200837393 九、發明說明 【發明所屬之技術領域】 本發明係關於一種含有熱塑性樹脂及特定的平均粒徑 的粒子之殘留相位差小的光擴散板及其製造方法。 【先前技術】 使用作爲液晶顯示裝置的光源之背光，爲了確保其亮 度的均勻性，通常使用光擴散板。特別於使用作爲大型液 晶顯示裝置的光源之複數的冷陰極管上，配置光擴散板， 於所謂直下式的背光的情況，確保亮度的均勻性成爲重要 的課題，使用透明的熱塑性樹脂中使有機或無機的微粒子 分散之光擴散性熱塑性樹脂組成物的光擴散板，實質上被 使用作爲必要零件（特開2006-2024號公報）。 這些賦予擴散功能用的粒子，係使用玻璃、二氧化 矽、碳酸鈣、氧化鉻、矽樹脂等的無機粒子、以丙烯酸單 體、苯乙烯單體等爲主成分之聚合·交聯的有機粒子狀的 聚合物。再者，爲了提高光擴散功能與亮度的平衡，也使 用中空的粒子狀物質（特開2006-2024號公報）。 而且，也有藉由於2片偏光板間設置光擴散層，可得 擴散狀態，利用其使光源隱蔽之技術（特開2006-98937 號公報）。但是，於該技術，偏光板之間作爲光擴散層之 層合的材質的扭曲等原因，產生起因於光學扭曲之漏光等 的問題，至今尙未解決該問題。 [專利文獻1]特開2006-2024號公報 -5- 200837393 [專利文獻2 ]特開2 0 0 6 - 9 8 9 3 7號公報 【發明內容】 [發明所欲解決之課題] 本發明係解決伴隨上述傳統技術的問題者，以提供隱 敝〖生ί土且與2片偏先板組合時的顯不對比良好之光擴散板 及其製造方法爲目的。 [解決課題之手段] 本發明人等，爲了解決上述問題點，專心硏究的結 果’發現在特定條件下製造的光擴散板，隱蔽性佳且殘留 相位差小，與2片偏光板組合時的顯示對比良好，因而完 成本發明。 亦即，關於本發明的光擴散板的製造方法，其特徵爲 藉由使含有熱塑性樹脂（Α)及平均粒徑爲1.5〜20μιη的 粒子（Β )而熱塑性樹脂（A )與粒子（Β )的折射率的差 的絕對値爲0.03〜0.08的範圍且該粒子（B)的含有率爲 0.1〜10重量％之樹脂薄片，夾於表面粗糙度〇.3s以下的 金屬滾輪及表面粗糙度〇.3s以下的金屬帶之間，在該金屬 滾輪的溫度比該熱塑性樹脂（A )的玻璃轉化溫度低20〜 5〇°C的條件下捲取。 前述樹脂薄片的捲取速度爲2〜8m/分較理想。而 且，前述樹脂薄片係將含有熱塑性樹脂（A )及平均粒徑 爲1 · 5〜2 Ο μιη的粒子（B )而該粒子（B )的含有率爲〇. 1 200837393 〜10重量％之樹脂組成物，在比前述熱塑性樹脂（A )的 玻璃轉化溫度高100〜13 0°c的溫度熔融擠出所得的薄片。 於本發明，熱塑性樹脂（A )爲環狀烯烴系樹脂較理 想。 _ 關於本發明之光擴散板，其特徵爲含有熱塑性樹脂 ^ (A)及平均粒徑爲1.5〜20μπι的粒子（B)，該粒子 (Β )的含有率爲0.1〜10重量％，殘留相位差爲20nm以 φ 下。於該光擴散板，熱塑性樹脂（A )與粒子（B )的折射 率差的絕對値爲0.03〜0.08的範圍較理想，而且該光擴散 板進而含有螢光增白劑較理想。 [發明的效果] 根據本發明，可得隱蔽性佳且殘留相位差小的光擴散 板。而且，該光擴散板夾於2片偏光板之光學零件，其顯 示對比良好。 【實施方式】 關於本發明之光擴散板，含有熱塑性樹脂（A )及平 均粒徑爲 1.5〜20 μιη的含有率爲 0.1〜10重量％之粒子 (Β )，殘留相位差爲20nm以下。而且，熱塑性樹脂 (A)與粒子（B)的折射率差的絕對値爲0.03〜〇·〇8的 範圍。如此的光擴散板，可藉由以上述含有率含有熱塑性 樹脂（A)及上述平均粒徑的粒子（B )之樹脂薄片，在特 定的條件下捲取而製造。 200837393 (A)熱塑性樹脂： 作爲本發明所使用的熱塑性樹脂（A )，只要是作爲 光學薄膜所使用的熱塑性樹脂，無特別限制，例如聚甲基 丙烯酸甲酯樹脂（PMM A )等丙烯酸酯樹脂、聚碳酸酯樹 脂、環狀烯烴系樹脂、聚芳酯（PAR )、聚碾樹脂 (PSF )、聚醚礪（PES )、聚對苯樹脂（PPP )、聚芳醚 氧化膦樹脂（PEPO )、聚醯亞胺樹脂（PPI )、聚醚醯亞 胺樹脂（PEI )、聚醯胺醯亞胺（PAI )等。這些之中，使 用光學特性、耐熱性及成形性的平衡佳之環狀烯烴系樹脂 特別理想。 作爲上述環狀烯烴系樹脂（以下亦稱爲「環狀烯烴系 樹脂（A )」），例如下述式.（I )所表示的環狀烯烴（以 下亦稱爲「環狀烯烴（I )」）的（共）聚合物。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light diffusing plate comprising a thermoplastic resin and a particle having a specific average particle diameter and having a small residual phase difference, and a method for producing the same. [Prior Art] Using a backlight as a light source of a liquid crystal display device, a light diffusing plate is generally used in order to ensure uniformity of brightness. In particular, when a light-diffusing plate is disposed on a plurality of cold-cathode tubes which are light sources of a large-sized liquid crystal display device, it is an important issue to ensure uniformity of brightness in the case of a so-called direct-type backlight, and organic is used in a transparent thermoplastic resin. A light-diffusing sheet of a light-diffusing thermoplastic resin composition in which inorganic fine particles are dispersed is used as an essential component (JP-A-2006-2024). These particles for imparting a function of diffusion include inorganic particles such as glass, ceria, calcium carbonate, chromium oxide, and ruthenium resin, and polymerized/crosslinked organic particles mainly composed of an acrylic monomer or a styrene monomer. Shaped polymer. Further, in order to improve the balance between the light diffusion function and the brightness, a hollow particulate material is also used (JP-A-2006-2024). Further, there is a technique in which a light diffusion layer is provided between two polarizing plates to obtain a diffused state, and a light source is concealed by the light source (JP-A-2006-98937). However, in this technique, the problem of light leakage due to optical distortion or the like occurs as a material of the laminated material of the light diffusion layer between the polarizing plates, and the like has not been solved. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-2024-5-200837393 [Patent Document 2] Japanese Patent Application Laid-Open No. Hei 2 0 0 6 - 9 8 9 3 7 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention is In order to solve the problems associated with the above-mentioned conventional techniques, it is intended to provide a light diffusing plate which is inferior in comparison with two sheets of partial slabs and a method for manufacturing the same. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have found that the light diffusing plate manufactured under specific conditions has good concealability and small residual phase difference, and is combined with two polarizing plates. The display is well contrasted and thus the present invention has been completed. That is, the method for producing a light-diffusing sheet according to the present invention is characterized in that the thermoplastic resin (A) and the particles (Β) are obtained by containing a thermoplastic resin (Α) and particles (Β) having an average particle diameter of 1.5 to 20 μm. A resin sheet having an absolute 値 of a difference in refractive index of 0.03 to 0.08 and a content of the particle (B) of 0.1 to 10% by weight, and a metal roller having a surface roughness of 〇.3 s or less and surface roughness 〇 The metal strips below 3 s are taken up under the condition that the temperature of the metal roller is 20 to 5 ° C lower than the glass transition temperature of the thermoplastic resin (A). The winding speed of the resin sheet is preferably 2 to 8 m/min. Further, the resin sheet contains the thermoplastic resin (A) and the particles (B) having an average particle diameter of 1 · 5 to 2 Ο μηη, and the content of the particles (B) is 〇. 1 200837393 〜10% by weight of the resin The composition is melt-extruded at a temperature higher by 100 to 13 ° C than the glass transition temperature of the thermoplastic resin (A). In the present invention, the thermoplastic resin (A) is preferably a cyclic olefin resin. _ The light diffusing plate of the present invention is characterized in that it contains a thermoplastic resin (A) and particles (B) having an average particle diameter of 1.5 to 20 μm, and the content of the particles (Β) is 0.1 to 10% by weight, and the residual phase The difference is 20 nm to φ. In the light-diffusing sheet, the absolute enthalpy of the difference in refractive index between the thermoplastic resin (A) and the particles (B) is preferably in the range of 0.03 to 0.08, and the light-diffusing sheet further contains a fluorescent whitening agent. [Effect of the Invention] According to the present invention, a light diffusing plate which is excellent in concealing property and has a small residual phase difference can be obtained. Moreover, the light diffusing plate was sandwiched between the optical components of the two polarizing plates, and the display was well contrasted. [Embodiment] The light-diffusing sheet of the present invention contains a thermoplastic resin (A) and particles (Β) having a content of 0.1 to 10% by weight of an average particle diameter of 1.5 to 20 μm, and a residual phase difference of 20 nm or less. Further, the absolute enthalpy of the difference in refractive index between the thermoplastic resin (A) and the particles (B) is in the range of 0.03 to 〇·〇8. Such a light-diffusing sheet can be produced by winding a resin sheet containing the thermoplastic resin (A) and the particles (B) having the above average particle diameter under the above-described conditions under specific conditions. 200837393 (A) Thermoplastic Resin: The thermoplastic resin (A) used in the present invention is not particularly limited as long as it is a thermoplastic resin used as an optical film, for example, an acrylate resin such as polymethyl methacrylate resin (PMM A ). , polycarbonate resin, cyclic olefin resin, polyarylate (PAR), poly-rolled resin (PSF), polyether oxime (PES), polyparaphenylene resin (PPP), polyarylene oxide phosphine oxide resin (PEPO) Polyimine resin (PPI), polyether phthalimide resin (PEI), polyamidimide (PAI), and the like. Among these, a cyclic olefin-based resin excellent in balance of optical properties, heat resistance and moldability is particularly preferable. The cyclic olefin resin (hereinafter also referred to as "cyclic olefin resin (A)"), for example, a cyclic olefin represented by the following formula (I) (hereinafter also referred to as "cyclic olefin (I)) ()) (co)polymer.
式（I)中，R1〜R4分別爲獨立的氫原子、鹵原子或 1價有機基，R1及R2、或R3及R4也可一體化形成2價有 機基，R1及R2、或R3及R4也可互相結合形成單環構造 或多環構造。m爲〇或正的整數，P爲〇或正的整數。 作爲更具體的環狀烯烴系樹脂（A ) ’例如 -8- 200837393 (1)環狀烯烴（I)的開環聚合物（以下亦稱爲「聚 合物（1 )」）； (2 )環狀烯烴（I )與共聚合性單體的開環聚合物 (以下亦稱爲「聚合物（2 )」）； _ (3)聚合物（1)或聚合物（2)的氫化（共）聚合 ‘物（以下亦稱爲「聚合物（3 )」）·， (4)聚合物（1)或聚合物（2)藉由夫-夸 φ ( Friedel-Krafts )反應環化後氫化的（共）聚合物（以下 亦稱爲「聚合物（4 )」）； (5)環狀烯烴（I)與含有不飽和雙鍵之化合物的飽 和共聚合物（以下亦稱爲「聚合物（5 )」）； (6 )環狀烯烴（I )與選自乙烯基系環狀烴系單體及 環戊二烯系單體中1種以上的單體之加成型（共）聚合物 及其氫化（共）聚合物（以下亦稱爲「聚合物 (6)」）； φ (7)環狀烯烴（1)與丙烯酸酯的交互共聚合物（以 下亦稱爲「聚合物（7)」）。 這些之中，以透明性佳的點，使用聚合物（3 )特別 理想。 <環狀烯烴（〇 > 作爲上述式（1 )之1價有機基，例如碳數1〜3 0的 烴基、烴基以外的1價極性基。作爲上述1價極性基，例 如羧基、羥基、烷氧基羰基、芳香氧基羰基、胺基、醯胺 -9- 200837393 基、氰基等，這些極性基可介由亞甲基等的連結基鍵結。 而且，介由羰基、醚基、矽醚基、硫醚基、亞胺基等具有 極性的2價有機基所構成的連結基鍵結的烴基等也可作爲 極性基。這些極性基中，以羧基、羥基、烷氧基羰基及芳 香氧基羰基較理想，以烷氧基羰基及芳香氧基羰基特別理 相 〇 上述式（I )所表示的環狀烯烴，可1種單獨使用， 也可倂用2種以上。 作爲上述式（I )所表示的環狀烯烴，例如以下的化 合物，但不限於這些化合物。 雙環[2·2·1]庚-2-烯； 三環[4.3·0·12’5]-8-癸烯； 三環[HO·：!2’5]-]·十一烯； 四環[4·4·0·12,5·17，1()]-3-十二烯； 五環[6.5.1.1 3,6.02,7.09，13]-4-十五烯等。 5-甲基雙環[2.2.1]庚-2-烯； 5-乙基雙環[2·2·1]庚-2-烯； 5-甲氧基羰基雙環[2·2·1]庚-2-烯； 5-甲基-5-甲氧基羰基雙環[2.2.1]庚-2-烯； 5-氰基雙環[2·2·1]庚-2-烯等。 8 -甲氧基鑛基四環[4.4.0.12,5·ι7，10]_3 -十二烯； 8-乙氧基羰基四環[4.十二烯； 8-正丙氧基羰基四環 8 -異丙氧基羰基四環[4.4.0.12,5.17，1()]-3-十二烯； -10- 200837393 8-正丁甲氧基羰基四環[4·4.0·12ΛΓ’1()]-3-十二烯； 8 -甲基-8 -甲氧基羰基四環[4·4·Ο·12,5·Γ’10]-3 -十二 烯； 8_甲基_8_乙氧基羰基四環[4·4·0.12,5·17，1()]-3 -十二 烯； 8_甲基-8-正丙氧基羰基四環[4.4.0· 烯； 8-甲基-8-異丙氧基羰基四環[4.4.O.l2’5·】7’1 G]-3-十二 烯； 8-甲基-8-正丁氧基羰基四環[4.4.0.12’5.；17，1()]-3-十二 烯等。 5-亞乙基雙環[2.2.1]庚-2-烯； 8-亞乙基四環[4.4.0.12’5.17’1()]-3-十二烯等。 5-苯基雙環[2·2·1]庚-2-烯； 8-苯基四環[4.4.0.12,5.17，1()]-3-十二烯等。 5-氟雙環[2.2.1]庚-2-烯； 5-氟甲基雙環[2.2.1]庚-2-烯； 5·三氟甲基雙環[2.2.1]庚-2-烯； 5-五氟乙基雙環[2.2.1]庚-2-烯等。 5.5- 二氟雙環[2.2.1]庚-2-烯； 5,6·二氟雙環[2.2.1]庚-2-烯； 5.5- 雙（三氟甲基）雙環[2.2.1]庚-2-烯； 5.6- 雙（三氟甲基）雙環[2.2.1]庚-2-烯； 5-甲基-5-三氟甲基雙環[2.2.1]庚-2-烯等。 -11 - 200837393 5.5.6- 三氟雙環[2·2·1]庚-2-烯； 5.5.6- 三（氟甲基）雙環[2·2·1]庚-2·烯等。 5.5.6.6- 四氟雙環[2.2.1]庚-2-烯； 5.5.6.6- 四（三氟甲基）雙環[2.2.1]庚-2-烯； 5.5- 二氟-6,6-雙（三氟甲基）雙環[2·2·1]庚-2-烯； 5.6- 二氟-5,6-雙（三氟甲基）雙環[2·2·1]庚-2-烯； 5.5.6- 三氟_5_三氟甲基雙環[2.2.1]庚-2-烯； 5-氟-5-五氟乙基-6,6-雙（三氟甲基）雙環[2.2.1]庚-2-烯； 5，6-二氟-5-七氟異丙基-6-三氟甲基雙環[2.2.1]庚-2· 烯； 5-氯-5,6,6-三氟雙環[2.2·1]庚-2-烯； 5.6- 二氯-5,6-雙（三氟甲基）雙環[2·2·1]庚-2-烯； 5.5.6- 三氟-6-三氟甲氧基雙環[2.2.1]庚-2-烯； 5.5.6- 三氟-6-七氟丙氧基雙環[2.2.1]庚-2-烯等。 8-氟四環[4.4.0.12’5.17’1()]-3-十二烯； 8-氟甲基四環[4.4.0.1 2’5 ·Γ，1ϋ]-3-十二烯； 8·二氟甲基四環[4·4.0·12,5·17，1()]-3-十二烯； 8-三氟甲基四環[4.4.0.12,5· 〗7，1 G]-3-十二烯； 8-五氟乙基四環[4.4.0.I2’5·〗7’1 G]-3-十二烯等。 8.8- 二氟四環[4 ·4· 0.1 2’5.17’10]-3-十二烯； 8，9-二氟四環[4.4.0· 1 2,5. 17，1G]-3-十二烯； 8.8- 雙（三氟甲基）四環[4.4.0.12,5.17，1()]-3-十二烯； 8.9- 雙（三氟甲基）四環[4.4.0.12,5.l7，1G]-3-十二烯； -12- 200837393 8-甲基-8-三氟甲基四環[4·4·0·12,5.Γ，1()]-3-十二烯 等。 8,859-三氟四環[4.4.0.12,5.17，1()]-3-十二烯； 8.8.9- 三（三氟甲基）四環[4·4·0·12,5·Γ，1{)]-3-十二烯 等。 8.8.9.9- 四氟四環[4·4.0.12,5·17，1()]-3-十二烯； 8.8.9.9- 四（三氟甲基）四環[4·4·〇·12,5·17，1()]·3-十二 烯； 8.8- 二氟-9,9-雙（三氟甲基）四環[4.4.0.12,5.17，1()]-3- 十二烯； 8.9- 二氟-8,9-雙（三氟甲基）四環[4.4.0.12,5.l7，1()]-3- 十 二烯； 8.8.9- 三氟-9_三氟甲基四環[4.4.0.12,5.17，1()]_3-十二 烯； 8.8.9- 三氟-9-三氟甲氧基四環[4.4.0.12,5.17，1()]-3-十二 烯； 8.8.9- 三氟-9-五氟丙氧基四環[4.4.0.12,5.17，1()]-3-十二 燒； 8-氟-8·五氟乙基-9,9-雙（三氟甲基）四環 [4.4·0·12,5·17，1()]·3-十二烯； 8,9-二氟-8-七氟異丙基-9-三氟甲基四環 [4·4.0.12’5·17’1()]>3·十二烯； 8-氯-859,9-三氟四環[4.4.0.12,5.17，1()]-3-十二烯； 8.9- 二氯-8,9-雙（三氟甲基）四環[4·4.0·12,5·17，1()]·3- -13- 200837393 十二烯等。 8- ( 2,2,2-三氟乙氧基羰基）四環[4.4.0.12,5.17，1g]-3-十二燒； 8 -甲基-8 - ( 2，2，2 -三氟乙氧基鑛基）四環 [4.4.0.12’5.17’1{)]-3-十二烯等。 如此的環狀烯烴中，於上述式（I )，R1及R3分別爲 獨立的氫原子或碳數較理想爲1〜10、更理想爲1〜4、特 別理想爲1或2的烴基，較理想爲烷基，特別理想爲甲 基；R2及R4分別爲獨立的氫原子或1價有機基，且R2及 R4中至少之一爲氫原子或上述1價極性基；m爲0〜3的 整數較理想，p爲0〜3的整數較理想，更理想地m + p爲〇 〜4，特別理想地m + p爲0〜2，最理想爲m= 1、p = 0之環 狀烯烴。m=l、p = 0之環狀烯烴，從可得玻璃轉化溫度高 且機械強度也佳之環狀烯烴系樹脂的點，故較理想。 再者，R2及R4中至少之一爲下述式（II)所表示的 極性基之環狀烯烴，從可得具有高玻璃轉化溫度及低吸濕 性、與各種材料的良好的密合性之環狀烯烴系樹脂的點， 故較理想。 -(CH2)nCOOR (II) 上述式（II)中，R爲碳數較理想爲1〜12、更理想 爲1〜4、特別理想爲1或2的烴基，較理想爲燒基。而 且，η通常爲0〜5，η値越小的環狀烯烴，因可得玻璃轉 -14- 200837393 化溫度越高的環狀烯烴系樹脂，所以較理想，η爲0之環 狀烯烴，因容易合成的點，所以較理想。 特別是上述式（II )所表示的極性基，係鍵結於作爲 烷基的R1或R3所鍵結的碳原子，因可得吸濕性低的環狀 烯烴系樹脂的點，所以較理想。 聚合物（1)及聚合物（2): 上述聚合物（1 )及聚合物（2 )，係藉由在複分解 (metathesis )觸媒存在下，使上述環狀嫌烴進行開環聚 合，或使上述環狀烯烴與共聚合性單體進行開環共聚合而 得。 <共聚合性單體> 作爲聚合物（2)所使用的共聚合性單體，例如環烯 烴，期望爲碳數較理想爲4〜20、更理想爲5〜12的環烯 烴。更具體地，例如環丁烯、環戊烯、環庚烯、環辛烯、 二環戊二烯等。這些環烯烴，可單獨1種使用，也可倂用 2種以上。 上述環狀烯烴與上述共聚合性單體的使用比例’以重 量比（環狀烯烴/共聚合性單體），1〇0/0〜50/5 0較理 想，1 00/0〜6〇/4〇較理想。而且，「環狀烯烴/共聚合性 單體=1 0 0/0」係指環狀烯烴單獨聚合的使用比例。 <開環聚合用觸媒> -15- 200837393 開環（共）聚合反應所使用的複分解觸媒，係由下述 化合物（a )及化合物（b )的組合所構成之觸媒。 (a)含有選自W、Mo及Re中至少1種的元素之化 合物。 (b )含有選自戴明（Deming )週期表IA族元素（例 如Li、Na、K等）、IIA族元素（例如Mg、Ca等）、：[IB 族元素（例如Zn、Cd、Hg等）、ΙΙΙΑ族元素（例如B、 A1等）、IVA族元素（例如Si、Sn、Pb等）及IVB族元 素（例如Ti、Zr等）中至少1種的元素之化合物，選自 至少具有前述元素與碳的鍵結或前述元素與氫的鍵結中之 一的化合物中至少1種的化合物。 而且’上述複分解觸媒，爲了提高其活性，也可含有 後述的添加劑（c )。 作爲上述化合物（a )的具體例，例如 WC16、 MoC16、ReOCl3等、由特開平1-132626號公報的第8頁左 上欄第6行〜第8頁右上欄第1 7行所記載的化合物。 作爲上述化合物（b )的具體例，n-C4H9Li、 (C2H5)3A1、（C2H5)2A1C1、（C2H5)15A1C115、（C2H5)A1C12、 甲基銘氧院（methylaluminoxane) 、LiH等、由特開平1-132626號公報的第8頁右上欄第18行〜第8頁右下欄第 3行所記載的化合物。 作爲上述添加劑（c )，可適合使用醇類、醛類、酮 類、胺類等，再者可使用由特開平1 - 1 32626號公報的第8 頁右下欄第16行〜第9頁左上欄第17行所記載的化合 •16- 200837393 物。 上述化合物（a )及化合物（b )的比例，以金屬原子 比[(a ) : ( b )]，通常爲1 : 1〜1 : 5 0，較理想爲1 : 2 〜1 : 3 0 〇 上述化合物（c )及化合物（a )的比例，以莫耳比 [(c) ： (a)]，通常爲0.005: 1〜15: 1，較理想爲 0.05 : 1 〜7 : 1。 複分解觸媒的使用量，上述化合物（a)與環狀烯烴 的莫耳比[(a):環狀烯烴]通常爲1 : 500〜1 : 50,000， 較理想爲1 : 1，000 : 1 : 1 〇,〇〇〇所成的量。 <聚合反應用溶劑> 於開環（共）聚合反應，溶劑可使用後述構成分子量 調節劑溶液的溶劑、作爲環狀烯烴及/或複分解觸媒的溶 劑。作爲如此的溶劑，例如戊烷、己烷、庚烷、辛烷、壬 烷、癸烷等的烷類；環己烷、環庚烷、環辛烷、十氫萘 (decalin)、降莰院（norbornane)等環院類；苯、甲 苯、二甲苯、乙苯、異丙苯等芳香族烴；氯丁烷、溴己 烷、二氯甲烷、二氯乙烷、二溴己烷、三氯甲烷、四氯乙 烯等鹵化烷；氯苯等鹵化芳香烴；乙酸乙酯、乙酸正丁 酯、乙酸異丁酯、丙酸甲酯、二甲氧基乙烷等飽和羧酸酯 類。這些溶劑，可單獨或混合使用。這些之中，以芳香族 烴較理想。 溶劑的使用量，以溶劑與環狀烯烴的重量比（溶劑： -17- 200837393 環狀嫌烴），通常期望爲hi〜1〇:1，較理想爲1:1〜 5 : 1所成的量。 <分子量調節劑> 所得的開環（共）聚合物的分子量，雖可藉由聚合的 溫度、觸媒的種類、溶劑的種類而進行調節，也可藉由使 分子量調節劑共存於反應系統而進行調節。 作爲適合的分子量調節劑，例如乙烯、丙烯、i _ 丁 烯、1 -戊細、1 -己稀、1 -庚烯、1 -辛燦、1 _壬烯、^癸嫌 等α -烯烴類及苯乙烯，這些之中，以1 · 丁烯、1 -己烯特別 理想。而且’這些分子量調節劑，可單獨或混合2種以上 使用。 分子量調節劑的使用量，對供應給開環聚合反應之環 狀烯煙1莫耳而言，通常爲0.005〜0.6莫耳，較理想爲 0.0 1〜〇 · 5莫耳。 上述開環共聚合物，可使環狀烯烴與共聚合性單體進 行開環共聚合而得，再者，也可在聚丁二烯、聚異戊二烯 等共軛二嫌化合物、苯乙烯-丁二烯共聚合物、乙烯-非共 軛二嫌共聚合物、聚冰片烯等的主鏈含有2個以上的碳_ 碳間雙鍵之不飽和烴系聚合物等的存在下，使環狀烯烴開 環共聚合。 (3 )氫化（共）聚合物： 上述開環（共）聚合物，可依照原樣使用，也可將其 -18- 200837393 氫化後所得的氫化（共）聚合物（3 )，也有用於作爲耐 衝擊性佳的樹脂。 氫化反應可藉由一般的方法進行，亦即於含有開環 (共）聚合物的溶液中添加氫化觸媒，將其與常壓〜300 大氣壓，較理想爲3〜200大氣壓的氫氣，在〇〜2〇〇。〇 下，較理想爲20〜18(TC下作用而進行。 <氫化觸媒> 作爲上述氫化觸媒，可使用一般的烯烴性化合物的氫 化反應所使用的觸媒。作爲該氫化觸媒，例如不均勻系觸 媒及均勻系觸媒。 作爲不均勻系觸媒，例如使鈀、鉑、鎳、铑、釕等貴 重金屬觸媒物質載持於碳、二氧化砍、氧化銘、氧化欽等 載體之固體觸媒。作爲均勻系觸媒，例如環烷酸鎳/三乙 基鋁、乙醯丙酮鎳/三乙基鋁、辛烯酸鈷/正丁基鋰、二氯 二茂鈦/氯化二乙基鋁、乙酸鍺、氯三（三苯膦）鍺、二 氯三（三苯膦）釕、二氯氫羰基三（三苯膦）釕等。這些 觸媒的形態，可爲粉末或粒狀。 這些氫化觸媒，以開環（共）聚合物與氫化觸媒的重 量比（開環（共）聚合物：氫化觸媒），以1 : 1 X 1 (Γ6〜 1 : 2所成的比例使用較理想。 上述氫化（共）聚合物（3)，具有良好的熱安定 性’即使成形加工時、作爲製品使用時的加熱，其特性也 不會劣化。 -19- 200837393 氫化（共）聚合物（3 )的氫化率，藉由500 MHz的 條件下1H-NMR之測定値，通常爲50%以上，較理想爲 70%以上，更理想爲90%以上，特別理想爲98%，最理想 爲99%以上。氫化率越高，可得具有對熱、光之安定性 ' 佳、歷經長時間安定的特性之光擴散板。 ' 而且，上述氫化（共）聚合物（3)，其凝膠含量爲5 重量％以下較理想，特別是1重量％以下較理想。 (4 )氫化（共）聚合物： 上述氫化（共）聚合物（4 )係上述（1)或（2)的 開環（共）聚合物藉由夫·夸（Friedel-Krafts )反應環化 後氫化而得。 上述開環（共）聚合物藉由夫-夸反應環化的方法， 無特別限制，可採用例如特開昭50- 1 543 99號公報所記載 的使用酸性化合物之習知的方法。 φ 作爲上述酸性化合物，具體地例如 A1C13、BF3、In the formula (I), R1 to R4 are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R1 and R2, or R3 and R4 may be integrated to form a divalent organic group, R1 and R2, or R3 and R4. They may also be combined with each other to form a single ring structure or a multi-ring structure. m is 〇 or a positive integer and P is 〇 or a positive integer. More specifically, the cyclic olefin-based resin (A) 'for example, -8-200837393 (1) a ring-opening polymer of a cyclic olefin (I) (hereinafter also referred to as "polymer (1)"); (2) a ring Ring-opening polymer of olefin (I) and copolymerizable monomer (hereinafter also referred to as "polymer (2)"); _ (3) hydrogenation of polymer (1) or polymer (2) Polymerization (hereinafter also referred to as "polymer (3)"), (4) polymer (1) or polymer (2) is hydrogenated by cyclization of Friedel-Krafts reaction (total a polymer (hereinafter also referred to as "polymer (4)"); (5) a saturated olefin of a cyclic olefin (I) and a compound containing an unsaturated double bond (hereinafter also referred to as "polymer (5) (6) Addition (co)polymer of a cyclic olefin (I) and one or more monomers selected from the group consisting of a vinyl-based cyclic hydrocarbon monomer and a cyclopentadiene monomer, and hydrogenation thereof (co)polymer (hereinafter also referred to as "polymer (6)"); π (7) cross-copolymer of cyclic olefin (1) and acrylate (hereinafter also referred to as "polymer (7)") . Among these, it is particularly preferable to use the polymer (3) at a point where transparency is good. <Cyclic olefin (〇) The monovalent organic group of the above formula (1), for example, a hydrocarbon group having 1 to 30 carbon atoms or a monovalent polar group other than a hydrocarbon group. Examples of the monovalent polar group include a carboxyl group and a hydroxyl group. , alkoxycarbonyl, aryloxycarbonyl, amine, decyl-9-200837393, cyano, etc., these polar groups may be bonded via a linking group such as a methylene group. Further, a carbonyl group or an ether group is bonded. A carboxyl group-bonded hydrocarbon group composed of a polar divalent organic group such as an anthranyl ether group, a thioether group or an imine group may be used as a polar group. Among these polar groups, a carboxyl group, a hydroxyl group, and an alkoxycarbonyl group are mentioned. And a aryloxycarbonyl group, and a cyclic olefin represented by the above formula (I), which may be used in combination with the alkoxycarbonyl group and the aryloxycarbonyl group, may be used singly or in combination of two or more. The cyclic olefin represented by the formula (I) is, for example, the following compounds, but is not limited thereto. Bicyclo[2·2·1]hept-2-ene; tricyclo[4.3·0·12'5]-8- Terpene; tricyclo[HO·:!2'5]-]·undecene; tetracyclo[4·4·0·12,5·17,1()]-3-dodecene; 6.5.1.1 3,6.02,7.09,13]-4-pentadecenyl, etc. 5-methylbicyclo[2.2.1]hept-2-ene; 5-ethylbicyclo[2·2·1]hept-2-ene; 5-methoxycarbonylbicyclo[2·2·1]hept-2-ene; 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene; 5-cyanobicyclo[2 ·2·1]hept-2-ene, etc. 8-methoxyl base tetracyclo[4.4.0.12,5·ι7,10]_3-dodecene; 8-ethoxycarbonyltetracyclo[4. Diene; 8-n-propoxycarbonyltetracyclo 8-isopropoxycarbonyltetracyclo[4.4.0.12,5.17,1()]-3-dodecene; -10- 200837393 8-n-butoxy Carbonyltetracyclo[4·4.0·12ΛΓ'1()]-3-dodecene; 8-methyl-8-methoxycarbonyltetracyclo[4·4·Ο·12,5·Γ'10]- 3-dodecene; 8_methyl_8_ethoxycarbonyltetracyclo[4·4·0.12,5·17,1()]-3-dodecene; 8_methyl-8-n-propene Oxycarbonylcarbonyltetracyclo[4.4.0·ene; 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.O.l2'5·]7'1 G]-3-dodecene; 8- Methyl-8-n-butoxycarbonyltetracyclo[4.4.0.12'5.;17,1()]-3-dodecene, etc. 5-Ethylenebicyclo[2.2.1]hept-2-ene ; 8-ethylenetetracyclo[4.4.0.12'5.17'1()]-3-dodecene, etc. 5-phenylbicyclo[2·2·1]g 2-ene; 8-phenyltetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, and the like. 5-fluorobicyclo[2.2.1]hept-2-ene; 5-fluoromethylbicyclo[2.2.1]hept-2-ene; 5·trifluoromethylbicyclo[2.2.1]hept-2-ene; 5-pentafluoroethylbicyclo[2.2.1]hept-2-ene and the like. 5.5-Difluorobicyclo[2.2.1]hept-2-ene; 5,6·difluorobicyclo[2.2.1]hept-2-ene; 5.5-bis(trifluoromethyl)bicyclo[2.2.1]g -2-ene; 5.6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene; 5-methyl-5-trifluoromethylbicyclo[2.2.1]hept-2-ene. -11 - 200837393 5.5.6-Trifluorobicyclo[2·2·1]hept-2-ene; 5.5.6-tris(fluoromethyl)bicyclo[2·2·1]heptane-2-ene. 5.5.6.6- Tetrafluorobicyclo[2.2.1]hept-2-ene; 5.5.6.6-tetrakis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene; 5.5-difluoro-6,6- Bis(trifluoromethyl)bicyclo[2·2·1]hept-2-ene; 5.6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2·2·1]hept-2-ene 5.5.6-Trifluoro-5-trifluoromethylbicyclo[2.2.1]hept-2-ene; 5-fluoro-5-pentafluoroethyl-6,6-bis(trifluoromethyl)bicyclo[ 2.2.1]hept-2-ene; 5,6-difluoro-5-heptafluoroisopropyl-6-trifluoromethylbicyclo[2.2.1]hept-2·ene; 5-chloro-5,6 , 6-trifluorobicyclo[2.2.1]hept-2-ene; 5.6-dichloro-5,6-bis(trifluoromethyl)bicyclo[2·2·1]hept-2-ene; 5.5.6 - Trifluoro-6-trifluoromethoxybicyclo[2.2.1]hept-2-ene; 5.5.6-Trifluoro-6-heptafluoropropoxybicyclo[2.2.1]hept-2-ene. 8-fluorotetracyclo[4.4.0.12'5.17'1()]-3-dodecene; 8-fluoromethyltetracyclo[4.4.0.1 2'5 ·Γ,1ϋ]-3-dodecene; 8 Difluoromethyltetracyclo[4·4.0·12,5·17,1()]-3-dodecene; 8-trifluoromethyltetracycline [4.4.0.12,5· 〗 7,1 G] 3-dodecene; 8-pentafluoroethyltetracyclo[4.4.0.I2'5·]7'1 G]-3-dodecene. 