201120121 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種光學成形體用樹脂組合物及其光學成 形體。 【先前技術】 於液晶顯示器顯示元件、電致發光元件等中，係使用控 制光學異向性之光學成形體。 光學用成形體有很多種類。例如有光學膜。作為光學膜 之一，有用作補償液晶顯示器之液晶之相位差、或者提昇 視角之稱為相位差膜之膜。 作為該等技術有如下者。 [專利文獻1 ]日本專利特開2002-040258號公報 [專利文獻2]曰本專利特開2〇〇5_2923 1 1號公報 [專利文獻3]曰本專利特開2008-094912號公報 【發明内容】 本發明係提供一種新穎的光學成形體用樹脂組合物及其 光學成形體。 本發明係將以下内容作為主旨。 (1) 一種光學成形體用樹脂組合物，其係含有以下物質 而成： (i)本乙稀-馬來酿亞胺系共聚物（A) 20〜50質量％，其含 有苯乙烯系單體單元45〜70質量％、馬來醯亞胺系單體單 元30〜55質量％及不飽和二羧酸酐單體單元〇〜5質量❶/〇，且 殘留馬來醯亞胺系單體量為300 ppm以下，及 150156.doc 201120121 (ii)苯乙烯-丙烯腈系共聚物（B) 50〜80質量。/。，其含有苯 乙烯系單體單元70〜84質量％、丙烯腈系單體單元丨6〜3 〇質 量％。 ，（2)如（1)之光學成形體用樹脂組合物，其中笨乙稀_馬來 醢亞胺系共聚物（A)係藉由以下方式獲得：於以苯乙稀系 單體之總量與不飽和二羧酸酐之總添加量之一部分為主體 之混合液中，分割或連續地添加不飽和二羧酸針之總添加 量之剩餘部分，同時使之聚合而獲得苯乙烯·不飽和二羧 酸酐系共聚物’再利用一級胺將所得之苯乙烯-不飽和二 幾酸酐系共聚物醯亞胺化》 (3) 如（2)之光學成形體用樹脂組合物，其中笨乙婦·不飽 和二羧酸酐系共聚物係於非聚合性溶劑中藉由溶液聚合而 獲得。 (4) 如（1)〜(3)中任一項之光學成形體用樹脂組合物，其 中苯乙烯-丙烯腈系共聚物（B)係藉由塊狀聚合或者溶液聚 合而獲得。 (5) —種光學成形體，其包含如（1)〜(4)中任一項之光學 成形體用樹脂組合物。 (6) 如（5)之光學成形體，其係熔融擠出膜。 (7) 如（6)之光學成形體，其係延伸膜。 (8) 如（7)之光學成形體，其係相位差膜。 此處’「光學成形體用樹脂組合物」係指可用於射出成 形體、片材、膜等公知成形體之製造的組合物。使膜成形 之方法並無特㈣制，但較佳為使用膜擠出機進行炫融擠 150156.doc 201120121 出之方法。 又’所謂「光學成形體」，係指導光板、擴散片材、相 位差膜、抗反射膜、偏光元件保護膜等光學用途所使用之 成形體’所5胃「炼融擠出胺 _ 、」，係心藉由熔融擠出而成形 之膜。 本發明之光學絲體用樹脂組合物因透明性m 熱穩定性、及色相良好’故而對光學成形體有用。又，包 含本發明之光學成形體用榭护知人& ^ 肢用树月曰組合物之熔融擠出膜對薄型 液晶顯示元件用之光學膜右用 予犋有用，尤其是經延伸之膜因顯示 負的配向雙折射性，且相位葚矣 作仅差表現性優異，故而對相位差 膜有用。 【實施方式】 <用語之說明> 於本申請案說明書中，「〜」之記號係指「以上」及「以 下」。例如「A〜B」之記载，係指八以上且_下。 以下，對本發明之實施形態進行說明。 <光學成形體用樹脂組合物> 本實施形態係關於一種含有笨乙烯馬來醯亞胺系共聚 物⑷與丙烯腈.苯乙稀系共聚物（B)而成之光學成形體用樹 脂組合物。以下’依序對苯乙烯_馬來醯亞胺系共聚物 (A)、丙烯腈-苯乙烯系共聚物（B)進行說明，其次，對含有 a亥等之光學成形體用樹脂組合物及其光學成形體進行說 明。 [苯乙稀-馬來酸亞胺系共聚物（A)] 150156.doc 201120121 苯乙烯馬來醯亞胺系共聚物⑷含有苯乙婦系單體與馬 來酿亞胺系單體，進而可任意地含有不飽和二叛酸料體 及其他可共聚合之乙烯系單體。 <苯乙稀系單體> 作為苯乙㈣單體’並無特別限定，可使用任意之公知 苯乙烯系單體，就易獲得性等觀點而言，可列舉：苯乙 烯、α-甲基苯乙烯、_甲基苯乙烯、μ甲基苯乙烯、對甲 基苯乙烯、第三丁基苯乙烯、氯苯己烯等苯乙烯系單體， 該等中就相溶性之觀點而言，尤佳為苯乙烯。又，該等苯 乙烯糸單體亦可為2種以上之混合。 <馬來醯亞胺系單體> 作為馬來醯亞胺系單體，並無特別限定，可使用任意之 公知馬來醯亞胺系單體，就易獲得性、耐熱賦予效果等觀 點而言，例如可列舉：Ν_曱基馬來醯亞胺、Ν_ 丁基馬來醯 亞胺、Ν-環己基馬來醯亞胺等N —烷基馬來醯亞胺，及N—苯 基馬來醯亞胺、Ν-氣苯基馬來醯亞胺、Ν_曱苯基馬來醯亞 胺、Ν-曱氧苯基馬來醯亞胺、N —三溴苯基馬來醯亞胺等Ν_ 芳基馬來酸亞胺等馬來醯亞胺系單體，該等中就耐熱賦予 效果之觀點而言’尤佳為Ν-環己基馬來醯亞胺、Ν-苯基馬 來酿亞胺》又’該等馬來醯亞胺系單體亦可為2種以上之 混合。 <不飽和二羧酸酐單體> 作為不飽和二羧酸酐單體，可列舉馬來酸、衣康酸、擰 康酸、烏頭酸等之酸酐，就與苯乙烯__丙烯腈系共聚物 150156.doc 201120121 之相溶性之觀點而言，尤佳為馬來酸酐。又，該等不飽和 一致酸Sf單體亦可為2種以上之混合。 〈其他可共聚合之乙烯系單體> 苯乙烯-馬來醯亞胺系共聚物（A)中，可含有未達5質量％ 之可共聚合之乙烯系單體單元，例如：丙烯腈、曱基丙烯 腈、丙烯酸、丙烯酸甲酯、丙烯酸乙酯 '丙烯酸正丁酯、 丙烯酸2-乙基己酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基 丙烯酸乙酯、曱基丙烯酸正丁酯、甲基丙烯酸2_乙基己酯 等之單體單元。若該等乙烯系單體單元未達5質量％，則 不會損害本案發明之效果。 〈苯乙烯-馬來醯亞胺系共聚物（A)之構成比> 苯乙烯-馬來醯亞胺系共聚物之構成比為：苯乙烯系 單體單元為45〜70質量％，馬來醯亞胺系單體單元為3〇〜55 質量％、不飽和二羧酸酐單體單元為〇〜5質量％ ;較佳為苯 乙稀系單體單元為50〜60質量。/〇，馬來醯亞胺系單體單元 為40〜50質量％，不飽和二羧酸酐單體單元為〇〜25質量 %。 若苯乙烯系單體單元為45質量％以上或馬來醯亞胺系單 體單元為5 5質量％以下，則熔融黏度不會變得過高，可良 好地保持與本實施形態之苯乙烯_丙烯腈系共聚物（B)之混 練性，因此可抑制未熔融顆粒之產生。 若苯乙烯系單體單元為7 0質量％以下或馬來醯亞胺系單 體單元為3 0質量°/〇以上，則可充分地確保透明性。 又’不飽和二羧酸酐單體單元係任意調配成分。藉由於 150156.doc 201120121 苯乙烯-馬來醯亞胺系共聚物中調配不飽和二羧酸酐單體 單元，有時會提昇相溶性。若不飽和二羧酸酐單體單元為 5質量％以下’則可良好地保持熱穩定性。 苯0烯_馬來醯亞胺系共聚物（A)中所含之殘留馬來醯亞 胺系單體量為300 ppm以下’較佳為250 ppm以下，更佳為 200 ppm以下。若該殘留馬來醯亞胺系單體量為3〇〇 ppm以 下’則可良好地維持色相，故而較佳。 再者，本乙婦-馬來醯亞胺糸共聚物（A)中所含之殘留馬 來醯亞胺系單體量係於下述記載之測定條件下進行測定。 裝置名：GC-2010(島津製作所製造） 管柱：毛細管柱DB-5MS(苯基丙二烯聚合物）[2011] The invention relates to a resin composition for an optical molded body and an optical molded body thereof. [Prior Art] In a liquid crystal display display element, an electroluminescence element, or the like, an optical molded body that controls optical anisotropy is used. There are many types of molded bodies for optics. For example, there is an optical film. As one of the optical films, there is a film called a retardation film which serves to compensate the phase difference of the liquid crystal of the liquid crystal display or to enhance the viewing angle. As such technologies, there are the following. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-040258 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. 2008-094912. The present invention provides a novel resin composition for an optical molded body and an optical molded body thereof. The present invention is based on the following. (1) A resin composition for an optical molded article, which comprises the following materials: (i) the ethylidene-maleimide copolymer (A) 20 to 50% by mass, which contains a styrene-based single 45 to 70% by mass of the bulk unit, 30 to 55% by mass of the maleimide monomer unit, and 〇5 to 5 mass% of the unsaturated dicarboxylic anhydride monomer unit, and the residual maleimide monomer amount It is 300 ppm or less, and 150156.doc 201120121 (ii) styrene-acrylonitrile copolymer (B) 50 to 80 mass. /. Further, it contains 70 to 84% by mass of the styrene monomer unit and acrylonitrile monomer unit 丨6 to 3% by mass. (2) The resin composition for an optical molded body according to (1), wherein the stupid ethylene-maleimide copolymer (A) is obtained by the following method: In the mixture of the amount of the total amount of the unsaturated and the dicarboxylic anhydride, the remainder of the total addition amount of the unsaturated dicarboxylic acid needle is divided or continuously added, and the styrene·unsaturated is obtained by polymerization. The carboxylic acid-forming resin composition of the (2), wherein the styrene-unsaturated bis-acid anhydride-based copolymer is imidized by the use of a primary amine, (2) The unsaturated dicarboxylic anhydride-based copolymer is obtained by solution polymerization in a non-polymerizable solvent. (4) The resin composition for an optical molded article according to any one of (1) to (3) wherein the styrene-acrylonitrile-based copolymer (B) is obtained by bulk polymerization or solution polymerization. (5) An optical molded article comprising the resin composition for an optical molded article according to any one of (1) to (4). (6) The optical molded body of (5) which is a melt extruded film. (7) The optical molded body of (6), which is a stretched film. (8) The optical molded body according to (7), which is a retardation film. Here, the "resin composition for optical molded body" means a composition which can be used for the production of a known molded body such as an injection molded article, a sheet, or a film. The method of forming the film is not specifically (four), but it is preferably a method of using a film extruder for squeezing and extruding 150156.doc 201120121. In addition, the "optical molded body" is a molded article used for optical applications such as a light plate, a diffusion sheet, a retardation film, an antireflection film, and a polarizing element protective film. a film formed by melt extrusion. The resin composition for an optical filament of the present invention is useful for an optical molded article because of its transparency m, thermal stability, and good hue. Further, the melt-extruded film containing the composition for the optical molded article of the present invention is useful for the right-handed optical film for a thin liquid crystal display device, particularly an extended film. The negative alignment birefringence is exhibited, and the phase contrast is excellent only in poor performance, and thus is useful for the retardation film. [Embodiment] <Description of Terms> In the specification of the present application, the symbol "~" means "above" and "below". For example, the description of "A to B" means eight or more and _ lower. Hereinafter, embodiments of the present invention will be described. <Resin Composition for Optical Molding Body> The present embodiment relates to a resin for an optical molded body comprising a stupid ethylene maleimide copolymer (4) and an acrylonitrile-styrene copolymer (B). combination. In the following, the styrene-maleimide-based copolymer (A) and the acrylonitrile-styrene-based copolymer (B) will be described in the following, and the resin composition for an optical molded article containing a hai and the like will be described. The optical molded body will be described. [Phenylethylene-maleic acid imide copolymer (A)] 150156.doc 201120121 The styrene maleic imine copolymer (4) contains a styrene monomer and a maleimide monomer, and further The unsaturated dioxonic acid material and other copolymerizable vinyl monomers may be optionally contained. <Phenylethylene monomer> The styrene (tetra) monomer is not particularly limited, and any known styrene monomer can be used. From the viewpoints of availability, etc., styrene, α- a styrene monomer such as methyl styrene, _methyl styrene, μ methyl styrene, p-methyl styrene, t-butyl styrene or chlorohexene, and the viewpoint of compatibility In particular, it is styrene. Further, these styrene fluorene monomers may be a mixture of two or more kinds. <Malayimide-based monomer> The maleic imine monomer is not particularly limited, and any known maleimide-based monomer can be used, and the availability and heat-resistant effect can be obtained. From the viewpoints, for example, N-alkylmaleimide such as Ν_曱-male-imine, Ν-butyl-maleimide, fluorene-cyclohexylmaleimine, and N- Phenyl maleimide, Ν-gas phenyl maleimide, Ν_曱 phenyl maleimide, Ν-曱 oxyphenyl maleimide, N-tribromophenyl mala A quinone imine or the like, a maleimide monomer such as an aryl maleimide, and in view of the effect of imparting heat resistance, 'espeth is Ν-cyclohexylmaleimide, Ν-benzene. Kamalyimine and "Malmaronimide monomers" may be a mixture of two or more. <Unsaturated dicarboxylic anhydride monomer> Examples of the unsaturated dicarboxylic anhydride monomer include an acid anhydride