TW200817736A - Optical film, polarizing plate, liquid crystal panel and manufacturing method of optical film - Google Patents

Optical film, polarizing plate, liquid crystal panel and manufacturing method of optical film Download PDF

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Publication number
TW200817736A
TW200817736A TW096131866A TW96131866A TW200817736A TW 200817736 A TW200817736 A TW 200817736A TW 096131866 A TW096131866 A TW 096131866A TW 96131866 A TW96131866 A TW 96131866A TW 200817736 A TW200817736 A TW 200817736A
Authority
TW
Taiwan
Prior art keywords
film
optical film
optical
resin
cyclic olefin
Prior art date
Application number
TW096131866A
Other languages
Chinese (zh)
Inventor
Takuhiro Ushino
Masayuki Sekiguchi
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200817736A publication Critical patent/TW200817736A/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033—Means for improving the coupling-out of light from the light guide
    • G02B6/0058—Means for improving the coupling-out of light from the light guide varying in density, size, shape or depth along the light guide
    • G02B6/0061—Means for improving the coupling-out of light from the light guide varying in density, size, shape or depth along the light guide to provide homogeneous light output intensity
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
    • G09G2320/00—Control of display operating conditions
    • G09G2320/02—Improving the quality of display appearance
    • G09G2320/028—Improving the quality of display appearance by changing the viewing angle properties, e.g. widening the viewing angle, adapting the viewing angle to the view direction

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

To obtain an optical film which is used as a viewing angle compensation film capable of obtaining a liquid crystal panel having no light leakage, no color shift and having a wide viewing angle and to obtain a polarizing plate and the liquid crystal panel using the optical film. The optical film is consisting of an annular olefinic resin. At a film surface remote from a film end part by ≥ 50mm, variation of retardation is +-10% or less and variation of the optical axes is central value +-10 DEG or less when retardation in a film surface (RO) and an optical axis in the film surface are measured at every 5mm distance along a longitudinal direction of the film.

Description

200817736 九、發明說明 【發明所屬之技術領域】 本發明係關於由環狀烯烴系樹脂所成，於長邊方向爲 均質之光學薄膜、其製造方法、使用該光學薄膜之偏光板 、及液晶面板。 【先前技術】 環狀烯烴系樹脂因具有優良的透明性、耐熱性、耐濕 性等，故可適用於光學薄膜用途上。一般由環狀烯烴系樹 脂所成的薄膜爲，藉由溶液流延法（溶液澆注法）、或熔 融押出法等製膜，視必要施予延伸等而製造。 光學薄膜爲不僅被要求於透明性等光學特性優良，同 時薄膜必須爲均質，且少有光學不均爲重要。作爲欲防止 或抑制光學薄膜製造時所產生的光學不均之製造光學薄膜 的方法，例如可藉由使用塑模唇之缺陷形狀經抑制的特定 T塑模，以熔融押出成形製造出光學薄膜時，抑制沿著薄 膜之押出方向連續產生的凹凸狀線狀模樣（分模線（line ))之產生的方法已被提出（參照專利文獻1 )。 然而，製造工業上的長邊薄膜時，依據原料樹脂供給 所用之幫浦特性、薄膜經捲取輥之轉動等，產生週期性厚 度變動，藉此所得之光學薄膜有者產生明·度週期性變化或 光學性彎曲（所謂交叉痕跡（cross mark ))之問題。 又，藉由上述溶液流延法或熔融押出成形製造光學薄 膜時，發現薄膜的長邊方向上因熔融黏度之變化會引起厚 -4- 200817736 度不均的產生等光學薄膜之均質性受到阻害。 於光學薄膜上產生不均勻性時，例如作爲偏光板之保 護薄膜或相位差薄膜使用時，有著產生光學性不均等問題 。特別爲近年來偏光板之偏光度、透過率提高，與過去相 比開始注意到細微的光學不均之問題。 〔專利文獻1〕特開2005 - 1 4 8 5 6 8號公報 【發明內容】 發明說明 本發明係以提供製造工業之長邊薄膜時’於由環狀烯 烴系樹脂所成的長邊方向爲均質之光學薄膜、及製造該光 學薄膜之方法作爲課題。 本發明係關於由環狀烯烴系樹脂所成的薄膜’對於自 薄膜端部離5 0mm以上之薄膜表面’沿著薄膜長邊方向於 每5 mm測定薄膜面内之相位差R 0與薄膜面内的光軸時之 R 〇的偏差爲± 1 〇 %以下’且光軸之偏差爲中心値土 1 0度以 下爲特徴之光學薄膜。 其中，作爲上述環狀烯烴系樹脂以下述一般式（I ) 所示化合物之（共）聚合物爲佳。 -5- 200817736 [化i] 一般式（i)[Technical Field] The present invention relates to an optical film formed of a cyclic olefin resin and homogeneous in the longitudinal direction, a method for producing the same, a polarizing plate using the optical film, and a liquid crystal panel. . [Prior Art] Since the cyclic olefin resin has excellent transparency, heat resistance, moisture resistance and the like, it can be suitably used for optical film applications. The film formed of the cyclic olefin resin is usually formed by a solution casting method (solution casting method) or a melt extrusion method, and is produced by stretching or the like as necessary. The optical film is not only required to have excellent optical properties such as transparency, but also the film must be homogeneous, and few opticals are important. As a method of producing an optical film to prevent or suppress optical unevenness generated in the production of an optical film, for example, when an optical film is formed by melt extrusion molding by using a specific T mold in which a defect shape of a molding lip is suppressed A method of suppressing generation of a concavo-convex linear pattern (line) which is continuously generated in the extrusion direction of the film has been proposed (see Patent Document 1). However, in the production of long-side films in the industry, periodic thickness variations are generated depending on the pump characteristics used for the supply of the raw material resin, the rotation of the film by the take-up rolls, and the like, whereby the resulting optical film has a periodicity of lightness. A problem of variation or optical bending (so-called cross mark). Further, when the optical film was produced by the above-described solution casting method or melt extrusion molding, it was found that the homogeneity of the optical film was suppressed due to the change in the melt viscosity in the longitudinal direction of the film, which caused the thickness of the thickness of -200817736 degree unevenness. . When unevenness occurs in the optical film, for example, when it is used as a protective film for a polarizing plate or a retardation film, there is a problem that optical unevenness occurs. In particular, in recent years, the polarization degree and transmittance of the polarizing plate have been improved, and the problem of fine optical unevenness has been noticed in comparison with the past. [Patent Document 1] JP-A-2005- 1 4 8 5 6 8 SUMMARY OF THE INVENTION The present invention provides a long-side direction formed by a cyclic olefin-based resin when providing a long-side film for industrial production. A homogeneous optical film and a method of producing the optical film are problems. The present invention relates to a film formed of a cyclic olefin-based resin, which has a phase difference R 0 and a film surface in a film surface every 5 mm along the longitudinal direction of the film from a film surface of 50 mm or more from the end of the film. The deviation of R 〇 in the optical axis of the inside is ± 1 〇 % or less and the deviation of the optical axis is an optical film which is characteristic of the central alumina of 10 degrees or less. Among them, the cyclic olefin resin is preferably a (co)polymer of a compound represented by the following general formula (I). -5- 200817736 [化i] General formula (i)

(一般式（I)中，R1〜R4爲氫、鹵素原子、碳數30的 烴基、或其他1價之有機基，各可爲相同或相異。又， Rl〜R4中任意2個彼此結合，可形成單環或多環結構。π 爲〇或正整數，ρ爲〇或正整數。） 其次’本發明係關於進一步延伸上述薄膜之光學薄膜 〇 其次’本發明係關於偏光子的至少單面上，上層合上 述光學薄膜爲特徵的偏光板。 其次’本發明係關於液晶顯示元件的至少單面上層合 上述偏光板爲特徴之液晶面板。 其次’本發明係關於環狀烯烴系樹脂經熔融，由塑模 押出並於冷卻輥壓著使其薄膜化時，塑模吐出口之溫度變 化爲± 1 °C /分鐘以内作爲特徴之光學薄膜的製造方法。 其次’本發明係關於將如上述之經熔融押出的薄膜， 進一步進行延伸爲特徴之上述光學薄膜之製造方法。 所謂本發明即可提供含有環狀烯烴系樹脂，於薄膜長 邊方向均質，且不具有光學性不均之光學薄膜及其製造方 -6- 200817736 法。又，光學薄膜爲施予延伸之薄膜的情況時，可適用於 相位差或光軸爲安定且無光學性不均之相位差薄膜上。有 關本發明之光學薄膜爲長邊方向上爲極均質者，故光學性 不均較少，且於延伸薄膜時，霧値較少透明性優良，使用 此於大畫面之液晶顯示器等時可達到全面之無彎曲或不均 的高性能。 實施發行的較佳型態 《光學薄膜》 本發明的光學薄膜係爲由環狀烯烴系樹脂所成的薄膜 <環狀烯烴系樹脂> 作爲使用於本發明的光學薄膜之環狀烯烴系樹脂，可 舉出如下述的（共）聚合物。 (1) 上述一般式（I )所示特定單體之開環聚合物。 (2) 上述一般式（I)所示特定單體與共聚合性單體 之開環共聚合物。 (3 )上述（1 )或（2 )之開環（共）聚合物的氫化 (共）聚合物。 (4 )將上述（1 )或（2 )之開環（共）聚合物藉由 費里德爾-克拉夫茨反應（Friedel-Crafts reaction)進行環 化後經氫化之（共）聚合物。 (5)上述一般式（I)所示特定單體與含有不飽和雙 200817736 鍵之化合物之飽和共聚合物。 (6) 1種以上選自上述一般式（I)所示特定單體、 乙烯系環狀烴系單體及環戊二烯系單體之單體的加成型（ 共）聚合物及其氫化（共）聚合物。 (7) 上述一般式（I)所示特定單體與丙烯酸酯之交 互共聚合物。 <特定單體〉 作爲上述特定單體之具體例，可舉出如下述的化合物 ，但本發明非限定於這些具體例者。 雙環〔2.2.1〕庚-2-烯、 三環〔4·3·0·12,5 〕-8-癸烯、 三環〔4·4·0·12,5 〕-3-十一碳烯、 四環〔4.4.0.12’5.17，1()〕-3-十二碳烯、 五環〔6·5·1·13’6 ·02’7 .09’13〕-4-十五碳烯、 5-甲基雙環〔2.2.1〕庚-2-烯、 5-乙基雙環〔2.2.1〕庚-2-烯、 5_甲氧基羰基雙環〔2.2.1〕庚-2-烯、 5-甲基-5-甲氧基羰基雙環〔2.2.1〕庚-2-烯、 5-氰基雙環〔2·2·1〕庚-2-烯、 8-甲氧基羰基四環〔4·4.0.12’5·Γ’1()〕-3·十二碳烯、 8-乙氧基羰基四環〔4·4·0.12’5·17’1()〕-3-十二碳烯、 8-η-丙氧基羰基四環〔4.4.0.I2’5 ·1 7’1G〕-3-十二碳烯、 8-異丙氧基羰基四環〔4.4.0.I2’5 ·17’1()〕-3-十二碳烯、 -8- 200817736 8-11-丁氧基羰基四環〔4.4.0.12’5.17’1()〕-3-十二碳烯、 8-甲基-8-甲氧基羰基四環〔4.4.0.12’5 ·17’1()〕-3-十二碳烯 8-甲基-8-乙氧基羰基四環〔4.4.0.12,5 ·17，1()〕-3-十二碳烯 、 8-甲基-8-η·丙氧基羰基四環〔mP」厂’^〕-3-十二碳 烯、 8-甲基-8-異丙氧基羰基四環〔4.4.0.12’5 ·17，1()〕-3-十二碳 烯、 8_甲基-8_η-丁氧基羰基四環〔HO·。/ 厂^〕-3-十二碳 烯、 5-亞乙基雙環〔2.2.1〕庚-2-烯、 8-亞乙基四環〔4.4.0.12,5.17，1()〕-3-十二碳烯、 5-苯基雙環〔2.2.1〕庚-2-烯、 8-苯基四環〔4·4·0.12,5·Γ，1()〕-3-十二碳烯、 5-氟雙環〔2.2.1〕庚-2-烯、 5-氟甲基雙環〔2.2.1〕庚-2-烯、 5-三氟甲基雙環〔2.2.1〕庚-2·烯、 5-五氟乙基雙環〔2_2.1〕庚-2-烯、 5.5- 二氟雙環〔2.2.1〕庚-2-烯、 5.6- 二氟雙環〔2.2.1〕庚-2-烯、 5.5- 雙（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5.6- 雙（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5-甲基-5-三氟甲基雙環〔2.2.1〕庚-2-烯、 -9- 200817736 5,5,6-三氟雙環〔2·2·1〕庚-2-烯、 5，5,6-參（氟甲基）雙環〔2.2.1〕庚-2-烯、 5,5,6,6·四氟雙環〔2.2.1〕庚-2-烯、 5，5,6,6-肆（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5.5- 二氟-6,6-雙（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5.6- 二氟-5,6-雙（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5，5,6·三氟-5-三氟甲基雙環〔2.2.1〕庚-2-烯、 5-氟-5-五氟乙基-6,6-雙（三氟甲基）雙環〔2.2.1〕庚-2 烯、 5.6- 二氟-5-七氟-異-丙基-6-三氟甲基雙環〔2.2.1〕庚-2 烯、 5-氯-5,6，6-三氟雙環〔2.2.1〕庚-2-烯、 5.6- 二氯-5,6-雙（三氟甲基）雙環〔2.2.1〕庚-2-烯、 5，5,6-三氟-6-三氟甲氧基雙環〔2.2.1〕庚-2-烯、 5，5,6-三氟-6-七氟丙氧基雙環〔2.2.1〕庚-2-烯、 8-氟四環〔4·4·0·12,5·17，1()〕-3-十二碳烯、 8-氟甲基四環〔4·4·0·12’5·Γ’1()〕-3-十二碳烯、 8-二氟甲基四環〔4.4.0.12,5 ·17，1()〕-3-十二碳烯、 8-三氟甲基四環〔4.4·0·12,5.Γ，1()〕-3-十二碳烯、 8-五氟乙基四環〔4.4·0·12’5·Γ’1()〕-3-十二碳烯、 8.8- 二氟四環〔4.4.0.12’5.17’1()〕-3-十二碳烯、 8.9- 二氟四環〔4.4.0.12,5.17，1()〕-3-十二碳烯、 8,8-雙（三氟甲基）四環〔4.4_0.12,5.17，1()〕-3-十二碳嫌 -10- 200817736 8,9-雙（三氟甲基）四環〔4.4.0.12,5.17，1()〕-3-十二碳烯 8-甲基-8-三氟甲基四環〔4·4·0·12’5·17，1()〕-3-十二碳烯、 8.8.9- 三氟四環〔4.4.0.12,5.17，1()〕-3-十二碳烯、 8.8.9- 參（三氟甲基）四環〔4.4.0.12,5.17，1()〕-3-十二碳 烯、 8.8.9.9- 四氟四環〔4.4.0.12,5.17，1()〕-3-十二碳烯、 8.8.9.9- 肆（三氟甲基）四環〔4.4.0.12,5.17，1()〕-3-十二碳 烯、 8,8-二氟-9,9-雙（三氟甲基）四環〔4.4.0.12,5.17，1()〕-3· 十二碳儲、 859-二氟-8,9-雙（三氟甲基）四環〔4.4.0.12,5.17，1()〕-3· 十二碳烯、 8，8,9-三氟-9-三氟甲基四環〔4.4.0.I2,5 .17，1G〕-3-十二碳 烯、 8.8.9- 三氟-9-三氟甲氧基四環〔4·4·0·12,5 .17，1()〕-3-十二 碳烯、 8.8.9- 三氟-9-五氟丙氧基四環〔4.4.0.12,5 .17，1G〕-3·十二 碳烯、 8-氟-8-五氟乙基-9,9-雙（三氟甲基）四環〔4.4.0.12,5 ·Γ，1()〕-3-十二碳烯、(In the general formula (I), R1 to R4 are hydrogen, a halogen atom, a hydrocarbon group having a carbon number of 30, or another monovalent organic group, and each may be the same or different. Further, any two of R1 to R4 are bonded to each other. A monocyclic or polycyclic structure may be formed. π is 〇 or a positive integer, ρ is 〇 or a positive integer.) Next, the present invention relates to an optical film which further extends the above film. Secondly, the present invention relates to at least a single photon. On the surface, a polarizing plate characterized by the above optical film is laminated. Next, the present invention relates to a liquid crystal panel in which at least one surface of a liquid crystal display element is laminated. Next, the present invention relates to an optical film in which a cyclic olefin-based resin is melted, extruded by a mold, and pressed into a film by a cooling roll, and the temperature of the mold discharge port is changed to within ± 1 ° C /min. Manufacturing method. Next, the present invention relates to a method for producing the above optical film by further extending the melt-extruded film as described above. In the present invention, it is possible to provide an optical film containing a cyclic olefin resin which is homogeneous in the longitudinal direction of the film and which does not have optical unevenness, and a method for producing the same. Further, when the optical film is a film to which an extension is applied, it can be applied to a phase difference film having a phase difference or an optical axis which is stable and free from optical unevenness. Since the optical film of the present invention is extremely uniform in the longitudinal direction, the optical unevenness is small, and when the film is stretched, the haze is less excellent in transparency, and can be achieved when used in a large-screen liquid crystal display or the like. Comprehensive high performance without bending or unevenness. The optical film of the present invention is a film formed of a cyclic olefin resin <a cyclic olefin resin> as a cyclic olefin system used in the optical film of the present invention. The resin may, for example, be a (co)polymer as described below. (1) A ring-opening polymer of a specific monomer represented by the above general formula (I). (2) A ring-opening copolymer of a specific monomer and a copolymerizable monomer represented by the above general formula (I). (3) A hydrogenated (co)polymer of the ring-opened (co)polymer of the above (1) or (2). (4) A hydrogenated (co)polymer obtained by subjecting the ring-opened (co)polymer of the above (1) or (2) to a cyclization by a Friedel-Crafts reaction. (5) A saturated copolymer of a specific monomer represented by the above general formula (I) and a compound containing an unsaturated double 200817736 bond. (6) Addition molding (co)polymer of one or more kinds of monomers selected from the above specific formula (I), a vinyl cyclic hydrocarbon monomer, and a cyclopentadiene monomer, and hydrogenation thereof (co)polymer. (7) A cross-polymer of a specific monomer and an acrylate represented by the above general formula (I). <Specific Monomers> Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples. Bicyclo[2.2.1]hept-2-ene, tricyclo[4·3·0·12,5]-8-decene, tricyclo[4·4·0·12,5]-3-undecene Alkene, tetracyclo[4.4.0.12'5.17,1()]-3-dodecene, pentacyclic [6·5·1·13'6 ·02'7 .09'13]-4-pentadecene Alkene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2·2·1]hept-2-ene, 8-methoxycarbonyltetra Ring [4·4.0.12'5·Γ'1()]-3·dodecene, 8-ethoxycarbonyltetracyclo[4·4·0.12'5·17'1()]-3- Dodecene, 8-η-propoxycarbonyltetracyclo [4.4.0.I2'5 ·1 7'1G]-3-dodecene, 8-isopropoxycarbonyltetracycline [4.4.0] .I2'5 ·17'1()]-3-dodecene, -8- 200817736 8-11-butoxycarbonyltetracyclo[4.4.0.12'5.17'1()]-3-dodecarb Alkene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12'5 ·17'1()]-3-dodecene 8-methyl-8-ethoxycarbonyltetracyclo [4.4 .0.12,5 ·17,1()]-3-dodecene, 8-methyl-8-η· Oxycarbonyl tetracycline [mP" plant '^〕-3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.12'5 ·17,1()]-3- Dodecene, 8-methyl-8-η-butoxycarbonyltetracycline [HO·. /厂^]-3-dodecene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 8-ethylenetetracycline [4.4.0.12, 5.17,1()]-3- Dodecene, 5-phenylbicyclo[2.2.1]hept-2-ene, 8-phenyltetracyclo[4·4·0.12,5·Γ,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-pentafluoroethylbicyclo[2_2.1]hept-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]hept-2-ene, 5.6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-three Fluoromethylbicyclo[2.2.1]hept-2-ene, -9- 200817736 5,5,6-trifluorobicyclo[2·2·1]hept-2-ene, 5,5,6-parade (fluorine Methyl)bicyclo[2.2.1]hept-2-ene, 5,5,6,6·tetrafluorobicyclo[2.2.1]hept-2-ene, 5,5,6,6-fluorene (trifluoromethyl) Bicyclo[2.2.1]hept-2-ene, 5.5-difluoro-6,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5.6-difluoro-5,6 - bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5, 5,6·trifluoro-5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis(trifluoromethyl)bicyclo[2.2 .1]heptane-2-ene, 5.6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-chloro-5,6,6- Trifluorobicyclo[2.2.1]hept-2-ene, 5.6-dichloro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5,6-trifluoro -6-trifluoromethoxybicyclo[2.2.1]hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo[2.2.1]hept-2-ene, 8- Fluorotetracycline [4·4·0·12,5·17,1()]-3-dodecene, 8-fluoromethyltetracycline [4·4·0·12'5·Γ'1 ( )]-3-dodecene, 8-difluoromethyltetracyclo[4.4.0.12,5·17,1()]-3-dodecene, 8-trifluoromethyltetracycline [4.4· 0·12,5.