201242753 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造光學薄膜之方法，更詳而言之 ’係關於一種製造相位差均一性及透明性優異，且局部之 缺陷（以下，有時記載爲「局部性缺陷」）少之光學薄膜 的方法。此處，所謂局部性缺陷係於薄膜被局部觀測到之 缺陷’源自於微小樹脂堆積之缺陷，其形狀係可舉例如與 薄膜之擠出方向平行的線紋狀、橢圓狀。 【先前技術】 於以液晶顯示裝置爲首之平面顯示器中，爲了提昇對 比度或視角，可使用相位差薄膜或偏光器保護薄膜等之光 學薄膜。於光學薄膜係尋求相位差均一性及透明性優異。 近年，探討了以丙烯系樹脂爲首之結晶性熱塑性樹脂 而製造光學薄膜之方法。例如，於專利文獻1、2中係記 載以特定之溫度條件的冷卻輥與特定之溫度條件的金屬彈 性輥，挾壓由丙烯系樹脂所構成之熔融狀薄膜，而得到透 明性及厚度精度優異之相位差薄膜用原材薄膜的方法。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2009-90652號公報 [專利文獻2]日本特開2009-9065 3號公報 201242753 【發明內容】 [發明之槪要] [發明欲解決之課題] 然而，在上述專利文獻1、2記載之方法中會於所得 到之薄膜產生局部性缺陷，爲了使用該薄膜作爲相位差薄 膜用原材薄膜，係必須避免缺陷部分，而有良率差之問題 〇 本發明之目的係有鑑於上述之習知技術之狀況，提供 一種使用丙烯系樹脂，而製造相位差均一性及透明性優異 且局部性缺陷少之光學薄膜的方法。 [用以解決課題之手段] 發明人等係累積專心硏究之結果，發現本發明可解決 上述之課題，終完成本發明。 亦即’本發明之方法係製造由丙烯系樹脂所構成之光 學薄膜的方法’其特徵係包含以彈性輥與澆鑄輥將由丙烯 系樹脂所構成之熔融狀薄膜挾壓之步驟，與前述彈性輥表 面之前述熔融狀薄膜相接之部分係由含有金屬氧化物及/ 或半金屬氧化物的材料所形成，且前述部分之表面粗度（ Ra)爲 0.04ym 以上 0.12ym 以下。 [發明之效果] 若依本發明’可製造相位差均一性及透明性優異且局 部性缺陷少之光學薄膜。 -6- 201242753 [用以實施發明之形態] 所謂使用於本發明之彈性輥係具有彈性之輥，與彈性 輥表面之熔融狀薄膜相接之部分係由含有金屬氧化物及/ 或半金屬氧化物的材料所形成，且前述部分之表面粗度 Ra爲0.04//m以上〇·12μιη以下之輥。以下，亦有時將 含金屬氧化物及/或半金屬氧化物之材料稱爲材料（1)。 彈性輥之表面，亦可僅與熔融狀薄膜相接之部分係由 材料（1 )所形成，亦可表面全體由材料（1 )所形成。彈 性輥係可爲由材料（1 )所形成之輥，亦可爲於與材料（1 )相異之材料所形成之輥的表面，具有由材料（1 )所形 成之部分的輥。 與材料（1)相異之材料所形成之輥係可舉例如橡膠 製輥；金屬製輥；於金屬之外筒的內側配設有橡膠輥之輥 ;由具有可撓性之薄金屬外筒、於該外筒呈同心狀內嵌之 高剛性的金屬內筒、與塡充於該外筒與該內筒之間的冷卻 介質所構成之輥。與材料（1)相異之材料所形成之輥較 佳係如於金屬之外筒的內側配設有橡膠輥之輥、或由具有 可撓性之薄金屬外筒、於該外筒呈同心狀內嵌之高剛性的 金屬內筒、與塡充於該外筒與該內筒之間的冷卻介質所構 成之輥之具有金屬製外筒之輥。以下，亦有時將金屬製輥 及具有金屬製外筒之輥一倂稱爲金屬彈性輥。 彈性輥係宜於金屬彈性輥之表面具有由材料（1 )所 形成之部分的輥。如此之輥的製造方法較佳爲於金屬彈性 201242753 輥之表面所希望的部分設有由材料（1)所構成之部分的 方法。此方法容易製造由材料（1)所構成之部分的表面 粗度滿足本發明之範圍的彈性輥。金屬彈性輥係可舉例如 曰本專利第3422798號公報記載之接觸輥、日本特開平7-040 3 70號公報記載之金屬製帶狀帶（循環帶）或日本特開 平1 1 -2 3 5 747號公報記載之具有可撓性的薄金屬外筒、與 於該外筒呈同心狀內嵌之高剛性的金屬內筒 '塡充於該外 筒與該內筒之間的冷卻介質所構成之輥等。該金屬彈性輥 只要其表面係以金屬所形成即可。形成金屬彈性輥之表面 的材料係可舉例如矽錳系、錳鉻系或鉻釩系等之彈簧鋼、 不鏽鋼、鎳鋼、鉻、鎳、鎳-磷合金、銅等。金屬彈性輥 爲具有金屬製外筒之輥時，該外筒之厚度宜爲1〇〇 以 上5000/zm以下。具有如此之厚度的外筒之金屬彈性輥係 具有近似橡膠彈性之柔軟性與可撓性、恢復性。金屬彈性 輥爲於金屬之外筒的內側配設有橡膠輥的輥時，該外筒之 厚度宜爲lOOym以上3000ym以下。金屬彈性輥爲由具 有可撓性的薄金屬外筒、於該外筒呈同心狀內嵌之高剛性 的金屬內筒、與塡充於該外筒與該內筒之間的冷卻介質所 構成之輥時，該外筒之厚度宜爲2000/zm以上5000//m 以下。 金屬製外筒亦可爲鍍敷有金屬製之筒的表面之筒。使 用於鍍敷之金屬可舉例如鉻、鎳、鎳-磷合金、銅等。從 鏡面精加工之容易性之點，宜爲硬質鍍鉻。硬質鍍鉻係以 鉻作爲主成分之比較厚的鍍敷，亦稱爲工業用鍍鉻。 201242753 鍍敷金屬製之筒的表面之方法係可舉例如於置入有含 使用於鍍敷之金屬的溶液之槽中浸漬筒，藉由使配置在槽 內之陰極與陽極通電，以於筒表面析出金屬之方法。亦可 硏磨形成於筒的表面之金屬層。藉鍍敷所形成之金屬層的 厚度宜爲5/zm以上ΙΟΟΟμιη以下。金屬層之硬度一般爲 維氏硬度400HV以上1 200Ην以下。從輥之彈性或強度之 點，本發明之彈性輥較佳爲於具有鑛敷金屬製之筒的表面 而得到之外筒的輥之表面，具有由材料（1 )所形成之部 分的輥。 本發明所用之彈性輥亦可僅與於其表面之熔融狀薄膜 相接之部分係由材料（1)所形成，亦可表面全體由材料 (1 )所形成。材料（1 )亦可含有金屬氧化物及半金屬氧 化物以外之成分。材料（1 )較佳爲只由金屬氧化物所構 成，或只由半金屬氧化物所構成。 金屬氧化物係由鹼金屬、鹼土族金屬、過渡金屬及基 卑金屬中選出之至少一種金屬的氧化物，可舉例如氧化鉻 (Cr203 )、氧化鋁（Α12〇3 )、氧化锆（Zr02 )、氧化釔 (Y2〇3 )等。 半金屬氧化物爲具有金屬與非金屬之中間性質之物質 之氧化物。半金屬係可舉例如硼、矽、鍺、砷、錫、碲、 釙等。半金屬氧化物係可舉例如二氧化矽（Si02 )等。 亦可倂用前述之金屬氧化物與半金屬氧化物而使用。 可舉例如以氧化鉻（Cr203 )與二氧化矽（Si02 )作爲主 成分之材料等。 201242753 含有使用於本發明之金屬氧化物及/或半金屬氧化物 的材料之市售品，可舉例如Tocalo股份公司製ZACROM 或 EDI 公司製 Ultra Chromium II 等。 彈性輥係爲於與材料（1 )相異之材料所形成之輥的 表面’具有由材料（1 )所形成之部分的輥的情況時，該 輥之製造方法係可舉例如日本專利第2 1 0 7 844號、日本專 利第3220012號、日本專利第1521696號或日本特開昭 63-487記載之方法。可舉例如於與材料（丨）相異之材料 所形成之輥的表面，塗佈含有材料（1 )之膠體溶液而形 成由該膠體溶液所構成之層，然後乾燥該層之方法》 彈性fib係爲於與材料（1 )相異之材料所形成之輕的 表面’具有由材料（1)所形成之部分的輥時，由材料（1 )所形成之部分的厚度宜爲〇.2nm以上200nm以下，更宜 爲lnm以上lOOnm以下。若厚度未滿〇.2nm，很難於輥上 均一地形成由材料（1)所形成之部分，有缺乏降低所製 造之薄膜的局部性缺陷之效果的傾向》若厚度超過200nm ’有時用以形成所希望的表面粗度之硏磨處理會耗時。 使用於本發明之彈性輥的表面粗度Ra係〇.〇4#m以 上0.12"m以下，較佳係〇.〇5//m以上O.lOym以下《前 述表面粗度若未達0.04 # m，很難得到局部缺陷少之薄膜 。若超過〇.12ym，彈性輥之表面粗度會轉印至薄膜，很 難得到可使用來作爲光學薄膜之薄膜。表面粗度Ra可由 JIS B 0601記載之方法測定。 使用於本發明之澆鑄輥係用以拉引而冷卻固化熔融狀 -10- 201242753 薄膜之輥。澆鑄輥係可例示其表面以硬質鉻、鎳、錬碟合 金、銅等鍍敷之輥或陶瓷等熔射之輥。澆鑄輥之表面粗度201242753 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing an optical film, and more particularly to a method for producing phase difference uniformity and transparency, and local defects (hereinafter, A method of describing an optical film that is less "localized defect" may be described. Here, the local defect is a defect in which the film is partially observed. The defect is derived from the defect of the deposition of the fine resin, and the shape thereof is, for example, a linear or elliptical shape parallel to the extrusion direction of the film. [Prior Art] In a flat panel display such as a liquid crystal display device, an optical film such as a retardation film or a polarizer protective film can be used in order to enhance the contrast or the viewing angle. The optical film system is excellent in phase difference uniformity and transparency. In recent years, a method of producing an optical film using a crystalline thermoplastic resin such as a propylene resin has been studied. For example, in Patent Documents 1 and 2, a metal foil having a specific temperature condition and a metal elastic roller having a specific temperature condition are pressed, and a molten film made of a propylene resin is pressed to obtain transparency and thickness precision. A method of using a raw material film for a phase difference film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-90652 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-9065 No. 3 201242753 [Summary of the Invention] [Inventions] Problem to be solved However, in the methods described in Patent Documents 1 and 2, local defects are caused in the obtained film, and in order to use the film as a film for a phase difference film, it is necessary to avoid defective portions. The problem of the rate difference of the present invention is to provide a method of producing an optical film having excellent phase difference uniformity and transparency and having few local defects by using a propylene-based resin in view of the above-described state of the art. [Means for Solving the Problem] The inventors have accumulated the results of the intensive research and found that the present invention can solve the above problems and finally complete the present invention. That is, the method of the present invention is a method for producing an optical film composed of a propylene resin, which is characterized in that it comprises a step of rolling a molten film composed of a propylene resin by an elastic roller and a casting roll, and