8.8-Difluorotetracyclo[4 ·4·0.1 2'5.17'10]-3-dodecene; 8,9-difluorotetracyclo[4.4.0· 1 2,5. 17,1G]-3- Decadiene; 8.8-bis(trifluoromethyl)tetracyclo[4.4.0.12,5.17,1()]-3-dodecene; 8.9-bis(trifluoromethyl)tetracyclo[4.4.0.12,5 .l7,1G]-3-dodecene; -12- 200837393 8-methyl-8-trifluoromethyltetracyclo[4·4·0·12,5.Γ,1()]-3-10 Diene, etc. 8,859-trifluorotetracyclo[4.4.0.12,5.17,1()]-3-dodecene; 8.8.9-tris(trifluoromethyl)tetracyclo[4·4·0·12,5·Γ, 1{)]-3-dodecene and the like. 8.8.9.9- Tetrafluorotetracyclo[4·4.0.12,5·17,1()]-3-dodecene; 8.8.9.9- Tetra(trifluoromethyl)tetracyclo[4·4·〇· 12,5·17,1()]·3-dodecene; 8.8-difluoro-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.12,5.17,1()]-3- Diene; 8.9-difluoro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.12,5.l7,1()]-3-decadiene; 8.8.9-trifluoro-9_ Trifluoromethyltetracyclo[4.4.0.12, 5.17,1()]-3-dodecene; 8.8.9-trifluoro-9-trifluoromethoxytetracyclo[4.4.0.12, 5.17,1()] -3-dodecene; 8.8.9-trifluoro-9-pentafluoropropoxytetracyclo[4.4.0.12,5.17,1()]-3-d-decyl; 8-fluoro-8·pentafluoro Base-9,9-bis(trifluoromethyl)tetracyclo[4.4.0·12,5·17,1()]·3-dodecene; 8,9-difluoro-8-heptafluoroisopropyl -9-trifluoromethyltetracyclo[4.4.0.12'5·17'1()]>3·dodecene; 8-chloro-859,9-trifluorotetracycline [4.4.0.12, 5.17,1()]-3-dodecene; 8.9-dichloro-8,9-bis(trifluoromethyl)tetracyclo[4·4.0·12,5·17,1()]·3- 13- 200837393 Decadiene, etc. 8-(2,2,2-Trifluoroethoxycarbonyl)tetracyclo[4.4.0.12,5.17,1g]-3-dodecan; 8-methyl-8 - (2,2,2-trifluoro Ethoxylate base) tetracyclo[4.4.0.12'5.17'1{)]-3-dodecene and the like. In such a cyclic olefin, in the above formula (I), R1 and R3 are each independently a hydrogen atom or a hydrocarbon group having a carbon number of preferably 1 to 10, more preferably 1 to 4, particularly preferably 1 or 2. It is preferably an alkyl group, particularly preferably a methyl group; R2 and R4 are each independently a hydrogen atom or a monovalent organic group, and at least one of R2 and R4 is a hydrogen atom or the above monovalent polar group; m is 0 to 3 The integer is more desirable, and the integer of p is 0 to 3 is more desirable, and more desirably, m + p is 〇 〜 4, particularly preferably m + p is 0 〜 2, and most preferably m = 1 and p = 0 cyclic olefin . The cyclic olefin having m = 1 and p = 0 is preferred from the viewpoint of obtaining a cyclic olefin-based resin having a high glass transition temperature and excellent mechanical strength. Further, at least one of R2 and R4 is a cyclic olefin having a polar group represented by the following formula (II), and has high glass transition temperature and low hygroscopicity, and good adhesion to various materials. The point of the cyclic olefin resin is preferable. -(CH2)nCOOR (II) In the above formula (II), R is preferably a hydrocarbon group having a carbon number of preferably 1 to 12, more preferably 1 to 4, particularly preferably 1 or 2. More preferably, it is an alkyl group. Further, η is usually 0 to 5, and a smaller η値 is a cyclic olefin, and since a cyclic olefin-based resin having a higher glass transition temperature of from 14 to 200837 is obtained, a cyclic olefin having a η of 0 is preferable. It is ideal because it is easy to synthesize. In particular, the polar group represented by the above formula (II) is bonded to a carbon atom bonded to R1 or R3 which is an alkyl group, and is preferable because a point of a cyclic olefin-based resin having low hygroscopicity can be obtained. . Polymer (1) and polymer (2): the above polymer (1) and polymer (2) are subjected to ring-opening polymerization in the presence of a metathesis catalyst, or The cyclic olefin is obtained by subjecting a copolymerizable monomer to ring-opening copolymerization. <Copolymerizable monomer> As the copolymerizable monomer used in the polymer (2), for example, a cycloolefin, a cycloolefin having a carbon number of preferably 4 to 20, more preferably 5 to 12 is desirable. More specifically, for example, cyclobutene, cyclopentene, cycloheptene, cyclooctene, dicyclopentadiene, and the like. These cyclic olefins may be used alone or in combination of two or more. The ratio of use of the above cyclic olefin to the above-mentioned copolymerizable monomer is preferably a weight ratio (cyclic olefin/copolymerizable monomer) of from 1 〇0/0 to 50/5 0, and is preferably from 100/0 to 6 Torr. /4〇 is ideal. Further, the "cyclic olefin / copolymerizable monomer = 1.0 / 0" means the use ratio of the cyclic olefin alone polymerization. <Catalyst for ring-opening polymerization> -15- 200837393 The metathesis catalyst used in the ring-opening (co)polymerization reaction is a catalyst composed of a combination of the following compound (a) and compound (b). (a) A compound containing an element selected from at least one of W, Mo and Re. (b) containing elements selected from Group IA of the Deming periodic table (eg, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), : [Group IB elements (eg, Zn, Cd, Hg, etc.) a compound of at least one of a lanthanide element (e.g., B, A1, etc.), an IVA group element (e.g., Si, Sn, Pb, etc.) and a group IVB element (e.g., Ti, Zr, etc.), selected from at least the foregoing A compound of at least one of a bond of an element to carbon or a bond of one of the aforementioned elements and hydrogen. Further, the above-mentioned metathesis catalyst may contain an additive (c) to be described later in order to enhance the activity. Specific examples of the compound (a) include, for example, WC16, MoC16, ReOCl3, and the like, which are described in JP-A-1-132626, page 8, page 6 of the upper left column, and line 7 of the upper right column of page 8. Specific examples of the compound (b) include n-C4H9Li, (C2H5)3A1, (C2H5)2A1C1, (C2H5)15A1C115, (C2H5)A1C12, methylaluminoxane, LiH, etc. The compound described in the third column of the upper right column of the eighth page of the -132626, and the third row of the lower right column of the eighth page. As the above-mentioned additive (c), alcohols, aldehydes, ketones, amines, and the like can be suitably used, and further, it is possible to use the eighth column from the lower right column of the Japanese Patent Publication No. 1 - 1 32626, the 16th to the 9th. Compound No. 16-200837393 recorded on the 17th line of the upper left column. The ratio of the above compound (a) to the compound (b) is, in terms of metal atomic ratio [(a) : (b)], usually 1:1 to 1:50, more preferably 1:2 to 1: 3 0 〇 The ratio of the above compound (c) to the compound (a) is, in terms of molar ratio [(c): (a)], usually 0.005:1 to 15:1, more preferably 0.05:1 to 7:1. The amount of the metathesis catalyst used, the molar ratio of the above compound (a) to the cyclic olefin [(a): cyclic olefin] is usually 1: 500 to 1: 50,000, more preferably 1: 1,000 : 1 : 1 〇, the amount of 〇〇〇. <Solvent for Polymerization> In the ring-opening (co)polymerization reaction, a solvent constituting the molecular weight modifier solution and a solvent of a cyclic olefin and/or a metathesis catalyst can be used as the solvent. As such a solvent, for example, alkane such as pentane, hexane, heptane, octane, decane or decane; cyclohexane, cycloheptane, cyclooctane, decalin, and phlegm (norbornane), etc.; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, dichloromethane, dichloroethane, dibromohexane, trichloro Halogenated alkane such as methane or tetrachloroethylene; halogenated aromatic hydrocarbon such as chlorobenzene; saturated carboxylic acid ester such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate or dimethoxyethane. These solvents may be used singly or in combination. Among these, aromatic hydrocarbons are preferred. The amount of the solvent used, in the weight ratio of the solvent to the cyclic olefin (solvent: -17-200837393 cyclic hydrocarbon), is usually expected to be hi~1〇:1, more preferably 1:1~5:1 the amount. <Molecular weight modifier> The molecular weight of the obtained ring-opened (co)polymer can be adjusted by the temperature of the polymerization, the type of the catalyst, and the type of the solvent, and the molecular weight modifier can be coexisted in the reaction. The system is adjusted. As suitable molecular weight regulators, for example, ethylene, propylene, i-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, etc. And styrene, among which, 1 · butene and 1-hexene are particularly preferable. Further, these molecular weight modifiers may be used alone or in combination of two or more. The amount of the molecular weight modifier used is usually 0.005 to 0.6 mol, and more preferably 0.0 1 to 〇 · 5 m, to the ring-shaped olefin 1 mol supplied to the ring-opening polymerization. The above-mentioned ring-opening copolymer can be obtained by subjecting a cyclic olefin to a ring-opening copolymerization of a copolymerizable monomer, and further, a conjugated compound such as polybutadiene or polyisoprene, or benzene. In the presence of an unsaturated hydrocarbon polymer having two or more carbon-carbon double bonds in a main chain such as an ethylene-butadiene copolymer, an ethylene-non-conjugated dimeric copolymer, or a polybornene, The cyclic olefin is subjected to ring-opening copolymerization. (3) Hydrogenated (co)polymer: The above-mentioned ring-opened (co)polymer may be used as it is, or the hydrogenated (co)polymer (3) obtained by