such as maleic acid, itaconic acid, tococanic acid or aconitic acid, which is copolymerized with styrene-acrylonitrile. From the viewpoint of the compatibility of the product 150156.doc 201120121, it is particularly preferred to be maleic anhydride. Further, these unsaturated acid Sf monomers may be a mixture of two or more kinds. <Other copolymerizable vinyl monomer> The styrene-maleimide copolymer (A) may contain less than 5% by mass of a copolymerizable vinyl monomer unit, for example, acrylonitrile. , mercapto acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate 'n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, decyl acrylate A monomer unit such as an ester or 2-ethylhexyl methacrylate. If the vinyl monomer unit is less than 5% by mass, the effects of the present invention are not impaired. <Composition ratio of styrene-maleimide copolymer (A)> The composition ratio of the styrene-maleimide copolymer is 45 to 70% by mass of the styrene monomer unit, and the horse The quinone imine monomer unit is from 3 to 55% by mass, the unsaturated dicarboxylic anhydride monomer unit is from 5% to 5% by mass, and the styrene monomer unit is preferably from 50 to 60% by mass. /〇, the maleimide monomer unit is 40 to 50% by mass, and the unsaturated dicarboxylic anhydride monomer unit is 〇255% by mass. When the styrene monomer unit is 45 mass% or more or the maleic imine monomer unit is 55 mass% or less, the melt viscosity does not become excessively high, and the styrene of the embodiment can be favorably maintained. The kneading property of the acrylonitrile-based copolymer (B) can suppress the generation of unmelted particles. When the styrene monomer unit is 70% by mass or less or the maleic imine monomer unit is 30% by mass or more, transparency can be sufficiently ensured. Further, the unsaturated dicarboxylic anhydride monomer unit is optionally formulated. By dissolving the unsaturated dicarboxylic anhydride monomer unit in the styrene-maleimide copolymer of 150156.doc 201120121, the compatibility is sometimes improved. When the unsaturated dicarboxylic anhydride monomer unit is 5% by mass or less, the thermal stability can be favorably maintained. The amount of the residual maleimide-based monomer contained in the benzoene-maleimide-based copolymer (A) is 300 ppm or less', preferably 250 ppm or less, more preferably 200 ppm or less. If the amount of the residual maleimide monomer is 3 〇〇 ppm or less, the hue can be favorably maintained, which is preferable. Further, the amount of the residual maleimide monomer contained in the present invention is as follows under the measurement conditions described below. Device name: GC-2010 (manufactured by Shimadzu Corporation) Column: capillary column DB-5MS (phenyl propylene diene polymer)
溫度：注入口 280。(：、檢測器280°C 於管柱溫度80°C (初期）下進行升溫分析。 (升溫分析條件）80°C :保持12分鐘 80〜280°C :以2(TC/分鐘升溫10分鐘 280°C :保持10分鐘 檢測器：FID(Flame Ionization Detector，火焰游離偵測器） 流程：將試樣〇·5 g溶解於含十一烷（内標物質）之丨，2· 一氣乙烧溶液（0.014 g/L)5 ml中。其後，加入正己烷5 ml 並利用振盪器振盪10〜15分鐘’使之析出。於使聚合物析 出、沈澱之狀態下，僅將上清液注入GC中。使用由内標 物質所求出之係數’由所得之馬來醯亞胺系單體之峰面積 算出定量值。 <苯乙烯-馬來醯亞胺系共聚物（A)之製造方法> 150156.doc 201120121 苯乙烯-馬來醯亞胺系共聚物之聚合方式並無特別限 定，例如可藉由溶液聚合、塊狀聚合等公知方法進行製 造，就可藉由-邊進行分割添加等一邊進行聚合而獲得共 聚組成更均勾之所期望之苯乙婦-馬來酿亞胺系共聚物二 觀點而言’更佳為溶液聚合。又，苯乙烯·馬來醯亞胺系 共聚物之溶液聚合所使用之溶劑，就不易產生副產物、不 良影響較小之觀點而言，較佳為非聚合性。進而，苯乙 烯-馬來醯亞胺系共聚物之聚合製程可為批次式聚合法、 半批次式聚合法、連續聚合法之任意方式。 苯乙烯-馬來醯亞胺系共聚物之聚合方法並無特別限 定，就可藉由簡潔之製程而高生產率地製造之觀點而言， 較佳為藉由自由基聚合而獲得。x ’作為苯乙婦馬來酿 亞胺系共聚物之聚合反應中所使用之聚合 別限定，綱得性、容易進行反應控制等觀；；而：:： 如可使用：偶氮二異丁腈、偶氮二環己甲_、偶氮二甲丙 腈、偶氮二曱丁腈等公知偶氣化合物，或過氧化苯甲醯、 過氧化苯甲酸第三丁 S旨、u•二（第三丁基過氧基）_3,3,5-三 甲基環己烷、過氧化異丙基碳酸第三丁酯' 過氧化(2_乙基 己酸)第三丁自旨 '過氧化二第三丁基、過氧化二異丙苯、 3,3-二（第三丁基過氧化基）丁酸乙酯等公知有機過氧化 物。該等聚合起始劑亦可併用2種以上。又，就聚合之反 應速度及聚合率控制之觀點而言，較佳為使用先前之苯乙 稀系樹脂之製造中常用者，例如1()小時半衰期溫度為 70〜120C之偶氮化合物或有機過氧化物。 150156.doc 201120121 該等聚合起始劑之用量並無特別限定，較佳為相對於全 部單體單元100質量份而使用0.1〜1.5質量份， 尺佳為 0.1〜1.0質量份。若該等聚合起始劑之用量為01質量^以 上，則可獲得充分之聚合速度，故而較佳。另一方面，4 該等聚合起始劑之用量控制為1 ·5質量份以下，則可抑制 聚合速度’故而反應控制變得容易’獲得苯乙烯_馬來酿 亞胺系共聚物之目標分子量變得簡單。 於苯乙稀-馬來酿亞胺系共聚物之製4中，彳使用鍵轉 移劑《作為所使用之鏈轉移劑’並無特別限定，就易拼得 性、分子量控制之簡便性等觀點而言，例如可使用：正十 二硫醇、第三（十二烷基）硫醇或2,4-二苯基甲基_丨_戊烯 等公知鏈轉移劑。該等鏈轉移劑之用量，只要為可獲得苯 乙稀-馬來酿亞胺系共聚物之目標分子量之範圍，貝特 別限定，較佳為相對於全部單體單元1〇〇質量份而使用 (Μ〜0.8質量份’更佳為(Μ5〜〇.5質4份。若該等鏈轉移劑 之用量為(Μ質量份以上且0.8質量份以下’則可容易地獲 得苯乙稀-馬來酿亞胺系共聚物之目標分子量。 作為苯乙烯-馬來醯亞胺系共聚物之溶液聚合中所使用 之非聚合性溶劑之種類，並無特別限定，就易獲得性、共 聚物之溶解性等觀點而·τ，例如有丙_、甲基乙基嗣、甲 基異丁基m酮等，類，四氫^南、m•二哼烧等醚 類，苯、甲苯、二甲苯、氣笨等芳香族烴，心二甲基甲 醯胺' 二甲基㈣、Ν·甲基n錢酮等溶劑，就於笨 乙稀-馬來醯亞胺系共聚物之脱揮回收時除去溶劑之容易 150156.doc • 10- 201120121 性方面而言，尤佳為甲基乙基酮、曱基異丁基酮。 此處，作為馬來醯亞胺單體單元之導入方法，有將馬來 醯亞胺系單體與苯乙稀系單體共聚合之方法（直接法广或 者預先將不飽和二羧酸酐與苯乙烯系單體共聚合，進而利 用-級胺使不飽和：基發生反應，藉此將不飽和二 羧酸奸基轉化為馬來酿亞胺單體單元的方法（後酿亞胺化 法）。後醯亞胺化法因共聚物中之殘留馬來醯亞胺系單體 量變少，故而較佳。 作為後醯亞胺化法中所使用之一級胺並無特別限定，就 易獲得性之觀點而言，例如可列舉曱胺、乙胺、正丙胺、 異丙胺、正丁胺、正戊胺、正己胺、正辛胺、環己胺、癸 胺等烷基胺類及氯或溴取代烷基胺，苯胺、甲苯胺、萘胺 等芳香族胺，就耐熱賦予性、反應性、操作簡便等觀點而 ° 該專中尤佳為本胺、環己胺。又，該等一級胺既可單 獨使用，亦可併用2種以上。再者，該等一級胺之添加量 並無特別限定，相對於不飽和二羧酸酐基較佳為〇7〜丨· i莫 耳當量，更佳為〇·85〜1_〇5莫耳當量。若該等一級胺之添加 Ϊ：為0.7莫耳當量或0 85莫耳當量以上，則可將苯乙烯-馬 來醯亞胺系共聚物中之不飽和二羧酸酐單體單元抑制為i 〇 質量％以下，維持良好之熱穩定性。又，若為丨丨莫耳當量 或1.05莫耳當量以下，則苯乙烯_馬來醯亞胺系共聚物中所 殘留之一級胺量變少，故而較佳。 於藉由後醯亞胺化法導入馬來醯亞胺單體單元時，一級 胺與不飽和二羧酸酐基之反應，尤其是_不飽和二羧酸酐 150I56.doc •】1 _ 201120121 基轉化為馬來酿亞胺基之反應中，為了提高脫水閉環反應 可視需要使用觸媒。觸媒之種類並無特別限定，例如可使 用二級胺。作為三級胺並無特別限定，例如可列舉.二甲 胺、三乙胺、三丙胺、三丁胺、N，N-二曱基苯胺、队沁二 乙基苯胺等。 二級胺之添加量並無特別限定，就提高生產率之觀點而 言，較佳為相對於不飽和二羧酸酐基而為〇〇1莫耳當量以 上。 本實施形態之醯亞胺化反應之溫度較佳為1 〇〇〜25〇t， 更佳為120〜200°C。若該醯亞胺化反應之溫度為1〇〇t>c以 上’則會使反應速度提昇，故而直至反應完畢無需長時 間，於生產率方面較佳。另一方面，於將該醯亞胺化反應 之溫度抑制為250。(：以下之情形時，不易發生由苯乙烯·馬 來醯亞胺系共聚物之加熱劣化所引起之物性低下，故而較 佳。 於藉由後酿亞胺化法進行聚合之情形時，亦可於聚合初 期添加不飽和二羧酸酐與苯乙烯系單體之總量而進行聚 合，但由於不飽和二羧酸酐與苯乙烯系單體交替共聚性較 強’故而於聚合初期會生成具有不飽和二羧酸酐與苯乙稀 系單體之莫耳比為1 : 1之組成的交替共聚物。為了獲得所 期望之苯乙烯-馬來醯亞胺系共聚物之構成單元，需要添 加高於不飽和二羧酸酐之莫耳比的苯乙烯系單體，因此於 初期添加總量而進行聚合之情形時，於聚合後期變得容易 生成笨乙稀系單體單元較多之共聚物，其結果為組成分佈 150156.doc 201120121 企大。為了獲得組成分佈較小之共聚物’較佳為於聚合初 期添加苯乙烯系單體之總量與不飽和二羧酸酐之總添加量 之一部分，分割或連續地添加不飽和二羧酸酐之總添加量 之剩餘部分，同時使之聚合。不飽和二羧酸酐於聚合初期 之添加量與分割或連續添加之量的比率較佳為 5/95〜50/50，更佳為10/90〜25/75。若不飽和二羧酸酐於聚 合初期之添加量與分割或連續添加之量的比率於該等範圍 内’則可獲得組成分佈較小之苯乙烯_馬來醯亞胺系共聚 物。 聚合之反應速度與聚合率之控制，可藉由聚合溫度、聚 合時間、聚合起始劑量、單體之添加速度等進行控制。由 於本乙烯-馬來醯亞胺系共聚物之殘留馬來醯亞胺系單體 罝為300 ppm以下，故而較佳為以於直接法中馬來醯亞胺 系單體之聚合率成為99.9%以上，於後醯亞胺化法中不飽 和一缓酸酐之聚合率成為99.9%以上之方式調整適合條 件。例如，於為後醯亞胺化法之情形時，初期之聚合溫度 較佳為80〜11(TC，於聚合後期為了提高聚合率，聚合溫度 較佳為設為iHTCMSOt。又，不飽和二羧酸之添加速 度，較佳為调整為於苯乙烯系單體之聚合率成為8 〇〜9 5% 之時刻添加完畢。進而，藉由調整聚合時間、聚合起始劑 里，可使不飽和二羧酸酐之聚合率成為99 9%以上。此 外，於苯乙烯-馬來醯亞胺系共聚物中之殘留馬來醯亞胺 系單體量為300 PPm以下（相當於聚合率為99 9%以上）之情 形時，可獲得色相優異之馬來醯亞胺系共聚物，又，使用 150156.doc 201120121 該聚合物所得之光學成形體用樹脂組合物亦可獲得色相良 好者。 並且，除去聚合所用之非聚合性之溶劑或未反應之單體 等揮發成分的方法並無特別限定，可利用公知方法，作為 可在工業規模上採用之方法，較佳為利用排氣型螺旋式擠 出機之方法。作為於利用排氣型螺旋式擠出機之情形之脫 揮條件，較佳為樹脂溫度設為31〇〜34〇(>c，且於92 W犯 以下之減壓下進行脫揮。藉由於真空減壓下提高樹脂溫 度非聚合性之溶劑或未反應之單體會變得易於揮發，但 若將樹脂溫度抑制在34〇。。以下，則馬來醯亞胺系共聚物 會因力:熱劣化而難以解聚合，因此馬來醯亞胺系單體量之 殘留:難以增加，&法實現獲得色相優異、料性賦予效 果較问、it而混練性優異之苯乙烯_馬來醯亞胺系共聚物 之目的。再者，樹脂溫度之調整方法，可藉由調整擠出機 之螺桿轉速或料缸溫度而進行。 旦 馬了抑制加熱劣化所致之馬來醯亞胺系單體之產生 —亦可使用自由基捕捉劑。自由基捕捉劑並無特別限 二:列舉：苯㈣化合物、有嶋化合物、有機硫系 獨：：：胺系化合物等抗氧化劑。該等自由基捕捉劑可單 巾可併用2種以上而使用。該等自由基捕捉劑由 於在利用排氣型螺旋式擠 丘 出機而將本乙烯-馬來醯亞胺系 ;:中之揮發性成分脫揮的步驟中會經受顯著之敎歷 耐熱性或熱敎性之化^ 劑，尤佳為具有 口物。例如更佳為1%加熱減量溫 150156.doc 201120121Temperature: Injection port 280. (:, the detector was subjected to temperature rise analysis at a column temperature of 80 ° C (initial) at 280 ° C. (temperature rising analysis conditions) 80 ° C: kept for 12 minutes 80 to 280 ° C: temperature was raised by 2 (TC/min for 10 minutes) 280 ° C: Hold for 10 minutes. Detector: FID (Flame Ionization Detector). Flow: Dissolve sample 〇·5 g in cesium (internal standard substance), 2·1 qi The solution (0.014 g/L) was added in 5 ml. Thereafter, 5 ml of n-hexane was added and shaken by a shaker for 10 to 15 minutes to precipitate. In the state where the polymer was precipitated and precipitated, only the supernatant was injected. In GC, a quantitative value is calculated from the peak area of the obtained maleimide-based monomer using the coefficient determined from the internal standard substance. <Manufacture of styrene-maleimide-based copolymer (A) [Methods] 150156.doc 201120121 The polymerization method of the styrene-maleimide copolymer is not particularly limited, and for example, it can be produced by a known method such as solution polymerization or bulk polymerization, and can be divided by - side Adding the same side to the polymerization to obtain the desired composition of the benzophenone-Malay From the viewpoint of the imine copolymer 2, it is more preferably a solution polymerization. Further, a solvent used for solution polymerization of a styrene-maleimide copolymer is less likely to cause by-products and has less adverse effects. Further, the polymerization process of the styrene-maleimide copolymer may be any one of a batch polymerization method, a semi-batch polymerization method, and a continuous polymerization method. The polymerization method of the maleic imine copolymer is not particularly limited, and it can be preferably produced by radical polymerization from the viewpoint of high productivity by a simple process. x 'as a benzene woman The polymerization used in the polymerization of the maleic amine-based copolymer is not limited, and the reaction is easy to control; and::: If used: azobisisobutyronitrile, azobicyclo a well-known azo compound such as hexamethylene methacrylate, azodicarbonitrile or azobisbutyronitrile, or benzamidine peroxide, benzoic acid benzoic acid, third butyl s, u• bis (t-butylperoxy) Base)_3,3,5-trimethylcyclohexane, isopropyl peroxycarbonate Ester 'peroxide (2-ethylhexanoic acid) third butyl from the purpose of 'dibutyl peroxide, dicumyl peroxide, 3,3-di(t-butylperoxy)butyric acid B A known