the elastic roller described above. The portion of the surface where the molten film is in contact with each other is formed of a material containing a metal oxide and/or a semimetal oxide, and the surface roughness (Ra) of the portion is 0.04 μm or more and 0.12 μm or less. [Effects of the Invention] According to the present invention, an optical film having excellent phase difference uniformity and transparency and having few local defects can be produced. -6- 201242753 [Formation for Carrying Out the Invention] The elastic roller used in the present invention has an elastic roller, and a portion in contact with the molten film on the surface of the elastic roller is oxidized by containing a metal oxide and/or a semimetal. The material of the material is formed, and the surface roughness Ra of the aforementioned portion is a roll of 0.04 / / m or more and 〇 · 12 μm or less. Hereinafter, a material containing a metal oxide and/or a semimetal oxide is sometimes referred to as a material (1). The surface of the elastic roller may be formed of only the material (1) in contact with the molten film, or the entire surface may be formed of the material (1). The elastic roller system may be a roller formed of the material (1), or a roller having a portion formed of the material (1) on the surface of a roller formed of a material different from the material (1). The roll formed by the material different from the material (1) may be, for example, a rubber roll; a metal roll; a roll of a rubber roll disposed inside the metal outer tube; and a thin metal outer tube having flexibility The outer cylinder is a roller formed by a highly rigid metal inner cylinder embedded in a concentric shape and a cooling medium interposed between the outer cylinder and the inner cylinder. The roller formed by the material different from the material (1) is preferably a roller provided with a rubber roller on the inner side of the metal outer cylinder, or a thin metal outer cylinder having flexibility, and is concentric with the outer cylinder A high-rigidity metal inner cylinder embedded in a shape and a roller having a metal outer cylinder and a roller formed by a cooling medium interposed between the outer cylinder and the inner cylinder. Hereinafter, a metal roll and a roll having a metal outer tube may be referred to as a metal elastic roll. The elastic roller is preferably a roller having a portion formed of the material (1) on the surface of the metal elastic roller. The method for producing such a roll is preferably a method of providing a portion composed of the material (1) at a desired portion of the surface of the metal elastic 201242753 roll. This method is easy to manufacture an elastic roller whose surface roughness of the portion composed of the material (1) satisfies the scope of the present invention. The metal elastic roller is, for example, a contact roller described in Japanese Laid-Open Patent Publication No. 3422798, a metal ribbon tape (recycling tape) described in Japanese Laid-Open Patent Publication No. Hei 7-040-370, or Japanese Patent Laid-Open No. 1 1 - 2 3 5 A flexible metal outer cylinder described in the No. 747, and a metal inner cylinder that is densely embedded in the outer cylinder and that is filled with a cooling medium between the outer cylinder and the inner cylinder Rolls, etc. The metal elastic roller may be formed as long as the surface thereof is made of metal. Examples of the material for forming the surface of the metal elastic roller include spring steel such as lanthanum manganese, manganese chrome or chrome vanadium, stainless steel, nickel steel, chromium, nickel, nickel-phosphorus alloy, copper, and the like. When the metal elastic roller is a roller having a metal outer cylinder, the thickness of the outer cylinder is preferably 1 〇〇 or more and 5000/zm or less. The metal elastic roller having the outer cylinder having such a thickness has flexibility, flexibility, and recovery similar to rubber elasticity. When the metal elastic roller is a roller in which a rubber roller is disposed inside the metal outer cylinder, the thickness of the outer cylinder is preferably from 100 μm to 3000 μm. The metal elastic roller is composed of a flexible thin metal outer cylinder, a metal inner cylinder which is concentrically embedded in the outer cylinder, and a cooling medium which is interposed between the outer cylinder and the inner cylinder. In the case of a roll, the thickness of the outer cylinder is preferably 2000/zm or more and 5000//m or less. The metal outer cylinder may also be a cylinder plated with a surface of a metal cylinder. The metal used for the plating may, for example, be chromium, nickel, nickel-phosphorus alloy, copper or the like. From the point of view of the ease of mirror finishing, it should be hard chrome plating. Hard chrome plating is a relatively thick plating with chromium as a main component, also known as industrial chrome plating. 201242753 The method of plating the surface of the metal cylinder is, for example, a dipping cylinder in a tank containing a solution containing a metal for plating, by energizing the cathode and the anode disposed in the tank, A method of depositing metal on the surface. The metal layer formed on the surface of the cylinder can also be honed. The thickness of the metal layer formed by plating is preferably 5/zm or more and ΙΟΟΟμηη or less. The hardness of the metal layer is generally 400 HV or more and 1 200 Η ν or less. From the point of elasticity or strength of the roll, the elastic roll of the present invention is preferably a roll having a surface of a cylinder made of a metallized metal to obtain a surface of a roll of the outer tube having a portion formed of the material (1). The elastic roller used in the present invention may be formed of only the material (1) which is in contact with the molten film on the surface thereof, or the entire surface may be formed of the material (1). The material (1) may also contain