hydrogenating -18-200837393 may also be used as A resin with good impact resistance. The hydrogenation reaction can be carried out by a general method, that is, adding a hydrogenation catalyst to a solution containing a ring-opening (co)polymer, and hydrogen gas at a pressure of from 300 to 300 atm, preferably from 3 to 200 atm. ~2〇〇. The underarm is preferably 20 to 18 (the action is carried out under TC. <Hydrogenation Catalyst> As the hydrogenation catalyst, a catalyst used for hydrogenation reaction of a general olefinic compound can be used as the hydrogenation catalyst. For example, a heterogeneous catalyst and a uniform catalyst. As a heterogeneous catalyst, for example, a precious metal catalyst such as palladium, platinum, nickel, rhodium or ruthenium is carried on carbon, oxidized, oxidized, oxidized. A solid catalyst for a carrier such as chin. As a homogeneous catalyst, such as nickel naphthenate/triethylaluminum, nickel acetonate/triethylaluminum, cobalt octylate/n-butyllithium, dichlorotitanium dichloride /Diethylaluminum chloride, cerium acetate, chlorotris(triphenylphosphine) ruthenium, dichlorotris(triphenylphosphine) ruthenium, dichlorohydrocarbonyltris(triphenylphosphine) ruthenium, etc. The form of these catalysts can be For the powder or granules. These hydrogenation catalysts are in a weight ratio of ring-opened (co)polymer to hydrogenation catalyst (open-loop (co)polymer: hydrogenation catalyst) to 1:1 X 1 (Γ6~1) : The ratio of 2 is ideal. The above hydrogenated (co)polymer (3) has good thermal stability 'even if formed The hydrogenation rate of the hydrogenated (co)polymer (3) is measured by 1H-NMR at 500 MHz, usually under the conditions of heating during use as a product. -19- 200837393 50% or more, more preferably 70% or more, more desirably 90% or more, particularly preferably 98%, and most desirably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light is. Further, the hydrogenated (co)polymer (3) has a gel content of preferably 5% by weight or less, particularly preferably 1% by weight or less. (4) Hydrogenation ( Co-polymer: The hydrogenated (co)polymer (4) is obtained by hydrogenating a ring-opened (co)polymer of the above (1) or (2) by cyclization followed by a Friedel-Krafts reaction. The method of cyclization of the ring-opening (co)polymer by the fu-Quarty reaction is not particularly limited, and a conventional method using an acidic compound described in JP-A--50-543-99, 99 can be employed. a compound, specifically for example A1C13, BF3,
FeCl3、Al2〇3、HC1、CH3CICOOH、沸石、活性陶 土等路 易斯酸（Lewis aicd)、布氏酸（Broensted acid)。 環化的開環（共）聚合物，可與上述開環（共）聚合 物的氫化反應同樣地，進行氫化。 (5 )飽和共聚合物： 上述飽和共聚合物（5)，係在加成聚合觸媒的存在 下，藉由於上述環狀烯烴使含有不飽和雙鍵的化合物進行 -20- 200837393 加成聚合而得。加成聚合法，可適合使用傳統習知的方 法。 <含有不飽和雙鍵的化合物> 作爲含有不飽和雙鍵的化合物，例如乙烯、丙烯、丁 烯等烯烴系化合物，這些之中，期望碳數較理想爲2〜 1 2，更理想爲2〜8的烯烴系化合物。 含有不飽和雙鍵的化合物的使用量，以環狀烯烴與含 有不飽和雙鍵的化合物的重量比（環狀烯烴：含有不飽和 雙鍵的化合物），以90/10〜40/60較理想，85/15〜50/50 更理想。但是，環狀烯烴與含有不飽和雙鍵的化合物的總 重量爲100。 <加成聚合觸媒> 作爲加成聚合觸媒，例如選自鈦化合物、鉻化合物及 釩化合物中至少1種化合物與作爲助觸媒之有機鋁化合物 的組合。 作爲上述鈦化合物，例如四氯化鈦、三氯化鈦等，作 爲鉻化合物，例如氯化雙（環戊二烯）銷、二氯化雙（環 戊二烯）鉻等，作爲釩化合物，例如下述式 VO(OR)aXb 或 V(OR)cXd [但，R爲烴基，X爲鹵原子，〇$a$3、0$b$3、2$ -21 - 200837393 (a + b ) S3、0Sc$4、0SdS4、3S (c + d) S4。] 所表示的釩化合物，或這些的賦予電子加成物。 作爲上述電子予體，例如醇、酚類、酮、醛、羧酸、 有機酸或無機酸酯、醚、醯胺、酸酐、烷氧基矽烷等的含 氧電子予體、氨、胺、腈、異氰酸酯等的含氮電子予體 等。 作爲上述有機鋁化合物，例如具有鋁-碳鍵結或鋁-氫 鍵結至少之一的化合物。該有機鋁化合物，可單獨使用， 也可倂用2種以上。 選自鈦化合物、錐化合物及釩化合物中至少1種化合 物的使用量（倂用2種以上時爲這些的總量）與有機鋁化 合物的使用量的比例，以對鈦原子等之鋁原子的比（Al/Ti 等），通常爲2以上，較理想爲2〜5 0，特別理想爲3〜 20 〇 作爲上述加成聚合反應所使用的溶劑，例如上述開環 (共）聚合反應所例示之溶劑。 而且，飽和共聚合物（5)的分子量的調節，通常使 用氫進行。 (6 )加成型（共）聚合物及其氫化（共）聚合物·· 上述加成型（共）聚合物（6 )，係於上述環狀烯 烴，使選自乙烯基系環狀烴系單體及環戊二烯系單體中1 種以上的單體進行加成聚合而得。 - 22- 200837393 <乙烯基系環狀烴系單體> 作爲上述乙烯基系環狀烴系單體，例如4 -乙烯基環戊 烯、2-甲基-4-異丙烯基環戊烯等的乙烯基環戊烯系單體、 4-乙烯基環戊院、4-異丙烯基環戊院寺乙烯基環戊院系單 體等的乙烯基化五員環烴系單體、4-乙烯基環己烯、4_異 丙烯基環己烯、1-甲基-4-異丙烯基環己烯、2-甲基-4-乙 烯基環己烯、2-甲基-4-異丙烯基環己烯等乙烯基環己烯系 單體、4 -乙烯基環己烷、2 -甲基-4-異丙烯基環己烷等乙烯 基環己院系單體、苯乙烯、α -甲基苯乙烯、2 -甲基苯乙 烯、3-甲基苯乙烯、4-甲基苯乙烯、1-乙烯基萘、2-乙烯 基萘、4-苯基萘、對-甲氧基苯乙烯等苯乙烯系單體、d-松 儲（d-terpene ) 、1-松烯、二蔽（diterpene ) 、d-挈燒 (d-limonene) 、1-挈烯、雙戊烯等松烯系單體、4 -乙烯 基環庚烯、4 -異丙烯基環庚烯等乙烯基環庚烯系單體、4 -乙烯基環庚烷、4-異丙烯基環庚烷等的乙烯基環庚烷系單 體等。這些單體中，以苯乙烯、α-甲基苯乙烯較理想。而 且，這些單體，可使用單獨1種，也可倂用2種以上。 <環戊二烯系單體> 作爲上述環戊二烯系單體，例如環戊二烯、1-甲基環 戊二烯、2 -甲基環戊二烯、2 -乙基環戊二烯、5 -甲基環戊 二烯、5，5_甲基環戊二烯等。這些單體中，以環戊二烯較 理想。而且，這些單體，可使用單獨1種，也可倂用2種 以上。 -23- 200837393 上述加成水口反應’可以與飽和共聚合物（5)之加 成聚合反應同樣地實施。 上述加成型（共）聚合物（6)的氫化（共）聚合 物，可將上述加成型（共）聚合物（6 )藉由與上述氫化 (共）聚合物（3 )的相同方法氫化而得。 (7)交互共聚合物： # 上述交互共聚合物（7)，可在路易斯酸的存在下， 使環狀烯烴與丙烯酸酯藉由進行自由基聚合而得。 <丙烯酸酯> 作爲上述的丙烯酸酯，例如丙烯酸甲酯、丙嫌酸2-乙 基己酯、丙烯酸環己酯等的碳數1〜20的直鏈狀、分支狀 或環狀烷基丙烯酸酯；丙烯酸縮水甘油酯、丙嫌酸2-四氫 呋喃酯等碳原子數2〜20的含有雜環基的丙烯酸酯；丙烯 ® 酸苯甲酯等的碳原子數6〜20的含有芳香族環基的丙烯酸 酯；丙烯酸異冰片酯、丙烯酸二環戊烯酯等碳數7〜3 〇的 . 具有多環構造之丙烯酸酯。 . 上述環狀烯烴與丙烯酸酯的比例，以這些總和爲！ 〇〇 莫耳，通常環狀嫌烴爲30〜70莫耳而丙燦酸酯爲7〇〜3〇 旲耳’較理想爲環狀％煙爲40〜60旲耳而丙嫌酸醋爲6〇 〜40莫耳，特別理想爲環狀烯烴爲45〜55莫耳而丙燒酸 酯爲55〜45莫耳。 上述路易斯酸的使用量，對丙烯酸酯1〇〇莫耳而言， -24- 200837393 爲0.001〜1莫耳較理想。 而且，可使用產生自由基之習知的有機過 氮系自由基聚合引發劑。 聚合反應的溫度，通常爲-20°C〜80°c，較 〜60 °C。而且，作爲聚合反應用溶劑，例； (共）聚合反應所例不之溶劑。 而且，所謂本發明之「交互共聚合物」， 狀烯烴的構造單元彼此不鄰接之共聚合物，亦 烯烴的構造單元旁必須與來自丙烯酸酯的構造 共聚合物。但是，也可存在來自丙烯酸酯的構 鄰接。 上述環狀烯烴系樹脂（A )的玻璃轉化溫 通常爲1 3 0 °C以上，較理想爲1 3 0〜3 5 0 °C，更 〜250°C，特別理想爲 140〜200°C。Tg爲上 脂，在高溫條件下使用、隨塗佈及印刷等的加 工，也難以變形，且成形加工性佳，難以引起 的熱所造成之樹脂的劣化。 (B )粒子： 本發明所使用的粒子（B )，只要粒子表 或有機的聚合物成分所構成的粒子，可爲由1 者，也可爲例如芯殼型粒子之由2成分以上所 粒子。粒子的外部形狀無特別限制’實質上表 之球狀粒子，因所得的光擴散板的光擴散性及 氧化物或偶 理想爲5Ϊ： 泊上述開環 係指來自環 即來自環狀 單元鍵結之 造單元彼此 度（Tg)， 理想爲1 3 0 述範圍之樹 熱之二次加 成形加工時 面是由無機 成分所構成 構成的複合 面沒有角部 亮度的平衡 -25- 200837393 佳的點，所以較理想。 上述粒子（B)的平均粒徑爲1.5〜20 μπι，較理想爲5 〜18μπι，特別理想爲10〜15μπι。使用平均粒徑爲上述範 圍之粒子時，可得充分的擴散效果。另一方面，平均粒徑 未達1 . 5 μιη時，無法發現充分的擴散效果，在薄片上無法 結成像。而且，平均粒徑超過2 0 μπι時，即使以目視也無 法得到表面平滑的薄片，增加太多反射光，無法有效地利 用擴散光。而且，於本發明，粒子的平均粒徑，係指使用 光遮斷式粒子計數器所測定之粒徑的平均値。 上述粒子（Β)的折射率nD爲1.44〜1·54較理想， 1.45〜1.52更理想。使用折射率爲上述範圍的粒子時，可 發現光擴散效果，使用不在該範圍內的粒子時，於添加量 少的情況時無法結成像，於添加量多的情況時光量變少， 變成無法得到明亮的圖像。而且，熱塑性樹脂（A )與粒 子（B )的折射率差的絕對値爲0.0 3〜0 · 0 8的範圍。選擇 折射率差的絕對値爲上述範圍之熱塑性樹脂（A )與粒子 (B )時，因以藉由擴散光可於擴散板上結成圖像的程度 利用光，所以較理想。 作爲上述粒子（B)，只要是具有上述特性的粒子， 可使用習知的無機粒子及/或有機粒子。作爲無機粒子， 例如玻璃、S i Ο 2、C a C 0 3及有機聚砍氧院系化合物等無機 粒子。作爲有機粒子，例如丙烯酸酯系或苯乙烯系等有機 交聯粒子等。這些粒子中，考慮與熱塑性樹脂（A )的親 和性、成形加工性等時，以有機交聯粒子較理想。該有機 -26- 200837393 父聯粒子’可藉由如下述的父聯性單體與其他聚合性單體 聚合而得。 作爲上述父聯性單體’以二乙烯苯等非共軛二乙烯基 化合物；三羥甲基丙烷三甲基丙烯酸酯、三羥甲基丙院三 丙細酸酯等多價丙細酸酯化合物等具有2個以上，較理想 爲2個的共聚合性雙鍵之化合物較理想。Lewis aicd, Brosented acid, such as FeCl3, Al2〇3, HC1, CH3CICOOH, zeolite, and activated clay. The cyclized ring-opened (co)polymer can be hydrogenated in the same manner as the hydrogenation reaction of the above-mentioned ring-opened (co)polymer. (5) Saturated Copolymer: The above saturated copolymer (5) is subjected to addition polymerization of a compound containing an unsaturated double bond by the above cyclic olefin in the presence of an addition polymerization catalyst, -20-200837393 And got it. The addition polymerization method can be suitably applied to a conventionally known method. <Compound containing unsaturated double bond> As the compound containing an unsaturated double bond, for example, an olefin-based compound such as ethylene, propylene or butene, among these, the desired carbon number is preferably 2 to 12, more preferably 2 to 8 olefinic compounds. The compound containing an unsaturated double bond is used in a weight ratio of a cyclic olefin to a compound containing an unsaturated double bond (cyclic olefin: a compound containing an unsaturated double bond), preferably 90/10 to 40/60. , 85/15~50/50 is more ideal. However, the total weight of the cyclic olefin and the compound containing an unsaturated double bond is 100. <Addition polymerization catalyst> The addition polymerization catalyst is, for example, a combination of at least one compound selected from the group consisting of a titanium compound, a chromium compound, and a vanadium compound, and an organoaluminum compound as a promoter. As the titanium compound, for example, titanium tetrachloride, titanium trichloride or the like, as a chromium compound, for example, a bis(cyclopentadienyl) pin, a bis(cyclopentadienyl) chromium dichloride or the like, as a vanadium compound, For example, the following formula VO(OR)aXb or V(OR)cXd [However, R is a hydrocarbon group, X is a halogen atom, 〇$a$3, 0$b$3, 2$-21 - 200837393 (a + b) S3, 0Sc$4, 0SdS4, 3S (c + d) S4. The vanadium compound represented by these, or the electron-added product of these. As the above electron donor, for example, an oxygen-containing electron donor such as an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an organic acid or an inorganic acid ester, an ether, a guanamine, an acid anhydride or an alkoxysilane, an ammonia, an amine, or a nitrile A nitrogen-containing electron donor such as an isocyanate. As the above organoaluminum compound, for example, a compound having at least one of an aluminum-carbon bond or an aluminum-hydrogen bond. The organoaluminum compound may be used singly or in combination of two or more. The ratio of the amount of at least one compound selected from the group consisting of a titanium compound, a cone compound, and a vanadium compound (the total amount of these compounds when two or more kinds are used) to the amount of the organoaluminum compound used is an aluminum atom such as a titanium atom. The ratio (Al/Ti or the like) is usually 2 or more, more preferably 2 to 50, and particularly preferably 3 to 20 〇 as a solvent used in the above-mentioned addition polymerization reaction, for example, the above-mentioned ring-opening (co)polymerization reaction is exemplified. Solvent. Further, the adjustment of the molecular weight of the saturated copolymer (5) is usually carried out using hydrogen. (6) Addition (co)polymer and its hydrogenated (co)polymer·· The above-mentioned addition (co)polymer (6), which is selected from the above-mentioned cyclic olefin, is selected from a vinyl-based cyclic hydrocarbon system One or more monomers of the compound and the cyclopentadiene monomer are subjected to addition polymerization. - 22- 200837393 <vinyl-based cyclic hydrocarbon monomer> As the vinyl-based cyclic hydrocarbon-based monomer, for example, 4-vinylcyclopentene, 