Γ,1()]-3-dodecene, 8-pentafluoroethyltetracyclo[4.4·0·12'5·Γ'1()]-3-dodecene 8.8-Difluorotetracycline [4.4.0.12'5.17'1()]-3-dodecene, 8.9-difluorotetracyclo[4.4.0.12,5.17,1()]-3-dodecene , 8,8-bis(trifluoromethyl)tetracyclo[4.4_0.12,5.17,1()]-3-tine carbon-10-27-1717736 8,9-double (three Fluoromethyl)tetracyclo[4.4.0.12, 5.17,1()]-3-dodecene 8-methyl-8-trifluoromethyltetracycline [4·4·0·12'5·17, 1()]-3-dodecene, 8.8.9-trifluorotetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8.8.9-paran (trifluoromethyl) Tetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8.8.9.9-tetrafluorotetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8.8. 9.9- 肆(trifluoromethyl)tetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8,8-difluoro-9,9-bis(trifluoromethyl)tetracyclic [4.4.0.12, 5.17, 1()]-3·12 carbon storage, 859-difluoro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.12, 5.17,1()]-3 · Dodecene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.I2,5 .17,1G]-3-dodecene, 8.8.9-trifluoro -9-trifluoromethoxytetracyclo[4·4·0·12,5 .17,1()]-3-dodecene, 8.8.9-trifluoro-9-pentafluoropropoxy-4 Ring [4.4.0.12, 5.17,1G]-3·dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.12,5 ·Γ,1()]-3-dodecene,

8,9·二氟-8-七氟異丙基-9-三氟甲基四環〔4.4.0.I2,5 .17，1G -十8,9·Difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracycline [4.4.0.I2,5 .17,1G -10

8-氯-8,9,9-三氟四環〔4·4·0.12,5·1 -11 - 200817736 8，9-二氯-8,9-雙（三氟甲基）四環〔4.4.0.12，5 ·&quot;，i〇〕-3- 十二碳烯、 8-(2，2，2-三氟乙氧基羰基）四環〔4.4.0.12,5 .i7，1G〕-3 -十二碳嫌、 8 -甲基-8- (2，2，2-三氟乙氧基羰基）四環〔4.4.0.I2,5 • 17’1Q〕-3-十二碳烯等。 這些可單獨使用1種、或倂用2種以上。 特定單體中較佳爲上述一般式（I)中，R1及R3爲氫 或碳數1〜10，更佳爲1〜4，特佳爲1〜2的烴基，R2及R4 爲氫或一價有機基，R2及R4的至少一個表示氫及烴基以 外之具有極性的極性基，m爲0〜3的整數，p爲0〜3的整 數，較佳爲m+p=0〜4，更佳爲0〜2，特佳爲m=l、p=0 。m = 1、p = 0之特定單體以所得環狀烯烴系樹脂之玻璃 轉移溫度較高且機械性強度亦優良者爲佳。 作爲上述特定單體之極性基，可舉出羧基、烴基、烷 氧基羰基、烯丙氧基羰基、胺基、醯胺基、氰基等，這些 極性基可介著亞甲基等連結基結合。又，可舉出羰基、醚 基、甲矽烷基醚基、硫醚基、亞胺基等具有極性之2價有 機基作爲連結基結合之烴基等亦可作爲極性基。這些中以 羧基、烴基、烷氧基羰基或烯丙氧基羰基爲佳，特佳爲烷 氧基羰基或烯丙氧基羰基爲佳。 且，R2及R4的至少1個爲式-(CH2 ) nCOOR所示極 性基之單體以所得之環狀烯烴系樹脂爲具有較高玻璃轉移 -12- 200817736 溫度與較低吸濕性、與各種材料之密著性優良之觀點來看 爲佳。對於上述特定之極性基的相關式’ R爲碳原子數 1〜12，更佳爲1〜4，特佳爲1〜2之煙基’較佳爲院基。又 ，η —般爲〇〜5，但η値越小所得之環狀儲烴系樹脂的玻 璃轉移溫度越高，故較佳’且11爲0之特定單體因容易合 成故較佳。 又，上述一般式（I )中，R1或R3以烷基爲佳’碳數 1〜4的烷基爲較佳，更佳爲1〜2的烷基’以甲基爲特佳’ 特別爲該烷基結合於與上述式-(CH2 ) nCOOR所示特定之 極性基所結合的碳原子爲相同之碳原子時，所得之環狀儲 烴系樹脂的吸濕性可降低故較佳。 &lt;共聚合性單體&gt; 作爲共聚合性單體之具體例，可舉出環丁烯、環戊烯 、環庚烯、環辛烯、二環戊二烯等環烯烴。 作爲環烯烴之碳數以4〜20爲佳，更佳爲5〜12。這些 可單獨使用1種、或並用2種以上。 特定單體/共聚合性單體之較佳使用範圍以重量比爲 100/0 〜5 0/50，更佳爲 100/0 〜60/40。 &lt;開環聚合觸媒&gt; 本發明中，欲得到（1 )特定單體之開環聚合物、及 (2 )特定單體與共聚合性單體之開環共聚合物的開環聚 合反應於複分解（Metathesis )觸媒之存在下進行。 -13- 200817736 該複分解觸媒爲（a)至少1種選自W、M〇及Re的 化合物、與（b ) Deming周期律表ΙΑ族元素（例如Li、 Na、K等）、IIA族元素（例如Mg、Ca等）、ΠΒ族元素 (例如Zn、Cd、Hg等）、ΙΠΑ族元素（例如B、A1等） 、IVA族元素（例如Si、Sn、Pb等）、或IVB族兀素（ 例如Ti、Zr等）之化合物，與具有至少1個該元素-碳鍵 或該元素-氫鍵者所選出的至少1種之組合所成的觸媒。 又，此時欲提高觸媒之活性，亦可添加後述（C )添加劑 〇 作爲（a)成分之適當W、Mo或作爲Re之化合物代 表例可舉出WCl6、M〇Cl6、ReOCl3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行所記載的 化合物。 作爲（b )成分之具體例可舉出n-C4H9Li、（C2H5)3A1 、（C2H5) 2A1C1、（C2H5) uAlCh」、（c2h5) aici2、 甲基鋁四氫喃、LiH等特開平1-132626號公報第8頁右上 攔第1 8行〜第8頁右下欄第3行所記載的化合物。 作爲添加劑之（c )成分代表例，可適用醇類、醛類 、酮類、胺類等，亦可使用特開平1 - 1 32626號公報第8 頁右下欄第1 6行〜第9頁左上欄第1 7行所示化合物。 作爲複分解（Metathesis )觸媒之使用量，以上述（a )成分與特定單體之莫耳比時，使「（a)成分：特定單 體」一般成爲1:500〜1:50,000之範圍，較佳成爲1: 1，000〜1: 10,000 之範圍。 -14- 200817736 (a)成分與（b)成分之比例以金屬原子比時，（a ):(b)爲1:1〜1:5〇，較佳爲1:2〜1:30的範圍。 (a )成分與（c )成分之比例，以莫耳比時，（c ) :(a)爲0.005: 1〜15: 1，較佳爲0·05: 1〜7: 1之範圍 &lt;聚合反應用溶劑&gt; 作爲開環聚合反應中所使用的溶劑（構成分子量調節 劑溶液之溶劑、特定單體及/或複分解（Metathesis )觸媒 之溶劑），例如可舉出戊烷、己烷、庚烷、辛烷、壬烷、 癸院等烷類、環己烷、環庚院、環辛烷、萘院、原冰片烷 等環烷類、苯、甲苯、二甲苯、乙基苯、枯烯等芳香族烴 、氯丁烷、溴己烷、二氯甲烷、二氯乙烷、二溴化六伸甲 基、氯苯、氯仿、四氯伸乙基等、鹵化鏈烷、鹵化芳基等 化合物、乙酸乙酯、乙酸η-丁酯、乙酸異丁酯、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，這些可單獨或混合後使用。其中 以芳香族烴爲佳。 作爲溶劑之使用量，「溶劑：特定單體（重量比）」 一般成爲1: 1〜10: 1之量，較佳成爲1: 1〜5: 1之量。 &lt;分子量調節劑&gt; 所得之開環（共）聚合物之分子量的調節，可藉由聚 合溫度、觸媒種類、溶劑種類而進行，但本發明中，藉由 -15- 200817736 將分子量調節劑共存於反應系中而調節。 其中，作爲較佳的分子量調節劑，例如可舉出乙烯、 丙烯、1 - 丁烯、1 -戊烯、1 -己烯' 1 -庚烯、1 -辛烯、1 -壬 烯、1 -癸烯等α -烯烴類及苯乙烯，此等中以1 - 丁嫌、1 -己烯爲特佳。 這些分子量調節劑可爲單獨或混合2種以上使用。 作爲分子量調節劑之使用量，對於提供於開環聚合反 應之特定單體1莫耳而言爲0.005〜0.6莫耳：，較佳爲 0.02〜0.5莫耳。 (2 )欲得到開環共聚合物，於開環聚合步驟中，可 使特定單體與共聚合性單體進行開環共聚合，再於聚丁二 矯、聚異丁細寺共輒一嫌化合物、苯乙靖-丁二嫌共聚合 物、乙烯-非共軛二烯共聚合物、聚原冰片烯等主鏈上含 有2個以上碳-碳間雙鍵之不飽和烴系聚合物等存在下使 特定單體進行開環聚合。 如以上所得之開環（共）聚合物可直接使用，或再進 行氫化所得之（3 )氫化（共）聚合物可作爲耐衝撃性大 之樹脂原料使用。 &lt;氫化觸媒&gt; 氫化反應可藉由一般方法，即藉由開環聚合物之溶液 中添加氫化觸媒，於常壓〜3〇〇氣壓，較佳爲3〜2〇〇氣壓 之氫氣下〇〜2 00 °C，較佳爲20〜180 °C中起作用而進行。 作爲氫化觸媒，可使用一般使用於烯烴性化合物之氯 -16- 200817736 化反應者。作爲該氫化觸媒，可舉出不均相系觸媒及均相 系觸媒。 作爲不均相系觸媒，可舉出將鈀、鉑、鎳、铑、釕等 貴金屬觸媒物質載持於碳、二氧化矽、氧化鋁、二氧化鈦 等載體之固體觸媒。又，作爲均相系觸媒可舉出環烷酸鎳 /三乙基鋁、乙醯丙酮鎳/三乙基鋁、辛烯酸鈷/正丁鋰、二 氯化二茂鈦/單氯化二乙基鋁、乙酸鍺、氯參（三苯基膦 )铑、二氯參（三苯基膦）釕、氯氫羰基參（三苯基膦） 釕、二氯羰基參（三苯基膦）釕等。觸媒的形態可爲粉末 狀或粒狀。 這些氫化觸媒可以開環（共）聚合物：氫化觸媒（重 量比）爲1 : 1x1 0_6〜1 : 2之比例下使用。 如此，藉由氫化所得之氫化（共）聚合物爲具有優良 熱安定性者，即使經成形加工時或作爲製品使用時的加熱 ，該特性亦不會劣化。其中，氫化率一般爲50%以上，較 佳爲70%以上，更佳爲90%以上。 又，氫化（共）聚合物之氫化率以5 00MHz，W-NMR 所測定的値爲50%以上，較佳爲90%以上，更佳爲98%以 上，特佳爲99%以上，最佳爲99.5%以上。氫化率越高’ 對於熱或光的安定性越優良，作爲本發明之波長板使用時 ，可得到長期使用亦可得到安定之特性。 且，作爲本發明的環狀烯烴系樹脂所使用之氫化（共 )聚合物爲，含於該氫化（共）聚合物中之凝膠含有量以 5重量％以下爲佳，更以1重量％以下時爲特佳。 -17- 200817736 又，作爲本發明之環狀儲烴系樹脂’將（4)上述（1 )或（2)之開環（共）聚合物藉由費里德爾-克拉夫茨反 應（Friedel-Crafts reaction)而環化後。，亦可使用經氫 化之（共）聚合物。 &lt;藉由費里德爾-克拉夫茨反應之環化&gt; 將（1 )或（2 )之開環（共）聚合物藉由費里德爾-克拉夫茨反應（Friedel-Crafts reaction)之環化方法並無 特別限定，但可採用使用特開昭5 0- 1 543 99號公報所記載 的酸性化合物之公知方法。作爲酸性化合物，具體可使用 A1C13、BF3、FeCl3、Al2〇3、HC1、CH3C1C00H、沸石、 活性白土等路易氏酸、布朗斯台德酸。 經環化之開環（共）聚合物可與（1 )或（2 )之開環 (共）聚合物同樣地進行氫化。 且，作爲本發明的環狀烯烴系樹脂，亦可使用（5 ) 上述特定單體與含有不飽和雙鍵之化合物之飽和共聚合物 &lt;含有不飽和雙鍵之化合物&gt; 作爲含有不飽和雙鍵之化合物，例如可舉出乙烯、丙 燦、丁烯等，較佳爲碳數2〜12，更佳爲碳數2〜8之烯烴 系化合物。 特定單體/含有不飽和雙鍵之化合物的較佳使用範圍 ’以重量比時爲90/10〜40/60 ，更佳爲85/15〜50/50 。 -18- 200817736 本發明中，欲得到（5 )特定單體與含有不飽和雙鍵 之化合物的飽和共聚合物，可使用一般的加成聚合法。 &lt;加成聚合觸媒&gt; 作爲欲合成上述（5 )飽和共聚合物之觸媒，可使用 至少一種選自鈦化合物、鉻化合物及鈀化合物、與作爲助 觸媒之有機鋁化合物。 其中，作爲鈦化合物可舉出四氯化鈦、三氯化鈦等， 又作爲锆化合物可舉出氯化雙（環戊二烯基）锆、二氯化 雙（環戊二烯基）鉻等。 且，作爲鈀化合物，可舉出一般式 VO(OR)aXb、或 V(OR)cXd 〔但，R爲烴基，X爲鹵素原子，〇SaS3、OSbS3、2 ^ (a+b) S3、0ScS4、0Sd^4、3- (c+d) ^4。 ] 所示鈀化合物、或這些電子供給加成物。 作爲上述電子供給體可舉出醇、酚類、酮、醛、竣酸 、有機酸或無機酸之酯、醚、酸醯胺、酸酐、烷氧基砂院 等含氧電子供給體、氨、胺、硝醯、異氰酸酯等含氮電子 供給體等。 且，作爲助觸媒之有機銘化合物，可使用至少1種選 自具有至少1個鋁-碳鍵或鋁-氫鍵者。 -19- 200817736 上述中，例如使用鈀化合物時的鈀化合物與有機鋁化 合物之比率，對於鈀原子的鋁原子之比（A1/V )爲2以上 ，較佳爲2〜50，特佳爲3〜20的範圍。 使用於加成聚合之聚合反應用溶劑，可使用與使用於 開環聚合反應之相同溶劑。又，所得之（5 )飽和共聚合 物之分子量的調節，一般使用氫進行。 且，作爲本發明之環狀烯烴系樹脂，可使用選自（6 )上述特定單體、及乙烯系環狀烴系單體或環戊二烯系單 體之1種以上的單體之成型共聚合物及亦可使用其氫化共 聚合物。 &lt;乙烯系環狀烴系單體&gt; 作爲乙烯系環狀烴系單體，例如可舉出4-乙烯環戊烯 、2-甲基-4-異丙烯基環戊烯等乙烯環戊烯系單體、4-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-乙烯環己烯、4-異丙烯基環己烯、1-甲基-4-異丙烯基環己烯、2-甲基-4-乙烯環己烯、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-4-異丙烯基環己烷等乙烯環己烷系單體、苯乙烯、 α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯 乙烯、1-乙烯萘、2-乙烯萘、4-苯基苯乙烯、ρ-甲氧基苯 乙烯等苯乙烯系單體、d-萜烯、1-萜烯、二萜烯、d-檸檬 烯、1-檸檬烯、二戊烯等萜烯系單體、4-乙烯環庚烯、4_ 異丙烯基環庚烯等乙烯環庚烯系單體、4-乙烯環庚烷、4- -20- 200817736 異丙烯基環庚烷等乙烯環庚烷系單體等。較佳爲苯乙 α -甲基苯乙烯。這些可單獨使用1種、或並用2種 &lt;環戊二烯系單體&gt; 作爲本發明之（6 )加成型共聚合物的單體所使 環戊二烯系單體，例如可舉出環戊二烯、i —甲基環戊 、2-甲基環戊二烯、2-乙基環戊二烯、5-甲基環戊二 5,5 -甲基環戊二烯等。較佳爲環戊二烯。這些可單獨 1種、或倂用2種以上。 選自上述特定單體、乙烯系環狀烴系單體及環戊 系單體之1種以上單體的加成型（共）聚合物，可由 述（5 )特定單體與含有不飽和雙鍵之化合物的飽和 i 合物之同樣加成聚合法得到。 又，上述加成型（共）聚合物之氫化（共）聚合 由與上述（3)開環（共）聚合物之氫化（共）聚合 同樣氫化法得到。 且，作爲本發明的環狀烯烴系樹脂，亦可使用 上述特定單體與丙烯酸酯之交互共聚合物。 &lt;丙烯酸酯&gt; 作爲本發明的（7 )上述特定單體與丙烯酸酯之 共聚合物的製造上所使用的丙烯酸酯，例如可舉出具 基丙烯酸酯、2 -乙基己基丙烯酸酯、環己基丙烯酸酯 燦、 以上 用之 二烯 烯、 使用 二烯 與上 共聚 物可 物之 ：7 ) 交互 有甲 等碳 -21 - 200817736 原子數1〜2G的直鏈狀、分岐狀或環狀烷基丙烯酸酯、縮 水甘油丙烯酸酯、2-四氫呋喃丙烯酸酯等碳原子數2〜20 的含雜環基的丙烯酸酯、苯甲基丙烯酸酯等碳原子數6〜20 的芳香族環基含有丙烯酸酯、異佛爾酮基丙烯酸酯、二環 戊基丙烯酸酯等碳數7〜30的多環結構之丙烯酸酯。 本發明中’欲得到（7)上述特定單體與丙烯酸酯之 交互共聚合物’於路易氏酸存在下，上述特定單體與丙烯 酸酯之總計爲100莫耳時，一般上述特定單體爲30〜70莫 耳’丙烯酸酯爲70〜30莫耳之比例下，較佳爲上述特定單 體爲40〜60莫耳，丙烯酸酯爲6〇〜40莫耳比例下，特佳爲 上述特定單體爲45〜55莫耳，丙烯酸酯爲55〜4 5莫耳之比 例下進行自由基聚合。 欲得當（7)上述特定單體與丙烯酸酯之交互共聚合 物所使用的路易氏酸之量，對於丙烯酸酯100莫耳而言爲 0.001〜1莫耳之量。又，可使用產生公知的自由基之有機 過酸化物或偶氮雙系的自由基聚合啓始劑，聚合反應溫度 一般爲-20°C〜80°C，較佳爲〜60°C。又，聚合反應用溶 劑中可使用與開環聚合反應所使用的相同溶劑。 且，本發明所謂「交互共聚合物」爲，未連接來自上 述特定單體之結構單位，即表示來自上述特定單體之結構 單位的旁邊必須具有來自丙烯酸酯之結構單位的結構之共 聚合物，並未否定來自丙烯酸酯之結構單位彼此爲隣接而 存在之結構。 本發明所使用的環狀烯烴系樹脂之較佳分子量爲’固 -22- 200817736 有黏度〔θ〕inh下爲〇·2〜5dl/g’更佳爲〇·3〜3dl/S’特佳 爲0.4〜1.5dl/g，以凝膠滲透層析儀（GPC )所測定的聚苯 乙烯換算之數平均分子量（Μη)爲8,000〜1 00,000，更佳 爲1 0,000〜80,000，特佳爲1 2,000〜50,000，重量平均分子 量（^〜）爲 20,000〜3 00,000，更佳爲 3 0,000〜2505000, 特佳爲40,000〜200,000的範圍。 固有黏度〔々〕inh、數平均分子量及重量平均分子量 若於上述範圍時，環狀烯烴系樹脂之耐熱性、耐水性、耐 藥品性、機械性特性與作爲本發明之光學薄膜的成形加工 性爲良好。 作爲使用於本發明的環狀烯烴系樹脂之玻璃轉移溫度 (Tg)，一般爲110°C以上，較佳爲110〜3 5 0 °C，更佳爲 120〜25 0 °C，特佳爲120〜200°C。Tg未達ll〇°C時，高溫 條件下之使用、或塗佈、印刷等二次加工會造成變形故不 佳。另一方面，Tg若超過3 5 0 °C時，成形加工會變困難， 切藉由成形加工時的熱會使樹脂劣化之可能性變高。 環狀烯烴系樹脂中以不損害本發明之效果的範圍下， 例如添加特開平9-22 1 5 77號公報、特開平10-28 773 2號公 報所記載的特定烴系樹脂、或公知熱可塑性樹脂、熱可塑 性彈性體、橡膠質聚合物、有機微粒子、無機微粒子等亦 佳。 又，本發明的環狀烯烴系樹脂中，以不損害本發明之 效果的範圍下，欲改良耐熱劣化性或耐光性，可添加公知 抗氧化劑或紫外線吸收劑等添加劑。例如將至少1種選自 -23- 200817736 下述酚系化合物、硫醇系化合物、硫化物系化合物、二硫 化物系化合物、磷系化合物所成群的化合物，以對本發明 的環狀烯烴系樹脂100重量份爲0.01〜10重量份添加時， 可提高耐熱劣化性。 酚系化合物： 作爲酚系化合物，可舉出三乙二醇-雙〔3-(3-t - 丁 基-5-甲基-4-羥基苯基）丙酸酯〕、1，6-己烷二醇_雙〔3-(3,5-二-t -丁基-4-羥基苯基）丙酸酯〕、2,4-雙-(η-辛 基硫）-6- (4-羥基-3,5-二-t - 丁基苯胺）-3，5-三嗪、季戊 四醇-肆〔3- (3，5_二-〖-丁基-4-羥基苯基）丙酸酯〕、 2，2-硫-二伸乙基雙〔3- (3，5-二-t-丁基-4-羥基苯基）丙 酸酯〕、十八烷基-3- ( 3,5-二-t -丁基-4-羥基苯基）丙酸 酯〕、1^,.六伸甲基雙（3,5-二-七-丁基-4-羥基-氫桂皮醯 胺）、1，3,5-三甲基-2,4,6-參（3,5-二-t-丁基-4-羥基苯甲 基）苯、參-(3,5·二-t - 丁基-4-羥基苯甲基）-異三聚異 氰酸、3,9-雙〔2-〔 3- ( 3-t - 丁基-4·羥基-5-甲基苯基） 丙醯氧基〕-1，1-二甲基乙基〕-2，4,8,10-四噁螺〔5.5〕十 一烷烷、等。較佳爲十八烷基-3- ( 3，5-二-t -丁基-4-羥基 苯基）丙酸酯〕、1，3,5-三甲基-2,4,6-參（3,5-二-1-丁 基-4-羥基苯甲基）苯、季戊四醇-肆〔3-(3，5-二-t-丁 基-4-羥基苯基）丙酸酯〕，特佳爲十八烷基-3-( 3，5-二-t -丁基-4-羥基苯基）丙酸酯〕等。 -24- 200817736 硫醇系化合物： 作爲硫醇系化合物，可舉出t -十二烷硫醇、己基硫 醇等烷基硫醇、2-氫硫基苯並咪唑、2-氫硫基-6-甲基苯並 咪唑、1-甲基-2-(甲基氫硫基）苯並咪唑、2-氫硫基-1-甲基苯並咪唑、2-氫硫基-4-甲基苯並咪唑、2-氫硫基- 5-甲基苯並咪唑、2-氫硫基-5,6 -二甲基苯並咪唑、2-(甲基 氫硫基）苯並咪唑、1-甲基-2-(甲基氫硫基）苯並咪唑、 2-氫硫基-1，3-二甲基苯並咪唑、氫硫基乙酸等。 硫化物系化合物： 作爲硫化物系化合物，可舉出2,2-硫-二伸乙基雙〔3-(3，5-二-t-丁基-4-羥基苯基）丙酸酯〕、2,2-硫雙（4-甲基- 6-t-丁基酚）、2，4-雙（η-辛基硫甲基）-6 -甲基酚 、二月桂基3,3’ -硫二丙酸酯、二肉豆蔻基3,3’ -硫二丙 酸酯、二硬脂醯基3，3’ -硫二丙酸酯、季戊四醇肆（3-月 桂基硫丙酸酯）、二十七烷基3,3’ -硫二丙酸酯等。 二硫化物系化合物： 作爲二硫化物系化合物，可舉出雙（4-氯苯基）二硫 化物、雙（2-氯苯基）二硫化物、雙（2,5-二氯苯基）二 硫化物、雙（2,4,6-三氯苯基）二硫化物、雙（2-硝基苯 基）二硫化物、2,2’ -二硫二安息香酸乙基、雙（4-乙醯 基苯基）二硫化物、雙（4-胺基甲醯基苯基）二硫化物、 1，Γ -二萘基二硫化物、2，2 ’ -二萘基二硫化物、1，2 ’ -二 -25- 200817736 萘基二硫化物、2,2，-雙（1-氯二萘基）二硫化物、U1 -雙（2-氯萘基）二硫化物、2,2，-雙（卜氰基萘基）二 硫化物、2,2’ -雙（；!_乙醯基萘基）二硫化物、二月桂基_ 3，3 ’ -硫二丙酸酯等。 磷系化合物： 作爲磷系化合物，可舉出參（4-甲氧基-3，S二苯基） 磷酸酯、參（壬基苯基）磷酸酯、參（2,4_二-^-丁基苯 基）磷酸酯、雙（2,6-二-t - 丁基-4-甲基苯基）季戊四醇 二磷酸酯、雙（2,4-二-t - 丁基苯基）季戊四醇二磷酸酯 等。 且將2,4·二羥基二苯甲酮、2 -經基-4-甲氧基二苯甲酮 等二苯甲酮系化合物、N-(苯甲基氧基羰氧基）苯並*** 等苯並***系化合物、或2 -乙基草醯替苯胺、2 -乙基-2 ’-乙氧基草醯替苯胺等草醯替苯胺系化合物，以對本發 明之環狀烯烴系樹脂100重量份爲0.01〜3重量份，較佳 爲0.0 5〜2重量份添加時，可提高耐光性。 又，有關本發明之環狀烯烴系樹脂，藉由熔融押出成 形爲薄膜等時，欲防止因熔融押出時之熱履歴所造成的該 樹脂之熱劣化防止，選擇所添加之抗氧化劑成爲重要之技 術要素。即，將藉由熔融押出所得之薄膜進行延伸加工時 ，欲不使相位差之表現性降低、或極力縮小其降低程度， 使用比熔融押出的環狀烯烴系樹脂的玻璃轉移溫度（Tg ) 高 + 2(TC 〜Tg+130°C ，較佳爲 Tg+30°C 〜Tg+130°C 之溫 -26- 200817736 度範圍內具有融點的受阻酚系化合物作爲抗氧化劑爲佳。 融點若比融押出之環狀烯烴系樹脂的τ g未達+ 2 0 °C 時，即使用受阻系化合物，添加量增加時，有時相位差 的表現性會大幅度降低。另一方面，融點比熔融押出之環 狀烯烴系樹脂的T g超過+ 1 3 0 °C時，有時於加工時抗氧化 劑無法溶解而成爲魚眼等薄膜缺陷或異物的原因。又，融 點即使爲環狀烯烴系樹脂之T g + 2 0 °C〜Tg + 1 3 0 °C，若使 用受阻酚系化合物以外之化合物作爲抗氧化劑，亦有相位 差的表現性降低之現象。 作爲藉由熔融押出本發明的環狀烯烴系樹脂成形時適 用的上述抗氧化劑之具體例，例如可舉出1 , 3,5 -三甲基-2,4,6-參（3,5-二 t -丁基-4-羥基苯甲基）苯、N，N’ -六 伸甲基雙（3,5-二-t -丁基-4-羥基·氫化肉桂醯胺）、參-(3,5-二-t -丁基-4-羥基苯甲基）-異氰酸酯、參（2,4-二-t - 丁基苯基）亞磷酸酯等，但本發明未僅限定於此，又 對於這些，熔融押出之環狀烯烴系樹脂的Tg會引起適當 情況。且以不損害本發明的效果下，這組合這些使用，或 單獨使用。 這些抗氧化劑的添加量，對於環狀烯烴系樹脂1 00重 量份，一般爲0.01〜5重量份，較佳爲〇.〇5〜4重量份，更 佳爲、〇 . 1〜1 · 5重量份。抗氧化劑的添加量若未達〇 . 〇 1重 量份時’押出加工時於樹脂容易產生凝膠，因此被辨識爲 作爲所得薄膜上之缺陷而不佳。另一方面，添加劑量若超 過5重量份時，加工時會引起殘渣物之產生等，該殘渣物 -27- 200817736 係成爲分模線（line )、薄膜上之魚眼、燒焦等原因故不 佳。 有關抗氧化劑，可於製造環狀烯烴系樹脂時添加、或 熔融押出時與環狀烯烴系樹脂之顆粒同時添加。 又，本發明的環狀烯烴系樹脂藉由熔融押出成形時， 以不損害本發明的效果之範圍，可使用滑劑、紫外線吸収 劑、染料或顔料等上述抗氧化劑以外之添加劑。當然此時 ，具有融點之添加劑時，該融點爲本發明之必須抗氧化劑 的融點範圍時較佳。 &lt;薄膜成形&gt; 作爲環狀烯烴系樹脂薄膜之成形方法，可舉出溶劑澆 注法（溶液流延法）或熔融押出法等。於膜厚之均勻性及 表面平滑性良好之觀點來看以溶劑澆注法爲佳，由製造成 本面來看以熔融押出法爲佳。 〔溶劑澆注法〕 作爲藉由溶劑澆注法得到環狀烯烴系樹脂薄膜之方法 ，並無特別限定，使用公知方法即可。例如將上述環狀烯 烴系樹脂於溶劑中溶解或分散後成爲適度濃度之液體，注 入或塗佈於適當的基材上，將此乾燥後由基材剝離之方法 〇 以下舉出藉由溶劑澆注法得到環狀烯烴系樹脂薄膜之 方法的各種條件，但本發明並未僅限定於該各種條件中。 -28- 200817736 將上述環狀烯烴系樹脂溶解或分散於溶劑時，該樹脂 的濃度一般爲0 . 1〜9 0重量％，較佳爲1〜5 0重量％，更佳 爲10〜35重量％。樹脂濃度若比上述範圍低時，難以確保 薄膜厚度，又具有溶劑蒸發所引起的發泡等會造成難以得 到薄膜之表面平滑性之傾向。另一方面，濃度若超過上述 範圍時，溶液黏度會過高而具有所得之環狀烯烴系樹脂薄 膜的厚度或表面難均勻之傾向。 又，室溫中上述溶液之黏度，一般爲1〜l，000,000mPa • s，較佳爲 1 0〜1 00,000mPa · S，更佳爲 1 0 0 〜5 0，0 0 0 m P a • S，特佳爲 1，000〜40,000mPa · S。 