transmittance and polarization of the polarizer were measured using "RETS" manufactured by Otsuka Electronics Co., Ltd. The measurement wavelength was 550 nm. [Thin film thickness distribution] The film thickness distribution measuring device (MOCON) was used to measure the film length direction. <Preparation Example 1 > A weight average molecular weight (Mw) of 1.2 million by weight of butyl acrylate (94.8 parts, 5 parts of acrylic acid, and 0.2 parts of 2-hydroxyethyl methacrylate), weight average molecular weight and number average molecular weight ( Μη) The ethyl phthalate solution of the acrylic polymer having a molecular weight of (Mw/ Μη) was diluted with toluene to form a 13% toluene solution of the acrylic polymer, and an isocyanate crosslinking agent was added [CORONA TEL (Japan) (available from Polyurethane Co., Ltd.)] 2.0 parts of the stirred solution is applied to the release film so as not to be foamed, and dried at 60 ° C for 5 minutes, and at 100 ° C for 5 minutes. The light release type release film was temporarily laminated on the adhesive surface to prepare an unsupported film having a thickness (average enthalpy) of 25 // m after drying. [Example 1] In the case of a resin, a cyclic olefin resin (manufactured by JSR Corporation: trade name "ARTON D45 3 1", glass transition temperature: 130 °C) was sealed in -38-200817166 8 00 kg. Resin particles were transported in a nitrogen circulating dryer (manufactured by Lishui Processing Co., Ltd.: Model NS-200) with an oxygen concentration of l.lppm of nitrogen 2001 / min. Under a nitrogen atmosphere, the drying temperature was i〇0 °C. Dehumidify and dry for 180 minutes. After that, the resin was introduced into an extruder (GM TECH CO., LTD.: GM-90) using a nitrogen concentration of 0.1 ppm in an oxygen concentration of 0.1 ppm, and the mixture was fed by a gear pump at 26 (TC). The foreign matter was removed using a 5 // m blade disc filter and extruded from a T die heated by an aluminum casting heater set at 250 ° C. At this time, the opening of the T die was 0.5 mm, T mode. When the distance between the head exit and the pressing point of the film of the cooling roll is 65 mm, the cooling roll is pressed against 25 mm φ. The temperature of the cooling car is 1 2 0 °c, and the lower side is set to 250 mm. The φ cooling roll 2 is provided with a 25 0 mm φ peeling roll on the lower side. The temperature of the individual rolls is 1 15 ° C, n 〇 ° c, and the film thickness is 1 00 peeled off by the peeling roll at the film surface temperature l 〇 8 t / The film of /m was obtained to obtain a raw spinel-based resin film. The number of dot defects of the obtained optical film was confirmed to be 〇·3/m2. Further, the total light transmittance of the optical film was 93%, and the haze was 0.2. [Comparative Example 1] The same procedure as in Example 1 was carried out except that the tank was conveyed to a dryer and conveyed by a dryer to an extruder under the same air atmosphere. 'The optical film (b-1) was obtained. It was confirmed that the number of dot defects of the optical film was 3.2·m2. Further, the total optical transmittance of the optical film roll (b-1) was 93%, and the haze was 0.3. -39- 200817166 [Example 2] The optical film (a - 1 ) obtained in Example 1 was used, and under the condition of 1 3 〇t, the roll-type vertical single-axis stretching machine was extended 1.2 times, and 1 3 0 (: The extension optical film (a-2) having a thickness of 70 // m is obtained by extending 1.4 times with a tenter type horizontal stretcher. The phase difference of the optical film (a-2) is the in-plane phase difference of the film ( R0) is 60 nm. Further, the optical film (a-2) has a total light transmittance of 93% and a haze of 0.1%. Further, it is confirmed that the number of dot defects of the optical film (a-2) is 〇. [Comparative Example 2] An optical film (b-2) was obtained in the same manner as in Example 2 except that the optical film (b-1) was used. The phase difference of the film was such that the film in-plane retardation (R0) was 63 nm. Further, the total light transmittance was 93%, and the haze was 0.2%. Further, it was confirmed that the number of dot defects of the optical film (b-2) was 3.5 / m2 〇 [Example 3] Thickness 5 The 0 / m m polyvinyl alcohol film is immersed in a 40 ° C bath formed by iodine 5 g, potassium iodide 250 g, boric acid l〇g, water i〇〇〇g for about 5 minutes, and uniaxially extended to 4 times. A polarizing film was used. The optical film (a-1) produced in Example 1 and the optical film (a-2) produced in Example 2 were each applied to one surface of the polarizing film using the adhesive obtained in the adjustment example 1 on the surface of the polarizing film. Even -40-200817166 continues to get the polarizing plate (a). The transmittance and the degree of polarization of the polarizing plate (a) were measured and found to be 43% and 99.99%, respectively. Further, when the two polarizing plates (a) were in a state of being orthogonally polarized and irradiated with a backlight having a luminance of 10 〇〇〇cd, when viewed from the other surface, it was confirmed that there was no light leakage due to the dot defects. [Comparative Example 3] A polarizing plate (b) was obtained in the same manner as in Example 3 except that the optical films (b-2) and (c-1) were used. The transmittance and the degree of polarization of the polarizing plate (b) were measured and found to be 42% and 98.77%, respectively. Further, when the polarizing plate (b) is inside the optical film roll (b-2) and the two sheets are in a state of being orthogonally polarized, when one side is irradiated with a backlight having a luminance of 1 0000 cd, when the other side is observed, the point is confirmed. The light leakage caused by the shape defect is 3.0 / m2. [Industrial Applicability] The optical film of the present invention does not cause dot defects on the surface of the optical film, and does not cause optical spots. Therefore, the optical film obtained by the optical film roll of the present invention can be used for display devices such as mobile phones, digital information terminals, pagers, satellite navigation, automotive liquid crystal displays, liquid crystal screens, liquid crystal televisions, dimming panels, and OA machines. Various liquid crystal display elements such as AV device displays, electroluminescence display elements, touch panels, and the like. Further, it can also be used as a wavelength plate in a recording/reproducing apparatus for optical discs such as CDs, CD-Rs, MDs, MOs, and DVDs. BRIEF DESCRIPTION OF THE DRAWINGS - 41 - 200817166 [Fig. 1] A schematic view of a resin particle transport path which is preferably used in the method for producing an optical film of the present invention. -42-