2-methyl-4-isopropenylcyclopentane a vinylated cyclopentene monomer such as a vinyl group, a vinylated five-membered cyclic hydrocarbon monomer such as a 4-vinylcyclopentene or a 4-isopropenylcyclopentanyl vinylcyclopentene monomer, 4-vinylcyclohexene, 4-isopropylisocyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4 a vinylcyclohexene monomer such as isopropenylcyclohexene, a vinylcyclohexene monomer such as 4-vinylcyclohexane or 2-methyl-4-isopropenylcyclohexane, or styrene , α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylnaphthalene, p-A Styrene monomer such as oxystyrene, d-terpene, 1-pinene, diterpene, d-limonene, 1-decene, dipentene a vinylcycloheptene monomer such as a terpene monomer, 4-vinylcycloheptene or 4-isopropenylcycloheptene, 4 - Alkenyl cycloheptane, 4-isopropenyl vinyl cycloheptane, cycloheptane and the like based monomers and the like. Among these monomers, styrene and α-methylstyrene are preferred. Further, these monomers may be used alone or in combination of two or more. <Cyclopentadiene-based monomer> As the above cyclopentadiene-based monomer, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclo Pentadiene, 5-methylcyclopentadiene, 5,5-methylcyclopentadiene, and the like. Among these monomers, cyclopentadiene is preferred. Further, these monomers may be used alone or in combination of two or more. -23- 200837393 The above-mentioned addition nozzle reaction ' can be carried out in the same manner as the addition polymerization of the saturated copolymer (5). The hydrogenated (co)polymer of the above-mentioned addition (co)polymer (6) can be hydrogenated by the same method as the above hydrogenation (co)polymer (3) by the above-mentioned addition (co)polymer (6) Got it. (7) Cross-copolymer: # The above-mentioned interactive copolymer (7) can be obtained by radical polymerization of a cyclic olefin and an acrylate in the presence of a Lewis acid. <Acrylate> As the above acrylate, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate or cyclohexyl acrylate An acrylate having a heterocyclic group having 2 to 20 carbon atoms such as acrylate, glycidyl acrylate or 2-tetrahydrofuran acrylate; and an aromatic ring having 6 to 20 carbon atoms such as propylene acrylate. Acrylate; isopropyl acrylate, dicyclopentenyl acrylate, etc. having a carbon number of 7 to 3 Å. A acrylate having a polycyclic structure. The ratio of the above cyclic olefin to acrylate is based on these sums! 〇〇莫耳, usually ring-shaped hydrocarbons are 30~70 moles and propionate is 7〇~3〇旲 ears' ideal for ring-shaped% smoke is 40~60 ears and C is sour vinegar is 6 〇 ~ 40 moles, particularly ideal for cyclic olefins of 45 to 55 moles and propionate for 55 to 45 moles. The amount of the above Lewis acid used is preferably from 0.001 to 1 mol per acrylate to 1 〇〇mol. Further, a conventional organic nitrogen-based radical polymerization initiator which generates a radical can be used. The temperature of the polymerization reaction is usually -20 ° C to 80 ° C, which is higher than ~ 60 ° C. Further, as a solvent for the polymerization reaction, for example, a solvent which is not exemplified in the polymerization reaction. Further, in the "inter-copolymer" of the present invention, the structural unit in which the structural units of the olefin are not adjacent to each other, and the structural unit derived from the acrylate must be adjacent to the structural unit derived from the acrylate. However, a structural adjacency from the acrylate may also be present. The glass transition temperature of the cyclic olefin resin (A) is usually 130 ° C or higher, preferably 1 30 0 to 350 ° C, more preferably 250 ° C, particularly preferably 140 to 200 ° C. Tg is a grease which is used under high temperature conditions, is difficult to be deformed by application such as coating and printing, and has good moldability and deterioration of resin due to heat which is difficult to cause. (B) Particles: The particles (B) used in the present invention may be one composed of particles or an organic polymer component, and may be, for example, two or more particles of the core-shell type particles. . The outer shape of the particles is not particularly limited to the substantially spherical particles, and the light diffusing property and the oxide or even ideal of the obtained light diffusing plate are 5 Ϊ: the above open ring means that the ring is derived from the ring. The degree of mutuality (Tg) of the unit is ideally set to 1 3 0. The secondary surface of the tree heat is formed by the inorganic component. The composite surface composed of inorganic components has no balance of corner brightness -25 - 200837393 Good point So it is ideal. The average particle diameter of the above particles (B) is from 1.5 to 20 μm, preferably from 5 to 18 μm, particularly preferably from 10 to 15 μm. When a particle having an average particle diameter of the above range is used, a sufficient diffusion effect can be obtained. On the other hand, when the average particle diameter is less than 1.5 μm, a sufficient diffusion effect cannot be found, and the film cannot be imaged on the sheet. Further, when the average particle diameter exceeds 20 μm, even if the surface is smooth, it is impossible to obtain a sheet having a smooth surface, and too much reflected light is added, and the diffused light cannot be effectively utilized. Further, in the present invention, the average particle diameter of the particles means the average enthalpy of the particle diameter measured by a photointerrupting particle counter. The refractive index nD of the above particles (Β) is preferably 1.44 to 1.54, and more preferably 1.45 to 1.52. When a particle having a refractive index of the above range is used, a light diffusing effect can be found. When a particle which is not in the range is used, when the amount of addition is small, image formation cannot be performed, and when the amount of addition is small, the amount of light is small, and it becomes impossible to obtain brightness. Image. Further, the absolute 値 of the refractive index difference between the thermoplastic resin (A) and the particles (B) is in the range of 0.0 3 to 0 · 0 8 . When the thermoplastic resin (A) and the particles (B) having the absolute refractive index difference in the above range are selected, it is preferable to use light by the extent that the diffused light can form an image on the diffusion plate. As the particles (B), conventional particles and/or organic particles can be used as long as they have the above characteristics. Examples of the inorganic particles include inorganic particles such as glass, S i Ο 2, C a C 0 3 and an organic polyoxene compound. The organic particles are, for example, organic crosslinked particles such as acrylate or styrene. Among these particles, organic crosslinking particles are preferred in consideration of affinity with the thermoplastic resin (A), moldability, and the like. The organic -26-200837393 parent-linked particle ' can be obtained by polymerizing a parent monomer as described below with another polymerizable monomer. As the above-mentioned parent monomer, a non-conjugated divinyl compound such as divinylbenzene; a polyvalent acrylic acid ester such as trimethylolpropane trimethacrylate or trimethylol propyl tripropionate; A compound having two or more compounds, preferably two copolymerized double bonds, is preferred.
作爲上述多價丙烯酸酯化合物，例如聚乙二醇二丙烯 酸酯、1，3-丁二醇二丙烯酸酯、；ι，6-己二醇二丙烯酸酯、 1，6_己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚丙二醇 一丙烯酸酯、2，2 -雙（4 -丙烯醯氧基丙氧基苯基）丙烷、 2,2-雙（4-丙烯醯氧基二乙氧基苯基）丙烷等二丙烯酸酯 化合物；三羥甲基丙烷三丙烯酸酯、三羥甲基乙烷三丙烯 酸酯、四羥甲基甲烷三丙烯酸酯等三丙烯酸酯化合物；乙 二醇二（甲基丙烯酸酯）、二乙二醇二（甲基丙烯酸 酯）、三乙二醇二（甲基丙烯酸酯）、聚乙二醇二（甲基 丙烯酸酯）、1，3-丁二醇二（甲基丙烯酸酯）、i，4_ 丁二 醇二（甲基丙烯酸酯）、1，6 -己二醇二（甲基丙烯酸 酯）、新戊二醇二（甲基丙烯酸酯）、二丙二醇二（甲基 丙烯酸酯）、聚丙二醇二（甲基丙烯酸酯）、2,2-雙（4-甲基丙烯醯氧基二乙氧基苯基）丙烷等二（甲基丙烯酸 酯）化合物；三羥甲基丙烷三（甲基丙烯酸酯）、三羥甲 基乙烷三（甲基丙烯酸酯）等三（甲基丙烯酸酯）化合 物。 上述交聯性單體中，以二乙烯苯、乙二醇二（甲基丙 -27- 200837393 烯酸酯）及三羥甲基丙烷三（甲基丙烯酸酯）較理想，以 二乙烯苯特別理想。而且，上述交聯性單體可單獨或混合 2種以上使用。 作爲其他聚合性單體，例如苯乙烯、OC-甲基苯乙烯、 氟苯乙烯、乙烯基砥D定等芳香族乙燒基化合物；丙;(：希腈、 甲基丙烯腈等氰化乙烯基化合物；（甲基）丙烯酸丁酯、 (甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸甲酯、（甲 基）丙烯酸2-羥基乙酯、（甲基）丙烯酸縮水甘油酯等 (甲基）丙烯酸酯；丙烯酸、甲基丙烯酸、順丁烯二酸、 亞甲基丁二酸等不飽和脂肪酸；丙烯醯胺、甲基丙烯醯胺 等醯胺系單體等。 上述樹脂薄片以射出成形、擠出成形將熱塑性樹脂在 加熱熔融的溫度下成形的情況，期望上述有機粒子在熱塑 性樹脂之加熱溶融的溫度下不熔融。而且，上述樹脂薄片 使用有機溶劑調製的情況，上述有機粒子不溶解於有機溶 劑較理想。 [樹脂薄片] 上述樹脂薄片，可將上述熱塑性樹脂（A )與上述粒 子（B)藉由成形爲薄片狀而製造。 <光擴散性樹脂組成物> 上述光擴散性樹脂組成物含有上述熱塑性樹脂（A ) 與上述粒子（B )，對這些總共1 〇〇重量％而言，粒子 -28- 200837393 (B)的含有率爲0.1〜10重量％，較理想爲0.3〜3重量 %。調配粒子（B )爲上述範圍時’可得一邊結成像，一 邊不降低光量之擴散板。 而且，於上述光擴散性樹脂組成物，在無損本發明的 效果之範圍下，例如在改善樹脂薄片的色相之目的下，可 調配螢光增白劑。 上述光擴散性樹脂組成物的調製方法，亦即上述熱塑 性樹脂（A )與粒子（B )的調配方法，無特別限制，可以 習知的方法進行混合。例如 (1 )熱塑性樹脂（A )在溶解於可溶的溶劑之狀態 下’使粒子（B )分散，以習知的方法去除溶劑而得到上 述樹脂組成物的方法； (2 )熱塑性樹脂（a )在熔融的狀態下使粒子（B ) 分散的方法等。 上述（1 )的調製方法，作爲含有熱塑性樹脂（A )的 溶液’可使用聚合後的溶液、氫化後的溶液、除去觸媒後 的溶液、濃縮的溶液、溶解顆粒狀的熱塑性樹脂（A )的 溶液等。 而且’混合的方法無特別限制，例如使用習知的攪拌 機進行混合的方法，或熱塑性樹脂（A )與粒子（B )同時 供應給習知的擠出機，再同時進行去除溶劑及分散的方 法。 另一方面，作爲上述（2 )的調製方法，例如使用習 知單軸或 2軸的擠出機之方法。擠出機的擠筒 -29- 200837393 (cylinder)的直徑通常爲1〇〜100 mm。螺桿可使用習知 者，例如單軸的情況下，組合全螺紋（full-flight )及副 螺紋（sub-flight )者、組合杜式（Dulmadge-type )者、 對相同的螺桿改變螺紋間隔或溝深者。於2軸的情況下， 可組合2條或3條螺桿、異方向或同方向旋轉的螺桿，於 螺桿的構件可自由組合之螺桿的情況下，螺桿的構件形狀 可從螺桿、逆向傳輸螺桿、槳式螺桿、螺旋槳式螺桿等中 自由選擇。 擠出機，可只使用1台，也可使用連結2台以上者、 組合連續式及批次式捏合機者。於擠出機，可藉由複數供 料器供應原料。而且，粒子（B )可在擠出機的中途供 應。 此外，將熱塑性樹脂（A )與粒子（B )使用習知的轉 筒（tumbler )式或旋轉式等混合機、漢氏混合機 (Henschel mixer)、行星式混合機等的混合機預先在固 體的狀態下混合後，供應給擠出機，可於熱塑性樹脂 (A)中使粒子（B)分散。 上述熱塑性樹脂（A )，或熱塑性樹脂（A )與粒子 (B )兩者’預先以習知的方法進行乾燥較理想。作爲乾 燥的方法，例如熱風乾燥、除濕乾燥、真空乾燥、氮氣乾 燥等。乾燥溫度、乾燥時間無特別限制，通常在（Tg_〗〇〇 C )〜（Tg-20°C )的範圍內可任意設定，乾燥時間通常 設定爲2〜6小時的範圍。 擒出機的送料斗、投入口、排氣口、模頭面等以氮氣 -30- 200837393 或氬氣等不活性氣體密封（封入）較理想。 上述光擴散性樹脂組成物，在成形爲光擴散板的情況 以目視可判定大小，較理想爲不存在50 μιη以上大小的異 物。如此的異物的含量期望爲5個/10g以下，較理想爲3 個/10g以下，更理想爲〇個/l〇g。 異物的含量，可藉由將上述樹脂組成物溶解於甲苯、 環己烷等具有樹脂溶解性的溶劑，以過濾器過濾後，以顯 微鏡觀察，計算其大小及個數而測定。而且，熱塑性樹脂 溶解於上述溶劑，以過濾器過濾後，也可使用以光散射原 理之市售微粒子計數器進行計數。 而且，上述光擴散性樹脂組成物，在供應給後述的成 形加工前，預先以習知的方法除去溶解存在的水分、氧成 分較理想。光擴散性樹脂組成物爲粒子或顆粒等固體形狀 的情況下，可以習知的方法進行乾燥。