components other than metal oxides and semimetal oxides. The material (1) is preferably composed of only a metal oxide or only a semimetal oxide. The metal oxide is an oxide of at least one metal selected from the group consisting of an alkali metal, an alkaline earth metal, a transition metal, and a base metal, and examples thereof include chromium oxide (Cr203), aluminum oxide (Α12〇3), and zirconium oxide (Zr02). , yttrium oxide (Y2 〇 3 ) and the like. A semimetal oxide is an oxide of a substance having an intermediate property between a metal and a nonmetal. The semimetal system may, for example, be boron, ruthenium, osmium, arsenic, tin, antimony or bismuth. The semimetal oxide system may, for example, be cerium oxide (SiO 2 ). It can also be used by using the aforementioned metal oxides and semimetal oxides. For example, a material containing chromium oxide (Cr203) and cerium oxide (SiO 2 ) as a main component may be mentioned. 201242753 A commercially available product containing a metal oxide and/or a semi-metal oxide of the present invention may, for example, be ZACROM manufactured by Tocalo Co., Ltd. or Ultra Chromium II manufactured by EDI. The elastic roller is a case where the surface of the roller formed of the material different from the material (1) has a portion having a portion formed of the material (1), and the manufacturing method of the roller is, for example, Japanese Patent No. 2 The method described in Japanese Patent No. 3220012, Japanese Patent No. 1521696, or JP-A-63-487. For example, a method of coating a surface of a roll formed of a material different from a material (丨), applying a colloidal solution containing the material (1) to form a layer composed of the colloidal solution, and then drying the layer" elastic fib The thickness of the portion formed by the material (1) is preferably 〇. 200 nm or less, more preferably 1 nm or more and 100 nm or less. If the thickness is less than 22 nm, it is difficult to form a portion formed of the material (1) uniformly on the roll, and there is a tendency to reduce the effect of reducing the local defects of the produced film. If the thickness exceeds 200 nm, it may be used. The honing process to form the desired surface roughness can be time consuming. The surface roughness Ra of the elastic roller used in the present invention is 〇.4#m or more and 0.12"m or less, preferably 〇.〇5//m or more and O.lOym or less. "The aforementioned surface roughness is less than 0.04. # m, it is difficult to get a film with less local defects. If it exceeds 〇.12 μm, the surface roughness of the elastic roller is transferred to the film, and it is difficult to obtain a film which can be used as an optical film. The surface roughness Ra can be measured by the method described in JIS B 0601. The casting rolls used in the present invention are used for drawing to cool and solidify the molten -10- 201242753 film roll. The casting roll system is exemplified by a roll which is coated with a roll of a hard chromium, nickel, a ruthenium alloy, copper or the like, or a ceramic. Casting roll surface roughness
Ra較佳係0.12"m以下’更佳係〇.〇8/zm以下。繞鑄輕 之表面亦較佳爲與熔融狀薄膜相接的部分由含有金屬氧化 物及/或半金屬氧化物的材料（1 )所形成。若使用如此之 澆鑄輥，薄膜易從輥剝離，故在製造生產線上可使薄膜安 定地移動。澆鑄輥較佳爲其表面全體由材料（1 )所形成 〇 光學薄膜係可舉例如偏光器保護薄膜、稜鏡片、相位 差薄膜前驅物等。前述相位差薄膜前驅物係表示未延伸薄 膜、且藉由延伸該薄膜而成爲相位差薄膜的薄膜。 丙烯系樹脂係可舉例如丙烯之均聚物、乙烯及碳數4 〜20之α -烯烴所構成之群中選出的1種以上的共單體與 丙烯之共聚物等。又，可爲此等之混合物。碳數4〜20之 α-烯烴可舉例如1-丁烯、2-甲基-1-丙烯、1-戊烯、2-甲 基-1-丁烯、3 -甲基-1-丁烯、1-己烯、2·乙基-1-丁烯、2,3-二甲基-1-丁烯、2-甲基-1-戊烯、3-甲基-1-戊烯、4-甲基-1-戊烯、3,3-二甲基-1-丁烯、1-庚烯、2-甲基-1-己烯、 2,3 -二甲基-1-戊燒、2 -乙基-1-戊嫌、2 -甲基-3-乙基-1-丁 烯、1-辛烯、2 -乙基-1-己烯、3,3 -二甲基·；1-己烯、2 -丙 基-1-庚烯、2 -甲基-3-乙基-1-庚烯、2,3,4 -三甲基-1-戊烯 、2-丙基-1-戊烯、2,3-二乙基-1-丁烯、1-壬烯、1-癸嫌、 1 Η--碳烯、1-十二碳烯、1-十三碳烯、1-十四碳烯、i- 十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1_十 -11 - 201242753 九碳烯等。丙烯系樹脂較佳係丙烯之均聚物、丙烯·乙嫌 共聚物、丙烯.1-丁烯共聚物、丙烯· 1-戊烯共聚物、丙 烯· 1-己烯共聚物、丙烯.1-辛烯共聚物、丙烯.乙烯· 1-丁烯共聚物或丙烯·乙烯· 1-己烯共聚物。又，在本發 明中之丙烯系樹脂爲由乙烯及碳數4〜20之α-烯烴所構 成之群中選出的1種以上的共單體與丙烯之共聚物時’該 樹脂係可爲隨機共聚物，亦可爲嵌段共聚物。丙烯系樹脂 爲共聚物時，在該共聚物中之源自共單體的構成單元之含 量，從薄膜之透明性與耐熱性之均衡的觀點，較佳係超過 3重量％，40重量％以下，更佳係超過5重量％，25重量％ 以下。又，爲2種類以上之共單體與丙烯之共聚物時，該 共聚物所含有之全部的源自共單體之構成單元的合計含量 宜爲上述之範圍。 丙烯系樹脂之製造方法係可舉例如使用公知之聚合用 觸媒而使丙烯均聚合之方法，或由乙烯及碳數4〜20之 α-烯烴所構成之群中選出的1種以上的共單體與丙烯共 聚合之方法。公知之聚合觸媒可舉例如（1 )以鎂、鈦及 鹵素作爲必要成分之固體觸媒成分等所構成之Ti-Mg系觸 媒、（2 )以鎂、鈦及鹵素作爲必要成分之固體觸媒成分 中組合有機鋁化合物、依需要之電子供給性化合物等之第 3成分的觸媒系、（3)二茂鐵系觸媒等。使用於丙烯系聚 合物之製造的觸媒系者’此等之中一般最常使用以鎂、鈦 及鹵素爲必要成分之固體觸媒成分中組合有機鋁化合物與 電子供給性化合物之觸媒系。更具體而言，有機鋁化合物 -12- 201242753 可舉例如三乙基鋁 '三異丁基鋁'三乙基鋁與氯化 鋁的混合物及四乙基二鋁氧烷，電子供給性化合物 可舉例如環己基乙基二甲氧基矽烷、第三丁基-正 甲氧基矽烷、第三丁基乙基二甲氧基矽烷、二環戊 氧基矽烷。以鎂、鈦及鹵素爲必要成分之固體觸媒 舉例如日本特開昭 6 1 -2 1 8606號公報、日本特開 287904號公報、特開平7-216017號公報等記載之 。二茂鐵觸媒可舉例如日本專利第25 8725 1號公報 專利第262^7669號公報、日本專利第2668732號公 載之觸媒系。 使用於丙烯系樹脂之製造的聚合方法可舉例如 己烷、庚烷、辛烷、癸烷、環己烷、甲基環己烷、 苯、二甲苯等之烴化合物所代表之惰性溶劑的溶劑 、使用液狀之單體作爲溶劑之塊狀聚合法、在氣體 中進行聚合之氣相聚合法等，較佳係塊狀聚合法或 合法。此等之聚合法可爲批次式，亦可爲連續式。 丙烯系樹脂之立體規則性可爲同排、對排、雜 一形式。丙烯系樹脂係從耐熱性之點，宜爲對排、 之丙烯系樹脂。 丙烯系樹脂係可爲分子量或源自丙烯之構成單 率、排列性等相異之2種類以上的丙烯系聚合物之 ’亦可適合含有丙烯系聚合物以外之聚合物或添加丨 丙烯系樹脂之熔融流動率（MFR)係依JIS K 所測定之値（試驗溫度、公稱荷重係依JIS K 72 10 二乙基 較佳係 丙基二 基二甲 成分可 昭 6 1-觸媒系 、日本 報等記 使用於 苯、甲 聚合法 之單體 氣相聚 排之任 或同排 元的比 摻混物 剖。 7210， 之附屬 -13- 201242753 書B表1而定），一般爲0.1 g/10分〜50g/10分 爲0.5g/10分〜20g/10分左右。藉由使用MFR爲 圍的丙烯系樹脂，不會對擠出機施加很大的負荷 一的薄膜成形。 丙稀系樹脂之分子量分布一般爲1〜20。分 係該樹脂之重量平均分子量（Mw)對數目平均 Μη )之比。Mw及Μη係於溶劑中使用140°C之 ，於標準試樣使用聚苯乙烯而測定及計算。 使用於本發明之丙烯系樹脂在不阻礙本發明 範圍，可調配公知之添加劑。添加劑可舉例如抗 紫外線吸收材、抗靜電劑、滑劑、造核劑、防霧 黏劑等，此等之中亦可使用1種或2種類以上。 抗氧化劑可舉例如酚系抗氧化劑、磷系抗氧 系抗氧化劑、受阻胺系抗氧化劑（HALS )、或方 中具有例如酚系與磷系之抗氧化機構的單元之複 化劑等。紫外線吸收劑可舉例如2-羥基二苯甲酮 三唑系等之紫外線吸收劑、或苯甲酸酯系等之紫 劑等。抗靜電劑可舉例如聚合物型、寡聚物型、 之劑。滑劑可舉例如芥酸醯胺、油酸醯胺等之高 醯胺、或硬脂酸等之高級脂肪酸、及其金屬鹽等 可舉例如山梨糖醇系造核劑、有機磷酸鹽系造核 烯基環烷等之高分子系造核劑等。抗壓黏劑可舉 、或近似其之形狀的微粒子。 使用圖1而詳細說明製造本發明之光學薄膜 左右，宜· 如此之範 ，可使均 子量分布 分子量（ 鄰二氯苯 之效果的 氧化劑、 劑、抗壓 化劑、硫 会1分子 合型抗氧 系、羥基 外線遮蔽 單體型等 級脂肪酸 。造核劑 劑、聚乙 例如球狀 的方法。 -14- 201242753 製造本發明之光學薄膜的方法係以前述彈性輥與前述澆鑄 輥將由丙烯系樹脂所構成之熔融狀薄膜挾壓而製造之方法 〇 最初，從供料斗（未圖示）於擠出機10投入丙烯系 樹脂。從供料斗投入於擠出機之丙烯系樹脂係爲抑制劣化 ，宜在惰性氣體環境下較佳係氮氣環境下事前預備乾燥1 小時至1 0小時。惰性氣體係可舉例如氮、氬等，從易操 作性，宜爲氮。此時之乾燥溫度宜爲4 0 °C以上1 3 0 °C以下 。對於擠出機內’同樣地爲抑制樹脂之劣化，宜形成惰性 氣體環境。 然後’在被加熱之擠出機10的缸筒內藉螺桿（未圖 示）熔融混練丙烯系樹脂（以下，有時記載爲「熔融步驟 」）。