作爲上述溶劑，例如可舉出苯、甲苯、二甲苯等芳香 族系溶劑；甲基溶纖劑、乙基溶纖劑、1-甲氧基-2-丙醇等 溶纖劑系溶劑；二丙酮醇、丙酮、環己酮、甲基乙基酮、 4-甲基-2-戊酮等酮系溶劑；乳酸甲酯、乳酸乙酯等酯系溶 劑；環己烷、乙基環己烷、1，2-二甲基環己烷等環烯烴系 溶劑；2,2,3,3-四氟-1-丙醇、二氯甲烷、氯仿等鹵素含有 溶劑；四氫呋喃、二噁烷等醚系溶劑；1 -戊醇、1 - 丁醇等 醇系溶劑等。 又，上述以外，僅使用 SP値（溶解度參數）爲 10〜30 ( MPa1/2 )，較佳爲 10〜25 ( MPa1/2 )，更佳爲 1 5〜2 5 ( MPa1/2 )，特佳爲1 5〜2 0 ( MP a 1/2 )之範圍的溶劑 ’即可得到具有良好表面均勻性及光學特性之環狀烯烴系 樹脂薄膜。 上述溶劑可單獨使用1種、或混合2種以上。混合系 -29- 200817736 時’以混合系時的SP値的範圍爲上述範圍内時爲佳。此 時，混合系中的S P値，可由重量比來預測，例如2種混 合中，各重量分率爲W1及W2，SP値爲SP1及SP2時之 混合系的SP値可由下述式求得： SP 値=W1 · SP1 + W2 · SP2 作爲將上述溶液塗佈於基材上的方法，例如使用模具 或塗佈器的方法以外，亦可採用噴霧法、刷毛塗佈法、輥 塗佈法、旋轉塗佈法、浸漬法等。特別使用模具或塗佈器 之方法中，可將基材的搬送速度或溶液供給速度的變動抑 制到最小限，而使薄膜長邊方向的厚度變動控制至最小限 。且，藉由重複塗佈亦可控制厚度或表面平滑性等。 作爲上述基材，可舉出例如金屬轉筒、鋼帶、聚對苯 二甲酸乙二酯 （PET)或聚萘二甲酸乙二醇酯（PEN)等 聚酯薄膜、聚四氟乙烯（商品名；鐵福隆（註冊商標）） 輸送帶等。 對於上述溶劑澆注法之乾燥步驟，並無特別限定，可 實施一般使用的方法，例如介著多數滾筒通過乾燥爐之方 法等。但，乾燥步驟中會產生因溶劑之蒸發所引起的氣泡 ，而使薄膜特性顯著降低，欲避免此，將乾燥步驟分爲2 段以上之複數步驟，並控制於各步驟之溫度或風量爲佳。 特別將自基材至剝離的乾燥步驟可分爲2段以上之複數步 驟，第1階段的乾燥步驟中溫度設置爲〇〜5 〇 °C ’較佳設定 -30- 200817736 爲10〜40 °c ，第 2階段以後之乾燥步驟的溫度設定爲 50〜200°C，較佳設定爲70〜180°C爲佳。 又，薄膜剝離時的應力TF ( MPa)以O.OIMPaS TFS 5 MPa之範圍爲佳。TF若未達0.01 MPa時，無法順利地剝 離，另一方面若超過5MPa時，薄膜會由滾筒剝離，薄膜 會延伸而成爲產生相位差不均之原因，長邊方向的薄膜厚 度分佈或相位差分佈以及光軸分佈會變大而不佳。 〔熔融押出法〕 作爲藉由熔融押出法得到環狀烯烴系樹脂薄膜之方法 ，並無特別限定，可適用公知方法。例如可舉出由附於押 出機之塑模押出熔融狀態環狀烯烴系樹，該樹脂以鏡面輥 表面壓著，其後經冷卻並剝離使其薄膜化之方法。 作爲熔融環狀烯烴系樹脂之方法，以藉由押出機熔融 樹脂之方法爲佳，該熔融樹脂可藉由齒輪幫浦進行定量供 給，將此經金屬過濾器等過濾後除去雜質後，於塑模賦予 薄膜形狀並押出之方法爲佳。 作爲冷卻由塑模被押出之薄膜並使其薄膜化的方法， 夾輥方式、靜電外加方式、氣刀方式、輪壓（calender) 方式、片面輸送帶方式、兩面輸送帶方式、3根輥方式等 ，但要製造光學變形較少的薄膜，使用片面輸送帶式中稱 爲套筒（Sleeve )式之薄膜製造裝置、靜電外加方式等爲 佳。例如可舉出塑模的吐出口下方配置鏡面輥與金屬輸送 帶，排列成語該鏡面輥並行之剝離輥經配置之薄膜製造裝 -31 - 200817736 置。上述金屬輸送帶藉由設置成銜接該内面之2個保持輥 ，保持於張力經作用之狀態。經吐出口所吐出之樹脂’通 過上述鏡面輥與金屬輸送帶之間被挾壓，轉印於鏡面輥並 經冷卻後，由剝離輥被剝離成薄膜化。又，以經吐出之薄 膜兩端之位置，配置成面對於塑模的吐出口下方之鏡面輥 ，自帶電電極將薄膜貼合於鏡面輥側，可得到無光學變形 且薄膜表面性良好之方法等爲較佳方法。 作爲押出機，可舉出單軸、二軸、行星式、混煉擠壓 器（ko-kneader)等之任一種，較佳爲使用單軸押出機。 又，作爲押出機之螺旋形狀，可舉出管彎頭型、先端帶刮 板（Dulmage)型、全螺文（full flight)型等，較佳爲全 螺文型。樹脂計量所使用的齒輪幫浦可使用内部潤滑式、 外部潤滑式任一種，其中以外部潤滑方式爲佳。 有關使用於異物過濾之過濾器，可舉出葉片型、蠟過 濾器型、葉子型、篩網等。其中，對於縮小樹脂的滯留時 間分佈作爲目的者，以葉片型最佳，過濾器孔徑以20μπι 以下，較佳爲ΙΟμηι以下，更佳爲5μπι以下。最佳爲3μιη 以下。公孔徑若大於2 0 μιη時，難以除去眼睛看的到的異 物以及凝膠等，故作爲使用於製造光學薄膜之過濾器上並 不佳。 作爲塑模，必須均勻塑模内部之樹脂流動，欲保持薄 膜之厚度均勻性，必須將塑模出口鄰近的塑模内部之壓力 分佈於寬方向爲一定。作爲滿足如此條件者，可使用歧管 塑模、魚尾式塑模、衣架式塑模等，其中以衣架式塑模爲 -32- 200817736 佳。又塑模之流量調整以彎曲唇型爲佳。又，附有可經熱 螺栓方式而藉由自動控制來進行厚薄調整功能之塑模爲特 佳。附有使用於流量調整之阻塞棍、或附有使用於厚度調 整之支撐墊塊時，連接部分會產生落差，於連接部分之隙 間等會有捲入空氣等，成爲產生燒焦的原因、或成爲分模 線之原因而不佳。塑模吐出口以鎢碳化物等超硬塗佈等塗 佈法爲佳。又，作爲塑模之材質可舉出SCM系之鋼鐵、 SUS等不鏽鋼材等，但並未僅限定於此。又，可使用於表 面施予鉻、鎳、鈦等鍍敷者、藉由PVD ( Physical Vapor Deposition)法等形成者、形成 TiN、TiA IN、TiC、CrN、 DLC (鑽石狀碳）等被膜者、其他陶瓷器經溶射所得者、 表面進行氮化處理者等。如此塑模其表面硬度高，與樹脂 之摩擦較小，故於所得之透明樹脂薄膜可防止燒焦殘渣等 混入，且可防止分模線（line )產生，故較佳。 以本發明之由環狀烯烴系樹脂所成的薄膜，得到其長 邊方向之相位差R0與光軸所測定時的R0的偏差爲±10% 以下，且光軸之偏差爲中心値± 1 〇度以下的薄膜，該薄膜 之長邊方向的厚度變動（不均）爲每l〇m爲±1 %以下，更 佳爲±0.5%以下，特佳爲，±0.3%以下爲佳。 因此，薄膜製造時之T塑模的溫度變化每1分鐘內較 佳爲±1.0 °C以下，更佳爲±0.5 °C以下，特佳爲±0.3 °C以下 〇 作爲使用於嚴密控制T塑模溫度之加熱器，可舉出加 熱板器、湊注加熱器、卡式電熱管（Cartridge Heater)、 -33- 200817736 環帶狀的電熱器等。其中以容易控制溫度者而言以澆注黃 銅或鋁之澆注加熱器’作爲卡式電熱管，熱媒體部分係由 黃銅、鋁、銅等構成者爲佳。特佳爲鋁澆注加熱器。 使用於縮小T塑模溫度變化時，以控制至T塑模的溫 度設定時流入T塑模之熱量可自由控制爲佳。 特別爲τ塑模溫度至加工溫度-2 0 °c時，與加速T塑 模之昇溫速度，流入電流至加熱器能力的上限，確認塑模 溫度提高至加工溫度_2〇 °C程度後，減低加熱器之消費電 力，控制至連續地於加熱器流入電流爲最佳。 又，欲使薄膜的長邊方向之厚度變動（不均）至上述 範圍時，將熔融樹脂的供給速度例如可舉出藉由如齒輪幫 浦以一定量連續地供給之方法、或轉印輥或其後之捲取輥 的轉動速度極力控制於一定之方法。 又，塑模吐出口的溫度於定點所測定之溫度變化設定 爲±l°c/l分鐘時，可防止長邊方向之厚度變動，其結果， 可防止薄膜的長邊方向之光學不均。塑模吐出口之溫度， 如圖1所示’於吐出薄膜之吐出口附近設置之感應器所測 定者，本發明中一般爲每1秒測定1次。 鏡面輥爲於内部具有加熱手段及冷卻手段者爲佳，該 表面粗度爲0.5 μιη以下，特佳爲0 · 3 μιη以下。作爲鏡面輥 以使用於金屬輥施予鍍敷者爲佳，施予鉻鍍敷、無電解鎳 鍍敷等爲特佳。 鏡面輥之加熱方法可使用包覆式油溫調節方式、或介 電加熱方式等較佳方法。輥的加熱方法並無特別限定，但 -34- 200817736 輥溫度爲薄膜製膜範圍，無溫度差爲佳，可被接受的輥溫 度差爲2 °C以内爲佳，更佳爲1 °C以内。 作爲單面輸送帶式裝置、或附有套筒式之裝置所使用 的金屬輸送帶，使用無連接痕跡的無端輸送帶爲佳。作爲 構成金屬輸送帶之材料，可使用不鏽鋼、鎳等。又，保持 金屬輸送帶之保持輥，其表面藉由聚矽氧橡膠或具有其他 耐熱性之彈性體等包覆爲佳。金屬輸送帶之厚度以 0.1〜0.4mm爲佳，未達0.1mm時撓性過大而使輸送帶容易 受傷故不佳。另一方面，若比0.4mm厚時，不會隨著加工 時的薄膜而變形故亦不佳。 藉由上述裝置，例如可製造出以下之薄膜。 作爲一般於押出機中投入環狀烯烴系樹脂前，預先除 去含於該樹脂之水分、氣體（氧等）、殘溶劑等之目的， 可進行該樹脂之Tg以下的適當溫度之樹脂乾燥。 使用於乾燥之乾燥機，較佳爲惰性氣體循環式乾燥機 、真空乾燥機。又，欲抑制料斗内之吸濕、或氧之吸收， 將料斗以氮或氬等惰性氣體封鎖、或使用可保持減壓狀態 之真空料斗亦爲較佳方法。 押出機量筒於欲防止熔融押出中樹脂被氧化而產生凝 膠等’可藉由氮或氬等惰性氣體進行封閉爲佳。 藉由押出機被熔融之環狀烯烴系樹脂，由塑模吐出口 往垂直方向之下方押出成薄膜狀。塑模出口之溫度分佈因 樹脂的熔融黏度差較少，故可控制於11：以下。 其後’押出之樹脂藉由鏡面輥與金屬輸送帶進行挾壓 -35- 200817736 並冷卻。然後於鏡面輥表面經轉印之樹脂藉由剝離用輥由 鏡面輥表面被剝離，而製造出薄膜狀薄膜。 本發明中，樹脂之加工溫度，即押出機及塑模的設定 溫度爲，由流動性爲均勻之熔融狀態樹脂可由塑模吐出、 且可抑制樹脂之劣化的觀點來看，以樹脂的T g + 1 0 0 °c以 上且Tg+ 200°C以下爲佳。 又，藉由鏡面輥與金屬輸送帶挾壓樹脂時，即於鏡面 輥將樹脂轉印時的壓力以面壓爲〇·〇1〜0.8 MPa爲佳，特佳 爲 0.1 〜0.6MPa。更特佳爲 0.15 〜0.45MPa。 此時’ 1¾面輕接近金屬輸迭帶之周速度爲佳。作爲較 佳範圍爲鏡面輥之周速度爲1.00，金屬輸送帶之周速度爲 0.95〜1.05，特佳爲 0.99〜1.01。 且，作爲薄膜剝離時之條件，剝離溫度Tt ( °c )，剝 離應力 TF(MPa)中，各爲 Tg-30°CSTtSTg+5°C ， 0.01MPa‘TFS5MPa 之範圍爲佳。 &lt;薄膜延伸加工&gt; 藉由如上述的流延法或熔融押出法所得之本發明的光 學薄膜可進一步地進行延伸。作爲此時的延伸加工方法， 具體可舉出公知的一軸延伸法或二軸延伸法。即，藉由拉 伸器法之橫一軸延伸法、輥間壓縮延伸法、利用圓周相異 的二組輥之縱一軸延伸法等、或組合橫一軸與縱一軸之二 軸延伸法、藉由吹塑法之延伸法等。 一軸延伸法時之延伸速度一^般爲1〜5，000% /分鐘，較 -36- 200817736 佳爲50〜1,000%/分鐘，更佳爲loo〜ι，〇00%/分鐘，特佳爲 100〜500%/分鐘。 二軸延伸法有同時往2方向進行延伸之情況、或一軸 延伸後往與最初延伸方向相異的方向延伸處理之情況。此 時，使用控制延伸後的薄膜之折射率楕圓體形狀之2個延 伸軸之相交角度，因取決於所望特性故無特別限定，一般 爲120〜60度之範圍。又，延伸速度爲各延伸方向可爲相 同或相異，一般爲1〜5,000%/分鐘，較佳爲50〜1,000%/分 鐘，更佳爲100〜1，000%/分鐘，特佳爲100〜500%/分鐘。 藉由使延伸速度更均勻，可抑制薄膜長邊方向之厚度 不均或相位差R0以及光軸等分佈至最小限。此時的延伸 速度之變動，較佳爲±5 %以内，更佳爲±1 %以内，特佳爲土 0.5 %以内。 延伸加工溫度雖無特別限定，但本發明的樹脂之玻璃 轉移溫度Tg作爲基準，一般爲Tg±30°C，較佳爲Tg±15°C ，更佳爲Tg-5°C〜Tg+ 15°C之範圍。又，此時的溫度變動 (不均）較佳爲±5%以内，更佳爲±1%以内，特佳爲±0.5% 以内。藉由使其爲上述範圍内時，相位差R0或光軸之變 動（不均）得產生可受到抑制故較佳。 延伸倍率因取決於所望之特性故無特別限定，一般爲 1.01〜10倍，較佳爲1.03〜5倍，更佳爲1.03〜3倍。延伸 倍率若爲1 〇倍以上時，有時相位差之控制變的困難。此 時的延伸倍率變動，較佳爲± 5 %以内，更佳爲± 1 %以内， 特佳爲± 〇 · 5 %以内。藉此薄膜長邊方向之厚度不均或相位 -37- 200817736 差R0以及光軸等分佈可抑制至最小限。 經延伸之薄膜可直接冷卻，於Tg-20°C〜Tg之 境下至少保持1 〇秒以上，較佳爲30秒〜60分鐘， 1分鐘〜60分鐘之加熱設定爲佳。藉此可得到透過 位差的經時變化較少且安定之相位差薄膜。 未施予延伸加工時的本發明的光學用薄膜之藉 的尺寸収縮率，於加熱l〇〇°C下進行5 00小時時， 5 %以下，較佳爲3%以下，更佳爲1%以下，特佳| 以下。 又，本發明之相位差薄膜的藉由加熱之尺寸収 於加熱100°C下進行5 00小時時，一般爲10%以下 爲5%以下，更佳爲3%以下，特佳爲1%以下。 如上述經延伸的薄膜爲，藉由延伸可使分子經 於透過光賦予相位差，但該相位差可藉由延伸倍率 溫度或薄膜厚度等控制。例如延伸前的薄膜厚度爲 ，延伸倍率越大之薄膜，其透過光之相位差絶対値 之傾向，藉由變更延伸倍率，可得到透過光賦予所 差之相位差薄膜。另一方面，延伸倍率相同的情況 前的薄膜厚度越厚，透過光之相位差絶対値有越大 ，故藉由變更延伸前的薄膜厚度，可得到透過光賦 相位差之相位差薄膜。又，上述延伸加工溫度範圍 伸溫度越低，透過光之相位差絶対値有越大傾向， 變更延伸溫度，可得到透過光賦予所望相位差之相 膜。 溫度環 更佳爲 光之相 由加熱 一般爲 I 0.5% 縮率， ，較佳 配向而 、延伸 相同時 有越大 望相位 ，延伸 的傾向 予所望 中，延 故藉由 位差薄 -38- 200817736 如上述經延伸所得之相位差薄膜厚度，一般爲100 μπι 以下，較佳爲100〜20 μιη，更佳爲 80〜20 μιη。使厚度變薄 時可達成使用相位差薄膜領域中製品所求之小型化、薄膜 化。其中，欲控制相位差薄膜之厚度，控制延伸前光學薄 膜之厚度、或控制延伸倍率而達到。例如薄化延伸前之光 學薄膜、或使延伸倍率變的較大，可使一層相位差薄膜之 厚度變薄。 &lt;薄膜特性&gt; 本發明的光學薄膜，於光線波長5 5 0nm之薄膜面内最 大折射率爲nx，薄膜面内對於nx成直交方向之折射率爲 ny，薄膜厚度方向之折射率爲nz，薄膜厚度爲d〔nm〕時 ，薄膜面内之相位差R0 ( 550) = (nx-ny) xd的値爲 0〜300nm爲佳，更佳爲10〜200nm，特佳爲30〜100nm。薄 膜面内相位差若超過3 OOnm時，恐怕容易產生光漏，對比 會降低。 本發明的光學薄膜中，對於自薄膜端部離50mm以上 之薄膜表面，沿著薄膜長邊方向之每5mm之薄膜面内的 上述R0的偏差爲±10%以下，較佳爲±5%以下，更佳爲土 2%以下。 其中，對於測定本發明之「對於自薄膜端部離50mm 以上之薄膜表面，沿著薄膜長邊方向之每5 mm的薄膜面 内」之R0的偏差、或光軸的偏差之理由爲，薄膜端部中 ，薄膜加工時R0或光軸大多會有偏差，故於長邊方向即 -39- 200817736 使以連續方式測定R〇或光軸，亦難以得到安定之數値。 其中，R0的偏差爲，使用大塚電子（股）製之相位 差薄膜検査裝置「RETS」，取樣出薄膜之任意部分lm2, 將薄膜面内以1 c m間隔進行測定所得之値。 R0的偏差若超過±10%時，使用於液晶顯示器會產生 光學性不均、以及部分性光漏或色不均而不佳。 又，本發明的光學薄膜爲，薄膜面内方向之光軸的偏 差爲中心値±10度以下，較佳爲中心値±3度以下，更佳爲 中心値±1度以下，最佳爲中心値±〇·5度以下。薄膜面内 之光軸偏差爲超過中心値± 1 0度時，使用於液晶顯示器時 ，會產生光學性不均、以及部分性光漏或色不均而不佳。 且’上述光軸之偏差爲，使用大塚電子（股）製之相 位差薄膜検査裝置「RETS」，取樣出薄膜之任意部分lm2 ，將薄膜面内以1 c m間隔進行測定所得之値。 其中，光軸爲表示遅相軸之方向，一般對應光學薄膜 之押出方向（MD方向）或延伸方向。因此，所謂光軸之 偏差爲’遲相軸方向之偏差，表示光學薄膜之押出方向（ MD方向）或延伸方向中所產生的對於遅相軸之偏差。 欲使上述R0的偏差於±10%以内且光軸之偏差爲中心 値± 1 0度以下，例如可藉由下述方法進行調整。 (1 )使所使用的環狀烯烴系樹脂之分子量分佈（ Mw/Mn )變小，使玻璃轉移溫度（Tg )均勻。 其中，分子量分佈一般爲1.2〜4.5，較佳爲1.3〜4.0, 玻璃轉移溫度之偏差一般爲±3 °C以内，較佳爲± 1 °C以内。 -40- 200817736 上述分子量分佈可使用凝膠滲透層析儀，將聚苯乙烯 換算之重量平均分子量以數平均分子量除所得之値。又， 玻璃轉移溫度之偏差可藉由差示操作熱量計，由樹脂經20 °C /分鐘加熱時的吸熱發熱指示求得。 分子量分佈狹窄，且玻璃轉移溫度之偏差較小的環狀 烯烴系樹脂，其本身的樹脂組成爲均勻，故可使所得之光 學薄膜於長邊方向之光學物性均勻化。 如此環狀烯烴系樹脂，例如可舉出如下的方法。 (甲）於特定有機過渡化合物與有機鋁羥基化合物所 成的觸媒與環狀烯烴單體接觸後製造出環狀烯烴聚合物之 方法（特開平8 - 1 6 5 3 09號公報之申請專利範圍第1項請 求項1 )。 (乙）將原冰片烯系環狀烯烴於含有周期律表第8〜1 0 的遷移金屬化合物成分之聚合觸媒存在下，且添加作爲分 子量調節劑之環狀非共軛聚烯，進行加成聚合，製造出原 冰片烯系環狀烯烴加成聚合物（特開2 0 0 2 - 2 1 2 2 0 9號公報 之申請專利範圍第1項至第4項）。 (丙）（A )於組合芳環烯金屬衍生物化合物與（B ) 鋁四氫喃、硼酸酯或硼化合物之觸媒存在下，製造出聚合 環狀烯烴之環狀烯烴聚合物的製造方法（特開2004-1 0 74 42號公報之申請專利範圍第1項至第4項）。 (2 )延伸前之薄膜厚度分佈對於平均値爲±1 %以内， 較佳爲±0.5%以内。 將延伸前的光學薄膜之厚度分佈控制於上述範圍内， •41 - 200817736 依情況進行延伸加工處理時，可防止相位差不均或光軸配 向不均。 使延伸前的薄膜厚度分佈爲對於平均値爲± 1 %以内， 例如可舉出如下的方法。 (甲）溶液流延法的情況爲，使將聚合物溶解於溶劑 時之聚合物溶液的溶液黏度爲一定、 (乙）溶融押出法的情況爲，抑制上述塑模之溫度變 動。 (3 )使延伸加工時之溫度不均較佳爲± 5 %以内，更佳 爲±1 %以内，特佳爲±0.5 %以内。 其中，溫度不均爲T塑模之唇側面貼合K型熱電對， 藉由數據讀取單位（KEYENCE製：GR3 5 00 )，以每1秒 進行1分鐘讀取所測定之値。 使延伸加工時之溫度不均爲± 1 %以内的方法，除溫度 設定方法以外亦可舉出風吹出方法或風量調整、排氣調整 等方法。 且，本發明的光學薄膜所使用的薄膜中之殘留溶劑量 ，一般爲10重量％以下，較佳爲5重量％以下，更佳爲1 重量％以下，特佳爲0.5重量％以下。其中若殘留溶劑量超 過上述範圍時，實際上使用時於經時上會有尺寸變化變大 的傾向，又殘留溶劑會使Tg降低，使的耐熱性減少。 《偏光板》 本發明的偏光板爲，PVA系薄膜等所成的偏光子的至 -42- 200817736 少單面上，將本發明的視野角補償薄膜之光學薄膜，使用 PVA樹脂作爲主體之水溶液所成的水系接著劑、極性基含 有黏接著劑、光硬化性接著劑等進行貼合，視必要將此經 加熱或曝光並壓著後，使偏光子與視野角補償薄膜接著（ 層合）而製造。 《液晶面板》 本發明的液晶面板爲，可於2片玻璃基板間挾持液晶 所成之液晶顯示元件的至少單面上，貼合本發明之偏光板 ，使液晶顯示元件與偏光板接著（層合）而製造。 【實施方式】 〔實施例〕 以下、對於本發明之具體實施例做説明，本發明並非 僅限定於這些實施例。且，以下中「份」、「％」若無特 別說明外皆表示「重量份」、「重量％」。 又，以下實施例中，玻璃轉移溫度、飽和吸水率、全 光線透過率、霧値、透過光之面内相位差、偏光板之透過 率及偏光度藉由下述方法測定。 〔玻璃轉移溫度（Tg)〕 使用 Seiko instruments公司製之差示掃描熱量計（ DSC )，氮氣環境下昇溫速度爲20°C /分鐘之條件中測定 玻璃轉移溫度。 -43- 200817736 〔飽和吸水率〕 依據 A S T M D 5 7 0，於2 3 °C水中浸漬樣品一週，測定 浸漬前後之樣品重量變化測定，由此値求得飽和吸水率。 〔全光線透過率、霧値〕 使用村上色彩技術硏究所製之霧値測定器「HM_ 1 5 0 型」，測定全光線透過率以及霧値。 〔透過光之面内相位差（R0 )〕 使用大塚電子（股）製之「RETS」，由薄膜之垂直 方向照射光時的面内相位差（R〇 )於波長 5 5 0nm時進行 測定。 〔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 0 nm。 〔薄膜厚度分佈〕 使用薄膜厚度分佈測定裝置（MOC ON )，於薄膜長 邊方向進行測定。 &lt;調製例1 &gt; 反應容器中裝入蒸餾水250份，於該反應容器中添加 丙烯酸酸丁基90份、2-羥基乙基甲基丙烯酸酯8份、二 乙烯苯2份、與油酸鉀〇. 1份後，將該系統以聚四氟伸乙 -44- 200817736 基（鐵福隆：註冊商標）製之攪拌翼進行攪拌並進行分散 處理。其後，該反應容器内以氮氣取代後，該系統昇溫至 5 0 °C，添加過硫酸鉀0 · 2份後開始聚合。聚合開始後2小 時，於聚合反應系統中添加過硫酸鉀0 · 1份後，將該系統 昇溫至8 0 °C，經1小時後繼續進行聚合反應而得到聚合物 分散液。 其次，使用蒸餾器，藉由將聚合物分散液濃縮至固形 成分濃度爲70%，得到丙烯酸酸酯系聚合物之水系分散體 所成的水系黏著劑（具有極性基之黏著劑）。 對於構成如此所得之水系黏著劑（以下亦稱爲「水系 黏著劑A」）之丙烯酸酸酯系聚合物，藉由凝膠滲透層析 儀（GPC、溶劑：四氫呋喃），測定聚苯乙烯換算之數平 均分子量（Μη)及重量平均分子量（Mw)，得到數平均 分子量（Μη )爲 69,〇〇〇，重量平均分子量（Mw)爲 1 3 5,000 ° 又’對於水系黏著劑A，測定3 (TC之氯仿中的固有黏 度（Θ inh)得到 1.2dl/g。 〔實施例1〕 作爲環狀j：希烴系樹脂，使用原冰片烯系樹脂（JSR有 限公司会社製：商品名r ARTON D45 3 l」，玻璃轉移溫 度130 C )。將該原料以乾燥溫度10(rc。氮氣下進行除 _草乙燥’導入押出機（Gm ENGINEERING CO.，LTD製： GM-65 )中以26(rc進行熔融，使用齒輪幫浦並定量下輸 -45- 200817736 送液體，使用5 μηι葉片過濾器，除去異物，實施自藉由設 定爲25 (TC之鋁澆注加熱器經加熱之Τ塑模押出。Τ塑模 之加熱爲，作爲220V、2kW之加熱器，於塑模溫度至230 °C，流入9A之電流，成爲230 °C以上時，藉由可空矽（ thyristor)通入電流2.7A，變更至流入加熱器之電流爲連 續電流。此時確認出押出之T塑模溫度爲，每1分鐘的溫 度變化爲±0.1 °C以内。 此時的T塑模之開口爲0.5mm，T塑模出口與冷卻輥 之薄膜的壓著點間之距離爲65mm，壓著於2 5 0mmq&gt;之冷 卻輥。冷卻輥的溫度爲120°C，於其下游側設置250mm(p 之冷卻輥2，再於下游側設定2 5 Ommcp之剝離輥。各輥之 溫度設定爲1 1 5 °C、1 1 〇 °C，以薄膜表面溫度1 〇 8 °C自剝離 輥剝離1〇〇μηι厚度之薄膜。 所得之薄膜（以下亦稱爲「光學薄膜（a-1 )」）沿 著長邊方向，測定其每5 mm之薄膜面内相位差R0與薄膜 面内之光軸後，得到尺〇爲1〇11111，其偏差爲±5%以下。又 ，光軸之偏差爲薄膜長邊方向作爲〇度時爲〇±5度以下。 〔實施例2〕 使用實施例1中所得之光學薄膜（a_l )，使用130°C 下輥夾子式之縱一軸延伸機進行1.2倍延伸後，使用130 °C下拉伸式之横延伸機進行1.4倍延伸，得到厚度70 μιη 之經延伸光學薄膜（a-2 )。延伸時的溫度不均爲未達土 0.5%。該光學薄膜（a-2 )之相位差 R0爲，中心値爲 -46 - 200817736 6 Onm下的偏差爲±3 %以下。又，光軸之偏差爲以薄膜長邊 方向作爲〇度時爲90±0.5度以下。 〔比較例1〕 與實施例1同樣方法下，熔融樹脂，使用鋁澆注加熱 器，加熱Τ塑模，即使於2 3 0 °C以上亦不用可空矽（ thyristor )，繼續通電9 A電流，設定T塑模之溫度爲2 5 0 °C。其他條件與實施例1相同，進行薄膜之加工。此時的 T塑模之溫度爲每1分鐘的溫度變化爲±2.0 °c。如此得到 ΙΟΟμιη厚度之光學薄膜（b-Ι)。 所得之薄膜沿著長邊方向，測定其每5 mm之薄膜面 内相位差R0與薄膜面内之光軸後，得到R0爲12nm，其 偏差爲±12%以下。又，光軸之偏差爲薄膜長邊方向作爲〇 度時爲0±13度以下。 〔比較例2〕 與實施例1同樣方法下，熔融樹脂，使用板加熱器， 加熱T塑模，即使於23 0 °C以上，與實施例1相同藉由可 空砂（thyristor)，繼續通電2.7A電流，設定τ塑模之 溫度爲2 5 0 °C。其他條件與實施例1相同，進行薄膜之加 工。此時的T塑模之溫度爲每1分鐘的溫度變化爲±1.6 °C 。如此得到ΙΟΟμιη厚度之光學薄膜（c-1 )。 所得之薄膜沿著長邊方向，測定其每 5 m m 之薄膜面 内相位差R0與薄膜面内之光軸後，得到R0爲14nm，其 -47- 200817736 偏差爲±13 %以下。又，光軸之偏差爲薄膜長邊方 度時爲0±15度以下。 〔實施例3〕 將厚度50μιη之聚乙烯醇薄膜一邊浸漬於碘 鉀250g、硼酸10g、水i〇00g所成之40°C水浴中 軸延伸約5分鐘至4倍後得到偏光膜。該偏光膜 使用調整例1所得之水系黏著劑，將實施例1所 學薄膜（a- 1 )與實施例2所製作的光學薄膜（： 偏光膜上一片遍地接著而得到偏光板（a )。測 板（a )之透過率與偏光度後，各得到43% ' 99 ，使該偏光板（a )於光學薄膜（a_2 )爲内側下 二片正交尼科耳狀態，由一方以亮度lOOOOcd之 時，由另一方進行觀察時確認完全無因光漏引起 之不均。 〔比較例3〕 使用光學薄膜（b-Ι)與（c-1)以外皆與實损 同，得到偏光板（b )。測定該偏光板（b )之透 光度時，各爲42%、99·87%。又，使該偏光板（ 學薄膜（c-1 )爲内側下使其成爲二片正交尼科: 由一方以亮度lOOOOcd之背光照射時，由另—方 時時確認出可能由光漏所引起的條紋狀之不均。 向作爲〇 5 g、碘化 ，進彳了一 表面上， 製作的光 1-2)於各 定該偏光 • 9 9%。又 使其成爲 背光照射 的條紋狀 S例3相 過率與偏 b)於光 耳狀態， 進行觀察 -48- 200817736 產業上可利用性 本發明的光學薄膜及偏光板，例如可使用於携帶電話 、數位情報端末、呼叫器、衛星導航、車載用液晶顯示器 、液晶監視器、液晶電視、調光面板、OA機器用顯示器 、AV機器用顯示器等各種液晶顯示元件或電致發光顯示 元件或接觸面板等。又，可適用於CD、CD-R、MD、MO 、DVD等光碟記錄·放送裝置所使用的波長板。 【圖式簡單說明】 〔圖1〕表示測定本發明塑模吐出口的溫度變化之測 定處模式圖。 -49-8-Chloro-8,9,9-trifluorotetracyclo[4·4·0.12,5·1 -11 - 200817736 8,9-dichloro-8,9-bis(trifluoromethyl)tetracycline [4.4 .0.12,5 ·&quot;,i〇]-3-dodecene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.12,5 .i7,1G]-3 - 12 carbon, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.I2,5 • 17'1Q]-3-dodecene, etc. . These may be used alone or in combination of two or more. Preferably, in the above specific formula (I), R1 and R3 are hydrogen or a carbon number of 1 to 10, more preferably 1 to 4, particularly preferably 1 to 2, and R2 and R4 are hydrogen or a The valence organic group, at least one of R2 and R4 represents a polar group having a polarity other than hydrogen and a hydrocarbon group, m is an integer of 0 to 3, p is an integer of 0 to 3, preferably m+p=0 to 4, more Preferably, it is 0 to 2, and particularly preferably m=l and p=0. The specific monomer having m = 1 and p = 0 is preferably such that the obtained cyclic olefin resin has a high glass transition temperature and excellent mechanical strength. Examples of the polar group of the specific monomer include a carboxyl group, a hydrocarbon group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amine group, a decylamino group, and a cyano group. These polar groups may be bonded via a methylene group or the like. Combine. Further, a hydrocarbon group such as a carbonyl group, an ether group, a methyl sulfonyl group, a thioether group or an imine group having a polar two-valent organic group as a linking group may be used as a polar group. Among these, a carboxyl group, a hydrocarbon 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 monomer having a polar group represented by the formula -(CH2)nCOOR, and the obtained cyclic olefin resin has a higher glass transition -12-200817736 temperature and lower hygroscopicity, and The viewpoint of excellent adhesion of various materials is preferred. The correlation formula R of the above specific polar group is preferably a ketone group having a carbon number of 1 to 12, more preferably 1 to 4, particularly preferably 1 to 2. Further, η is generally 〇5, but the smaller the η値 is, the higher the glass transition temperature of the cyclic hydrocarbon-containing resin