organic peroxide such as an ester, etc. These polymerization initiators may be used in combination of two or more kinds. Further, in terms of the reaction rate of polymerization and the polymerization rate control, it is preferred to use a conventional styrene resin. A commonly used one, for example, an azo compound or an organic peroxide having an hour half-life temperature of 70 to 120 C. 150156.doc 201120121 The amount of the polymerization initiator to be used is not particularly limited, and is preferably relative to all monomers. The unit is used in an amount of 0.1 to 1.5 parts by mass, and preferably 0.1 to 1.0 part by mass. When the amount of the polymerization initiator is 0.1 mass or more, a sufficient polymerization rate can be obtained, which is preferable. On the other hand, when the amount of the polymerization initiator to be controlled is 1 to 5 parts by mass or less, the polymerization rate can be suppressed, so that the reaction control becomes easy to obtain the target molecular weight of the styrene-maleimide copolymer. It becomes simple. In the production of styrene-maleimide copolymer 4, the use of a bond transfer agent "as a chain transfer agent to be used" is not particularly limited, and the ease of use and the ease of molecular weight control are also considered. For example, a known chain transfer agent such as n-dodecylmercaptan, a third (dodecyl)thiol or 2,4-diphenylmethyl-nonane-pentene can be used. The amount of the chain transfer agent used is particularly limited as long as it is a target molecular weight of the styrene-maleimide copolymer, and is preferably used in an amount of 1 part by mass based on all the monomer units. (Μ~0.8 parts by mass) is more preferably (Μ5~〇.5 mass 4 parts. If the amount of the chain transfer agent is (Μ part by mass or more and 0.8 parts by mass or less), styrene-max can be easily obtained. The target molecular weight of the acryl-based copolymer is not particularly limited as long as it is a non-polymerizable solvent used for solution polymerization of a styrene-maleimide-based copolymer. From the viewpoints of solubility, etc., for example, there are C-type, methyl ethyl hydrazine, methyl isobutyl ketone, etc., and ethers such as tetrahydrogen hydride, m. bismuth hydride, benzene, toluene, xylene, An aromatic hydrocarbon such as a gas, a solvent such as dimethylformamide, dimethyl (tetra) or hydrazine methyl ketone, is removed in the devolatilization of the stupid ethylene-maleimide copolymer. Solvents are easy 150156.doc • 10- 201120121 In terms of sex, it is especially preferred to be methyl ethyl ketone or decyl isobutyl ketone. As a method for introducing a maleimide monomer unit, there is a method of copolymerizing a maleimide monomer and a styrene monomer (direct method or pre-saturation of unsaturated dicarboxylic anhydride and styrene) A method in which a monomer is copolymerized, and then an unsaturated group is reacted with a -amine to thereby convert an unsaturated dicarboxylic acid group into a maleimide monomer unit (post-imidization method). The ruthenium imidization method is preferred because the amount of the residual maleimide-based monomer in the copolymer is small. The monoamine used in the ruthenium imidization method is not particularly limited, and is easily available. From the viewpoints, for example, alkylamines such as decylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, decylamine, and chlorine or bromine may be mentioned. Alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine are preferable in terms of heat resistance, reactivity, and ease of handling. In particular, the amine and the cyclohexylamine are preferred. They may be used singly or in combination of two or more. Further, the amount of the primary amines added is not particularly limited. Preferably, the unsaturated dicarboxylic anhydride group is preferably 〇7~丨·i molar equivalent, more preferably 〇85~1_〇5 molar equivalent. If the primary amine is added Ϊ: 0.7 When the amount of the ear is 0 or more, the unsaturated dicarboxylic anhydride monomer unit in the styrene-maleimide copolymer is suppressed to i 〇 by mass or less to maintain good thermal stability. In the case of the oxime equivalent or 1.05 mol equivalent or less, the amount of the monoamine remaining in the styrene-maleimide copolymer is small, so that it is preferably introduced by the ruthenium imidization method. In the maleimide monomer unit, the reaction of a primary amine with an unsaturated dicarboxylic anhydride group, especially _unsaturated dicarboxylic anhydride 150I56.doc •]1 _ 201120121 The reaction of the base into a maleimine group In order to improve the dehydration ring closure reaction, it is necessary to use a catalyst. The type of the catalyst is not particularly limited, and for example, a secondary amine can be used. The tertiary amine is not particularly limited, and examples thereof include dimethylamine, triethylamine, tripropylamine, tributylamine, N,N-didecylaniline, and quinonediethylaniline. The amount of the secondary amine to be added is not particularly limited, and from the viewpoint of improving productivity, it is preferably 〇〇1 molar equivalent or more with respect to the unsaturated dicarboxylic anhydride group. The temperature of the oxime imidization reaction in the present embodiment is preferably from 1 Torr to 25 Torr, more preferably from 120 to 200 °C. If the temperature of the ruthenium iodide reaction is 1 〇〇t > c or more, the reaction rate is increased, so that it is not necessary to have a long time until the reaction is completed, and it is preferable in terms of productivity. On the other hand, the temperature of the ruthenium iodization reaction was suppressed to 250. (In the case of the following, it is preferable that the physical properties caused by the heating deterioration of the styrene-maleimide-based copolymer are less likely to occur, and it is preferred when the polymerization is carried out by the post-incipient imidization method. The polymerization may be carried out by adding the total amount of the unsaturated dicarboxylic anhydride and the styrene monomer in the initial stage of the polymerization. However, since the unsaturated dicarboxylic anhydride and the styrene monomer have a high degree of copolymerizability, they are formed at the initial stage of polymerization. An alternating copolymer of a saturated dicarboxylic anhydride and a styrene monomer having a molar ratio of 1:1. In order to obtain a desired constituent unit of the styrene-maleimide copolymer, it is necessary to add higher than When the styrene-based monomer having a molar ratio of the unsaturated dicarboxylic anhydride is added to the total amount in the initial stage, it is easy to form a copolymer having a large amount of a stupid ethylene monomer unit in the late stage of polymerization. The result is a composition distribution of 150156.doc 201120121. In order to obtain a copolymer having a small composition distribution, it is preferable to add a part of the total amount of the styrene monomer and the total amount of the unsaturated dicarboxylic anhydride in the initial stage of the polymerization. The remainder of the total addition amount of the unsaturated dicarboxylic anhydride is divided or continuously added while being polymerized. The ratio of the amount of the unsaturated dicarboxylic anhydride added in the initial stage of polymerization to the amount of the divided or continuously added is preferably 5/95~ 50/50, more preferably 10/90 to 25/75. If the ratio of the amount of the unsaturated dicarboxylic anhydride added in the initial stage of polymerization to the amount of the divided or continuously added is within the ranges, the composition distribution is small. Styrene-maleimide copolymer. The reaction rate and polymerization rate of polymerization can be controlled by polymerization temperature, polymerization time, polymerization starting dose, monomer addition rate, etc. Since the residual maleic imine monomer enthalpy of the ruthenium-based copolymer is 300 ppm or less, it is preferred that the polymerization ratio of the maleimide-based monomer in the direct method is 99.9% or more. The suitable conditions are adjusted in such a manner that the polymerization rate of the unsaturated monosodium hydride in the ruthenium imidization method is 99.9% or more. For example, in the case of the ruthenium imidization method, the initial polymerization temperature is preferably 80 to 11 (TC). In order to increase the polymerization rate in the later stage of polymerization, The addition temperature is preferably set to iHTCMSOt. Further, the addition rate of the unsaturated dicarboxylic acid is preferably adjusted so as to be added at a time when the polymerization ratio of the styrene monomer is 8 〇 to 9 5%. When the polymerization time is adjusted and the polymerization initiator is used, the polymerization rate of the unsaturated dicarboxylic anhydride can be 99.9% or more. Further, the residual maleimide in the styrene-maleimide copolymer is single. When the amount is 300 ppm or less (corresponding to a polymerization ratio of 99 9% or more), a maleic imine copolymer excellent in hue can be obtained, and an optical molded body obtained by using the polymer 150156.doc 201120121 can be obtained. A method of obtaining a volatile component such as a non-polymerizable