在熔融步驟中被熔融混練之丙烯系樹脂係從T模頭 12之吐出口擠出成薄膜狀（以下，有時記載爲「成形步驟 j )。在熔融步驟及成形步驟中之成形溫度宜爲1 8 (TC以 上3 0 0 °C以下，更佳係2 2 0 °C以上2 8 0 t以下。若樹脂之溫 度爲180°C以上3 00°C以下，易得到厚度不均爲小的薄膜 ’又’樹脂之劣化變少，故樹脂劣化成分所造成之唇部的 污染或模線的發生變少，易得到外觀優異之薄膜。 繼而’以彈性輥1 4與澆鑄輥1 6將熔融狀薄膜挾壓並 冷卻固化。 於彈性輥14之表面係形成由含有金屬氧化物及/或半 金屬氧化物之材料（1 )所構成的部分。彈性輥爲於由與 材料（1 )相異之材料所形成之輥的表面，具有由材料（1Ra is preferably 0.12 "m or less' better than 〇8/zm. The portion of the surface to be cast light is preferably formed by a material (1) containing a metal oxide and/or a semimetal oxide. If such a casting roll is used, the film is easily peeled off from the roll, so that the film can be stably moved on the manufacturing line. The casting roll is preferably formed of the material (1) as a whole. The optical film may be, for example, a polarizer protective film, a ruthenium film, a retardation film precursor or the like. The retardation film precursor is a film which is a film which is not stretched and which is a retardation film by stretching the film. The propylene-based resin may, for example, be a homopolymer of propylene, a copolymer of one or more kinds of comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms, and propylene. Also, a mixture of these can be used. The α-olefin having 4 to 20 carbon atoms may, for example, be 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene or 3-methyl-1-butene. , 1-hexene, 2·ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4 -methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-penta-, 2-methyl-3-ethyl-1-butene, 1-octene, 2-ethyl-1-hexene, 3,3-dimethyl-; -hexene, 2-propyl-1-heptene, 2-methyl-3-ethyl-1-heptene, 2,3,4-trimethyl-1-pentene, 2-propyl-1 -pentene, 2,3-diethyl-1-butene, 1-decene, 1-anthracene, 1 fluorene-carbene, 1-dodecene, 1-tridecene, 1- Tetradecene, i-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1_10-11 - 201242753 nonacarbene, and the like. The propylene resin is preferably a homopolymer of propylene, a propylene/ethyl propylene copolymer, a propylene. 1-butene copolymer, a propylene·1-pentene copolymer, a propylene·1-hexene copolymer, or a propylene. An octene copolymer, a propylene.ethylene·1-butene copolymer or a propylene·ethylene·1-hexene copolymer. Further, when the propylene resin in the present invention is a copolymer of one or more kinds of comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms and propylene, the resin system may be random. The copolymer may also be a block copolymer. When the propylene resin is a copolymer, the content of the constituent unit derived from the comonomer in the copolymer is preferably from 3% by weight to 40% by weight from the viewpoint of balance between transparency and heat resistance of the film. More preferably, it is more than 5% by weight and not more than 25% by weight. Further, when a copolymer of two or more kinds of comonomers and propylene is used, the total content of all the constituent units derived from the comonomer contained in the copolymer is preferably in the above range. The method for producing the propylene-based resin is, for example, a method in which propylene is uniformly polymerized using a known polymerization catalyst, or one or more selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. A method of copolymerizing a monomer with propylene. The known polymerization catalyst may, for example, be a Ti-Mg catalyst composed of a solid catalyst component containing magnesium, titanium, and a halogen as essential components, and (2) a solid containing magnesium, titanium, and halogen as essential components. In the catalyst component, a catalyst system of a third component such as an organoaluminum compound or an electron-donating compound, and (3) a ferrocene-based catalyst are combined. Catalysts used in the manufacture of propylene-based polymers. Among these, the catalyst system in which an organoaluminum compound and an electron-donating compound are combined in a solid catalyst component containing magnesium, titanium, and halogen as essential components is generally used. . More specifically, the organoaluminum compound -12-201242753 may, for example, be a mixture of triethylaluminum 'triisobutylaluminum' triethylaluminum and aluminum chloride and tetraethyldialuminoxane, and an electron-donating compound may be used. For example, cyclohexylethyldimethoxydecane, tert-butyl-n-methoxydecane, tert-butylethyldimethoxydecane, dicyclopentyloxydecane. A solid catalyst containing magnesium, titanium, and a halogen as an essential component is described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The ferrocene catalyst may, for example, be a catalyst system disclosed in Japanese Patent No. 25 8725 1 Patent No. 262/7669, and Japanese Patent No. 2668732. The polymerization method used for the production of the propylene resin may, for example, be a solvent of an inert solvent represented by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene or xylene. A bulk polymerization method using a liquid monomer as a solvent, a gas phase polymerization method in which a polymerization is carried out in a gas, or the like is preferably a bulk polymerization method or a law. These polymerization methods can be batch or continuous. The stereoregularity of the propylene resin may be in the same row, in the opposite row, or in the heterogeneous form. The propylene-based resin is preferably a pair of propylene-based resins from the viewpoint of heat resistance. The propylene-based resin may be a polymer having a molecular weight or a propylene-based polymer of two or more types different in composition ratio and alignment property of propylene, and may be preferably a polymer other than the propylene-based polymer or a propylene-based resin. The melt flow rate (MFR) is measured by JIS K (test temperature, nominal load according to JIS K 72 10 diethyl preferably propyl diyl dimethyl component can be shown in 6 1-catalyst system, Japan The report is used for the cross-linking of the monomer in the gas phase polymerization of benzene or a polymerization method or