is. Therefore, it is preferred that the specific monomer having a size of 0 is preferable because it is easily synthesized. Further, in the above general formula (I), R1 or R3 is preferably an alkyl group having a carbon number of 1 to 4, more preferably an alkyl group of 1 to 2, and particularly preferably a methyl group. When the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula -(CH2)nCOOR is bonded, the resulting cyclic hydrocarbon-storage resin can be preferably reduced in hygroscopicity. &lt;Copolymerizable monomer&gt; Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The carbon number of the cyclic olefin is preferably 4 to 20, more preferably 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 5 0/50, more preferably from 100/0 to 60/40. &lt;Open-loop polymerization catalyst&gt; In the present invention, a ring-opening polymerization of (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening copolymer of a specific monomer and a copolymerizable monomer is obtained. The reaction is carried out in the presence of a metathesis catalyst. -13- 200817736 The metathesis catalyst is (a) at least one compound selected from the group consisting of W, M〇, and Re, and (b) Deming periodic table steroid elements (such as Li, Na, K, etc.), IIA elements. (eg, Mg, Ca, etc.), lanthanum elements (eg, Zn, Cd, Hg, etc.), lanthanum elements (eg, B, A1, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or IVB family of halogens A catalyst of a compound (for example, Ti, Zr, etc.) in combination with at least one selected from the group consisting of at least one element-carbon bond or the element-hydrogen bond. In addition, at this time, in order to increase the activity of the catalyst, it is also possible to add an additive (C) as a component (a), and a representative compound of W, Mo or Re as a representative example of WCl6, M〇Cl6, ReOCl3, etc. 1-132626, page 8 of the left-right column, line 6 to page 8, the upper right column, the compound described in line 17. Specific examples of the component (b) include n-C4H9Li, (C2H5)3A1, (C2H5) 2A1C1, (C2H5) uAlCh", (c2h5) aici2, methylaluminum tetrahydrofuran, LiH, etc. 1-132626 On page 8 of the bulletin, the compound described in the third line from the right side of the eighth line to the third line on the eighth line of the eighth page. As a representative example of the component (c) as an additive, alcohols, aldehydes, ketones, amines, and the like can be used, and it is also possible to use the special opening of the first and second columns of the first and second columns of the first and second columns. The compound shown in row 1 7 of the upper left column. When the amount of the metathesis catalyst is used, the "(a) component: specific monomer" is generally in the range of 1:500 to 1:50,000 when the molar ratio of the component (a) to the specific monomer is used. It preferably ranges from 1:1,000 to 1:10,000. -14- 200817736 When the ratio of (a) component to component (b) is in the atomic ratio of metal, (a): (b) is in the range of 1:1 to 1:5 〇, preferably 1:2 to 1:30. . The ratio of (a) component to (c) component, in the case of molar ratio, (c): (a) is 0.005: 1 to 15: 1, preferably 0:05: 1 to 7: 1 &lt;Solvent for polymerization reaction&gt; The solvent used in the ring-opening polymerization reaction (solvent constituting the solvent of the molecular weight modifier solution, the specific monomer and/or the solvent of the metathesis catalyst) may, for example, be pentane. Hexanes such as hexane, heptane, octane, decane, brothel, cyclohexane, cycloheptane, cyclooctane, naphthalene, norbornane, etc., benzene, toluene, xylene, ethyl An aromatic hydrocarbon such as benzene or cumene, chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, etc., halogenated alkane, a compound such as a halogenated aryl group, ethyl acetate, η-butyl acetate, isobutyl acetate, methyl propionate, saturated carboxylic acid ester such as dimethoxyethane, dibutyl ether, tetrahydrofuran, dimethoxy Ethers such as ethane, etc., which can be used singly or in combination. Among them, aromatic hydrocarbons are preferred. As the amount of the solvent to be used, "solvent: specific monomer (weight ratio)" is generally an amount of from 1:1 to 10:1, preferably from 1:1 to 5:1. &lt;Molecular weight modifier&gt; The molecular weight of the obtained ring-opened (co)polymer can be adjusted by polymerization temperature, catalyst type, solvent type, but in the present invention, molecular weight is adjusted by -15-200817736 The agent is adjusted by coexisting in the reaction system. Among them, preferred examples of the molecular weight modifier include ethylene, propylene, 1-butene, 1-pentene, 1-hexene '1-heptene, 1-octene, 1-decene, and 1- Α-olefins such as terpenes and styrene, among which 1-butene and 1-hexene are particularly preferable. These molecular weight modifiers can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol per mol of the specific monomer supplied to the ring-opening polymerization reaction, preferably 0.02 to 0.5 mol. (2) In order to obtain a ring-opening copolymer, in a ring-opening polymerization step, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization, and then a polybutadiene or a polyisobutyl An unsaturated hydrocarbon polymer containing two or more carbon-carbon double bonds in a main chain such as a stilbene compound, a styrene-butadiene copolymer, an ethylene-non-conjugated diene copolymer, or a polynorbornene The specific monomer is subjected to ring-opening polymerization in the presence of the same. The ring-opening (co)polymer obtained as above can be used as it is, or the hydrogenated (co)polymer obtained by further hydrogenation can be used as a resin material having high impact resistance. &lt;Hydrogenation Catalyst&gt; The hydrogenation reaction can be carried out by a usual method, that is, by adding a hydrogenation catalyst to a solution of a ring-opening polymer, at a pressure of 3% to 3 Torr, preferably 3 to 2 Torr. It is carried out under the action of 〇 ～ 00 ° C, preferably 20 to 180 ° C. As the hydrogenation catalyst, a chlorine-based compound which is generally used for an olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst. The heterogeneous catalyst may be a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium or ruthenium is supported on a carrier such as carbon, cerium oxide, alumina or titania. Further, as the homogeneous catalyst, nickel naphthenate/triethylaluminum, acetonitrile acetone/triethylaluminum, cobalt octylate/n-butyllithium, titanocene dichloride/monochlorination may be mentioned. Diethylaluminum, barium acetate, chloroform (triphenylphosphine) ruthenium, dichlorostilbene (triphenylphosphine) ruthenium, chlorohydrocarbonyl carbonyl (triphenylphosphine) ruthenium, dichlorocarbonyl ginseng (triphenylphosphine) )钌. The form of the catalyst may be in the form of powder or granules. These hydrogenation catalysts can be used in a ring-opening (co)polymer: hydrogenation catalyst (weight ratio) of 1:1x1 0_6 to 1:2. Thus, the hydrogenated (co)polymer obtained by hydrogenation is excellent in thermal stability, and the characteristics are not deteriorated even by heat treatment during molding or as a product. Among them, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more. Further, the hydrogenation ratio of the hydrogenated (co)polymer is 50% or more as measured by W-NMR, preferably 90% or more, more preferably 98% or more, and particularly preferably 99% or more. It is 99.5% or more. The higher the hydrogenation rate, the more excellent the stability to heat or light, and when used as the wave plate of the present invention, it is possible to obtain stable properties for long-term use. Further, the hydrogenated (co)polymer used in the cyclic olefin resin of the present invention is preferably contained in the hydrogenated (co)polymer in an amount of 5 wt% or less, more preferably 1 wt%. The following is especially good. -17- 200817736 Further, as the cyclic hydrocarbon-storage resin of the present invention, (4) the ring-opening (co)polymer of the above (1) or (2) is subjected to a Ferridel-Crafts reaction (Friedel- Crafts reaction) and after cyclization. Hydrogenated (co)polymers can also be used. &lt;cyclization by the Ferridell-Crafts reaction&gt; The ring-opening (co)polymer of (1) or (2) is subjected to the Friedel-Crafts reaction The cyclization method is not particularly limited, and a known method using the acidic compound described in JP-A-105-543-99 can be employed. Specific examples of the acidic compound include Lewis acid such as A1C13, BF3, FeCl3, Al2〇3, HCl, CH3C1C00H, zeolite, and activated clay, and Bronsted acid. The cyclized ring-opened (co)polymer can be hydrogenated in the same manner as the ring-opened (co)polymer of (1) or (2). Further, as the cyclic olefin resin of the present invention, (5) a saturated copolymer of the above specific monomer and a compound containing an unsaturated double bond may be used. &lt;Compound containing unsaturated double bond&gt; Examples of the compound containing an unsaturated double bond include ethylene, propylene, butylene, etc., preferably a carbon number of 2 to 12, more preferably a carbon number of 2 to 8. An olefin compound. The preferred use range of the specific monomer/compound containing an unsaturated double bond is 90/10 to 40/60, more preferably 85/15 to 50/50 by weight. -18- 200817736 In the present invention, in order to obtain (5) a saturated copolymer of a specific monomer and a compound containing an unsaturated double bond, a general addition polymerization method can be used. &lt;Addition Polymerization Catalyst&gt; As the catalyst for synthesizing the above (5) saturated copolymer, at least one selected from the group consisting of a titanium compound, a chromium compound, and a palladium compound, and an organoaluminum compound as a catalyst can be used. In addition, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis(cyclopentadienyl)zirconium chloride and bis(cyclopentadienyl)chromium dichloride. Wait. Further, examples of the palladium compound include a general formula VO(OR)aXb or V(OR)cXd [however, R is a hydrocarbon group, X is a halogen atom, 〇SaS3, OSbS3, 2^(a+b) S3, 0ScS4 , 0Sd^4, 3- (c+d) ^4. The palladium compound shown or these electrons are supplied to the adduct. Examples of the electron donor include an alcohol, a phenol, a ketone, an aldehyde, a citric acid, an ester of an organic acid or an inorganic acid, an ether, an acid amide, an acid anhydride, an oxygen-containing electron donor such as an alkoxy sand, and ammonia. A nitrogen-containing electron donor such as an amine, a guanidine or an isocyanate. Further, as the organic compound of the promoter, at least one selected from the group consisting of having at least one aluminum-carbon bond or aluminum-hydrogen bond can be used. -19- 200817736 In the above, the ratio of the palladium compound to the organoaluminum compound when the palladium compound is used, for example, the ratio (A1/V) to the aluminum atom of the palladium atom is 2 or more, preferably 2 to 50, and particularly preferably 3 ~20 range. The solvent used for the polymerization reaction in the addition polymerization can be used in the same solvent as that used in the ring-opening polymerization. Further, the adjustment of the molecular weight of the obtained (5) saturated copolymer is generally carried out using hydrogen. Further, as the cyclic olefin-based resin of the present invention, molding of at least one selected from the group consisting of the above-mentioned specific monomer, and the ethylene-based cyclic hydrocarbon monomer or the cyclopentadiene monomer can be used. Copolymers and hydrogenated copolymers thereof can also be used. &lt;Ethylene-based cyclic hydrocarbon-based monomer&gt; Examples of the ethylene-based cyclic hydrocarbon-based monomer include vinylcyclopentanyl such as 4-vinylcyclopentene or 2-methyl-4-isopropenylcyclopentene. Ethylene 5-membered cyclic hydrocarbon monomer such as an ethylenic monomer, an ethylene cyclopentane monomer such as 4-vinylcyclopentane or 4-isopropenylcyclopentane, 4-vinylcyclohexene or 4-isopropene Ethylene cyclohexene such as cyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-ethenecyclohexene, 2-methyl-4-isopropenylcyclohexene Monomer, ethylene cyclohexane monomer such as 4-vinylcyclohexane or 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3 - styrene monomer such as methyl styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, ρ-methoxystyrene, d-pinene, 1 - a terpene monomer such as terpene, diterpene, d-limonene, 1-limonene or dipentene, an ethylene cycloheptene monomer such as 4-vinylcycloheptene or 4-isopropenylcycloheptene, 4 - an ethylene cycloheptane monomer such as ethylene cycloheptane or 4--20-200817736 isopropenylcycloheptane. Preferred is phenethyl α-methylstyrene. These can be used alone or in combination of two &lt;Cyclopentadiene-based monomer&gt; The cyclopentadiene-based monomer which is a monomer of the (6) addition-forming copolymer of the present invention may, for example, be a cyclopentadiene or an i-methyl ring. Ethyl, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopenta-5,5-methylcyclopentadiene, and the like. Preferred is cyclopentadiene. These may be used alone or in combination of two or more. An addition (co)polymer selected from the group consisting of a specific monomer, a vinyl cyclic hydrocarbon monomer, and a cyclopentene monomer; and (5) a specific monomer and an unsaturated double bond The saturated i complex of the compound is obtained by the same addition polymerization method. Further, hydrogenation (co)polymerization of the above-mentioned addition (co)polymer is obtained by the same hydrogenation