solvent or an unreacted monomer used for polymerization is not particularly limited, and a known method can be used as an industrial scale. The method is preferably a method using an exhaust type screw extruder. In the case of the devolatilization condition in the case of using the exhaust type screw extruder, it is preferable that the resin temperature is 31 〇 to 34 〇 (>c, and the devolatilization is performed under the reduced pressure of 92 W or less. The solvent or the unreacted monomer which raises the resin temperature under vacuum decompression becomes easy to volatilize, but if the resin temperature is suppressed to 34 Å. Below, the maleic amide copolymer will be forced. : It is difficult to depolymerize by heat deterioration, so it is difficult to increase the amount of maleimide-based monomer: & method to obtain styrene which is excellent in hue and imparts effect on the property, and which is excellent in kneading property. The purpose of the ruthenium-based copolymer is to adjust the resin temperature by adjusting the screw speed of the extruder or the temperature of the cylinder. The generation of a monomer - a radical scavenger can also be used. The radical scavenger is not particularly limited to two: exemplified by a benzene (tetra) compound, an anthracene compound, an organic sulfur system: an amine compound, and the like. Base trapping agent can be used in combination of two or more types The radical scavengers are subjected to a significant period in the step of devolatilizing the volatile components in the present ethylene-maleimide system by using a vented spiral extrusion machine. A heat-resistant or heat-resistant chemical, particularly preferably having a mouth. For example, it is preferably 1% heating and reducing the temperature 150156.doc 201120121
度超過300 C之自由基捕捉劑。本實施形態所使用之 基捕捉劑較佳為添加至聚合後之聚合生成物中。若於聚人 前或者聚合過程中添加，則有聚合速度降低之情形。“。 [丙烯腈-苯乙烯系共聚物（B)J 丙烯腈·苯乙烯系 系單體，可進而任意 <丙烯腈系單體> 共聚物（B)含有丙烯腈系單體與苯乙烯 地含有其他可共聚合之乙烯系單體。 作為丙烯腈系單體，並無特別限I可使用任意之公知 丙婦猜系單體，就易獲得性 '相溶性等觀點而f，可列兴 =婦腈、甲基丙烯腈等，該等中尤其就相溶性之觀點而 。較佳為丙烯腈。又’該等丙烯腈系單體亦可為2種以 上之混合。 〈苯乙烯系單體> 作為苯乙婦-丙埽猜系共聚物（b)之苯乙稀系單體，並無 特別限疋，可使用任意之公知苯乙烯系單體，就易獲得 )生與本實把形態之苯乙稀_馬來酿亞胺系共聚物⑷之相 ^生等觀點而t，可列舉苯乙稀、α•甲基苯乙稀、鄰甲基 本乙間甲基苯乙烯、對曱基苯乙烯、第三丁基苯乙 '苯乙稀等笨乙烯系單體’該等中尤其就相溶性之觀 點1^ ^ ’較佳為笨乙烯。又’該等苯乙稀系單體亦可為2 種以上之混合。 〈其他可共聚合之乙烯系單體> —烯丙烯腈系共聚物（Β)中可含有未達5質量％之可共 a之乙烯系單體單元，例如：丙稀酸、丙稀酸甲醋、丙 150156.doc •15· 201120121 烯酸乙酯、丙烯酸正丁酯、丙烯酸2_乙基己酯、甲基丙烯 酸、▼基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁 酯、甲基丙烯酸2-乙基己酯、馬來酸酐等之單體單元。若 該等乙烯系單體單元未達5質量％，則不會損害本案發明 之效果。 <苯乙烯-丙烯腈系共聚物之構成比> 苯乙烯-丙烯腈系共聚物（B)之構成比為：苯乙烯系單體 單元為70〜84質量％，丙烯腈系單體單元為16〜3〇質量％ ; 較佳為苯乙烯系單體為72〜82質量％，丙烯腈系單體為 18〜28質量％。 ~ 右苯乙烯系單體單元為7〇質量％以上或丙烯腈系單體單 元為30質量％以下’則可確保充分之色相。 -若苯乙烯系單體單元為84質量％以下或丙烯腈系單體單 兀為16質量％以i ’則可充分地確保光學成形體之透明 <苯乙烯-丙烯腈系共聚物（B)之製造法> 作為苯乙烯-丙稀腈系共聚物⑻之製造法，可採用公 方法’例如可列舉：使包含苯乙烯系單體、丙烯腈系單; 及可共聚合之乙烯單體的單體混合物共聚合之方法。又 水口方式可利用公知之聚合方法。其中就光學成形體之 明性之觀點而言，較佳為塊狀聚合或溶液聚合，更佳More than 300 C of free radical scavenger. The base scavenger used in the present embodiment is preferably added to the polymerization product after polymerization. If it is added before or during the polymerization, there is a case where the polymerization rate is lowered. "Acrylonitrile-styrene-based copolymer (B) J acrylonitrile-styrene-based monomer, and any <acrylonitrile-based monomer> copolymer (B) contains acrylonitrile-based monomer and benzene In the case of the acrylonitrile-based monomer, there is no particular limitation. I can use any of the well-known known monomers, and it is easy to obtain 'compatibility'. In particular, it is acrylonitrile, and acrylonitrile is preferable. The acrylonitrile-based monomer may be a mixture of two or more kinds. The monomer is a styrene monomer which is a styrene-acrylic copolymer (b), and is not particularly limited, and any known styrene monomer can be used, which is easy to obtain. In view of the fact that the form of styrene-Malay-bromide-based copolymer (4) is related to t, styrene, α-methylstyrene, o-methylbenz-methylstyrene And the stupid vinyl monomer such as decyl styrene and tert-butyl phenethyl styrene. The viewpoint of compatibility in particular is 1 ^ ^ ' is preferably stupid. Ethylene. Further, the styrene monomer may be a mixture of two or more kinds. <Other copolymerizable vinyl monomers> The olefinic acrylic copolymer (Β) may contain less than 5 masses. % of the vinyl monomer units of a, such as: acrylic acid, acetoacetic acid, propyl 150156.doc • 15· 201120121 ethyl enoate, n-butyl acrylate, 2-ethylhexyl acrylate, Monomer units such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride, etc., if such vinyl monomer units When the amount is less than 5% by mass, the effect of the invention of the present invention is not impaired. <Configuration ratio of styrene-acrylonitrile-based copolymer> The composition ratio of the styrene-acrylonitrile-based copolymer (B) is: styrene-based The volume unit is 70 to 84% by mass, and the acrylonitrile monomer unit is 16 to 3% by mass. The styrene monomer is preferably 72 to 82% by mass, and the acrylonitrile monomer is 18 to 28% by mass. ~ The right styrene monomer unit is 7 〇 mass% or more, or the acrylonitrile monomer unit is 30 mass% or less ' In order to ensure a sufficient hue. - If the styrene monomer unit is 84% by mass or less or the acrylonitrile monomer is 16% by mass or more, the transparency of the optical molded body can be sufficiently ensured. Method for producing copolymer (B) As a method for producing the styrene-acrylonitrile-based copolymer (8), a public method can be employed, for example, a styrene-based monomer or an acrylic-based monomer can be used; A method of copolymerizing a monomer mixture of a copolymerized ethylene monomer, and a known polymerization method can be used for the nozzle method, and in view of the clarity of the optical molded body, a bulk polymerization or a solution polymerization is preferred.
狀聚合。 WPolymerization. W
[光學成形體用樹脂組合物] 光干成形體用樹脂組合物包含苯乙烯-馬來醯亞胺系 150156.doc • 16· 201120121 聚物（A)20〜50質量％與苯乙烯-丙烯腈系共聚物（B)50〜80質 量％，較佳為包含笨乙烯-馬來醯亞胺系共聚物（A)25〜45質 量％與苯乙烯-丙烯腈系共聚物（B)55〜75質量％，更佳為包 含苯乙烯-馬來醯亞胺系共聚物（A)27.5〜40質量。/。、苯乙烯- 丙烯腈系共聚物（B)60〜72.5質量0Λ。在該範圍内可獲得良 好之物性。 若苯乙烯-馬來醯亞胺系共聚物為2〇質量％以上、苯 乙烯-丙烯腈系共聚物（Β)為80質量％以下，則可確保充分 之财熱性；若苯乙烯-馬來醯亞胺系共聚物為5〇質量0/〇 以下、苯乙烯-丙烯腈系共聚物（Β)為5〇質量％以上，則可 確保充分之透明性。 作為光學成形體用樹脂組合物之製造方法，只要為可將 苯乙烯-馬來醯亞胺系共聚物（Α)與苯乙烯-丙烯腈系共聚物 (Β)均勻地分散之方法，則無特別限定，可利用公知之混 練方法。例如可列舉使用班布裏混合機、捏合機、單轴或 雙軸擠出機等進行炫融混練之方法，特別是為了獲得美觀 之膜，較佳為使用雙軸擠出機進行熔融混練之方法。 共聚物（Β)之擠出方法 及將笨乙烯-馬來醯亞j 乍為苯乙稀-馬來酿亞胺系共聚物⑷與苯乙稀-丙婦猜系 ’可列舉將總量一並進料之方法，[Resin Composition for Optical Molding Body] The resin composition for a light-drying molded body contains styrene-maleimide 150156.doc • 16· 201120121 Polymer (A) 20 to 50% by mass and styrene-acrylonitrile The copolymer (B) is 50 to 80% by mass, preferably containing a stupid ethylene-maleimide copolymer (A) of 25 to 45 mass% and a styrene-acrylonitrile copolymer (B) 55 to 75. The mass% is more preferably 27.5 to 40 masses including the styrene-maleimide copolymer (A). /. , styrene-acrylonitrile-based copolymer (B) 60 to 72.5 mass 0 Λ. Good physical properties are obtained within this range. When the styrene-maleimide copolymer is 2% by mass or more and the styrene-acrylonitrile copolymer (Β) is 80% by mass or less, sufficient finernity can be ensured; if styrene-Malay When the quinone imine copolymer is 5 Å by mass or less and the styrene-acrylonitrile-based copolymer (Β) is 5% by mass or more, sufficient transparency can be ensured. The method for producing the resin composition for an optical molded article is not particularly limited as long as it can uniformly disperse the styrene-maleimide copolymer (Α) and the styrene-acrylonitrile copolymer (Β). It is specifically limited, and a well-known kneading method can be utilized. For example, a method of performing blending and kneading using a Banbury mixer, a kneader, a uniaxial or twin-screw extruder, or the like, in particular, in order to obtain an aesthetic film, it is preferable to use a twin-screw extruder for melt-kneading. method. The extrusion method of the copolymer (Β) and the stupid ethylene-Malayiya j 乍 is a styrene-Malay-bromide copolymer (4) and a styrene-cyanine-method And the method of feeding,