in the same row. 7210, Affiliated-13-201242753, Book B, Table 1), generally 0.1 g/ 10 minutes to 50g/10 is divided into 0.5g/10 minutes to 20g/10 minutes. By using a propylene-based resin surrounded by MFR, a film which does not exert a large load on the extruder is formed. The molecular weight distribution of the acrylic resin is generally from 1 to 20. The ratio of the weight average molecular weight (Mw) of the resin to the number average Μη) is classified. Mw and Μη were measured and calculated using 140 ° C in a solvent and polystyrene in a standard sample. The propylene-based resin to be used in the present invention can be blended with a known additive without hindering the scope of the present invention. The additive may, for example, be an ultraviolet ray absorbing material, an antistatic agent, a lubricant, a nucleating agent or an antifogging agent, and one or more types may be used. The antioxidant may, for example, be a phenol-based antioxidant, a phosphorus-based antioxidant, a hindered amine-based antioxidant (HALS), or a reconstituting agent having a unit such as a phenol-based or phosphorus-based antioxidant mechanism. The ultraviolet absorber may, for example, be a UV absorber such as a 2-hydroxybenzophenone triazole or a violet such as a benzoate. The antistatic agent may, for example, be a polymer type or an oligomer type. Examples of the slip agent include decylamine such as erucylamine and decylamine oleate, and higher fatty acids such as stearic acid, and metal salts thereof, and the like, for example, a sorbitol-based nucleating agent or an organic phosphate system. A polymer nucleating agent such as a nucleoside cycloalkane. The anti-adhesive agent may be, or approximate to, the shape of the microparticles. The optical film of the present invention will be described in detail with reference to Fig. 1, which is suitable for the purpose of distributing the molecular weight (the oxidizing agent, the agent, the anti-pressurizing agent, and the sulfur of the effect of o-dichlorobenzene). An anti-oxidation system, a hydroxyl group-line shielding monomeric grade fatty acid, a nucleating agent, and a method of forming a polyethylene such as a spherical material. -14- 201242753 The method for producing the optical film of the present invention is that the elastic roller and the casting roller are made of propylene. In the first step, a propylene resin is introduced into the extruder from a supply hopper (not shown). The propylene resin is supplied to the extruder from the supply hopper to suppress deterioration. It is preferable to prepare for drying in an inert gas atmosphere under a nitrogen atmosphere for 1 hour to 10 hours. The inert gas system may, for example, be nitrogen, argon, etc., and is easy to handle, and is preferably nitrogen. 4 0 °C or more and 130 ° C or less. For the extruder, 'the same is to suppress the deterioration of the resin, it is preferable to form an inert gas atmosphere. Then 'in the cylinder of the heated extruder 10 (not shown) The propylene-based resin is melt-kneaded (hereinafter referred to as "melting step"). The propylene-based resin which is melt-kneaded in the melting step is extruded from the discharge port of the T-die 12 into a film shape (hereinafter, It may be described as "forming step j." The molding temperature in the melting step and the molding step is preferably 18 (TC or more and 300 ° C or less, more preferably 2, 2 0 ° C or more and 2,800 ° or less). If the temperature of the resin is 180 ° C or more and 300 ° C or less, it is easy to obtain a film having a small thickness, and the deterioration of the resin is small, so that the contamination of the lip or the occurrence of the mold line caused by the deteriorated component of the resin is changed. The film is excellent in appearance, and then the molten film is pressed and cooled and solidified by the elastic roller 14 and the casting roller 16. The surface of the elastic roller 14 is formed by oxidation containing metal oxides and/or semimetals. a portion of the material (1). The elastic roller is a surface of a roller formed of a material different from the material (1), and has a material (1)
C -15- 201242753 )所形成之部分的輥時’於由與材料（n相異之材料所 形成之輥的表面’有時產生微龜裂。其時，爲使微龜裂以 材料（1)掩埋’宜爲形成由材料（！）所構成之部分。彈 性輥之表面的狀態係可以X射線光電子分光（以下，有時 曰己載爲「XPS」）分析確認。從以材料（！）所形成之部分 採取試樣，實施該試樣之寬掃描測定。使用之X線源係可 例不A丨-κ α線。實施寬掃描測定，從所得到之光譜特定 兀素’问時並贯施局解析度測定，得到窄掃描光譜。藉此 ’導出如何的原子以如何的鍵結存在（推定歸屬）、或在 某鍵結狀態之原子以如何的比率存在（狀態比率）。 以彈性輥與澆鑄輥將熔融狀薄膜挾壓時之壓力（以下 ，有時記載爲「線壓」）係藉由使彈性輥1 4押住澆鑄輥 16之壓力來決定。線壓較佳係〇.5N/mm以上l〇〇N/mm以 下。若線壓爲〇.5N/mm以上100N/mm以下，易均一地控 制線壓，且線壓比較小，故易得到相位差値小的薄膜。 控制線壓之方法一般係於挾壓熔融狀薄膜之部分設置 被稱爲栓（cotter )之三角形的楔形之「塡塞物」，藉由 控制該栓，以調整輥間隔之方法；於彈性輥1 4與澆鑄輥 16之任一者或兩者使用油壓、空氣等而賦予特定的壓力， 押住至抵接於經調整之栓的方法。其他，不使用栓，而爲 調整一對之輥各別的軸承區塊的間隙，於前述一對之輥的 軸承部至少一者設置螺絲，控制前述螺絲之旋轉數，機械 性以無階段調整軸承區塊至特定的位置，俾以1對之輥壓 接熔融狀薄膜的方法；或於油壓系使用伺服馬達的方法等 -16- 201242753 其後’熔融狀薄膜係被輥挾壓後，被冷卻固化而成爲 薄膜’依需要而裁切（切斷）其毛邊，以捲取機捲取。丙 烯系樹脂薄膜係可在裁切毛邊之前、及/或裁切之後的單 面或雙面層合保護薄膜。丙烯系樹脂薄膜之厚度係從本發 明之效果最佳顯現的觀點，宜爲40 // m〜500 # m。 以本發明的方法所得到之丙烯系樹脂薄膜係無配向、 高透明’故可使用來作爲偏光板保護薄膜，進一步，亦可 利用於其他各種液晶構件。又，使以本發明的方法所得到 之丙烯系樹脂薄膜延伸所得到的延伸薄膜，就相位差薄膜 而言，從電視、個人電腦用監視器、汽車導航器、數位相 機、行動電話等之大型液晶面板至中小型液晶面扳可廣泛 使用。藉由控制延伸丙烯系樹脂薄膜之倍率，而可製造具 有所希望的相位差之延伸薄膜。延伸方法係可舉例如縱延 伸、橫延伸、逐次二軸延伸、同時二軸延伸。逐次二軸延 伸的情況時，先進行縱延伸後，進行橫延伸之方法；先進 行橫延伸之後，進行縱延伸之方法的任一方法。 偏光板保護薄膜或相位差薄膜用原材薄膜係要求無配 向。此處，所謂無配向係由熱塑性樹脂所構成之材料中的 聚合物之分子鏈完全無配向，而在於無秩序狀態。配向之 程度係可求出相位差値進行評估，相位差値係可使用市售 之相位差計而測定。相位差薄膜用原材薄膜之相位差値較 佳爲其厚度100#m時之値爲0nm〜50nm。相位差薄膜用 原材薄膜之相位差値在於此範圍內的情況下，使該相位差 -17- 201242753 薄膜用原材薄膜延伸，形成相位差薄膜時，相位差薄膜用 原材薄膜起初具有之相位差小，故即使調節延伸條件，亦 容易控制相位差。 在本發明中，使熔融狀薄膜以澆鑄輥16與彈性輥14 挾壓。因此，熔融狀薄膜的兩面藉彈性輥14及澆鑄輥16 而冷卻，故可使熔融狀薄膜迅速冷卻固化。依據本發明， 即使爲使用結晶性樹脂之丙烯系樹脂作爲薄膜的材料時， 丙烯系樹脂之結晶成長之前，可使熔融狀薄膜冷卻固化， 故可製造具有高的透明性之丙烯系樹脂薄膜。 又，在本實施形態中，係使用一種於其表面具有由澆 鑄輥1 6及含有金屬氧化物及/或半金屬氧化物的材料所形 成之部分的可彈性變形之輥1 4。若以如此之輥挾壓熔融狀 薄膜，可得到局部性缺陷少之光學薄膜。局部性缺陷係於 彈性輥之直徑的整數倍的周期有易發生的傾向。局部性缺 陷的形狀係可例示與薄膜之擠出方向與平行的條紋狀、橢 圓形狀等。在本發明所得到之薄膜係因如此之局部性缺陷 少，故可使用所得到之薄膜全體作爲製品。 又，以本發明之方法所得到的薄膜係相位差小且於薄 膜之寬方向幾乎無相位差不均。如此之薄膜係適宜作爲相 位差薄膜用原材薄膜。 【實施方式】 [實施例] 以下，舉出實施例而詳細地說明本發明。又，各特性 -18- 201242753 値係以下述之方法測定、評估。