method as the hydrogenation (co)polymerization of the above (3) ring-opened (co)polymer. Further, as the cyclic olefin resin of the present invention, an interactive copolymer of the above specific monomer and acrylate can also be used. &lt;Acrylate&gt; The acrylate used in the production of the above-mentioned (7) copolymer of the specific monomer and the acrylate of the present invention may, for example, be a acrylate, a 2-ethylhexyl acrylate or a ring. Hexyl acrylate can be used, the above diene is used, and the diene and the upper copolymer can be used: 7) Interaction with a carbon such as carbon-21 - 200817736 Linear, branched or cyclic alkane having an atomic number of 1 to 2G An aromatic ring group having 6 to 20 carbon atoms such as a heterocyclic group-containing acrylate or a phenyl methacrylate having 2 to 20 carbon atoms such as a acrylate, a glycidyl acrylate or a 2-tetrahydrofuran acrylate, which contains an acrylate An acrylate having a polycyclic structure having a carbon number of 7 to 30, such as isophorone acrylate or dicyclopentyl acrylate. In the present invention, "(7) the above-mentioned specific monomer and acrylate interpolymer" in the presence of Lewis acid, when the specific monomer and acrylate are 100 mu in total, generally the above specific monomer is 30 to 70 moles of acrylate at a ratio of 70 to 30 moles, preferably 40 to 60 moles of the above specific monomer, and acrylate to 6 to 40 moles, particularly preferably for the above specific single The body is 45 to 55 moles, and the acrylate is radically polymerized at a ratio of 55 to 4 5 moles. The amount of Lewis acid used in the interactive copolymer of (7) the above specific monomer and acrylate is 0.001 to 1 mole per 100 moles of the acrylate. Further, a radical polymerization initiator which produces a known radical organic peroxide or an azobis system can be used, and the polymerization temperature is usually -20 ° C to 80 ° C, preferably 〜 60 ° C. Further, the same solvent as used in the ring-opening polymerization reaction can be used for the solvent for the polymerization reaction. Further, the "interactive copolymer" of the present invention is a structural unit which is not linked to the specific monomer, that is, a copolymer which has a structure derived from a structural unit of an acrylate from a structural unit of the above specific monomer. The structure from which the structural units of the acrylate are adjacent to each other is not denied. The preferred molecular weight of the cyclic olefin resin used in the present invention is 'solid-22-200817736. Viscosity [θ] inh is 〇·2~5dl/g', more preferably 〇·3~3dl/S' is particularly good. The average molecular weight (?η) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 10,000,000, more preferably 10,000 to 80,000, and particularly preferably 1 2,000 to 50,000, the weight average molecular weight (^~) is 20,000 to 30,000,000, more preferably 3,000 to 250,5000, and particularly preferably 40,000 to 200,000. When the intrinsic viscosity [々] inh, the number average molecular weight, and the weight average molecular weight are in the above range, the heat resistance, water resistance, chemical resistance, and mechanical properties of the cyclic olefin resin and the moldability of the optical film of the present invention For the good. The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is generally 110 ° C or higher, preferably 110 to 350 ° C, more preferably 120 to 25 ° C, particularly preferably 120~200 °C. When the Tg is less than ll 〇 ° C, the use under high temperature conditions, or secondary processing such as coating and printing may cause deformation, which is not preferable. On the other hand, when the Tg exceeds 550 °C, the molding process becomes difficult, and the possibility of deterioration of the resin by the heat during the forming process is increased. In the case of the cyclic olefin-based resin, the specific hydrocarbon-based resin described in the Unexamined-Japanese-Patent Publication No. Hei 9-22 1 5 77 Plastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles, and the like are also preferred. Further, in the cyclic olefin-based resin of the present invention, an additive such as a known antioxidant or an ultraviolet absorber may be added in order to improve heat deterioration resistance or light resistance without impairing the effects of the present invention. For example, at least one compound selected from the group consisting of phenolic compounds, thiol compounds, sulfide compounds, disulfide compounds, and phosphorus compounds selected from the group consisting of -23-200817736 is used as the cyclic olefin system of the present invention. When 100 parts by weight of the resin is added in an amount of 0.01 to 10 parts by weight, heat deterioration resistance can be improved. Phenolic compound: Examples of the phenolic compound include triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexyl Alkanediol_bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(η-octylsulfanyl)-6- (4- Hydroxy-3,5-di-t-butylaniline-3,5-triazine, pentaerythritol-indole [3-(3,5-di-[-butyl-4-hydroxyphenyl)propionate] , 2,2-thio-di-extended ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5- Di-t-butyl-4-hydroxyphenyl)propionate], 1^,.hexamethylbis(3,5-di-hepta-butyl-4-hydroxy-hydrocinnamate), 1 ,3,5-trimethyl-2,4,6-gin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, gins-(3,5·di-t-butyl -4-hydroxybenzyl)-isotrimeric isocyanate, 3,9-bis[2-[3-(3-t-butyl-4.hydroxy-5-methylphenyl)propanoxy -1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like. Preferred is octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-para (3,5-di-1-butyl-4-hydroxybenzyl)benzene, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Particularly preferred is octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. -24- 200817736 Mercaptan-based compound: Examples of the thiol-based compound include alkyl mercaptan such as t-dodecyl mercaptan or hexyl mercaptan, 2-hydrothiobenzimidazole, and 2-hydrogenthio group. 6-methylbenzimidazole, 1-methyl-2-(methylhydrothio)benzimidazole, 2-hydrothio-1-methylbenzimidazole, 2-hydrothio-4-methyl Benzimidazole, 2-hydrothio- 5-methylbenzimidazole, 2-hydrothio-5,6-dimethylbenzimidazole, 2-(methylhydrothio)benzimidazole, 1- Methyl-2-(methylhydrothio)benzimidazole, 2-hydrothio-1,3-1,3-benzimidazole, thioacetic acid, and the like. Sulfide-based compound: As the sulfide-based compound, 2,2-sulfan-di-extended ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , 2,2-thiobis(4-methyl-6-t-butylphenol), 2,4-bis(η-octylthiomethyl)-6-methylphenol, dilauryl 3,3' - thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol bismuth (3-lauryl thiopropionate) , hexadecyl 3,3'-thiodipropionate, and the like. Disulfide-based compound: Examples of the disulfide-based compound include bis(4-chlorophenyl)disulfide, bis(2-chlorophenyl)disulfide, and bis(2,5-dichlorophenyl). Disulfide, bis(2,4,6-trichlorophenyl)disulfide, bis(2-nitrophenyl)disulfide, 2,2'-dithiodibenzoic acid ethyl, double ( 4-Ethylphenyl)disulfide, bis(4-aminoformamidophenyl) disulfide, 1,Γ-dinaphthyl disulfide, 2,2 '-dinaphthyl disulfide 1,2 '-di-25- 200817736 Naphthyl disulfide, 2,2,-bis(1-chlorodinaphthyl) disulfide, U1-bis(2-chloronaphthyl) disulfide, 2 , 2,-bis(cyanonaphthyl) disulfide, 2,2'-bis(;!-ethylcyanophthalenyl) disulfide, dilauryl-3,3'-thiodipropionate Wait. Phosphorus-based compound: Examples of the phosphorus-based compound include stilbene (4-methoxy-3,S diphenyl)phosphate, hexamethylenephenyl phosphate, and ginseng (2,4_di-^-). Butyl phenyl) phosphate, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphate, bis(2,4-di-t-butylphenyl)pentaerythritol II Phosphate esters, etc. Further, a benzophenone compound such as 2,4. dihydroxybenzophenone or 2-carbyl-4-methoxybenzophenone, N-(benzyloxycarbonyloxy)benzotriene a benzotriazole-based compound such as oxazole or a oxalic acid-based compound such as 2-ethyloxatolide or 2-ethyl-2'-ethoxyxantanilide, which is a cyclic olefin system of the present invention. When 100 parts by weight of the resin is 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, the light resistance can be improved. In addition, when the cyclic olefin-based resin of the present invention is formed into a film or the like by melt extrusion, it is important to prevent the thermal deterioration of the resin due to heat stagnation during melt extrusion, and it is important to select the added antioxidant. Technical elements. In other words, when the film obtained by the melt extrusion is subjected to the stretching process, the glass transition temperature (Tg) of the cyclic olefin resin which is melted and extruded is used so as not to lower the expression of the phase difference or to reduce the degree of reduction as much as possible. + 2 (TC ~ Tg + 130 ° C, preferably Tg + 30 ° C ~ Tg + 130 ° C temperature -26 - 200817736 degree range with a melting point of the hindered phenolic compound as an antioxidant is preferred. When the τ g of the cyclic olefin resin which is melted is less than + 20 °C, the hindered compound is used, and when the amount of addition is increased, the expression of the phase difference may be greatly lowered. When the T g of the cyclic olefin resin which is melted and extruded is more than + 1 30 ° C, the antioxidant may not be dissolved during processing, and may become a film defect such as a fish eye or a foreign matter. Further, even if the melting point is a ring When Tg + 20 ° C to Tg + 130 ° C of the olefin-based resin, when a compound other than the hindered phenol-based compound is used as the antioxidant, the expression of the phase difference is also lowered. The cyclic olefin resin of the present invention is suitable for molding Specific examples of the antioxidant include, for example, 1,3,5-trimethyl-2,4,6-cis (3,5-di-t-butyl-4-hydroxybenzyl)benzene, and N. N'-hexamethyl-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamylamine), gins-(3,5-di-t-butyl-4-hydroxybenzyl) - isocyanate, ginseng (2,4-di-t-butylphenyl) phosphite, etc., but the present invention is not limited thereto, and the Tg of the melt-extruded cyclic olefin-based resin may be appropriately caused. In the case where the effect of the present invention is not impaired, these may be used in combination or alone. The amount of the antioxidant added is usually 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin resin. 〇. 〇 5 to 4 parts by weight, more preferably 〇. 1 to 1 · 5 parts by weight. If the amount of the antioxidant is not reached 〇. 〇 1 part by weight, the resin is likely to be gelled during the extrusion process, so It is recognized that it is not preferable as a defect on the obtained film. On the other hand, when the amount of the additive exceeds 5 parts by weight, the residue may be generated during processing, and the residue -27-200817736 is a parting mold. It is not preferable because the line (line), the fisheye on the film, and the scorching are not preferable. The antioxidant may be added at the same time as the production of the cyclic olefin resin, or may be simultaneously added to the particles of the cyclic olefin resin when it is melted and extruded. When the cyclic olefin resin of the present invention is molded by melt extrusion, an additive other than the above-mentioned antioxidant such as a slip agent, an ultraviolet absorber, a dye or a pigment can be used without impairing the effects of the present invention. In the case of an additive having a melting point, the melting point is preferred in the range of the melting point of the essential antioxidant of the present invention. &lt;Film Forming&gt; Examples of the method for forming the cyclic olefin-based resin film include a solvent casting method (solution casting method), a melt extrusion method, and the like. The solvent casting method is preferred from the viewpoints of uniformity of film thickness and surface smoothness, and it is preferable to use a melt extrusion method from the viewpoint of production. [Solvent Casting Method] The method for obtaining a cyclic olefin-based resin film by a solvent casting method is not particularly limited, and a known method may be used. For example, the above-mentioned cyclic olefin-based resin is dissolved or dispersed in a solvent to form a liquid having a moderate concentration, and is injected or coated on a suitable substrate, and then dried and then peeled off from the substrate. Various conditions of the method for obtaining a cyclic olefin-based resin film are obtained, but the present invention is not limited to these various conditions. -28- 200817736 When the cyclic olefin-based resin is dissolved or dispersed in a solvent, the concentration of the resin is generally from 0.1 to 90% by weight, preferably from 1 to 50% by weight, more preferably from 10 to 35 parts by weight. %. When the resin concentration is lower than the above range, it is difficult to secure the thickness of the film, and foaming due to evaporation of the solvent tends to make it difficult to obtain smoothness of the surface of the film. On the other hand, when the concentration exceeds the above range, the viscosity of the solution is too high, and the thickness or surface of the obtained cyclic olefin-based resin film tends to be difficult to be uniform. Further, the viscosity of the above solution at room temperature is generally 1 to 1,000,000 mPa·s, preferably 10 to 10,000,000 mPa·s, more preferably 1 0 0 to 5 0,0 0 0 m P a • S, particularly preferably 1,000 to 40,000 mPa · S. Examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; and cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and 1-methoxy-2-propanol; a ketone solvent such as