作為使用雙軸擠出機 進行熔融混練時之擠出條件，樹脂 150156.doc 201120121 溫度較佳為26〇〜赋，更佳為27〇〜赠。可藉由調整料 缸溫度、螺桿轉速及原料進料量而調節樹脂溫度。 雙轴擠出機之螺桿長度/料紅直徑™)為21〜48之範 圍。螺桿構成並無特職定，較佳為將複數個以下之捏合 盤組合而成者··將複數個槳葉式圓盤沿右方向錯開重叠之 右旋捏合盤、將複數㈣葉式圓盤沿左方向錯開重疊之左 叙捏合盤、將_葉式圓盤以9G度錯開重疊之中性捏合盤等 為了除去異物，可將網眼為5G μηι以下之絲網或锻燒過 滤^聚合物過濾n等設置於擠出機前端之模具部。 光學成形體用樹脂組合物_視需要亦可調配受阻盼系化 合物、内醋系化合物、射、化合物、硫系化合物等耐轨釋 定劑’受阻胺系化合物、苯并三唾系化合物等耐光穩定 劑’潤滑劑及增塑劑，著色劑’抗靜電劑，礦物油等添加 ^其調配量較佳為相對於光學成形體㈣脂組合物ι〇〇 質量份而未達1質量份。 光學成形體㈣脂組合物，若於製成料進而進行延伸 而使之配向’則膜會顯示出負的配向雙折射性。 j學成形體用樹脂組合物可用於射出成形體、片材、膜 卜 成形體，使膜成形之方法並無特別限制，較佳為 使用膜擠出機進行熔融擠出之方法。 [光學成形體] 所°月光學成形體，係指用於光學用途之成形體、片材 膜’所謂熔融擠出膜’係指藉由熔融擠出所形成之膜。 150156.doc 201120121 膜係指相位差膜 '抗反射膜、偏光元件保護膜等公知之 光學臈。 本發明之膜可藉由公知方法進行延伸而使之配向。若於 製成膜時進而進行延伸而使之配向，則膜會產生負的配向 雙折射性’因此最適合相位差膜用途。 以上’對本發明之實施形態進行了闡述，但該等為本發 明之例示，亦可採用上述以外之各種構成。 [實施例] 以下，藉由實施例進一步說明本發明，但本發明並不限 定於該等。 [實驗例A-1] 於具備攪拌機之容積約25公升之高壓釜中添加苯乙烯65 質量份、馬來酸酐7質量份、2,4-二笨基-4-曱基-1-戊燁〇.2 質量份、曱基乙基酮25質量份，將體系内置換為氮氣後， 將溫度升溫至92度，用7小時連續地添加將馬來酸酐28質 量份與過氧化（2-乙基己酸）第三丁酯〇· 1 8質量份溶解於甲 基乙基酮1 00質量份而成之溶液。添加後’進而添加過氧 化（2-乙基己酸）第三丁酯〇.03質量份並升溫至i2〇〇c，進而 使之反應1小時而獲得笨乙烯-馬來酸酐共聚物。其後，於 黏稠之樹脂液中加入笨胺32質量份、三乙胺0.6質量份並 於140°C下使之反應7小時。將反應完畢後之醯亞胺化反應 液投入排氣型螺旋式擠出機，除去揮發分而獲得顆粒狀之 本乙稀-馬來酿亞胺系共聚物A-1。 [實驗例A-2] 150156.doc •19- 201120121 於具備攪拌機之容積約25公升之高壓釜中添加苯乙烯60 質量份、馬來酸酐8質量份、2,4_二苯基冰甲基_丨_戍烯〇3 I量份、曱基乙基酮25質量份，將體系内置換為氮氣後， 將溫度升溫至92度，用9小時連續地添加將馬來酸酐32質 量份與過氧化（2-乙基己酸）第三丁酯〇18質量份溶解於甲 基乙基酮100質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯〇.03質量份並升溫至ι2〇β(：，進而 使之反應1.5小時而獲得苯乙烯-馬來酸酐共聚物。其後， 於黏稠之樹脂液中加入苯胺37質量份、三乙胺〇6質量份 並於140。(：下使之反應7小時。將反應完畢後之酿亞胺化反 應液投入排氣型螺旋式擠出機，除去揮發分而獲得顆粒狀 之苯乙烯-馬來醯亞胺系共聚物A-2。 0 [實驗例A-3] 於具備授拌機之容積約25公升之高壓爸中添加苯乙浠85 質量份、馬來酸酐3質量份、2,4-二笨基-4-甲基-1-戊稀0.3 質量份、曱基乙基酮25質量份，將體系内置換為氮氣後， 將溫度升溫至92度，用7小時連續地添加將馬來酸酐12質 量份與過氧化（2-乙基己酸）第三丁酯0· 1 8質量份溶解於曱 基乙基酮1 00質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯0.03質量份並升溫至120。(：，進而 使之反應1小時而獲得苯乙烯-馬來酸酐共聚物。其後，於 黏稠之樹脂液中加入苯胺13.5質量份、三乙胺0.23質量份 並於140°C下使之反應7小時。將反應完畢後之醯亞胺化反 應液投入排氣型螺旋式擠出機，除去揮發分而獲得顆粒狀 150156.doc -20- 201120121 之本乙烤-馬來酿亞胺系共聚物A-3。 [實驗例A-4] 於具備授拌機之容積約25公升之高壓蚤中添加苯乙稀76 質量份、馬來酸酐6質量份、2,4-二苯基-4-甲基-i_戊稀〇.3 質量份、曱基乙基酮25質量份’將體系内置換為氮氣後， 將溫度升溫至92度，用7小時連續地添加將馬來酸酐14質 量份與過氧化（2-乙基己酸）第三丁酯0.1 8質量份溶解於甲 基乙基酮100質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯0.03質量份並升溫至}“^，進而 使之反應1小時而獲得笨乙浠-馬來酸針共聚物。其後，於 黏稠之樹脂液中加入苯胺21.6質量份、三乙胺0.36質量份 並於140°C下使之反應7小時。將反應完畢後之醯亞胺化反 應液4又入排氣型螺旋式擠出機’除去揮發分而獲得顆粒狀 之苯乙稀-馬來酿亞胺系共聚物A-4。 [實驗例A-5] 於具備授拌機之容積約25公升之高壓爸中添加笨乙稀37 質量份、2,4-二苯基-4-曱基-1-戊烯〇·2質量份、甲基乙基 酮2 5質ϊ份’將體系内置換為氮氣後，升溫至9 2 ，用1 〇 小時連續地添加將N-苯基馬來醯亞胺63質量份與過氧化 (2-乙基己酸）第三丁酯0.18質量份溶解於甲基乙基酮1〇〇質 量份而成之溶液。添加後，進而添加過氡化（2_乙基己酸) 第三丁酯0.03質量份並升溫至110。〇：，進而使之反應々小 時。將反應το畢後之樹脂液投入排氣型螺旋式擠出機，除 去揮發分而獲得顆粒狀之苯乙烯-馬來醯亞胺系共聚物 I50156.doc 21 201120121 A-5。 [實驗例A-6] 於具備攪拌機之容積約25公升之高壓釜中添加苯乙烯51 邊里伤、丙烯腈9質量份、2,4-二苯基_4_曱基戊烯0.2質 量份、曱基乙基酮25質量份，將體系内置換為氮氣後，升 恤至92 C，用7小時連續地添加將N_苯基馬來醯亞胺4〇質 里伤與過氧化（2-乙基己酸）第三丁酯〇丨8質量份溶解於曱 基乙基酮100質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯〇.〇3質量份並升溫至12〇。(：，進而 使之反應1小時。將反應完畢後之樹脂液投入排氣型螺旋 式擠出機，除去揮發分而獲得顆粒狀之苯乙烯_馬來醯亞 胺系共聚物A-6。 [實驗例A-7] 於具備攪拌機之容積約2 5公升之高壓釜中添加苯乙烯6 5 質量份、馬來酸酐7質量份' 2,4_二苯基_4_甲基_丨_戊烯〇2 夤置份、甲基乙基酮25質量份，將體系内置換為氮氣後， 將溫度升溫至92度，用7小時連續地添加將馬來酸肝㈣ 量份與過氧化(2-乙基己酸)第三丁酯〇18質量份溶解於子 基乙棊酮100質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯0 03質量份並升溫至12〇它，進而 使之反應1小時而獲得苯乙烯_馬來酸酐共聚物。其後，於 黏稠之樹脂液中加入環己胺32質量份、三乙胺〇·6質量份 並於140t下使之反應7小時。將反應完畢後之醯亞胺化： 應液投入排氣型螺旋式擠出機，除去揮發分而獲得顆粒狀 150J56.doc •22· 201120121 之苯乙烯-馬來醯亞胺系共聚物A。。 [實驗例A-8] 於具備攪拌機之容積約25公升之高壓爸中添加苯乙烯60 質量份、馬來酸酐8質量份、2,4-二苯基-4-甲基-1-戊烯0.2 質量份、曱基乙基酮25質量份，將體系内置換為氮氣後， 將溫度升溫至92度，用7小時連續地添加將馬來酸酐32質 量份與過氧化（2-乙基己酸）第三丁酯0.18質量份溶解於甲 基乙基酮100質量份而成之溶液。添加後，進而添加過氧 化（2-乙基己酸）第三丁酯0.03質量份並升溫至120°c，進而 使之反應1小時而獲得苯乙烯-馬來酸酐共聚物。其後，於 黏稠之樹脂液中加入苯胺37質量份、三乙胺0.6質量份並 於140°C下使之反應7小時。將反應完畢後之醯亞胺化反應 液投入排氣型螺旋式擠出機，除去揮發分而獲得顆粒狀之 苯乙烯-馬來醯亞胺系共聚物A-8。 [實驗例A-9] 於具備攪拌機之容積約25公升之高壓釜中添加苯乙烯65 質量份、2,4-二苯基-4-曱基-1-戊烯〇_3質量份、曱基乙基 酮25質量份’將體系内置換為氮氣後，將溫度升溫至 92°C，用8小時連續地添加將馬來酸酐35質量份與過氧化 (2 -乙基己酸）第三丁酯〇_18質量份溶解於甲基乙基酮1〇〇質 $份而成之溶液。添加後’進而添加過氧化（2_乙基己酸） 第三丁酯0.03質量份並升溫至120。(：，進而使之反應}小時 而獲得苯乙浠-馬來酸酐共聚物。其後，於黏稠之樹脂液 中加入苯胺32質量份、三乙胺〇·6質量份並於mo。〇下使之 150l56.doc •23· 201120121 反應7小時。將反應完畢後之醯亞胺化反應液投入排氣型 螺旋式擠出機，除去揮發分而獲得顆粒狀之苯乙烯-馬來 醯亞胺系共聚物A-9。 將上述實驗例A-1〜A-9之分析結果示於表1。 [表1] 記號 成分組成 殘留馬來醯亞胺系單體量 [ppm] 黃色度[-] A-1 笨乙烯 52% 180 1.6 苯基馬來醯亞胺 47% 馬來酸酐 1% A-2 苯乙烯 48% 230 2.2 N-苯基馬來醯亞胺 51% 馬來酸酐 1% A-3 苯乙烯 77% 290 1.7 N-苯基馬來醯亞胺 22% 馬來酸酐 1% A-4 苯乙烯 65% 280 2.1 N-苯基馬來醯亞胺 34% 馬來酸酐 1% A-5 苯乙烯 37% 1,350 6.8 N-苯基馬來醯亞胺 63% 馬來酸酐 0% A-6 苯乙烯 51% 200 2.4 N-苯基馬來醯亞胺 40% 丙烯腈 9% A-7 苯乙烯 52% 260 2.1 N-環己基馬來醯亞胺 47% 馬來酸酐 1% A-8 苯乙烯 48% 550 3.4 N-苯基馬來醯亞胺 51% 馬來酸酐 1% A-9 苯乙烯 53% 950 2.9 N-苯基馬來醯亞胺 46% 馬來酸酐 1% 150156.doc -24· 201120121 [實驗例B-l] 將附帶攪拌機之容積約2〇公升之完全混合型反應器斑附 帶預熱器之脫揮槽連接而構成。製備由苯乙稀㈣量份、 丙烯腈15質里份、乙苯15質量份所構成之單體混合液，進 而混合過氧化異丙基碳酸第三丁醋〇〇15質量份與正十二 硫醇0.013質詈份，制+ m ,, — . 氣成原料溶液。將該原料溶液以每小 時5 l^g導入至溫度控制為12代之完全混合型反應器。再 者7°王此合型反應器之授拌數係以180 rpm而實施。繼 而’自完全混合型反應器連續地抽出反應液’利用預教器 將該反應液加熱，並導入至溫度控制為2饥、壓力控制 為kPa之脫揮槽，除去未反應單體等揮發分。利用齒輪 泵抽出》亥樹月g液，擠出為股線狀並切斷，藉此獲得顆粒 狀之聚合體B_i。 u [實驗例B-2] 蛛將附帶搜拌機之容積約2〇公升之完全混合型反應器與附 、’、·、器之脫揮槽連接而構成。製備由苯乙烯乃沁質量 知' 丙烯腈26.4質量份、乙苯2〇質量份所構成之單體混合 進而/¾ 口過氧化異丙基碳酸第三丁醋〇 〇丄5質量份與 、π醇〇·01 3邊里份’製成原料溶液。將該原料溶液 ::每小時5 kg導入至溫度控制為12〇t之完全混合型反應 盗。再者’完全混合型反應器之攪拌數係以18〇啊而實 施。，而’自完全混合型反應器連續地抽出反應液，利用 預熱咨將該反應液加熱，並導入至溫度控制為2饥、壓 制為1.0 kPa之脫揮槽，除去未反應單體等揮發分。利 150156.doc •25· 201120121 用齒輪系抽出該樹脂液，擠 顆粒形狀之聚合體B_2。 &線狀抽斷，藉此獲得 [實驗例]3-3] 將附帶攪拌機之容積約2〇公 罄箱舳吳— 全混合型反應器與附 丙稀腈質量份、乙苯18質晋々、備由本乙稀69質量份、 伤所構成之單體混合液，進 而處合過氧化異丙基碳酸第- 基反酸第二丁酯0.015質量份與正十二 硫醇0.013質量份，製成屌+ ^ 氙成原枓，奋液。將該原料溶液以每小 、 g導入至溫度控制為120。(：之6 + ,¾ Α π = ^ —入 凡全混合型反應器。再 t二混合型反應器之授拌數係以180rpm而實施。繼 自7C全混合型反應器連續 貝吧柚出反應液，利用預熱器 -〜液加熱’並導入至溫度控制為2 為1.〇 kPa之脫揮槽，除去夫及虛力㈣1 平熠除去未反應早體等揮發分。利用齒輪 聚抽出4樹月日液’擠出為股線狀並切斷，藉此獲得顆粒形 狀之聚合體B-3。 [實驗例B-4] 將附帶攪拌機之容積約2〇公升之完全混合型反應器與附 帶預熱器之脫揮槽連接而構成。製備由苯乙烯56ι質量 份二甲基苯乙稀17.5質量份、两稀猜26 4質量份、乙笨 18質1伤所構成之單體混合液，進而混合過氧化異丙基碳 酸第三T_.G15f量份與正十二硫醇〇別3質量份，製： 原料溶液。將該原料溶液以每小時5 kg導入至溫度控制為 120 C之完全混合型反應器。再者完全混合型反應器之 ㈣數係以180 rpm而實施。繼而’自完全混合型反應器 150156.doc -26- 201120121 連續地抽出反應液，利用預哉哭 顶热益將該反應液加熱，並導入 至溫度控制為23 5°C、壓力护制头， 仡制為1.0 kPa之脫揮槽，除去 未反應卓體等揮發分。利用齒私$ & , 向粟抽出該树脂液，擠出為 股線狀並切斷，藉此獲得顆粒形狀之聚合體Μ。 ·'、' [實驗例B-5] 將附帶授拌機之容積約2 〇公并 胃彳之完全混合型反應器與附 π預熱器之脫揮槽連接而構成 俾战。製備由笨乙烯91.8質量 份、丙稀腈9.2質量份、乙苯18質量份所構成之單體混人 液，進而混合過氧化異丙基碳酸第三丁醋〇〇15質量份血 正十二硫醇0.013質量份，塑Λ店』， 、 — 製成原料溶液。將該原料溶液 以每小時5 kg導入至溫度控制為 。。 又枉刺為丨2〇 C之完全混合型反應 益。再者’完全混合型反岸夕典灿批〆 馮器之撹拌數係以180 rpm而實 施。繼而，自完全混合型反庠 汉應益連續地抽出反應液，利用 預熱器將該反應液加哉，並導_人Jg、w点1 …亚導入至溫度控制為235t、壓 力控制為1.0 kPa之脫揮梓，哈土土 c 土 a除去未反應單體等揮發分。利 用齒輪泵抽出該樹脂液，播懕為 曰狀潸M為線狀並切斷，藉此獲得顆 粒形狀之聚合體B-5。 [實驗例B-6] 册將附帶授摔機之容積約20公升之完全混合型反應器與附 ▼預熱盗之脫揮槽連接而構成。製備由苯乙烯後5質量 :、丙婦猜則質量份、乙苯18質#份所構成之單體混合 攻，進而處合過氧化異丙基碳酸第三丁較〇15質量份與 ' —醇0.013質量份’製成原料溶液。將該原料溶液 以母小時5 kg導入至溫度控制為I2〇t之完全混合型反應 150156.doc 27· 201120121 器。再者，完全混合型反應器之攪拌數係以1 80 rpm而實 施。繼而，自完全混合型反應器連續地抽出反應液，利用 預熱器將該反應液加熱，並導入至溫度控制為235°C、壓 力控制為1.0 kPa之脫揮槽，除去未反應單體等揮發分。利 用齒輪泵抽出該樹脂液，擠出為股線狀並切斷，藉此獲得 顆粒形狀之聚合體B-6。 將上述實驗例B-1〜B-6之分析結果示於表2。 [表2] 記號 成分組成 B-1 丙稀腈 16% 苯乙烯 84% B-2 丙烯腈 26% 苯乙烯 74% B-3 丙烯腈 30% 苯乙烯 70% B-4 丙烯腈 26% 苯乙烯 60% α-曱基苯乙烯 14% B-5 丙稀腈 10% 苯乙烯 90% B-6 丙稀腈 35% 苯乙烯 65% 各分析值之測定方法如以下。 (1)苯乙烯-馬來醯亞胺系共聚物之構成單元 以下述記載之測定條件測定NMR，並根據醯亞胺基之羰 基碳之積分值、與未反應二羧酸酐基及醯亞胺化反應中間 150156.doc •28- 201120121 物之馬來醯胺酸中間物之羰基碳之積分值的比值等，求出 苯乙烯-馬來醢亞胺系共聚物之構成單元。 裝置名 AVANCE-300(BRUKER公司製造） 測定核種 C13 溫 度 110°C 濃 度 10質量％ 溶 媒 DMSO-d6 累計次數 1萬次 (2) 殘留馬來醯亞胺系單體量 裝置名：GC-2010(島津製作所製造） 管柱：毛細管柱DB-5MS(苯基丙二烯聚合物）As the extrusion conditions for melt-kneading using a twin-screw extruder, the temperature of the resin 150156.doc 201120121 is preferably 26 〇 ~ Fu, more preferably 27 〇 ~ gift. The resin temperature can be adjusted by adjusting the cylinder temperature, the screw speed, and the feed amount of the raw material. The screw length/red diameter TM of the twin screw extruder is in the range of 21 to 48. The screw structure has no special purpose, and it is preferable to combine a plurality of kneading discs of the following number. · A right-hand kneading disc in which a plurality of paddle discs are overlapped in the right direction, and a plurality of (four) leaf discs In the left direction, the left-hand kneading disc is overlapped, the _leaf disc is shifted by 9G degrees, and the neutral kneading disc is overlapped. In order to remove foreign matter, the mesh may be a mesh or sinter filter of 5G μηι or less. Filter n or the like to be placed in the mold part at the front end of the extruder. Resin composition for optical moldings _ If necessary, a weather-resistant release agent such as a hindered-resistant compound, an internal vinegar-based compound, a shot, a compound or a sulfur-based compound, or a benzotris-based compound, may be blended. The stabilizer 'lubricant and plasticizer, colorant' antistatic agent, mineral oil, etc. are preferably added in an amount of less than 1 part by mass relative to the mass of the optical molded body (iv). The optical molded body (iv) fat composition exhibits negative alignment birefringence if it is stretched and then aligned in the finished material. The resin composition for a molded article can be used for injection molding of a molded article, a sheet, or a film. The method for forming the film is not particularly limited, and a method of melt-extruding using a film extruder is preferred. [Optical Molded Body] The optical molded article of the month is a molded article or sheet film for optical use. The term "melt extruded film" means a film formed by melt extrusion. 150156.doc 201120121 Membrane is a known retardation film, such as an antireflection film or a polarizing element protective film. The film of the present invention can be oriented by extension by a known method. If the film is further stretched and aligned when it is formed into a film, the film will have a negative alignment birefringence. Therefore, it is most suitable for use in a retardation film. The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above may be employed. [Examples] Hereinafter, the present invention will be further described by way of Examples, but the present invention is not limited thereto. [Experimental Example A-1] 65 parts by mass of styrene, 7 parts by mass of maleic anhydride, and 2,4-dipyridyl-4-mercapto-1-pentanthene were added to an autoclave having a volume of about 25 liters of a stirrer.质量. 2 parts by mass, 25 parts by mass of mercaptoethyl ketone, after replacing the system with nitrogen, the temperature was raised to 92 degrees, and 28 parts by mass of maleic anhydride and peroxidation (2-B) were continuously added over 7 hours. A solution prepared by dissolving 100 parts by weight of methyl ethyl ketone in 100 parts by weight of butyl hexanoate. After the addition, a portion of 0.03 parts by mass of (2-ethylhexanoic acid) tributyl acrylate was further added and heated to i2 〇〇c, and further reacted for 1 hour to obtain a stupid ethylene-maleic anhydride copolymer. Thereafter, 32 parts by mass of strepamine and 0.6 parts by mass of triethylamine were added to the viscous resin liquid, and the mixture was reacted at 140 ° C for 7 hours. The hydrazine imidization reaction liquid after the completion of the reaction was placed in a vented screw extruder to remove volatile matter to obtain a granulated biphenyl-maleimide copolymer A-1. [Experimental Example A-2] 150156.doc • 19- 201120121 60 parts by mass of styrene, 8 parts by mass of maleic anhydride, 2,4-diphenyl ice methyl group were added to an autoclave having a volume of about 25 liters of a stirrer. _丨_戍烯〇3 I parts, 25 parts by mass of mercaptoethyl ketone, after replacing the system with nitrogen, the temperature was raised to 92 degrees, and 32 parts by mass of maleic anhydride was continuously added over 9 hours. 