C -15- 201242753 ) When the part of the roll is formed, the micro-crack is sometimes generated by the surface of the roll formed of the material different from n. In the meantime, the material is cracked by the material (1) The burial 'should be formed by a material (!). The state of the surface of the elastic roller can be confirmed by X-ray photoelectron spectroscopy (hereinafter, sometimes referred to as "XPS"). The formed portion is subjected to a sample and a wide scan measurement of the sample is carried out. The X-ray source used may be, for example, an A丨-κα line. A wide scan measurement is performed, and the obtained spectrum is specific to the element. Through the resolution measurement, a narrow scan spectrum is obtained, thereby 'deriving how the atoms exist (presumed attribution), or how the atoms in a bonding state exist (state ratio). The pressure at which the roll and the casting roll are pressed by the molten film (hereinafter sometimes referred to as "linear pressure") is determined by pressing the pressure of the elastic roll 14 against the casting roll 16. The line pressure is preferably 〇. 5N/mm or more l〇〇N/mm or less. If the line pressure is 〇.5N/mm Above 100N/mm, it is easy to uniformly control the line pressure, and the line pressure is relatively small, so it is easy to obtain a film with a small phase difference. The method of controlling the line pressure is generally set in a part of the rolling molten film called a plug ( a triangular wedge-shaped "crust" of cotter), which is controlled by adjusting the plug to adjust the interval of the rolls; and is applied to either or both of the elastic roll 14 and the casting roll 16 by using oil pressure, air, or the like. The specific pressure is held until the method of abutting the adjusted bolt. Others, without using a bolt, to adjust the gap of each bearing block of the pair of rollers, at least one of the bearing portions of the pair of rollers Set screws to control the number of rotations of the above screws, mechanically adjust the bearing block to a specific position without stage, and press the molten film with a pair of rolls; or use a servo motor for hydraulic system. -16- 201242753 Thereafter, the molten film is pressed by a roll and then solidified by cooling to form a film. If necessary, the burrs are cut (cut) and wound up by a coiler. The propylene resin film can be used. Before cutting the burrs, and/or cutting The single-sided or double-sided laminated protective film. The thickness of the propylene-based resin film is preferably from 40 // m to 500 #m from the viewpoint of the best effect of the present invention. The propylene obtained by the method of the present invention The resin film is unaligned and highly transparent, so it can be used as a polarizing plate protective film, and can be used in various other liquid crystal members. Further, the propylene resin film obtained by the method of the present invention is extended. The stretch film, in terms of the retardation film, can be widely used from a large liquid crystal panel such as a television, a personal computer monitor, a car navigator, a digital camera, a mobile phone, etc. to a small and medium-sized liquid crystal panel. By controlling the extension of the propylene resin The film is stretched to produce a stretched film having a desired phase difference. The stretching method is, for example, longitudinal stretching, lateral stretching, sequential biaxial stretching, and simultaneous biaxial stretching. In the case of successive biaxial stretching, a method of performing lateral stretching after longitudinal stretching is first performed, and any method of longitudinal stretching is performed after advanced horizontal stretching. The polarizer protective film or the phase film for the retardation film is required to have no alignment. Here, the molecular chain of the polymer in the material of the non-alignment type composed of the thermoplastic resin is completely unaligned, but is in an disorderly state. The degree of alignment can be evaluated by determining the phase difference ,, and the phase difference 测定 can be measured using a commercially available phase difference meter. The phase difference 原 of the raw material film for the retardation film is preferably from 0 nm to 50 nm when the thickness is 100 #m. When the phase difference of the raw material film for the retardation film is within this range, the film of the phase difference -17-201242753 is stretched to form a retardation film, and the film for the retardation film is initially provided. Since the phase difference is small, it is easy to control the phase difference even if the extension condition is adjusted. In the present invention, the molten film is pressed by the casting rolls 16 and the elastic rolls 14. Therefore, both sides of the molten film are cooled by the elastic roller 14 and the casting roll 16, so that the molten film can be rapidly cooled and solidified. According to the present invention, even when a propylene-based resin using a crystalline resin is used as a material of a film, the molten film can be cooled and solidified before the crystal growth of the propylene-based resin is grown, so that a propylene-based resin film having high transparency can be produced. Further, in the present embodiment, an elastically deformable roller 14 having a portion formed of a casting roll 16 and a material containing a metal oxide and/or a semi-metal oxide is used. When the molten film is pressed by such a roll, an optical film having few local defects can be obtained. The local defect is a tendency that a period of an integral multiple of the diameter of the elastic roller tends to occur. The shape of the local defect can be exemplified by a stripe shape, an elliptical shape, and the like which are parallel to the extrusion direction of the film. Since the film obtained by the present invention has few local defects, the entire film obtained can be used as a product. Further, the film obtained by the method of the present invention has a small phase difference and almost no phase difference unevenness in the width direction of the film. Such a film is suitable as a raw material film for a phase difference film. [Embodiment] [Examples] Hereinafter, the present invention will be described in detail by way of examples. In addition, each characteristic -18-201242753 is measured and evaluated by the following method.