acetol, acetone, cyclohexanone, methyl ethyl ketone or 4-methyl-2-pentanone; an ester solvent such as methyl lactate or ethyl lactate; cyclohexane and ethylcyclohexane a cycloolefin solvent such as 1,2-dimethylcyclohexane; a halogen containing solvent such as 2,2,3,3-tetrafluoro-1-propanol, dichloromethane or chloroform; an ether such as tetrahydrofuran or dioxane; A solvent; an alcohol solvent such as 1-pentanol or 1-butanol. Further, in addition to the above, only SP 値 (solubility parameter) is used to be 10 to 30 (MPa1/2), preferably 10 to 25 (MPa1/2), more preferably 1 5 to 2 5 (MPa1/2), A solvent of a range of from 1 5 to 2 0 (MP a 1/2 ) can provide a cyclic olefin-based resin film having good surface uniformity and optical properties. These solvents may be used alone or in combination of two or more. In the case of the mixing system -29-200817736, it is preferable that the range of SP値 in the case of mixing is within the above range. In this case, the SP値 in the mixed system can be predicted from the weight ratio. For example, in the two types of mixing, the weight fractions are W1 and W2, and the SP値 of the mixed system when SP値 is SP1 and SP2 can be obtained by the following formula. : SP 値=W1 · SP1 + W2 · SP2 As a method of applying the above solution to a substrate, for example, a method using a mold or an applicator, a spray method, a brush coating method, or a roll coating method may be employed. , spin coating method, dipping method, and the like. In the method using a mold or an applicator in particular, the variation in the conveying speed of the substrate or the solution supply speed can be minimized, and the thickness variation in the longitudinal direction of the film can be minimized. Further, thickness, surface smoothness, and the like can be controlled by repeated coating. Examples of the substrate include a metal film such as a metal drum, a steel strip, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and polytetrafluoroethylene (product). Name; Tie Fulong (registered trademark)) Conveyor belt, etc. The drying step of the solvent casting method is not particularly limited, and a general method can be used, for example, a method in which a plurality of rolls pass through a drying furnace. However, in the drying step, bubbles caused by evaporation of the solvent are generated, and the film characteristics are remarkably lowered. To avoid this, the drying step is divided into two or more steps, and the temperature or air volume controlled in each step is preferably controlled. . In particular, the drying step from the substrate to the peeling can be divided into a plurality of steps of two or more stages, and the temperature in the drying step of the first stage is set to 〇~5 〇°C 'better setting -30- 200817736 is 10~40 °c The temperature of the drying step after the second stage is set to 50 to 200 ° C, preferably 70 to 180 ° C. Further, the stress TF (MPa) at the time of film peeling is preferably in the range of O.OIMPaS TFS 5 MPa. If the TF is less than 0.01 MPa, the film cannot be peeled off smoothly. On the other hand, when it exceeds 5 MPa, the film is peeled off by the roll, and the film is stretched to cause uneven phase difference, and the film thickness distribution or phase difference in the long-side direction. Distribution and optical axis distribution will become larger and poorer. [Melting and Extruding Method] The method for obtaining a cyclic olefin-based resin film by a melt extrusion method is not particularly limited, and a known method can be applied. For example, a method in which a molten olefin-based tree is extruded from a mold attached to an extruder, which is pressed against the surface of a mirror roll, and then cooled and peeled off to form a film. As a method of melting the cyclic olefin-based resin, it is preferred to melt the resin by an extruder, and the molten resin can be quantitatively supplied by a gear pump, and the metal filter or the like is filtered to remove impurities, and then molded. It is preferred that the mold imparts a shape to the film and is extruded. As a method of cooling and thinning a film extruded from a mold, a nip roll method, an electrostatic addition method, an air knife method, a wheel press method, a one-side conveyance belt method, a double-sided conveyor belt method, and a three-roll method Etc. However, in order to manufacture a film having less optical distortion, it is preferable to use a film manufacturing apparatus called a sleeve type in a one-side conveyance belt type, an electrostatic addition method, and the like. For example, a mirror roll and a metal conveyance belt are disposed under the discharge port of the mold, and the film roll assembly is arranged in a thin film manufacturing apparatus in which the mirror roll is arranged in parallel. The metal conveyor belt is held in a state in which the tension is applied by the two holding rollers provided to engage the inner surface. The resin discharged through the discharge port is pressed between the mirror roll and the metal conveyer belt, transferred to the mirror roll, and cooled, and then peeled off by a peeling roll to form a film. Further, a mirror roll disposed below the discharge port of the mold is disposed at a position of both ends of the film to be discharged, and the film is bonded to the mirror roll side from the charged electrode, thereby obtaining a method of no optical distortion and good surface properties of the film. Wait for the better method. The extruding machine may be any of a single shaft, a two shaft, a planetary type, a kneading extruder (ko-kneader), and the like, and a uniaxial extruder is preferably used. Further, the spiral shape of the extruder may be a tube elbow type, a tip type with a squeegee type, a full flight type, or the like, and is preferably a full snail type. The gear pump used for resin metering can be either internal lubrication or external lubrication, with external lubrication being preferred. Examples of the filter used for foreign matter filtration include a blade type, a wax filter type, a leaf type, a screen, and the like. Among them, the blade type is preferable for reducing the retention time distribution of the resin, and the filter pore diameter is 20 μm or less, preferably ΙΟμηι or less, more preferably 5 μm or less. The best is below 3μηη. When the pore diameter is more than 20 μm, it is difficult to remove foreign matter and gel, which are seen from the eyes, and it is not preferable as a filter for producing an optical film. As a mold, it is necessary to uniformly mold the flow of the resin inside. To maintain the uniformity of the thickness of the film, it is necessary to distribute the pressure inside the mold adjacent to the exit of the mold to a certain width. As such a condition, a manifold mold, a fishtail mold, a coat hanger mold, or the like can be used, and a coat hanger type mold is preferably -32-200817736. The flow adjustment of the mold is preferably performed by bending the lip shape. Further, it is preferable to have a mold which can be subjected to the thickness adjustment function by means of automatic control by means of a hot bolt. When there is a blocking rod for flow adjustment or a support pad for thickness adjustment, there is a drop in the connecting portion, and air may be trapped in the gap between the connecting portions, etc., causing burnt, or The reason for becoming a parting line is not good. The mold discharge port is preferably a coating method such as superhard coating such as tungsten carbide. In addition, the material of the mold is SCM-based steel, stainless steel such as SUS, etc., but is not limited thereto. In addition, it is possible to form a coating such as TiN, TiA IN, TiC, CrN or DLC (diamond-like carbon) by a person who is coated with a surface such as chromium, nickel or titanium and formed by a PVD (Physical Vapor Deposition) method. Other ceramics are obtained by spraying, and the surface is nitrided. Since the surface hardness of the mold is high and the friction with the resin is small, the obtained transparent resin film can prevent the incorporation of scorch residue and the like, and can prevent the generation of a parting line, which is preferable. According to the film of the cyclic olefin resin of the present invention, the phase difference R0 in the longitudinal direction and the R0 in the measurement of the optical axis are ±10% or less, and the deviation of the optical axis is the center 値±1. The thickness variation (unevenness) in the longitudinal direction of the film is preferably ±1% or less per 1 μm, more preferably ±0.5% or less, and particularly preferably ±0.3% or less. Therefore, the temperature change of the T mold at the time of film production is preferably ±1.0 ° C or less per 1 minute, more preferably ± 0.5 ° C or less, and particularly preferably ± 0.3 ° C or less, as a tightly controlled T-plastic. For the heater of the mold temperature, a heater plate, a heater, a Cartridge Heater, a -33-200817736 ring-shaped electric heater, and the like can be given. Among them, a cast heater for pouring copper or aluminum is used as a card type electric heating tube for those who are easy to control the temperature, and a heat medium portion is preferably composed of brass, aluminum, copper or the like. Particularly good for aluminum casting heaters. When used to reduce the temperature change of the T mold, the heat flowing into the T mold can be freely controlled to control the temperature to the T mold. In particular, when the temperature is from τ to -2 ° °C, and the temperature rise rate of the T mold is accelerated, the current flows to the upper limit of the heater capacity, and it is confirmed that the mold temperature is increased to the processing temperature of _2 〇 °C. It is best to reduce the power consumption of the heater and control it to continuously flow into the heater. In addition, when the thickness of the film in the longitudinal direction is varied (uneven) to the above range, the supply rate of the molten resin is, for example, a method of continuously supplying a predetermined amount by a gear pump, or a transfer roller. Or the speed of rotation of the take-up rolls or the like is controlled to a certain extent. Further, when the temperature change at the fixed point of the mold is set to ± l ° c / 1 minute, the thickness variation in the longitudinal direction can be prevented, and as a result, optical unevenness in the longitudinal direction of the film can be prevented. The temperature of the mold discharge port is measured as shown in Fig. 1 by an inductor provided near the discharge port of the discharge film, and is generally measured once per second in the present invention. The mirror roll preferably has a heating means and a cooling means inside, and the surface roughness is 0.5 μm or less, particularly preferably 0 · 3 μmη or less. As the mirror roll, it is preferable to use a metal roll for plating, and it is particularly preferable to apply chromium plating or electroless nickel plating. The method of heating the mirror roll can be carried out by a preferred method such as a coated oil temperature adjustment method or a dielectric heating method. The heating method of the roller is not particularly limited, but the temperature of the roll is -34-200817736. The temperature of the roll is the film forming range, and the temperature difference is not preferable. The acceptable roll temperature difference is preferably within 2 ° C, more preferably within 1 ° C. . As the single-sided belt type device or the metal belt used for the sleeve type device, it is preferable to use an endless conveyor belt having no connection marks. As the material constituting the metal conveyor belt, stainless steel, nickel, or the like can be used. Further, the holding roller for holding the metal conveyor belt is preferably coated with a silicone rubber or an elastomer having other heat resistance. The thickness of the metal conveyor belt is preferably 0.1 to 0.4 mm, and when the thickness is less than 0.1 mm, the flexibility is too large, so that the conveyor belt is easily damaged, which is not preferable. On the other hand, when it is thicker than 0.4 mm, it does not deform with the film during processing, which is not preferable. By the above apparatus, for example, the following film can be produced. The resin is dried at a suitable temperature of Tg or less of the resin for the purpose of removing moisture, gas (oxygen, etc.), residual solvent, and the like contained in the resin before the injection of the cyclic olefin resin into the extruder. The dryer used for drying is preferably an inert gas circulation dryer or a vacuum dryer. Further, in order to suppress moisture absorption or absorption of oxygen in the hopper, it is preferable to block the hopper with an inert gas such as nitrogen or argon or to use a vacuum hopper capable of maintaining a reduced pressure state. It is preferable to press the measuring cylinder to prevent the resin from being oxidized to generate a gel or the like during the melt extrusion, and it is preferably blocked by an inert gas such as nitrogen or argon. The cyclic olefin resin which is melted by the extruder is extruded into a film shape from the lower side of the mold discharge port in the vertical direction. The temperature distribution at the exit of the mold can be controlled to 11 or less because of the small difference in the melt viscosity of the resin. The resin that was subsequently extruded was pressed by a mirror roll and a metal conveyor belt -35-200817736 and cooled. Then, the resin transferred on 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 processing temperature of the resin, that is, the set temperature of the