18 parts by mass of oxidized (2-ethylhexanoic acid) tert-butyl ester oxime was dissolved in 100 parts by mass of methyl ethyl ketone. After the addition, further, 03 parts by mass of (2-ethylhexanoic acid) tributyl acrylate was added and the temperature was raised to ι 2 〇β (:, and further reacted for 1.5 hours to obtain a styrene-maleic anhydride copolymer. Thereafter, 37 parts by mass of aniline and 6 parts by mass of triethylamine oxime were added to the viscous resin solution and reacted at 140. (: The reaction was carried out for 7 hours. The imidization reaction liquid after the completion of the reaction was put into the vent type. A spiral extruder was used to remove volatile matter to obtain a granulated styrene-maleimide copolymer A-2. [Experimental Example A-3] A high pressure dad having a volume of about 25 liters of a blender 85 parts by mass of phenethyl hydrazine, 3 parts by mass of maleic anhydride, 0.3 parts by mass of 2,4-dipyridyl-4-methyl-1-pentane, and 25 parts by mass of mercaptoethyl ketone were added, and the system was replaced. After nitrogen gas, the temperature was raised to 92 degrees, and 12 parts by mass of maleic anhydride and 0. 18 parts by mass of (2-ethylhexanoic acid) tert-butyl peroxide were dissolved in the thiol group by continuously adding for 7 hours. A solution of 100 parts by mass of the ketone. After the addition, 0.03 parts by mass of (2-ethylhexanoic acid) tributyl acrylate was further added and the temperature was raised to 120. (:, The styrene-maleic anhydride copolymer was obtained by reacting for 1 hour. Thereafter, 13.5 parts by mass of aniline and 0.23 parts by mass of triethylamine were added to the viscous resin solution, and the mixture was reacted at 140 ° C for 7 hours. After the completion of the reaction, the hydrazine imidization reaction liquid is put into a vented screw extruder to remove the volatile matter to obtain a granulated 150156.doc -20- 201120121 B-baked-Malay-bromide copolymer A-3 [Experimental Example A-4] 76 parts by mass of styrene, 6 parts by mass of maleic anhydride, and 2,4-diphenyl-4-methyl group were added to a high pressure crucible having a volume of about 25 liters of a mixer. I_pentanthene. 3 parts by mass, 25 parts by mass of mercaptoethyl ketone. After replacing the system with nitrogen, the temperature was raised to 92 degrees, and 14 parts by mass of maleic anhydride and peroxidation were continuously added over 7 hours. (2-ethylhexanoic acid) tert-butyl ester 0.18 parts by mass of a solution obtained by dissolving 100 parts by mass of methyl ethyl ketone. After the addition, further adding (2-ethylhexanoic acid) tert-butyl ester 0.03 parts by mass and heated to a value of "", and then allowed to react for 1 hour to obtain a stupid-maleic acid needle copolymer. Thereafter, in a viscous resin liquid 21.6 parts by mass of aniline and 0.36 parts by mass of triethylamine were added and reacted at 140 ° C for 7 hours. After the completion of the reaction, the hydrazine imidization reaction liquid 4 was again introduced into a vented screw extruder to remove volatiles. The styrene-maleimide copolymer A-4 in the form of granules was obtained. [Experimental Example A-5] 37 parts by mass of stupid ethylene was added to a high-pressure dad having a volume of about 25 liters of a mixer. 2,4-diphenyl-4-mercapto-1-pentene oxime · 2 parts by mass, methyl ethyl ketone 25 ϊ ' ' After replacing the system with nitrogen, the temperature is raised to 9 2 with 1 〇 Adding 63 parts by mass of N-phenylmaleimide and 0.18 parts by mass of (2-ethylhexanoic acid) tributyl acrylate to 1 part by mass of methyl ethyl ketone continuously Solution. After the addition, 0.03 parts by mass of deuterated (2-ethylhexanoic acid) third butyl ester was further added and the temperature was raised to 110. 〇:, and then let it react for a small time. The resin liquid after the reaction was put into a vented screw extruder, and the volatile matter was removed to obtain a granulated styrene-maleimide copolymer I50156.doc 21 201120121 A-5. [Experimental Example A-6] In an autoclave having a volume of about 25 liters of a stirrer, styrene 51 was added, 9 parts by mass of acrylonitrile, and 0.2 parts by mass of 2,4-diphenyl-4-methylpentene. 25 parts by mass of mercaptoethyl ketone, after replacing the system with nitrogen, the shirt was lifted to 92 C, and the N-phenyl maleimide 4 enamel was damaged and peroxidized continuously for 7 hours (2 -ethylhexanoic acid) 3 parts by mass of a solution of the tert-butyl ester oxime dissolved in 100 parts by mass of mercaptoethyl ketone. After the addition, 3 parts by mass of peroxy(2-ethylhexanoic acid) tert-butyl phthalate was further added and the temperature was raised to 12 Torr. (: Further, the reaction was carried out for 1 hour. The resin liquid after completion of the reaction was placed in a vented screw extruder to remove volatile matter to obtain a granulated styrene-maleimide copolymer A-6. [Experimental Example A-7] 6 parts by mass of styrene and 7 parts by mass of maleic anhydride were added to an autoclave having a volume of about 25 liters of a stirrer ' 2,4_diphenyl_4_methyl_丨_ After the pentene oxime 2 夤 part and methyl ethyl ketone 25 parts by mass, after replacing the system with nitrogen, the temperature was raised to 92 degrees, and the maleic acid (four) parts and peroxidation were continuously added for 7 hours ( 18 parts by mass of 2-ethylhexanoic acid) tert-butyl ester oxime dissolved in 100 parts by mass of ketone ketone. After addition, further added (2-ethylhexanoic acid) tert-butyl ester 0 03 parts by mass and heated to 12 Torr, and further reacted for 1 hour to obtain a styrene-maleic anhydride copolymer. Thereafter, 32 parts by mass of cyclohexylamine and triethylamine 〇·6 were added to the viscous resin solution. The mass fraction was reacted at 140t for 7 hours. After the reaction was completed, the hydrazine was imidized: the liquid was put into a vented screw extruder to remove volatiles. A styrene-maleimide copolymer A of 150J56.doc •22·201120121 was obtained. [Experimental Example A-8] 60 parts by mass of styrene was added to a high pressure dad having a volume of about 25 liters of a blender. 8 parts by mass of maleic anhydride, 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 25 parts by mass of mercaptoethyl ketone. After replacing the system with nitrogen, the temperature is raised to At 92 degrees, a solution obtained by dissolving 32 parts by mass of maleic anhydride and 0.18 parts by mass of (2-ethylhexanoic acid) tert-butyl peroxide in 100 parts by mass of methyl ethyl ketone was continuously added over 7 hours. Thereafter, 0.03 parts by mass of (2-ethylhexanoic acid) tert-butyl peroxide was further added and the temperature was raised to 120 ° C, and further reacted for 1 hour to obtain a styrene-maleic anhydride copolymer. Thereafter, it was thick. 37 parts by mass of aniline and 0.6 parts by mass of triethylamine were added to the resin liquid, and the mixture was reacted at 140 ° C for 7 hours. The hydrazine imidization reaction liquid after completion of the reaction was placed in an exhaust type screw extruder to remove Volatile matter was obtained to obtain a granulated styrene-maleimide copolymer A-8. [Experimental Example A-9] With a blender 65 parts by weight of styrene, 2,4-diphenyl-4-mercapto-1-pentenyl _3 parts by mass, and 25 parts by mass of mercaptoethyl ketone added to the autoclave of about 25 liters After replacing with nitrogen, the temperature was raised to 92 ° C, and 35 parts by mass of maleic anhydride and 18 parts by mass of dibutyl acrylate (2-ethylhexanoate) were dissolved in the methyl group continuously for 8 hours. Ethyl ketone 1 〇〇 $ 份 份 份 份 份 份 份 份 份 份 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙A styrene-maleic anhydride copolymer is obtained. Thereafter, 32 parts by mass of aniline and 6 parts by mass of triethylamine were added to the viscous resin liquid to obtain mo. Underarms make it 150l56.doc •23· 201120121 Reaction 7 hours. The hydrazine imidization reaction liquid after completion of the reaction was placed in a vented screw extruder to remove volatile matter to obtain a granulated styrene-maleimide copolymer A-9. The analysis results of the above Experimental Examples A-1 to A-9 are shown in Table 1. [Table 1] Symbol composition Residue maleimide monomer amount [ppm] Yellowness [-] A-1 Stupid ethylene 52% 180 1.6 Phenyl maleate imino 47% Maleic anhydride 1% A- 2 Styrene 48% 230 2.2 N-phenylmaleimide 51% Maleic anhydride 1% A-3 Styrene 77% 290 1.7 N-phenylmaleimide 22% Maleic anhydride 1% A- 4 Styrene 65% 280 2.1 N-phenylmaleimide 34% Maleic anhydride 1% A-5 Styrene 37% 1,350 6.8 N-phenylmaleimide 63% Maleic