(透明性） 以HAZE評估透明性。HAZE係依據JIS K 7 1 3 6測定 (相位差値） 使所得到之薄膜從薄膜寬方向的中央朝薄膜 向以100mm間隔切出40mmx40mm。切出總共9 。使用王子計測機器股份有限公司製相位差計 WPR ) ’而測定前述試樣之面內相位差r〇。 (相位差均一性） 從所測定之總共9點的相位差値之最大値減 之値’ 20nm以下時評估爲「〇」，超過20nm時 端部兩方 點之試樣 (KOBRA- 去最小値 評估爲^ (局部性缺陷） 以薄膜10m中之相當於下述式的1mm以上 行評估。 局部性缺陷=(局部性缺陷之最長邊+與前 缺陷之最長邊成爲90度之角的缺陷長度）/2。 缺陷數進 述局部性 (表面粗度） -19- 201242753 使用東京精密股份有限公司製之表面粗度計（Surfcom 130A)，以JIS B 0601記載的方法，測定算術平均粗度 Ra » Ra之値爲本發明之表面粗度。 (XPS分析） 使用 Surface Science Instruments 公司製（S-Probe ESCA Model 2803 )，實施寬掃描測定及高解析度測定。 此處，深度資訊爲6〜7nm，可檢測元素爲Li以上。從高 解析度測定結果求出鍵結能量、所推定之狀態比率及推定 歸屬。鍵結能量係c - C、C - Η爲2 8 4.6 e V而基準化之値。 狀態比率以原子百分率（Atomic % )表示。 [實施例1] 使用如圖1所示之裝置。彈性輥14係於表面爲硬質 鍍鉻之薄金屬外筒14b的表面全體，形成由含有二氧化矽 的材料（EDI公司製Ultra Chromium II)所構成的層14d 之輥》爲確認彈性輥之表面狀態，實施XPS分析。結果表 示於表1中。彈性輥14之表面的XPS分析結果係存在有 源自於矽化合物的SiOx ( x = 2 )的譜峯，同時顯示源自 Si-〇鍵之譜峯的狀態比率高。此係表示於彈性輥之表面形 成由含有半金屬氧化物之材料所構成之層14d。又，所使 用之彈性輥的表面粗度Ra爲0.05 // m。 使丙烯系樹脂（丙烯-乙烯隨機共聚物、乙烯含量=4 重量％、熔融流動率（以下，亦稱爲M F R ) = 8 · 0、融點 -20- 201242753 =:134 °C )，加熱至2501：之75 mm Φ擠出機熔融混練，從T 模頭對於澆鑄輥，吐出由丙烯系樹脂所構成之熔融狀薄膜 。繼擠出機而設置之由連接頭至Τ模頭全部設定於2 5 0°C 。T模頭12之吐出口 12a部分中的熔融樹脂之溫度爲250 °C。繼而，使該熔融狀薄膜藉由圖1所示之彈性輥14、與 澆鑄輥16而以挾壓長度5mm挾壓同時並拉引。熔融狀薄 膜係藉由彈性輥1 4及澆鑄輥1 6、冷卻輥1 8而冷卻固化， 厚度成爲l〇〇//m之丙烯系樹脂薄膜。此處，彈性輥14之 溫度設定於120°C，澆鑄輥16之溫度設定於20°C。將所 得到之丙烯系樹脂薄膜的評估結果表示於表2中。 [實施例2] 作爲彈性輥，其表面由含有與實施例1同樣之二氧化 矽的材料形成，且使用表面粗度Ra爲〇.〇9//m之彈性輥 以外’其餘係與實施例1同樣做法而得到丙烯系樹脂薄膜 。結果表示於表1中。(Transparency) The transparency was evaluated by HAZE. The HAZE was measured in accordance with JIS K 7 1 3 6 (phase difference 値), and the obtained film was cut out from the center in the film width direction toward the film by 40 mm x 40 mm at intervals of 100 mm. Cut out a total of 9. The in-plane retardation r〇 of the sample was measured using a phase difference meter WPR)' manufactured by Oji Scientific Instruments Co., Ltd. (Phase difference uniformity) It is evaluated as "〇" when the maximum deviation of the phase difference 値 of the total of 9 points measured is less than 20 nm, and the sample at both ends of the end point exceeds 20 nm (KOBRA-minimum 値The evaluation is ^ (local defect) evaluated in a film of 10 m which is equivalent to the following formula: 1 mm or more. Local defect = (the longest side of the local defect + the length of the defect with the longest side of the front defect at an angle of 90 degrees /2. The number of defects is described as local (surface roughness) -19- 201242753 The arithmetic mean roughness Ra is measured by the method described in JIS B 0601 using a surface roughness meter (Surfcom 130A) manufactured by Tokyo Seimitsu Co., Ltd. » Ra is the surface roughness of the present invention. (XPS analysis) Wide scan measurement and high-resolution measurement were performed using Surface Science Instruments (S-Probe ESCA Model 2803). Here, the depth information is 6 to 7 nm. The detectable element is Li or higher. The bonding energy, the estimated state ratio, and the estimated attribution are obtained from the high-resolution measurement result. The bonding energy systems c - C and C - Η are 2 8 4.6 e V and are benchmarked.状态. State ratio is atomic The fraction (Atomic %) is shown. [Example 1] A device as shown in Fig. 1 was used. The elastic roller 14 was attached to the entire surface of a thin metal outer cylinder 14b having a hard chrome plating surface to form a material containing cerium oxide ( XPS analysis was carried out to confirm the surface state of the elastic roller by the "Roller 14d of Ultra Chromium II" manufactured by EDI Co., Ltd. The results are shown in Table 1. The results of XPS analysis of the surface of the elastic roller 14 were derived from 矽The peak of SiOx (x = 2) of the compound also shows a high ratio of the state of the peak derived from the Si-〇 bond. This means that a layer 14d composed of a material containing a semimetal oxide is formed on the surface of the elastic roller. Further, the surface roughness Ra of the elastic roller used was 0.05 // m. A propylene resin (propylene-ethylene random copolymer, ethylene content = 4% by weight, melt flow rate (hereinafter, also referred to as MFR) = 8 · 0, melting point -20- 201242753 =:134 °C), heating to 2501: 75 mm Φ extruder melt-kneading, from the T die to the casting roll, spit out a molten film composed of propylene resin Depending on the extruder, the connector is connected to the die. All were set at 250 ° C. The temperature of the molten resin in the portion of the discharge port 12a of the T die 12 was 250 ° C. Then, the molten film was passed through the elastic roller 14 shown in Fig. 1 and the casting roll. 16 and simultaneously rolling and pulling at a rolling length of 5 mm. The molten film is cooled and solidified by an elastic roller 14 and a casting roller 16 and a cooling roller 18, and the propylene resin having a thickness of 10 Å/m is obtained. film. Here, the temperature of the elastic roller 14 was set at 120 ° C, and the temperature of the casting roller 16 was set at 20 °C. The evaluation results of the obtained propylene-based resin film are shown in Table 2. [Example 2] The surface of the elastic roller was formed of a material containing the same cerium oxide as in Example 1, and an elastic roller having a surface roughness Ra of 〇.〇9//m was used. In the same manner, a propylene resin film was obtained. The results are shown in Table 1.