extruder and the mold is a Tg of the resin from the viewpoint that the molten resin in which the fluidity is uniform can be discharged from the mold and the deterioration of the resin can be suppressed. + 1 0 0 °c or more and Tg+200 °C or less is preferred. Further, when the resin is pressed by the mirror roll and the metal transfer belt, the pressure at the time of transfer of the resin by the mirror roll is preferably 面·〇1 to 0.8 MPa, particularly preferably 0.1 to 0.6 MPa. More preferably 0.15 to 0.45 MPa. At this time, the speed of the '13⁄4 face lightly close to the metal belt is better. As a preferred range, the peripheral speed of the mirror roll is 1.00, and the peripheral speed of the metal conveyor belt is 0.95 to 1.05, particularly preferably 0.99 to 1.01. Further, as the conditions for peeling off the film, the peeling temperature Tt (°c) and the peeling stress TF (MPa) are each preferably in the range of Tg - 30 ° CSTtSTg + 5 ° C and 0.01 MPa - TFS 5 MPa. &lt;Film stretching processing&gt; The optical film of the present invention obtained by the above-described casting method or melt extrusion method can be further extended. Specific examples of the stretching processing method at this time include a known one-axis stretching method or a biaxial stretching method. That is, by the transverse one-axis stretching method of the stretcher method, the inter-roller compression stretching method, the longitudinal one-axis stretching method using two sets of circumferentially different rolls, or the two-axis extension method of combining the horizontal one axis and the vertical one axis, The extension method of the blow molding method. The extension speed of the one-axis extension method is generally from 1 to 5,000% / minute, preferably from -36 to 200817736, preferably from 50 to 1,000% / minute, more preferably from loo to ι, 〇 00% / minute, especially good 100~500%/min. The two-axis stretching method may be performed by extending in two directions at the same time or extending in a direction different from the initial extending direction after the one-axis extension. In this case, the angle of intersection between the two extension axes of the refractive index and the circular shape of the film after the extension is controlled is not particularly limited depending on the desired characteristics, and is generally in the range of 120 to 60 degrees. Further, the stretching speed may be the same or different for each extending direction, and is generally 1 to 5,000%/min, preferably 50 to 1,000%/min, more preferably 100 to 1,000%/min, and particularly preferably 100. ~500% / minute. By making the stretching speed more uniform, the thickness unevenness in the longitudinal direction of the film or the phase difference R0 and the distribution of the optical axis and the like can be suppressed to the minimum. The variation of the elongation speed at this time is preferably within ±5 %, more preferably within ±1%, and particularly preferably within 0.5% of the soil. The stretching processing temperature is not particularly limited, but the glass transition temperature Tg of the resin of the present invention is generally Tg ± 30 ° C, preferably Tg ± 15 ° C, more preferably Tg - 5 ° C to Tg + 15 °. The scope of C. Further, the temperature variation (unevenness) at this time is preferably within ±5%, more preferably within ±1%, and particularly preferably within ±0.5%. When the ratio is within the above range, the phase difference R0 or the change (unevenness) of the optical axis can be suppressed, which is preferable. The stretching ratio is not particularly limited depending on the desired properties, and is usually 1.01 to 10 times, preferably 1.03 to 5 times, more preferably 1.03 to 3 times. When the stretching ratio is 1 〇 or more, the control of the phase difference may become difficult. The change in the stretching ratio at this time is preferably within ± 5 %, more preferably within ± 1 %, and particularly preferably within ± 〇 · 5 %. In this way, the thickness unevenness or phase of the film in the longitudinal direction can be suppressed to a minimum. -37-200817736 The difference between the R0 and the optical axis can be suppressed to a minimum. The stretched film can be directly cooled, and is maintained at a temperature of from Tg - 20 ° C to Tg for at least 1 sec., preferably from 30 sec to 60 min. The heating setting of from 1 minute to 60 minutes is preferred. Thereby, a phase difference film having a small variation in the transmission time and a stable stability can be obtained. The dimensional shrinkage ratio of the optical film of the present invention when the stretching process is not applied is 5% or less, preferably 3% or less, and more preferably 1% at 500 ° C under heating at 10 ° C. Below, especially good | below. Further, when the retardation film of the present invention is heated to a temperature of 100 ° C for 500 hours, it is usually 10% or less, preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. . The above-mentioned stretched film is such that the molecule imparts a phase difference by the transmitted light by stretching, but the phase difference can be controlled by the stretching ratio temperature or the film thickness or the like. For example, the thickness of the film before stretching is such that the film having a larger stretching ratio tends to have a phase difference in transmitted light, and by changing the stretching ratio, a retardation film having poor transmittance can be obtained. On the other hand, the thicker the film thickness before the stretching ratio is, the larger the phase difference of the transmitted light is. Therefore, by changing the thickness of the film before stretching, a retardation film having a phase difference of transmitted light can be obtained. Further, the lower the stretching temperature range, the lower the phase difference of the transmitted light tends to be, and the extension temperature is changed to obtain a phase film in which the transmitted light is given a desired phase difference. The temperature loop is more preferably the phase of the light is generally 0.5% shrinkage by heating, and is preferably aligned. When the extension is the same, there is a greater tendency to phase, and the tendency to extend is expected, and the delay is delayed by the thinness -38- 200817736 The thickness of the retardation film obtained by the above stretching is generally 100 μm or less, preferably 100 to 20 μm, more preferably 80 to 20 μm. When the thickness is made thinner, it is possible to achieve miniaturization and thinning of the product in the field of the phase difference film. Among them, it is desired to control the thickness of the retardation film, control the thickness of the optical film before stretching, or control the stretching ratio. For example, if the optical film before thinning is stretched or the stretching ratio is made large, the thickness of one retardation film can be made thin. &lt;Thin film characteristics&gt; The optical film of the present invention has a maximum refractive index of nx in the film surface at a light wavelength of 550 nm, a refractive index ny in the film surface for the direction of nx orthogonal direction, and a refractive index in the thickness direction of the film nz. When the film thickness is d [nm], the phase difference R0 ( 550) = (nx - ny) in the film surface is preferably 0 to 300 nm, more preferably 10 to 200 nm, and particularly preferably 30 to 100 nm. If the phase difference in the in-plane of the film exceeds 30,000 nm, light leakage may occur easily, and the contrast may decrease. In the optical film of the present invention, the deviation of the R0 in the film surface per 5 mm from the film longitudinal direction in the longitudinal direction of the film is ±10% or less, preferably ±5% or less. More preferably, it is less than 2%. The reason for measuring the deviation of R0 or the deviation of the optical axis in the film surface of the film from the film end portion of 50 mm or more from the edge of the film in the longitudinal direction of the film is as follows. In the end portion, R0 or the optical axis is often deviated during the film processing, so that the R 〇 or the optical axis is measured in a continuous manner in the longitudinal direction, that is, -39-200817736, and it is difficult to obtain a stable number 値. Here, the deviation of R0 was obtained by using a phase difference film inspection device "RETS" manufactured by Otsuka Electronics Co., Ltd., and sampling any portion lm2 of the film, and measuring the film surface at intervals of 1 cm. When the deviation of R0 exceeds ±10%, it is not preferable for the liquid crystal display to cause optical unevenness and partial light leakage or color unevenness. Further, in the optical film of the present invention, the deviation of the optical axis in the in-plane direction of the film is center 値 ± 10 degrees or less, preferably center 値 ± 3 degrees or less, more preferably center 値 ± 1 degree or less, and most preferably center.値±〇·5 degrees or less. When the optical axis deviation in the plane of the film exceeds the center 値 ± 10 degrees, when used in a liquid crystal display, optical unevenness, partial light leakage, or color unevenness may occur. Further, the deviation of the optical axis was measured by using a phase difference film inspection device "RETS" manufactured by Otsuka Electronics Co., Ltd., and an arbitrary portion lm2 of the film was sampled, and the film was measured at intervals of 1 cm. Here, the optical axis indicates the direction of the 遅 phase axis, and generally corresponds to the extrusion direction (MD direction) or the extending direction of the optical film. Therefore, the deviation of the optical axis is the deviation of the retardation axis direction, and indicates the deviation from the x-phase axis generated in the extrusion direction (MD direction) or the extending direction of the optical film. If the deviation of the above R0 is within ±10% and the deviation of the optical axis is center 値±10 degrees or less, for example, the following method can be used for adjustment. (1) The molecular weight distribution (Mw/Mn) of the cyclic olefin-based resin to be used is made small, and the glass transition temperature (Tg) is made uniform. The molecular weight distribution is generally from 1.2 to 4.5, preferably from 1.3 to 4.0, and the deviation of the glass transition temperature is generally within ±3 °C, preferably within ±1 °C. -40- 200817736 The above molecular weight distribution can be obtained by dividing the weight average molecular weight in terms of polystyrene by a number average molecular weight using a gel permeation chromatography. Further, the deviation of the glass transition temperature can be obtained by a differential operation calorimeter and an indication of the endothermic heat generation when the resin is heated at 20 ° C /min. The cyclic olefin-based resin having a narrow molecular weight distribution and a small variation in the glass transition temperature has a uniform resin composition, so that the optical properties of the obtained optical film in the longitudinal direction can be made uniform. Examples of such a cyclic olefin-based resin include the following methods. (a) A method for producing a cyclic olefin polymer by contacting a catalyst of a specific organic transition compound with an organoaluminum hydroxy compound with a cyclic olefin monomer (Application No. 8 - 1 6 5 3 09) Range 1 item 1). (b) adding a norbornene-based cyclic olefin to a polymerization catalyst containing a transition metal compound component of the eighth to tenths of the periodic table, and adding a cyclic non-conjugated polyene as a molecular weight modifier, and adding The polymerization is carried out to produce an orniolene-based cyclic olefin addition polymer (Japanese Patent Application Laid-Open No. Hei. No. Hei. (C) (A) Production of a cyclic olefin polymer producing a polymerized cyclic olefin in the presence of a catalyst comprising a combination of an aromatic cycloolefin metal derivative compound and (B) an aluminum tetrahydrofuran, a boric acid ester or a boron compound Method (Japanese Patent Application Laid-Open No. 2004-1 0 74 42) Patent Application No. 1 to Item 4. (2) The film thickness distribution before stretching is within ±1%, preferably within ±0.5%, for the average enthalpy. The thickness distribution of the optical film before stretching is controlled within the above range. • 41 - 200817736 When the stretching process is performed as appropriate, unevenness in phase difference or uneven alignment of the optical axis can be prevented. The film thickness distribution before stretching is within ± 1% with respect to the average enthalpy, and examples thereof include the following methods. (A) In the case of the solution casting method, the solution viscosity of the polymer solution when the polymer is dissolved in a solvent is constant, and the (B) melt extrusion method is used to suppress the temperature change of the mold. (3) The temperature unevenness during the extension processing is preferably within ± 5 %, more preferably within ±1%, and particularly preferably within ±0.5%. Among them, the temperature is not the same as the K-type thermoelectric pair on the lip side of the T-die, and the measured enthalpy is read by one reading every one second by the data reading unit (made by KEYENCE: GR3 5 00). The method of making the temperature during the extension processing not within ± 1% may be exemplified by a method of wind blowing, a method of adjusting the air volume, and an adjustment of the exhaust gas, in addition to the temperature setting method. Further, the