anhydride 0% A- 6 Styrene 51% 200 2.4 N-phenylmaleimide 40% Acrylonitrile 9% A-7 Styrene 52% 260 2.1 N-cyclohexylmaleimide 47% Maleic anhydride 1% A-8 Styrene 48% 550 3.4 N-phenylmaleimide 51% Maleic anhydride 1% A-9 Styrene 53% 950 2.9 N-phenylmaleimide 46% Maleic anhydride 1% 150156.doc -24· 201120121 [Experimental Example B1] A fully mixed reactor spot having a volume of about 2 liters of a mixer was attached to the detachment groove of the preheater. Preparing a monomer mixture consisting of styrene (four) parts, 15 parts by weight of acrylonitrile, and 15 parts by mass of ethylbenzene, and further mixing 15 parts by mass of butyl acetoacetate perylene with 15 parts by weight Mercaptan 0.013 mass fraction, made + m ,, — . Gasification raw material solution. The raw material solution was introduced at a rate of 5 lg per hour to a fully mixed reactor having a temperature control of 12 passages. Further, the number of batches of the 7° King reactor was carried out at 180 rpm. Then, 'the reaction mixture is continuously extracted from the complete mixing reactor', the reaction liquid is heated by the pre-teaching device, and introduced into a devolatilization tank with a temperature control of 2 hunger and a pressure control of kPa to remove volatiles such as unreacted monomers. . The gel liquid pump was used to extract the "Huishuyue g liquid, which was extruded into a strand shape and cut, thereby obtaining a granular polymer B_i. u [Experimental Example B-2] The spider was constructed by connecting a fully-mixed reactor with a volume of about 2 liters of the mixer to the de-flushing tank of the attached, ', ·, and. Preparing a monomer composed of 26.4 parts by mass of acrylonitrile and 2 parts by mass of ethylbenzene, and then 5 parts by mass of isopropyl acetoacetate, 3 parts by mass, and π Alcohol 〇·01 3 side parts 'made into a raw material solution. The raw material solution :: 5 kg per hour was introduced into a fully mixed type reaction with a temperature control of 12 〇t. Further, the stirring number of the 'fully mixed type reactor was implemented at 18 Torr. And 'removing the reaction liquid continuously from the complete mixing type reactor, heating the reaction liquid by preheating, and introducing it into a devolatilization tank with a temperature control of 2 hunger and pressing to 1.0 kPa to remove volatiles such as unreacted monomers. Minute. Lee 150156.doc •25· 201120121 The resin liquid is extracted by a gear train to extrude the particle-shaped polymer B_2. & linear drawing, thereby obtaining [Experimental Example] 3-3] The volume of the mixer is about 2 〇 罄 舳 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 々 々 々 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 69 Made of 屌 + ^ 氙 into the original 奋, Fen liquid. The raw material solution was introduced to a temperature of 120 per small g. (: 6 + , 3⁄4 Α π = ^ - into the full-mix reactor. The mixing number of the t-mixed reactor was carried out at 180 rpm. Continued from the 7C full-mix reactor The reaction solution is heated by a preheater-~liquid and introduced into a devolatilization tank with a temperature control of 2 to 1. kPa, and the volatile matter of the unreacted early body is removed by removing the fusiform and the imaginary force (4). 4 tree moon liquid was extruded into a strand shape and cut, thereby obtaining a pellet-shaped polymer B-3. [Experimental Example B-4] A fully mixed reactor having a volume of about 2 liters with a mixer was used. It is configured by connecting with a devolatilization tank with a preheater. Preparation of a monomer mixture composed of styrene 56 1 part by mass of dimethyl styrene 17.5 parts by mass, two rare pieces guessing 26 4 parts by mass, and B stupid 18 type 1 wound. The liquid is further mixed with a third T_.G15f portion of isopropyl carbonate and 3 parts by mass of n-dodecyl thiol to prepare a raw material solution. The raw material solution is introduced at a rate of 5 kg per hour to a temperature of 120 C. a fully mixed reactor. The (4) number of the fully mixed reactor was carried out at 180 rpm. Completely mixed reactor 150156.doc -26- 201120121 The reaction liquid was continuously withdrawn, and the reaction liquid was heated by pre-heating and heat-introduced, and introduced to a temperature control of 23 5 ° C, a pressure protection head, and tanning was The devolatilization tank of 1.0 kPa was used to remove volatile matter such as unreacted spheroids, and the resin liquid was taken out from the millet by using the teeth <>, and extruded into strands and cut, thereby obtaining a polymer enthalpy in the form of particles. - ', ' [Experimental Example B-5] A fully-mixed reactor with a volume of about 2 〇 and a stomach sputum with a mixer is connected to a detachment tank with a π preheater to form a battle. 91.8 parts by mass of ethylene, 9.2 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene, and then mixed with isopropyl acetoacetate, 15 parts by mass of ruthenium pentoxide, 0.013 The mass of the product, plastic shop 』,, - is made into a raw material solution. The raw material solution is introduced at a temperature of 5 kg per hour to control the temperature. The spur is a completely mixed type of reaction benefit of 丨2〇C. The mixed type of anti-bank eve 灿 〆 〆 〆 〆 〆 〆 〆 器 以 以 以 以 180 180 180 180 180 180 180 180 The fully mixed anti-tanning agent should continuously extract the reaction liquid, and use the preheater to twist the reaction liquid, and introduce the _ human Jg, w point 1 ... sub-introduction to a temperature control of 235t, pressure control of 1.0 kPa The smoldering, the earth soil a removes volatiles such as unreacted monomers, and the resin liquid is extracted by a gear pump, and the seedling is 曰-shaped 潸M is linear and cut, thereby obtaining a particle-shaped polymer B- 5. [Experimental Example B-6] A complete hybrid reactor with a volume of about 20 liters with a weight-bearing machine is attached to the detachment tank with a preheating thief. Prepare a monomer mixture consisting of 5 masses of styrene: a mass fraction of propylene, a mass fraction of ethylbenzene 18, and a mixture of 15 parts by weight of isopropylated isopropyl carbonate. The alcohol was made into a raw material solution in an amount of 0.013 parts by mass. The raw material solution was introduced at a parent hour of 5 kg to a fully mixed type reaction with a temperature control of I2〇t 150156.doc 27·201120121. Further, the number of stirrings of the fully mixed reactor was carried out at 180 rpm. Then, the reaction liquid was continuously withdrawn from the completely mixed reactor, and the reaction liquid was heated by a preheater and introduced into a devolatilization tank having a temperature control of 235 ° C and a pressure control of 1.0 kPa to remove unreacted monomers. Volatile matter. The resin liquid was taken out by a gear pump, extruded into strands and cut, whereby a pellet-shaped polymer B-6 was obtained. The analysis results of the above Experimental Examples B-1 to B-6 are shown in Table 2. [Table 2] Symbol Composition B-1 Acrylonitrile 16% Styrene 84% B-2 Acrylonitrile 26% Styrene 74% B-3 Acrylonitrile 30% Styrene 70% B-4 Acrylonitrile 26% Styrene 60% α-mercaptostyrene 14% B-5 acrylonitrile 10% styrene 90% B-6 acrylonitrile 35% styrene 65% The respective analytical values were determined as follows. (1) Structural unit of styrene-maleimide copolymer The NMR was measured under the measurement conditions described below, and based on the integral value of the carbonyl group of the quinone imine group, and the unreacted dicarboxylic anhydride group and the quinone imine In the middle of the reaction, 150156.doc • 28-201120121 The ratio of the integral value of the carbonyl carbon of the maleic acid intermediate of the substance, etc., and the constituent unit of the styrene-maleimide copolymer. Device name AVANCE-300 (manufactured by BRUKER) Determination of nuclear species C13 Temperature 110 °C Concentration 10% by mass Solvent DMSO-d6 Accumulated number of 10,000 times (2) Residual maleimide monomer amount: GC-2010 ( Manufactured by Shimadzu Corporation) Column: capillary column DB-5MS (phenyl propylene diene polymer)
溫度：注入口 280。(：、檢測器280°C 以管柱溫度80°C (初期）進行升溫分析。 (升溫分析條件） 80°C :保持12分鐘 80〜280°C :以20°C/分鐘升溫10分鐘 280°C :保持1〇分鐘Temperature: Injection port 280. (:, 280 ° C detector temperature rise analysis at 80 ° C (initial) column temperature (temperature analysis conditions) 80 ° C: hold 12 minutes 80 ~ 280 ° C: 20 ° C / min temperature 10 minutes 280 °C : Keep 1 minute