[比較例U 作爲彈性輥，使用表面具有硬質鍍鉻的薄金屬外筒 14b的輥。該彈性輕於表面不具有由材料（1)所構成之部 分。該彈性輥之表面粗度Ra爲O.OSym。使用該彈性輥 以外’其餘係與實施例1同樣做法而得到丙烯系樹脂薄膜 。結果表示於表1中。又，與實施例1同樣地實施彈性輥 表面之X P S分析。結果表示於表1中。顯示源自於砂化合 -21 - 201242753 物的Si Ox ( X = 2 )之譜峯係不存在。 [比較例2 ] 作爲彈性輥，使用表面具有硬質鍍鉻的薄金屬外筒 14b的輥。該彈性輥係於表面不具有由材料（1)所構成之 部分。該彈性輥之Ra爲〇.〇8 μ m。使用該彈性輥以外， 其餘係與實施例1同樣做法而得到丙烯系樹脂薄膜。結果 表示於表1中。 [比較例3 ] 作爲彈性輥而言’於表面爲硬質鍍鉻之薄金屬外筒 14b的表面全體’形成由含有二氧化砍的材料（EDI公司 製Ultra Chromium II)所構成的層之輥。該彈性輥之表面 粗度Ra爲0.02 μ m。使用該彈性輥以外，其餘係與實施 例1同樣做法而得到丙烯系樹脂薄膜。結果表示於表！中 〇 實施例1〜2及比較例1〜3之任一者均相位差値爲 3 5 nm以下，配向少，且良好。又，相位差均—性任—者 均小’且爲良好「〇」。即使在透明性中，全H A Z E爲優 異達0.4%以下。使用未形成含有半金屬氧化物之材料的 金屬彈性輥的比較例1及比較例2、以及使用表面粗度Ra 小之金屬彈性輥的比較例3中，係局部產生缺陷。另外， 在實施例1中係有於1處產生，但幾乎不發生。在實施例 2中局部性缺陷完全未發生，薄膜整體均可作爲製品。 -22- 201242753 [表i][Comparative Example U As the elastic roller, a roller having a thin metal outer cylinder 14b having a hard chrome plating on its surface was used. This elasticity is lighter than the surface does not have a portion composed of the material (1). The surface roughness Ra of the elastic roller was O.OSym. A propylene-based resin film was obtained in the same manner as in Example 1 except that the elastic roller was used. The results are shown in Table 1. Further, XPS analysis of the surface of the elastic roller was carried out in the same manner as in Example 1. The results are shown in Table 1. It is shown that the peak of Si Ox ( X = 2 ) derived from the sand compound -21 - 201242753 does not exist. [Comparative Example 2] As the elastic roller, a roller having a thin metal outer cylinder 14b having a hard chrome plating on its surface was used. The elastic roller is attached to the surface without a portion composed of the material (1). The elastic roller has a Ra of 〇.〇8 μm. A propylene-based resin film was obtained in the same manner as in Example 1 except that the elastic roller was used. The results are shown in Table 1. [Comparative Example 3] As the elastic roller, a roll of a layer composed of a material containing a oxidized chopping material (Ultra Chromium II manufactured by EDI Co., Ltd.) was formed on the entire surface of the thin metal outer tube 14b having a hard chrome plating surface. The elastic roller had a surface roughness Ra of 0.02 μm. A propylene-based resin film was obtained in the same manner as in Example 1 except that the elastic roller was used. The results are shown in the table! In any of Examples 1 to 2 and Comparative Examples 1 to 3, the phase difference 値 was 35 nm or less, and the alignment was small and good. Moreover, the phase difference is always - the sex is small - and is good "〇". Even in transparency, the total H A Z E is preferably 0.4% or less. In Comparative Example 1 and Comparative Example 2 in which a metal elastic roller which does not form a material containing a semimetal oxide was used, and Comparative Example 3 in which a metal elastic roller having a small surface roughness Ra was used, defects were locally generated. Further, in Example 1, it was produced at one place, but hardly occurred. In Example 2, the local defects did not occur at all, and the entire film could be used as a product. -22- 201242753 [Table i]
實施例1 實施例2 比較例1 比較例2 比較例3 輥規格 表面材質 二氧化矽 二氧化矽 絡 鉻 二氧化矽 表面粗度Ra 0.05 β m 0.09# m 0.03 β m 0.08 jU m 0.02 μ m 評估 局部性缺陷 1 0 >20 10 >20 相位差R0 35 35 33 35 33 相位差不均 〇 〇 〇 〇 〇 透明性 0.2 0.2 0.4 0.2 0.2 綜合評估| 〇 ◎ X X XExample 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Roll specification surface material ceria cerium oxide cerium ceria cerium oxide surface roughness Ra 0.05 β m 0.09# m 0.03 β m 0.08 jU m 0.02 μ m evaluation Local defect 1 0 >20 10 >20 Phase difference R0 35 35 33 35 33 Uneven phase difference 〇〇〇〇〇Transparency 0.2 0.2 0.4 0.2 0.2 Comprehensive evaluation | 〇◎ XXX
[表2] 光電子 a施例1 比較例1 推定蹄屬 表面材質：二氧化矽 表面材質：路 鍵結能量 狀態比率 鍵結能量 狀態比率 Cls*' 284.6 31.5 284.6 59.7 C-C. C-H 286.0 4.9 286.0 8.2 C-0 288.6 3.7 288.5 3.9 0=0, 0-0=：0 013s52 530.3 8.6 530.3 9.8 金屬-〇 532.2 31.9 531.7 13.6 Si-O, C-O. C=0. 金屬-OH Si2p*J 102.7 14.1 - Si化合物 Cr2p 3/2*4 573.6 1.8 573.7 1 Cr 575,6 2.8 575.8 2.7 Cr20s 577.2 577.3 Cr(0H)3. CrOOH Zn2p 3/2*5 1021.7 (0.3) 1021.7 (0.9) Zn化合物 Ba3d 5/2*® 780.1 (0.4) 780.0 (0.2) Ba化合物 ※l :依據從試料中之Cls電子準位所放出之光電子譜峯的分析結果。 ※之：依據從試料中之Ols電子準位所放出之光電子譜峯的分析結果。 ※:3 :依據從試料中之Si2p電子準位所放出之光電子譜峯的分析結果。 ※斗：依據從試料中之Cr2p 3Q電子準位所放出之光電子譜峯的分析結果。 ※亏：依據從試料中之Zn2p 3/2電子準位所放出之光電子譜峯的分析結果。 ※6 :依據從試料中之Ba3d 5/2電子準位所放出之光電子譜峯的分析結果。 【圖式簡單說明】 圖1係表示製造本發明之光學薄膜的方法中所使用之 較佳的設備配置之一例的圖。 -23- 201242753 【主要元件符號說明】 10 :擠出機 1 2 : T模頭 1 2 a :吐出口 1 4 :彈性輥 14a :金屬內筒 14b :薄金屬外筒 14c :流體軸筒 1 6 :澆鑄輥 1 8 :冷卻輥 Η :空氣間隙 F :薄膜 14d :由材料（1 )所形成之部分 -24-[Table 2] Photoelectron a Example 1 Comparative Example 1 Presumed hoof surface material: cerium oxide surface material: road bonding energy state ratio bonding energy state ratio Cls*' 284.6 31.5 284.6 59.7 CC. CH 286.0 4.9 286.0 8.2 C -0 288.6 3.7 288.5 3.9 0=0, 0-0=:0 013s52 530.3 8.6 530.3 9.8 Metal-〇532.2 31.9 531.7 13.6 Si-O, CO. C=0. Metal-OH Si2p*J 102.7 14.1 - Si compound Cr2p 3/2*4 573.6 1.8 573.7 1 Cr 575,6 2.8 575.8 2.7 Cr20s 577.2 577.3 Cr(0H)3. CrOOH Zn2p 3/2*5 1021.7 (0.3) 1021.7 (0.9) Zn compound Ba3d 5/2*® 780.1 ( 0.4) 780.0 (0.2) Ba compound *l : Analysis result of photoelectron peaks emitted from the Cls electron level in the sample. ※: Based on the analysis results of the photoelectron peaks emitted from the Ols electron level in the sample. *:3: Based on the analysis results of the photoelectron peaks emitted from the Si2p electron level in the sample. * Bucket: Based on the analysis results of the photoelectron peaks emitted from the Cr2p 3Q electronic level in the sample. ※ Loss: Based on the analysis results of the photoelectron peaks emitted from the Zn2p 3/2 electron level in the sample. *6: Based on the analysis results of the photoelectron peaks emitted from the Ba3d 5/2 electron level in the sample. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a preferred apparatus configuration used in a method of producing an optical film of the present invention. -23- 201242753 [Explanation of main component symbols] 10 : Extruder 1 2 : T die 1 2 a : Exhaust port 1 4 : Elastic roller 14a : Metal inner cylinder 14b : Thin metal outer cylinder 14c : Fluid shaft cylinder 1 6 : casting roll 1 8 : cooling roll Η : air gap F : film 14d : part formed by material (1 ) - 24 -