amount of the residual solvent in the film used in the optical film of the present invention is generally 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. When the amount of the residual solvent exceeds the above range, the dimensional change tends to increase over time, and the residual solvent lowers the Tg and reduces the heat resistance. <<Polarizing Plate>> The polarizing plate of the present invention is one in which the polarizer of the PVA-based film or the like is formed on a single surface of -42 to 200817736, and the optical film of the viewing angle compensation film of the present invention is made of PVA resin as a main solution. The formed water-based adhesive, the polar group contains a binder, a photocurable adhesive, etc., and if necessary, it is heated or exposed and pressed, and then the polarizer and the viewing angle compensation film are laminated (laminated). And manufacturing. <<Liquid Crystal Panel>> The liquid crystal panel of the present invention is capable of bonding the polarizing plate of the present invention to at least one surface of a liquid crystal display element in which liquid crystal is sandwiched between two glass substrates, so that the liquid crystal display element and the polarizing plate are next (layer Manufactured. [Embodiment] [Embodiment] Hereinafter, specific embodiments of the present invention will be described, and the present invention is not limited to these embodiments. In addition, the following "parts" and "%" indicate "parts by weight" and "% by weight" unless otherwise specified. Further, in the following examples, the glass transition temperature, the saturated water absorption ratio, the total light transmittance, the haze, the in-plane retardation of the transmitted light, the transmittance of the polarizing plate, and the degree of polarization were measured by the following methods. [Glass transfer temperature (Tg)] The glass transition temperature was measured under the conditions of a temperature rise rate of 20 ° C /min in a nitrogen atmosphere using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments. -43- 200817736 [Saturated water absorption rate] According to A S T M D 5 7 0, the sample was immersed in water at 23 ° C for one week, and the change in the weight change of the sample before and after the immersion was measured, whereby the saturated water absorption rate was obtained. [Full light transmittance, smog] The HM measuring device "HM_1 5 0" manufactured by Murakami Color Technology Co., Ltd. was used to measure the total light transmittance and haze. [In-plane retardation (R0)] The "RETS" manufactured by Otsuka Electronics Co., Ltd. was used to measure the in-plane phase difference (R〇) when the light was irradiated in the vertical direction of the film at a wavelength of 550 nm. [Transmittance and Polarization of Polarizing Plate] The transmittance and polarization of the polarizing plate 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 (MOC ON ) was used to measure in the longitudinal direction of the film. &lt;Preparation Example 1&gt; 250 parts of distilled water was placed in a reaction container, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and oleic acid were added to the reaction container. After one part of potassium ruthenium, the system was stirred and dispersed by a stirring blade made of polytetrafluoroethylene-44-200817736 (Teflon: registered trademark). Thereafter, after the inside of the reaction vessel was replaced with nitrogen, the system was heated to 50 ° C, and polymerization was started after adding 0.2 parts of potassium persulfate. Two hours after the start of the polymerization, 0 to 1 part of potassium persulfate was added to the polymerization reaction system, and the system was heated to 80 ° C, and after 1 hour, the polymerization reaction was continued to obtain a polymer dispersion. Next, using a distiller, the polymer dispersion was concentrated to a solid content concentration of 70% to obtain an aqueous adhesive (adhesive having a polar group) derived from an aqueous dispersion of an acrylate polymer. The acrylate-based polymer constituting the water-based adhesive thus obtained (hereinafter also referred to as "water-based adhesive A") is measured by a gel permeation chromatography (GPC, solvent: tetrahydrofuran). The number average molecular weight (??) and the weight average molecular weight (Mw) give a number average molecular weight (??) of 69, 〇〇〇, weight average molecular weight (Mw) of 1 3 5,000 ° and 'for water-based adhesive A, 3 ( Intrinsic viscosity (Θ inh) in chloroform of TC was 1.2 dl/g. [Example 1] As a ring-shaped j:heterocarbon resin, a raw borneol-based resin (manufactured by JSR Co., Ltd.: trade name r ARTON D45) was used. 3 l", glass transition temperature 130 C). The raw material was introduced into a extruder (manufactured by Gm ENGINEERING CO., LTD: GM-65) at a drying temperature of 10 (rc. under nitrogen). Rc is melted, using a gear pump and quantitatively delivering -45-200817736 to deliver liquid, using a 5 μηι blade filter to remove foreign matter, and self-propelled by 25 (TC aluminum casting heater heated to mold extrusion) ΤThe heating of the mold is made The 220V and 2kW heaters flow to a current of 9A at a mold temperature of 230 °C. When the temperature is 230 °C or higher, the current flowing into the heater is changed by a thyristor current of 2.7A. Continuous current. At this time, the temperature of the T mold is confirmed to be within ±0.1 °C per 1 minute. At this time, the opening of the T mold is 0.5 mm, and the film of the T mold exits the film of the cooling roll. The distance between the pressing points is 65 mm, and the cooling roller is pressed at 250 mm. The temperature of the cooling roller is 120 ° C, and the downstream side is set to 250 mm (p cooling roller 2, and then the downstream side is set to 2 5 Ommcp). The peeling roll was set to a temperature of 1 1 5 ° C, 1 1 〇 ° C, and a film having a thickness of 1 μηηι was peeled off from the peeling roll at a film surface temperature of 1 〇 8 ° C. The film obtained (hereinafter also referred to as For the "optical film (a-1)"), the film in-plane phase difference R0 and the optical axis in the film plane are measured every 5 mm along the longitudinal direction, and the ruler is 1〇11111, and the deviation is ± Further, the deviation of the optical axis is 〇±5 degrees or less when the longitudinal direction of the film is the 〇 degree. [Example 2] The optical film (a-1) obtained in Example 1 was stretched by 1.2 times using a roll-type vertical axis stretching machine at 130 ° C, and then stretched 1.4 times using a stretching type transverse stretching machine at 130 ° C to obtain a thickness. 70 μηη extended optical film (a-2). The temperature at the time of extension is not 0.5% of the soil. The phase difference R0 of the optical film (a-2) is -46 - 200817736 6 Onm The deviation is less than ±3 %. Further, the deviation of the optical axis is 90 ± 0.5 degrees or less when the longitudinal direction of the film is used as the twist. [Comparative Example 1] In the same manner as in Example 1, the molten resin was heated by using an aluminum casting heater, and the thyristor was not required to be energized at a temperature of 2300 ° C or higher, and the current was further increased by 9 A. Set the temperature of the T mold to 2 50 °C. Other conditions were the same as in Example 1, and the film was processed. The temperature of the T mold at this time was ±2.0 °c per 1 minute. Thus, an optical film (b-Ι) having a thickness of ΙΟΟμηη was obtained. The obtained film was measured for its in-plane phase difference R0 of 5 mm and the optical axis in the film plane along the longitudinal direction, and then R0 was 12 nm, and the deviation was ±12% or less. Further, the deviation of the optical axis is 0 ± 13 degrees or less when the longitudinal direction of the film is 〇. [Comparative Example 2] In the same manner as in Example 1, the molten resin was used, and the T-die was heated by using a plate heater. Even at 23 ° C or higher, the thyristor was continuously energized in the same manner as in Example 1. For 2.7A current, set the temperature of the τ mold to 250 °C. Other conditions were the same as in Example 1, and processing of the film was carried out. The temperature of the T mold at this time is ±1.6 °C per 1 minute. Thus, an optical film (c-1) having a thickness of ΙΟΟμηη was obtained. The film obtained was measured along the longitudinal direction, and the film in-plane phase difference R0 of 5 m m and the optical axis in the film plane were measured to obtain R0 of 14 nm and a deviation of -47 to 200817736 of ±13% or less. Further, when the deviation of the optical axis is the long side of the film, it is 0 ± 15 degrees or less. [Example 3] A polyvinyl alcohol film having a thickness of 50 μm was immersed in a 40 ° C water bath formed of 250 g of potassium iodate, 10 g of boric acid, and water of 00 g to extend the axis for about 5 minutes to 4 times to obtain a polarizing film. The polarizing film was obtained by using the water-based adhesive obtained in the first modification, and the optical film (a-1) of the first embodiment and the optical film (the polarizing film produced in the second embodiment) were passed one by one to obtain a polarizing plate (a). After the transmittance and the degree of polarization of the measuring plate (a), each obtained 43% '99, so that the polarizing plate (a) is in the inner side of the optical film (a_2) in two orthogonal Nicols states, one side with a brightness of 1000 cd At the time of observation by the other side, it was confirmed that there was no unevenness due to light leakage. [Comparative Example 3] A polarizing plate was obtained by using the optical film (b-Ι) and (c-1) except for the actual loss. b) When the transmittance of the polarizing plate (b) is measured, it is 42% and 99.87%, respectively. Further, the polarizing plate (the film (c-1) is made inside and becomes two orthogonal Nico: When one side is illuminated by a backlight with a brightness of 100 cd, the unevenness of the stripe which may be caused by light leakage is confirmed from the other side. As a 〇5 g, iodized, it enters a surface. The produced light 1-2) is set to be 9 9% of the polarized light. It is also made into a stripe-like S-phase 3 phase overshoot and bias b) Ear state, observation - 48-200817736 INDUSTRIAL APPLICABILITY The optical film and polarizing plate of the present invention can be used, for example, for a mobile phone, a digital information terminal, a pager, a satellite navigation, a vehicle-mounted liquid crystal display, a liquid crystal monitor, and a liquid crystal. Various liquid crystal display elements, electroluminescence display elements, contact panels, and the like, such as a television, a dimming panel, an OA machine display, and an AV device display. Moreover, it can be applied to a wavelength plate used for a disc recording/discharging apparatus such as a CD, a CD-R, an MD, an MO, or a DVD. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the measurement of the temperature change of the mold discharge port of the present invention. -49-

Claims (1)

200817736 十、申請專利範圍 1. 一種光學薄膜，其爲由環狀烯烴系樹脂所成之薄膜 ，其特徵爲對於離薄膜端部50mm以上之薄膜表面，沿著 薄膜長邊方向於每5mm測定薄膜面内之相位差R〇與薄膜 面内的光軸時之R0的偏差爲±10%以下，且光軸的偏差爲 中心値± 1 〇度以下。 2. 如申請專利範圍第1項之光學薄膜，其中環狀烯烴 系樹脂爲下述一般式（1)所示化合物之（共）聚合物； [化1] 一般式⑴200817736 X. Patent Application No. 1. An optical film which is a film made of a cyclic olefin resin and which is characterized in that a film is measured every 5 mm along the longitudinal direction of the film for a film surface of 50 mm or more from the end of the film. The deviation between the phase difference R 面 in the plane and R0 at the optical axis in the film plane is ±10% or less, and the deviation of the optical axis is equal to or less than the center 値 ± 1 〇. 2. The optical film according to claim 1, wherein the cyclic olefin resin is a (co)polymer of a compound represented by the following general formula (1); [Chemical Formula 1] General Formula (1) (一般式（I )中，R1〜R4爲氫原子、鹵素原子、碳數 1〜3 0的烴基、或其他1價有機基，各可爲相同或相異；又 ，R1〜R4中任意2個彼此結合，可形成單環或多環結構； m爲0或正整數，p爲0或正整數）。 3 · —種光學薄膜，其特徵爲進一步延伸如申請專利範 圍第1項之薄膜。 4·一種偏光板，其特徵爲偏光子的至少單面上，層合 如申請專利範圍第1項之光學薄膜。 -50- 200817736 5 . —種液晶面板，其特徵爲液晶顯示元件的至少單面 上，層合如申請專利範圍第4項之偏光板。 6. —種光學薄膜之製造方法，其特徵爲熔融環狀烯烴 系樹脂，自塑模擠出於冷卻輥壓著使其薄膜化時，塑模吐 出口的溫度變化爲± KC /分鐘以内。 7·如申請專利範圍第6項之光學薄膜之製造方法，其 爲進一步進行延伸。 -51 -(In the general formula (I), R1 to R4 are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and each may be the same or different; and any of R1 to R4 may be 2 The ones are combined with each other to form a single or polycyclic structure; m is 0 or a positive integer, and p is 0 or a positive integer). An optical film characterized by further extending the film of the first item of the patent application. A polarizing plate characterized in that at least one side of a polarizer is laminated with an optical film as in the first aspect of the patent application. A liquid crystal panel characterized in that a polarizing plate of the fourth aspect of the patent application is laminated on at least one side of the liquid crystal display element. A method for producing an optical film characterized by melting a cyclic olefin-based resin, which is subjected to a film extrusion from a cooling roll by a die, and a temperature change of the mold discharge port is within ± KC /min. 7. The method of producing an optical film according to item 6 of the patent application, which is further extended. -51 -
TW096131866A 2006-08-30 2007-08-28 Optical film, polarizing plate, liquid crystal panel and manufacturing method of optical film TW200817736A (en)

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