檢測器：FID 抓転.將試樣0·5 g溶解於含十一烷（内標物質）之1,2- 二氯乙烷溶液(0.014 g/L)5 ml中。其後，加入正己烷5 ml 並利用振覆益振盈1 〇〜i 5分鐘，使之析&。於使聚合物析 出沈板之狀態下僅將上清液注入中。利用由内標物 質所求出之係數’由所得之馬來醯亞胺系單體之峰面積算 出定量值。 (3) 黃色度 裝置名.SZ-IC80測色色差計（日本電色公司製造） 150156.doc -29- 201120121 流程：將試樣1 g溶解於25 ml之四氫呋喃。溶解後， 移至測定用之方形單元。將四氫呋喃溶液之方形單元作為 空白，藉由透射法求出色差，將該值設為黃色度。 (4)笨乙婦-丙烯腈系共聚物之構成單元 藉由下述s己載之凱氏法（Kjeldahl meth〇d)求出丙烯腈系 共聚物之構成單元。 流程：將試樣〇.3 g溶解於硫酸20 nU，分別加入硫酸 鉀4.5 g、硫酸銅〇.5 g並於35〇〜4〇〇亡下進行加熱使之分 解:冷卻至室溫後，加入4〇%氮氧化鈉，以ι/ι〇 N硫酸溶 液實施滴定，算出氮分而求出苯乙稀_.丙稀猜共聚物之構 成單元。 [貫施例1〜9及比較例1〜§ ] 將實驗例所製造之苯乙婦-馬來酿亞胺系共聚物⑷與苯 乙烯丙烯腈系共聚物⑻以表3〜表4所示之比例（質量％)利 用亨舍爾混合機進行混合後，利用雙轴擠出機（東芝機械 (股）公司製造之TEM_35B，L/D=32)，於料虹溫度26〇〇C ' 進料量2。kg/小時、螺桿轉速25。—之條件下進行炫融混 練而製成顆粒，獲得光學成形體用樹脂组合物。再者，樹 月曰>ja度均為2 7 0〜3 10 °C之範圍。 利用附帶Τ字模之膜擠出成形機，於料缸溫度240t、模 具溫度2贼之條件下，將光學成形體用樹脂組合物擠出 為厚度100 μηι之膜，並捲取成捲筒。 使用拉幅式橫置延伸機，於Tg+2Gt：下將所得之膜單轴 延伸為1.8倍’獲得經延伸之光學膜。將所得之膜之測定 結果示於表3〜表4。 150156-doc -30· 201120121Detector: FID grab. Dissolve 0. 5 g of the sample in 5 ml of 1,2-dichloroethane solution (0.014 g/L) containing undecane (internal standard substance). Thereafter, add 5 ml of n-hexane and use a vibrating cover to enhance the 1~i 5 minutes to make it & Only the supernatant was injected while the polymer was allowed to settle. The quantitative value was calculated from the peak area of the obtained maleimide-based monomer using the coefficient determined by the internal standard substance. (3) Yellowness Device name. SZ-IC80 colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd.) 150156.doc -29- 201120121 Procedure: Dissolve 1 g of sample in 25 ml of tetrahydrofuran. After dissolution, move to the square unit for measurement. The square unit of the tetrahydrofuran solution was used as a blank, and the color difference was determined by a transmission method, and the value was set to a yellow degree. (4) Structural unit of the styrene-acrylonitrile-based copolymer The constituent unit of the acrylonitrile-based copolymer was determined by the following Kjeldahl meth〇d method. Process: Dissolve the sample 〇.3 g in 20 nU of sulfuric acid, add 4.5 g of potassium sulfate, 5 g of barium sulfate, and heat to decompose after 35 〇~4 :: after cooling to room temperature, 4% by weight of sodium oxynitride was added, and titration was carried out in an ι/ι〇N sulfuric acid solution, and nitrogen was calculated to obtain a constituent unit of the styrene copolymer. [Examples 1 to 9 and Comparative Examples 1 to §] The styrene-maleimide copolymer (4) and the styrene acrylonitrile copolymer (8) produced in the experimental examples are shown in Tables 3 to 4. The ratio (% by mass) was mixed using a Henschel mixer, and a twin-screw extruder (TEM_35B, manufactured by Toshiba Machine Co., Ltd., L/D = 32) was used. Feed amount 2. Kg / hour, screw speed 25 . Under the conditions of the mixture, the particles were granulated to obtain pellets, and a resin composition for an optical molded body was obtained. Furthermore, the tree 曰 曰 > ja degrees are in the range of 2 7 0 to 3 10 ° C. The resin composition for an optical molded body was extruded into a film having a thickness of 100 μm under a condition of a cylinder temperature of 240 t and a mold temperature of 2 in a film extrusion molding machine with a stencil, and wound up into a roll. The resulting film was uniaxially stretched 1.8 times at Tg + 2 Gt: using a tenter transverse stretcher to obtain an extended optical film. The measurement results of the obtained film are shown in Tables 3 to 4. 150156-doc -30· 201120121
【ε<1_—I 實施例9 〇 m 〇 <··Η 〇 (N ΓΟ i Η m m 實施例8 〇 〇 Os o 407 實施例7 〇 in On 寸 o as t—H 00 ο 513 實施例6 〇 in H d 卜 00 ο cn 實施例5 〇 o Q\ 寸 d 卜 r-H ο 470 實施例4 〇 m Q\ 寸 o 122 ν〇 ο 467 實施例3 〇 yn 〇 r-H o 132 as ο 454 實施例2 ο 〇 m cK 寸 d 455 | ,實施例1 ο <N § o od d cn 『丨_一 r—Η ，"··Η oi 寸 [質量％] [質量％] 1 [質量％] 1 1 [質量％] 1 [質量％] 1 [質量％] 1 1 [質量％] 1 [1質量％] 1 [質量％] [質量％] 1 1 [質量％] [質量％] [質量％] [質量％] [質量％] Γ-—1 U»! r—» 1—ί P S^J [g/10 min] [nm] A-l A-2 | A-3 A-4 A-5 A-6 A-7 A-8 A-9 1 B-2 B-3 B-4 B-5 ________J B-6 色相：YI值 霧度 玻璃轉移溫度 MFR 相位差表現性 150156.doc -31 - 201120121 【寸ΐ 比較例8 〇 19.5 wo CN <N <N f—( | 339 I 比較例7 〇 m 00 >10 oo ψ i l> 459 比較例6 〇 <N 寸 ο ON t-H 寸· r-H 1 455 比較例5 〇 13.5 Ο o CN cn T-H 453 比較例4 〇 24.3 m CN 〇\ o 469 比較例3 〇 11.1 c5 g in (N 405 比較例2 12.2 vq o m H 00 o 451 比較例1 〇 vn rn O g r4 | 396 [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] [質量％] r—1 1 U_l (—1 1—1 P [g/10 min] [nm] A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 1 PQ B-2 B-3 B-4 B-5 B-6 色相：YI值 霧度 玻璃轉移溫度 MFR 相位差表現性 150156.doc -32· 201120121 各評價之測定方法如下述。 (1) 色相：YI(Yell〇wIndex，黃色指數）值 色相：YI值係利用射出成形機（東芝機械公司製造之 IS-50EP) ’對以料缸溫度260°C、模具溫度60。(：成形之2 mm之T型板進行成形，根據jis K7105，使用色差計（日本 電色工公司製造之SZ-IIS80)進行測定。色相：將γ〗值為 12 · 0以下者設為色相合格。 (2) 霧度 根據ASTM D1003，使用霧度計（日本電色工業公司製造 之NDH-1 001DP型）測定厚度100 μηι之未延伸膜之霧度（單 位：°/〇)。將霧度之值為1 ·〇%以下者設為未延伸膜之透明性 合格。 (3) 玻璃轉移溫度 玻璃轉移溫度係於下述測定條件下藉由示差掃描熱量測 定（DSC，Differential Scanning Calorimeter)進行測定。 測定機：Robot DSC6200(曰本 Seiko Instruments 公司 製造） 升溫速度：10°C/分鐘 • 將玻璃轉移溫度為110°C以上者設為耐熱性合格。 ' (4)熔體質量流率（MFR，Melt mass-flow rate) 根據JIS K7210，於溫度2〇0°C、負載49 N之條件下測定 熔體質量流率（MFR)。將MFR為0.1〜3(g/l〇 min)設為流動 性合格。 (5)相位差表現性 150156.doc 33· 201120121 使用相位差測定裝置（王子計剛公司製造之k〇bra_wr) 測定延伸膜之延遲（以下稱為「Re」，單位：μιη)，將延遲 為3〇〇 nm以上言史為合格。X，藉由利用相位差顯微鏡進行 觀察，確認實施例與比較例中全部樣品之配向雙折射之符 號均為負。 <結果之研究> 由上述之表3、4之結果可知如下内容。 即，實施例1〜9之光學成形體用樹脂組合物，由於苯乙 烯-馬來醯亞胺系共聚物中之殘留馬來醯亞胺單體量為3〇〇 PPm以下，故而色相.·ΥΙ值較小，其光學成形體之色相優 異。 進而，透明十生、对熱性優異，相位差表現性亦良好，顯 示負的配向雙折射性，因此具備最適合相位差膜之特性。 另一方面，比較例1〜8之光學成形體用樹脂組合物之色 相、透明性、财熱性之任-者均未顯示出作為光學膜之良 好值。 以上，根據實施例對本發明進行了說明。從業者應當理 解該實施例僅為例示，可有各種變形例，且該些變形例亦 包括在本發明之範圍内。 本發明之光學成形體用樹脂組合物及光學成形體，其色 相、透明性、耐熱性良好，對薄型液晶顯示元件用之光學 膜有用，尤其是將其延伸而配向之獏顯示出負的配向雙折 射性，因此對相位差膜有用。 150I56.doc -34-[ε<1_-I Example 9 〇m 〇<··Η 〇(N ΓΟ i Η mm Example 8 〇〇Os o 407 Example 7 〇in On inch o as t-H 00 ο 513 Example 6 〇in H d 卜 ο cn Example 5 Qo Q\ inch d 卜rH ο 470 Example 4 〇m Q\ inch o 122 ν〇ο 467 Example 3 〇yn 〇rH o 132 as ο Example 2 ο 〇m cK inch d 455 |, Example 1 ο <N § o od d cn 『丨_一r—Η ,"··Η oi 寸 [% by mass] [% by mass] 1 [% by mass] 1 1 [% by mass] 1 [% by mass] 1 [% by mass] 1 1 [% by mass] 1 [1% by mass] 1 [% by mass] [% by mass] 1 1 [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] Γ-—1 U»! r—» 1—ί PS^J [g/10 min] [nm] Al A-2 | A-3 A-4 A-5 A-6 A-7 A-8 A-9 1 B-2 B-3 B-4 B-5 ________J B-6 Hue: YI value Haze glass transition temperature MFR Phase difference performance 150156.doc -31 - 201120121 [Inch ΐ Comparative Example 8 19.5 wo CN <N <N f - ( | 339 I Comparative Example 7 〇m 00 > 10 oo ψ i l> 459 Comparative Example 6 〇 <N inch ο ON tH inch · rH 1 455 Comparative Example 5 13.5 Ο o CN cn TH 453 Comparative Example 4 〇24.3 m CN 〇\ o 469 Comparative Example 3 〇11.1 c5 g in (N 405 Comparative Example 2 12.2 vq om H 00 o 451 Comparative Example 1 〇vn rn O g r4 | 396 [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [% by mass] [Quality] %] [% by mass] [% by mass] r—1 1 U_l (—1 1—1 P [g/10 min] [nm] A-1 A-2 A-3 A-4 A-5 A-6 A -7 A-8 A-9 1 PQ B-2 B-3 B-4 B-5 B-6 Hue: YI value Haze glass transition temperature MFR Phase difference performance 150156.doc -32· 201120121 Determination of each evaluation The method is as follows. (1) Hue: YI (Yell 〇 w Index, yellow index) value Hue phase: YI value is obtained by using an injection molding machine (IS-50EP manufactured by Toshiba Machine Co., Ltd.) to a cylinder temperature of 260 ° C and a mold temperature of 60 Å. (: A 2 mm T-shaped plate was formed, and it was measured using a color difference meter (SZ-IIS80 manufactured by Nippon Denshoku Industries Co., Ltd.) according to jis K7105. Hue: Hue with a γ value of 12 · 0 or less (2) Haze According to ASTM D1003, a haze (NDH-1 001DP type manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze of an unstretched film having a thickness of 100 μm (unit: °/〇). The value of the degree is 1% or less, and the transparency of the unstretched film is acceptable. (3) Glass transition temperature The glass transition temperature is measured by Differential Scanning Calorimeter (DSC) under the following measurement conditions. Measurement: Robot DSC6200 (manufactured by Seiko Instruments Co., Ltd.) Heating rate: 10 ° C / min • The glass transition temperature was 110 ° C or higher, and the heat resistance was qualified. ' (4) Melt mass flow rate ( MFR, Melt mass-flow rate) According to JIS K7210, the melt mass flow rate (MFR) is measured at a temperature of 2 〇 0 ° C and a load of 49 N. The MFR is set to 0.1 to 3 (g/l 〇 min). Qualified for mobility. (5) Phase difference performance 150156.doc 33· 201120121 Using a phase difference measuring device (k〇bra_wr manufactured by Oji-ji, Ltd.) The delay of the stretched film (hereinafter referred to as "Re", unit: μιη) was measured, and the delay was 3 〇〇 nm or more. It was confirmed by observation with a phase difference microscope that the signs of the alignment birefringence of all the samples in the examples and the comparative examples were negative. <Results of the results> From the results of Tables 3 and 4 above, the following were known. In the resin composition for optical molded articles of Examples 1 to 9, since the amount of the residual maleimide monomer in the styrene-maleimide copolymer is 3 〇〇 PPm or less, the hue is In addition, it is excellent in the hue of the optical molded body. Further, it is excellent in transparency, excellent in heat resistance, excellent in phase difference expression, and exhibits negative alignment birefringence, and therefore has characteristics most suitable for retardation films. The hue, transparency, and heat-preservation of the resin composition for optical molded articles of Comparative Examples 1 to 8 did not show good values as optical films. The present invention has been described based on the examples. It is to be understood that the embodiment is merely illustrative, and various modifications are possible, and the modifications are also included in the scope of the present invention. The resin composition for optical molded body of the present invention and the optical molded body have hue and transparency. It is excellent in heat resistance, and is useful for an optical film for a thin liquid crystal display device, and particularly exhibits negative alignment birefringence when it is stretched and aligned, and thus is useful for a retardation film. 150I56.doc -34-