作爲乾燥裝置，可 使用熱風乾燥機、除濕乾燥機、氮氣循環式乾燥機、除濕 氮氣循環式乾燥機、真空乾燥機等習知的乾燥裝置。這些 乾燥裝置中，從容易得到具有色相均勻性之成形品的點， 使用減壓乾燥機或氮氣等不活性氣體循環之乾燥機較理 想。 乾燥溫度、乾燥時間無特別限制，通常在Tg-1〇〇 °C〜 Tg-20°C的範圍內可任意設定，乾燥時間通常設定爲2〜6 小時的範圍。 <樹脂薄片> -31 - 200837393 本發明所使用的樹脂薄片，可藉由將上述光擴散性樹 脂組成物成形爲薄片狀而得。該樹脂薄片含有上述熱塑性 樹脂（A )與上述粒子（B )，對這些的總和1 00重量％而 言，粒子（B )的含有率爲0.1〜10重量％，較理想爲0.3 〜3重量％。成形爲薄片狀的方法，可採用習知的方法， 從設備簡單，抑制設備費的觀點，藉由熔融擠出而成形較 理想。 作爲熔融擠出上述樹脂薄片的方法，例如以一般的擠 出機熔融光擴散性樹脂組成物，以齒輪泵定量地計量，通 過具有狹縫狀出口的模頭而擠出，延伸成薄片狀或薄膜狀 之方法。 光擴散性樹脂組成物的熔融溫度爲比熱塑性樹脂 (A )的玻璃轉化溫度高100〜150 °C的溫度較理想，高 100〜140 °C的溫度更理想。熱塑性樹脂（A)的玻璃轉化 溫度與光擴散性樹脂組成物的熔融溫度的差爲上述範圍 時，因難以產生加工溫度下的發生樹脂燒焦等的損壞，可 抑制模頭線等的發生於薄片表面的缺陷。 擠出成形使用之較理想的擠出機，其長度（L) /直徑 (D)比（L/D)爲28以上40以下，螺桿直徑係由擠出量 決定，例如通常爲30 mm〜125 mm的擠出機。L/D爲上述 範圍時，可得適合的滯留時間，可充分地熔融本發明的樹 脂組成物。而且，螺桿直徑未達3 0 m m時，無法安定地計 量’且生產性低，所以不理想。此外，超過12 5 mm時， 計量後原料容易滯留，所以不理想。 -32- 200837393 爲了謀求薄片等的膜厚安定性，使用齒輪泵較理想。 作爲齒輪泵，可使用習知者，特別是以排出潤滑使用的樹 脂方式之外潤式較理想。 延伸本發明的樹脂組成物成爲膜狀用的模頭，使用T 型模頭較理想，作爲其形狀，例如衣架式模頭、魚尾式模 頭等，以衣架式模頭特別理想。歧管（manifold )的形狀 無特別限制，以滯留小者較理想。而且，T型模頭的前端 爲銳利的邊緣較理想，邊緣破損時成爲得到模頭線的原 因，所以不理想。特別是藉由熔射等手法進行鎢-碳化物 等的超硬包覆之邊緣處理，對模頭線的防止較合適。 [光擴散板] 關於本發明的光擴散板，係將上述樹脂薄片夾於表面 粗糙度〇.3s以下的金屬滾輪及表面粗糙度0.3s以下的金 屬帶之間藉由捲取而製造。此時該金屬滾輪的溫度設定爲 比該熱塑性樹脂（A )的玻璃轉化溫度Tg低20〜50°C， 較理想爲低25〜45°C的溫度。金屬滾輪的溫度設定爲上述 範圍時，薄片難以產生翹曲等變形，難以發生殘留相位差 之扭曲的原因。而且，樹脂薄片的捲取速度，以2〜8m/ 分較理想，2〜6 m/分更理想。特別理想爲2.5〜5 m/分。 捲取速度爲上述範圍時，薄片的厚度平衡不會惡化，可得 表面外觀良好的薄片。 金屬滾輪與金屬帶的材質，以鐵、不鏽鋼、施以硬鉻 電鍍之鐵等較理想。而且，爲了改善離型性，藉由熔射， -33- 200837393 以鎢、碳化鎢等超硬金屬對鐵、不鏽鋼進行處理較理想。 如此所製造的光擴散板，隱蔽性佳的同時，殘留相位 差小，例如與偏光板組合時，顯示對比也良好。 [實施例] 以下，藉由實施例說明本發明，但本發明不限於該實 施例。而且，以下的「份」及「％」，在沒有特別限制 Φ 下，係指「重量份」及「重量％」。 (玻璃轉化溫度：Tg) 使用精工儀器公司製（Seiko Instrument)的 DSC6200，以升溫速度20°C /分，在氮氣氣流下進行測 定。 (平均粒徑） φ 使用粒度分佈測定裝置（日機裝公司製As the above polyvalent acrylate compound, for example, polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, iota, 6-hexanediol diacrylate, 1,6-hexanediol diacrylate , neopentyl glycol diacrylate, polypropylene glycol monoacrylate, 2,2-bis(4-propenyloxypropoxyphenyl)propane, 2,2-bis(4-propenyloxydiethoxylate) Diacrylate compound such as phenyl)propane; triacrylate compound such as trimethylolpropane triacrylate, trimethylolethane triacrylate or tetramethylol methane triacrylate; Acrylate), diethylene glycol di(methacrylate), triethylene glycol di(methacrylate), polyethylene glycol di(methacrylate), 1,3-butanediol di Methacrylate), i, 4-butanediol di(methacrylate), 1,6-hexanediol di(methacrylate), neopentyl glycol di(methacrylate), dipropylene glycol (methacrylate), polypropylene glycol bis(methacrylate), 2,2-bis(4-methylpropenyloxydiethoxylate) Di(methacrylate) compound such as phenyl)propane; tris(methacrylate) compound such as trimethylolpropane tri(methacrylate) or trimethylolethane tris(methacrylate) . Among the above crosslinkable monomers, divinylbenzene, ethylene glycol bis(methylpropane-27-200837393 enoate) and trimethylolpropane tri(methacrylate) are preferred, and divinylbenzene is particularly preferred. ideal. Further, the above crosslinkable monomers may be used singly or in combination of two or more kinds. As another polymerizable monomer, for example, an aromatic ethylenic compound such as styrene, OC-methylstyrene, fluorostyrene or vinyl anthracene D; C; (: vinyl cyanide such as nitrile or methacrylonitrile) Base compound; butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate (meth) acrylate; unsaturated fatty acid such as acrylic acid, methacrylic acid, maleic acid or methylene succinic acid; guanamine monomer such as acrylamide or methacrylamide; When the sheet is molded by injection molding or extrusion molding at a temperature at which the thermoplastic resin is heated and melted, it is desirable that the organic particles are not melted at a temperature at which the thermoplastic resin is heated and melted. Further, when the resin sheet is prepared by using an organic solvent, the above-mentioned resin sheet is used. The organic particles are preferably not dissolved in the organic solvent. [Resin Sheet] The resin sheet can be produced by molding the thermoplastic resin (A) and the particles (B) into a sheet shape. The resin composition of the above-mentioned light-diffusing resin composition contains the above-mentioned thermoplastic resin (A) and the above-mentioned particles (B), and the content ratio of the particles -28 to 200837393 (B) is 1% by weight in total. 0.1 to 10% by weight, preferably 0.3 to 3% by weight, and when the particles (B) are in the above range, a diffusion plate which can form a film without reducing the amount of light can be obtained. Further, in the above light-diffusing resin composition, The fluorescent whitening agent may be blended, for example, in the range of the effect of the present invention, for example, in order to improve the hue of the resin sheet. The method for preparing the light diffusing resin composition, that is, the above thermoplastic resin (A) and particles The method of blending (B) is not particularly limited and may be carried out by a conventional method. For example, (1) the thermoplastic resin (A) is dispersed in a soluble solvent to cause the particles (B) to be dispersed, as is conventional. A method of removing a solvent to obtain the above resin composition; (2) a method of dispersing the thermoplastic resin (a) in a molten state, etc. The preparation method of the above (1), as a thermoplastic The solution of the resin (A) can be a solution after the polymerization, a solution after hydrogenation, a solution after removing the catalyst, a concentrated solution, a solution in which the particulate thermoplastic resin (A) is dissolved, etc. The method of mixing, for example, using a conventional agitator, or the simultaneous supply of the thermoplastic resin (A) and the particles (B) to a conventional extruder, and simultaneously removing the solvent and dispersing. The preparation method of (2) is, for example, a conventional one-axis or two-axis extruder. The diameter of the extruder -29-200837393 (cylinder) is usually from 1 〇 to 100 mm. For example, in the case of a single shaft, a person who combines a full-flight and a sub-flight, a Dulmage-type, and a screw pitch or a groove depth for the same screw. In the case of 2 axes, two or three screws, different directions or the same direction of rotation of the screw can be combined. In the case where the components of the screw can be freely combined, the shape of the screw can be from the screw, the reverse transmission screw, Freely selected among paddle screws, propeller screws, and the like. The extruder may be used alone or in combination of two or more, and a continuous type and a batch type kneader. In the extruder, the raw materials can be supplied by a plurality of feeders. Further, the particles (B) can be supplied in the middle of the extruder. Further, the thermoplastic resin (A) and the particles (B) are previously solid in a mixer using a conventional mixer such as a tumbler type or a rotary type, a Henschel mixer, or a planetary mixer. After mixing in the state, it is supplied to an extruder to disperse the particles (B) in the thermoplastic resin (A). The thermoplastic resin (A) or both the thermoplastic resin (A) and the particles (B) are preferably dried in advance by a known method. As a drying method, for example, hot air drying, dehumidifying drying, vacuum drying, nitrogen drying, or the like. The drying temperature and the drying time are not particularly limited, and are usually arbitrarily set within the range of (Tg_? 〇〇 C ) to (Tg - 20 ° C), and the drying time is usually set to a range of 2 to 6 hours. It is preferable to seal (enclose) the inertia gas such as nitrogen gas -30-200837393 or argon gas to the hopper, input port, exhaust port, and die surface of the ejector. In the case where the light-diffusing resin composition is formed into a light-diffusing sheet, the size can be determined visually, and it is preferable that no foreign matter having a size of 50 μm or more is present. The content of such a foreign matter is desirably 5 /10 g or less, preferably 3 /10 g or less, more preferably 〇 / l 〇 g. The content of the foreign matter can be measured by dissolving the above-mentioned resin composition in a solvent having a resin solubility such as toluene or cyclohexane, filtering it with a filter, and observing it by a microscope to calculate the size and the number. Further, the thermoplastic resin is dissolved in the above solvent and filtered by a filter, and may be counted using a commercially available microparticle counter using a light scattering principle. Further, it is preferable that the light-diffusing resin composition is previously removed from the dissolved moisture and oxygen components by a conventional method before being supplied to a forming process to be described later. When the light diffusing resin composition is a solid shape such as particles or particles, it can be dried by a known method. As the drying device, a conventional drying device such as a hot air dryer, a dehumidifying dryer, a nitrogen circulating dryer, a dehumidifying nitrogen circulating dryer, or a vacuum dryer can be used. Among these drying apparatuses, it is preferable to use a vacuum dryer or a dryer which circulates an inert gas such as nitrogen from a point where a molded article having a hue uniformity is easily obtained. The drying temperature and the drying time are not particularly limited, and are usually arbitrarily set within the range of Tg-1 〇〇 ° C to Tg -20 ° C, and the drying time is usually set to a range of 2 to 6 hours. <Resin Sheet> -31 - 200837393 The resin sheet used in the present invention can be obtained by molding the light diffusing resin composition into a sheet shape. The resin sheet contains the thermoplastic resin (A) and the particles (B). The total content of the particles (B) is 0.1 to 10% by weight, preferably 0.3 to 3% by weight based on 100% by weight of the total of these. . The method of forming into a sheet shape can be carried out by a conventional method, and is preferably formed by melt extrusion from the viewpoint of simplicity of equipment and suppression of equipment cost. As a method of melt-extruding the above-mentioned resin sheet, for example, a light-diffusing resin composition is melted in a general extruder, quantitatively measured by a gear pump, extruded through a die having a slit-like outlet, and extended into a sheet shape or Film-like method. The melting temperature of the light-diffusing resin composition is preferably 100 to 150 ° C higher than the glass transition temperature of the thermoplastic resin (A ), and more preferably 100 to 140 ° C higher. When the difference between the glass transition temperature of the thermoplastic resin (A) and the melting temperature of the light-diffusing resin composition is within the above range, it is difficult to cause damage such as resin scorching at the processing temperature, and it is possible to suppress occurrence of a die line or the like. Defects on the surface of the sheet. An ideal extruder for extrusion molding has a length (L) / diameter (D) ratio (L/D) of 28 or more and 40 or less, and the screw diameter is determined by the amount of extrusion, for example, usually 30 mm to 125. Mm extruder. When L/D is in the above range, a suitable residence time can be obtained, and the resin composition of the present invention can be sufficiently melted. Further, when the diameter of the screw is less than 30 m, it cannot be measured stably and the productivity is low, which is not preferable. Further, when it exceeds 12 5 mm, the raw material is easily retained after the metering, which is not preferable. -32- 200837393 It is preferable to use a gear pump in order to achieve film thickness stability such as a sheet. As the gear pump, it is possible to use a conventional one, and it is preferable to use a resin type which is used for discharge lubrication. The resin composition of the present invention is preferably a film-shaped die, and a T-die is preferably used. For example, a coat hanger die or a fishtail die is preferable, and a coat hanger die is particularly preferable. The shape of the manifold is not particularly limited, and it is preferable to retain the small one. Further, the tip end of the T-die is ideal for sharp edges, and the edge is broken to cause the die line, which is not preferable. In particular, the edge treatment of the ultra-hard coating of tungsten-carbide or the like is carried out by a method such as spraying, and the prevention of the die line is suitable. [Light-diffusing sheet] The light-diffusing sheet of the present invention is produced by winding a metal roll having a surface roughness of 33s or less and a metal strip having a surface roughness of 0.3 s or less. At this time, the temperature of the metal roller is set to be 20 to 50 ° C lower than the glass transition temperature Tg of the thermoplastic resin (A ), and preferably 25 to 45 ° C lower. When the temperature of the metal roller is set to the above range, the sheet is less likely to be deformed such as warpage, and it is difficult to cause distortion of the residual phase difference. Further, the winding speed of the resin sheet is preferably 2 to 8 m/min, more preferably 2 to 6 m/min. It is particularly desirable to be 2.5 to 5 m/min. When the winding speed is in the above range, the thickness balance of the sheet does not deteriorate, and a sheet having a good surface appearance can be obtained. The material of the metal roller and the metal strip is preferably iron, stainless steel or iron plated with hard chrome plating. Moreover, in order to improve the release property, it is preferable to treat iron and stainless steel with a superhard metal such as tungsten or tungsten carbide by spraying, -33-200837393. The light diffusing plate thus produced has a good concealing property and a small residual phase difference. For example, when combined with a polarizing plate, the display contrast is also good. [Examples] Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. In addition, the following "parts" and "%" are referred to as "parts by weight" and "% by weight" unless otherwise specified. (Glass transition temperature: Tg) The measurement was carried out under a nitrogen gas flow using a DSC6200 manufactured by Seiko Instruments, Inc. at a temperature increase rate of 20 ° C /min. (Average particle size) φ Using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.
MicrotracUAPISO )，以光散射法，測定粒度分佈。所得 的粒度分佈描繪於對數機率紙，以累積至50%的粒徑作爲 平均粒徑。 (折射率） 將粒子以60網目的金網過濾，於過濾殘渣滴下折射 率標準液（Cargille公司製）混合後，以光學顯微鏡觀 察，變成無法見到粒子的輪廓之標準液的d線之折射率爲 -34- 200837393 粒子的折射率。測定係於2 5 °C下進行。 (全光線透過率及霧度） 光擴散板的全光線透過率及霧度，係使用霧度計（村 上色彩硏究所製HM-150)，根據 AS TM D 1 003進行測 定。 (殘留相位差） 光擴散板的殘留相位差，係將所得的光擴散板切削成 A4版大小，製作測試片，使用微小面積雙折射計（王子 計測公司製KOBRA-CCD)進行測定。 (顯示對比） 於偏光板A(LUCEO公司製POLAX-38S)上使光擴 散板貼合，於其上，使光軸與偏光板A的光軸垂直地貼合 偏光板B(LUCEO公司製POLAX-3 8S )，製作光學構件 C。另一方面，於偏光板A上使光擴散板貼合，於其上使 光軸與偏光板A的光軸平行地貼合偏光板B，製作光學構 件P。對光學構件C及光學構件P，藉由以下的方法測定 亮度，由下述式求出對比L。 L =光學構件P的亮度/光學構件C的亮度 將光學構件配置於距離光箱（電通產業公司製，大型 -35· 200837393 面照明，亮度：9000 cd/m2 ) 3 00 mm的位置，使用亮度計 (Konica-Minolta科尼卡公司製LS-1 10 )，測定透過光學 構件的光之亮度。 而且，上述 1片偏光板的透過光的亮度爲 4500 cd/m2，上述偏光板A，B以光軸垂直地貼合之光學構件的 透過光的亮度爲15 cd/m2，上述偏光板A，B以光軸平行地 貼合之光學構件的透過光的亮度爲4000 cd/m2。所以，只 φ 有2片偏光板之對比爲270。 (隱蔽性） 以夾子固定光擴散板的四個角，站立成螢幕狀而配 置，將其使用液晶投影機（精工愛普生公司製，型號 EMP-1710)從光擴散板的背面照射影像，從光擴散板的前 面以目視觀察，以下述的基準評價其隱蔽性。 A :見不到投影機的光源的輪廓 • B ··可見到投影機的光源的輪廓 [實施例1] 將環狀烯烴系樹脂（JSR公司製、商品名：ARTON D45 3 1、Tg = 13 0°C、折射率=1.515 ) 97.5重量份及擴散粒 子（積水化成品工業公司製、商品名：TECHPOLYMER SBX-12、折射率η〇=1·59、平均粒徑12μηι) 2.5重量份以 漢氏混合機（Henschel mixer )混合，再混合螢光增白劑 (Chiba千葉特殊化學製、商品名：UVITEX OB_ONE ) 30 -36- 200837393 ppm ’調製光擴散性樹脂組成物A1。 將該樹脂組成物A1使用除濕乾燥機於90°C下乾燥2 小時’除去表面的水分。然後，使用重量供料器，定量供 應給二軸擠出機（東芝機械公司製TEM-37 )，於270 °C，使上述樹脂組成物A 1顆粒化。 將顆粒狀的上述樹脂組成物A 1使用除濕乾燥機於 1 00 °C下乾燥4小時，於265 °C下熔融，使用齒輪泵以80 公斤/小時定量供應給二軸擠出機（GM engineering工程 公司製、螺桿外徑D = 75 mm、L/D = 36)，使用寬度600 mm的衣架式T型模頭，於270 °C熔融擠出，得到樹脂薄 片A1。 使用具有0.3 mm厚的無接縫金屬帶（表面粗糙度 0.2s)及金屬滾輪（表面粗糙度0.1s)之套筒式捲取裝 置，將上述樹脂薄片A1 —起夾於調整爲80 °C之金屬帶及 金屬滾輪之間，以2.5m/分的速度捲取，製作1 mm厚的 光擴散板A1。 對所得的光擴散板A1進行評價，結果表示於表1。 [實施例2] 使苯乙烯95重量份及二乙烯苯5重量份共聚合，調 製交聯粒子（折射率nD=1.5 92、平均粒徑Ιίμιη)。除使 用該交聯粒子取代TECHPOLYMER SBX-12以外，與實施 例1同樣地，製作1 mm厚的光擴散板Β1。 對所得的光擴散板B1進行評價，結果表示於表1。 -37- 200837393 [實施例3] 除改變環狀烯烴系樹脂的量爲98.7重量份、擴散粒 子的量爲1.3重量份以外，與實施例1同樣地，製作樹脂 薄片A2 (厚度1 ·〇 mm )。 使用該樹脂薄片A2，捲取速度改變爲3 m/分以外，與 實施例1同樣地，製作0.8 mm後的光擴散板A2。 對所得的光擴散板A2進行評價，結果表示於表1。 [實施例4] (環狀，烯烴系樹脂的合成） 將8-甲基-8-甲氧基羰基四環[4.4.0.1 2,5.17，10]-3-十二 烯（單體A) 175份、5-苯基-雙環[2 ·2·1]庚-2-烯（單體 Β ) 7 5份、1 ·己烯（分子量調節劑）：! 8份及甲苯7 5 0份放 入氮氣取代之反應容器，將該溶液加熱至6 0 °C。然後。於 反應容器內的溶液，添加作爲聚合觸媒之三乙基銨（1.5 莫耳/升）的甲苯溶液0.62份及第3 丁醇及甲醇改性之六 氯化鎢（第3 丁醇：甲醇：鎢=〇·35莫耳：0.3莫耳：1莫 耳）的甲苯溶液（濃度0.05莫耳/升）3.7份，將該系統於 8 0°C下藉由加熱攪拌，得到開環共聚合物溶液。該聚合反 應之聚合轉化率爲97%，對所得的開環共聚合物，測定於 3 0°C的三氯甲烷中的特性黏度（tiinh)爲〇·48 dl/g。 將如此所得的開環共聚合物溶液4000份放入高壓 釜，於該開環共聚合物溶液中添加RuHC1(CO)[P(C6H5)3]3 -38- 200837393 0.48份，在氫氣壓力100 kg/cm2、反應溫度160 °C的條件 下，加熱攪拌3小時，進行氫化反應。 所得的反應溶液（氫化聚合物溶液）冷卻後，釋放氫 氣壓力。將該反應溶液注入大量的甲醇中，分離收回凝固 物，將其乾燥，得到氫化的環狀烯烴系樹脂C1。 對如此所得的環狀烯烴系樹脂C 1 (以下稱爲「樹脂 C1」），使用 500 MHz iH-NMR，測定氫化率時，爲 9 9.9%。使用500 MHz 4-NMR測定來自單體B的構造單 元b的比例時爲30.2%。此處，構造單元b的比例係由出 現於約3.7 ppm附近的來自單體A的構造單元a的甲酯的 甲基之質子的吸收及出現於7 PPm的構造單元B芳香環構 造之質子的吸收所算出。 樹脂C1的Tg爲130°C。而且，藉由GPC法（溶劑： 四氫呋喃），測定苯乙烯換算的數平均分子量（Μη)及重 量平均分子量（Mw)時，Μη爲16,000，Mw爲58,000, 分子量分佈（Mw/Mn)爲3.62，特性黏度（t]lnh)爲0.50 dl/g。再者，測定23°C之飽和吸水率時爲0.15%。該樹脂 的折射率爲1.531。 (擴散粒子的調製） 於分離式燒瓶，添加離子交換水25〇重量份、甲基丙 烯酸甲酯98重量份、乙二醇二甲基丙烯酸酯2重量份、 油酸鉀1重量份，進行氮氣取代後，升溫至6 0 °C，添加過 硫酸鉀〇 · 2重量份後，進行反應3小時’再添加過硫酸鉀 -39- 200837393 〇. 1重量份，進行反應1小時，得到樹脂乳膠。 該樹脂乳膠滴入氯化鈣水溶液中，得到凝固樹脂粒 子。該凝固樹脂粒子的折射率爲 1.492，平均粒徑爲 1 2 μιη 〇 (光擴散板的製作） 混合99重量份的上述樹脂C 1、1重量份的上述凝固 樹脂粒子、0.3重量份的作爲抗氧化劑之千葉特殊化學公 司製IRGANOX1010，調製光擴散性樹脂組成物C1。除使 用樹脂組成物C 1取代樹脂組成物Α1以外，與實施例1同 樣地製作1 ·〇 mm厚的光擴散板C 1。 對所得的光擴散板C 1進行評價，結果表示於表1。 [實施例5] (擴散粒子的調製） • 於分離式燒瓶，添加離子交換水250重量份、甲基丙 烯酸甲酯55重量份、苯乙烯43重量份、二乙烯苯2重量 份、油酸鉀1重量份，進行氮氣取代後，升溫至60°C，添 加過硫酸鉀0.2重量份後，進行反應3小時，再添加過硫 酸鉀0.1重量份，進行反應1小時，得到樹脂乳膠。 該樹脂乳膠滴入氯化鈣水溶液中，得到凝固樹脂粒 子。該凝固樹脂粒子的折射率爲1.545，.平均粒徑爲 1 2 μιη 〇 -40- 200837393 (光擴散板的製作） 除使用聚碳酸酯樹脂（帝人化成公司製：Paulite AD5 5 03、Tg=145°C、折射率nD= 1 . 5 8 3 ) 99重量份取代環 狀烯烴系樹脂，及上述凝固樹脂粒子1重量份作爲擴散粒 子外，與實施例1同樣地製作樹脂薄片D1 (厚度1.0 mm ) ° 除使用該樹脂薄片D1，設定金屬帶及金屬滾輪的溫 度皆爲125 °C以外，與實施例1同樣地製作1.〇 mm厚的 光擴散板D 1。 對所得的光擴散板D1進行評價，結果表示於表1。 [比較例1 ] 除不使用擴散粒子，改變環狀烯烴系樹脂的量爲100 重量份以外，與實施例1同樣地製作0.5 mm厚的光擴散 板al。 • 對所得的光擴散板al進行評價，結果表示於表1。 [比較例2] 與實施例1同樣地製作樹脂薄片Α1。 使用平行配置的3個滾輪（表面鍍硬鉻，直徑300 mm，表面粗糙度0.1s)，將上述樹脂薄片A1夾於調整爲 120°C的上述滾輪間，以2.5m/分的速度捲取，製作1.0 mm厚的光擴散板a2。 對所得的光擴散板a2進行評價，結果表示於表1。 -41 - 200837393 [比較例3] 實施例5所使用的擴散粒子變更爲實施例 擴散粒子外，藉由與實施例5相同的方法，製 D1 (厚度 1.0 mm)。 除使用該樹脂薄片D1，設定金屬帶及金 度皆爲1 3 5 °C以外，與實施例5同樣地製作1 光擴散板d 1。 對所得的光擴散板dl進行評價，結果表示 [比較例4 ] 除環狀烯烴系樹脂的量變更爲98.8重量 子變更爲平均粒徑5μιη的擴散粒子（積水化成 商品名：TECHPOLYMER ΜΒΧ-5、折射率 nD = 重量份以外，與實施例1同樣地製作I·0 mm 板el。 對所得的光擴散板e 1進行評價，結果表示 1所使用的 作樹脂薄片 屬滾輪的溫 • 〇 mm厚的 於表1。 份，擴散粒 品公司製、 =1.492) 1.2 厚的光擴散 於表1。 -42 - 200837393MicrotracUAPISO), the particle size distribution was determined by light scattering. The resulting particle size distribution is depicted on a logarithmic probability paper with a particle size accumulated to 50% as the average particle size. (refractive index) The particles were filtered through a gold mesh of 60 mesh, and the refractive index standard solution (manufactured by Cargille Co., Ltd.) was mixed with the filter residue, and observed by an optical microscope to become a refractive index of the d line of the standard liquid in which the outline of the particle could not be seen. The refractive index of the particles is -34- 200837393. The measurement was carried out at 25 °C. (Total Light Transmittance and Haze) The total light transmittance and haze of the light diffusing plate were measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) in accordance with ASTM D 1 003. (Residual phase difference) The residual phase difference of the light-diffusing sheet was measured by cutting the obtained light-diffusing sheet into A4 size, and a test piece was produced, and measurement was performed using a micro-area birefringence meter (KOBRA-CCD manufactured by Oji Scientific Co., Ltd.). (display comparison) The light diffusion plate was bonded to a polarizing plate A (POLAX-38S manufactured by LUCEO Co., Ltd.), and the optical axis and the optical axis of the polarizing plate A were perpendicularly attached to the polarizing plate B (POLAX manufactured by LUCEO Co., Ltd.) -3 8S ), optical member C is produced. On the other hand, the light diffusing plate is bonded to the polarizing plate A, and the optical axis P is produced by bonding the optical axis to the polarizing plate B in parallel with the optical axis of the polarizing plate A. The optical member C and the optical member P were measured for luminance by the following method, and the contrast L was obtained by the following formula. L = brightness of the optical member P / brightness of the optical member C. The optical member is placed at a position of 300 mm from the light box (manufactured by Dentsu Kogyo Co., Ltd., large-35 · 200837393, brightness: 9000 cd/m 2 ), and brightness is used. The brightness of light transmitted through the optical member was measured by Konica-Minolta LS-1 10 manufactured by Konica Corporation. Further, the luminance of the transmitted light of the one polarizing plate is 4500 cd/m 2 , and the luminance of the transmitted light of the optical member in which the polarizing plates A and B are perpendicularly bonded to each other is 15 cd/m 2 , and the polarizing plate A is B The brightness of the transmitted light of the optical member in which the optical axes are bonded in parallel is 4000 cd/m2. Therefore, only φ has 2 polarizers with a contrast of 270. (Concealed) The four corners of the light diffusing plate are fixed by clips, and they are arranged in a screen shape. The liquid crystal projector (manufactured by Seiko Epson Co., model EMP-1710) is used to illuminate the image from the back of the light diffusing plate. The front side of the diffusion plate was visually observed, and the concealability was evaluated on the basis of the following criteria. A: The outline of the light source of the projector is not visible. B. The outline of the light source of the projector is visible. [Example 1] A cyclic olefin resin (product name: ARTON D45 3 1 , Tg = 13, manufactured by JSR Corporation) 0°C, refractive index=1.515) 97.5 parts by weight and diffusion particles (product name: TECHPOLYMER SBX-12, refractive index η〇=1·59, average particle diameter 12μηι) manufactured by Sekisui Kogyo Co., Ltd. 2.5 parts by weight Mixing with a Henschel mixer, and mixing a fluorescent whitening agent (Chiba Chiba Special Chemicals, trade name: UVITEX OB_ONE) 30 -36- 200837393 ppm 'Modified light diffusing resin composition A1. The resin composition A1 was dried at 90 ° C for 2 hours using a dehumidifying dryer to remove moisture on the surface. Then, it was quantitatively supplied to a two-axis extruder (TEM-37, manufactured by Toshiba Machine Co., Ltd.) using a weight feeder, and the resin composition A 1 was pelletized at 270 °C. The above-mentioned resin composition A 1 in a granular form was dried at 100 ° C for 4 hours using a dehumidifying dryer, melted at 265 ° C, and supplied to a two-axis extruder at a weight of 80 kg / hour using a gear pump (GM engineering) Co., Ltd., screw outer diameter D = 75 mm, L/D = 36), and a 600 mm wide coat hanger type T die was melt extruded at 270 ° C to obtain a resin sheet A1. The above-mentioned resin sheet A1 was sandwiched and adjusted to 80 ° C using a sleeve type winding device having a 0.3 mm thick seamless metal strip (surface roughness 0.2 s) and a metal roller (surface roughness 0.1 s). A strip of light diffusion plate A1 having a thickness of 1 mm was produced by winding the metal strip and the metal roller at a speed of 2.5 m/min. The obtained light-diffusing sheet A1 was evaluated, and the results are shown in Table 1. [Example 2] 95 parts by weight of styrene and 5 parts by weight of divinylbenzene were copolymerized to prepare crosslinked particles (refractive index nD = 1.592, average particle diameter Ιίμιη). A light diffusing plate 1 having a thickness of 1 mm was produced in the same manner as in Example 1 except that the crosslinked particles were used instead of TECHPOLYMER SBX-12. The obtained light-diffusing sheet B1 was evaluated, and the results are shown in Table 1. -37-200837393 [Example 3] A resin sheet A2 (thickness 1 · 〇 mm) was produced in the same manner as in Example 1 except that the amount of the cyclic olefin resin was changed to 98.7 parts by weight and the amount of the diffusion particles was 1.3 parts by weight. ). Using the resin sheet A2, the light-diffusing sheet A2 after 0.8 mm was produced in the same manner as in Example 1 except that the winding speed was changed to 3 m/min. The obtained light-diffusing sheet A2 was evaluated, and the results are shown in Table 1. [Example 4] (Synthesis of a cyclic, olefin-based resin) 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5.17,10]-3-dodecene (monomer A) 175 parts, 5-phenyl-bicyclo[2 ·2·1]hept-2-ene (monomer Β) 7 5 parts, 1 · hexene (molecular weight regulator): 8 parts and toluene 7 5 0 parts The reaction vessel was replaced with nitrogen and the solution was heated to 60 °C. then. To the solution in the reaction vessel, 0.62 parts of a toluene solution of triethylammonium (1.5 mol/liter) as a polymerization catalyst, and a third butanol and methanol-modified tungsten hexachloride (third butanol: methanol) : Tungsten = 〇 · 35 moles: 0.3 moles: 1 moles of toluene solution (concentration 0.05 mol / liter) 3.7 parts, the system was heated and stirred at 80 ° C to obtain ring-opening copolymerization Solution. The polymerization conversion ratio of the polymerization reaction was 97%, and the intrinsic viscosity (tiinh) of the obtained ring-opening copolymer in chloroform at 30 ° C was 〇·48 dl/g. 4000 parts of the thus obtained ring-opening copolymer solution was placed in an autoclave, and 0.46 parts of RuHC1(CO)[P(C6H5)3]3 -38-200837393 was added to the ring-opening copolymer solution at a hydrogen pressure of 100 The mixture was heated and stirred for 3 hours under the conditions of a reaction temperature of 160 ° C and a hydrogenation reaction. After the obtained reaction solution (hydrogenated polymer solution) was cooled, hydrogen pressure was released. This reaction solution was poured into a large amount of methanol, and the solidified product was separated and recovered, and dried to obtain a hydrogenated cyclic olefin-based resin C1. The cyclic olefin-based resin C 1 (hereinafter referred to as "resin C1") thus obtained was subjected to 500 MHz iH-NMR, and when the hydrogenation ratio was measured, it was 9 9.9%. The ratio of the structural unit b derived from the monomer B was measured by 500 MHz 4-NMR to be 30.2%. Here, the ratio of the structural unit b is the absorption of the proton of the methyl group of the methyl ester of the structural unit a from the monomer A present at about 3.7 ppm and the proton of the aromatic ring structure of the structural unit B of 7 PPm. Absorbed by the calculation. The Tg of the resin C1 was 130 °C. Further, when the number average molecular weight (??) and the weight average molecular weight (Mw) in terms of styrene were measured by a GPC method (solvent: tetrahydrofuran), Μη was 16,000, Mw was 58,000, and molecular weight distribution (Mw/Mn) was 3.62. The intrinsic viscosity (t]lnh) is 0.50 dl/g. Further, when the saturated water absorption at 23 ° C was measured, it was 0.15%. The resin had a refractive index of 1.531. (Preparation of the diffusing particles) In a separate flask, 25 parts by weight of ion-exchanged water, 98 parts by weight of methyl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate, and 1 part by weight of potassium oleate were added to carry out nitrogen gas. After the substitution, the temperature was raised to 60 ° C, and 2 parts by weight of potassium persulfate was added, and then the reaction was carried out for 3 hours. Then, potassium persulfate-39-200837393 〇. 1 part by weight was added, and the reaction was carried out for 1 hour to obtain a resin latex. The resin latex was dropped into an aqueous solution of calcium chloride to obtain solidified resin particles. The solidified resin particles had a refractive index of 1.492 and an average particle diameter of 12 μm 〇 (Production of a light-diffusing sheet) 99 parts by weight of the above-mentioned resin C 1 and 1 part by weight of the above-mentioned solidified resin particles and 0.3 parts by weight of an anti-serum IRGANOX 1010 manufactured by Chiba Special Chemical Co., Ltd., an oxidizing agent, modulates the light diffusing resin composition C1. A light diffusion plate C 1 having a thickness of 1 mm was produced in the same manner as in Example 1 except that the resin composition C 1 was used instead of the resin composition Α1. The obtained light-diffusing sheet C 1 was evaluated, and the results are shown in Table 1. [Example 5] (Preparation of diffusing particles) • 250 parts by weight of ion-exchanged water, 55 parts by weight of methyl methacrylate, 43 parts by weight of styrene, 2 parts by weight of divinylbenzene, and potassium oleate were added to a separate flask. After 1 part by weight, after nitrogen substitution, the temperature was raised to 60 ° C, and 0.2 parts by weight of potassium persulfate was added, and then the reaction was carried out for 3 hours, and 0.1 part by weight of potassium persulfate was further added thereto, and the reaction was carried out for 1 hour to obtain a resin latex. The resin latex was dropped into an aqueous solution of calcium chloride to obtain solidified resin particles. The solidified resin particles had a refractive index of 1.545, and an average particle diameter of 12 μm 〇 -40 - 200837393 (manufacture of a light-diffusing sheet), except that a polycarbonate resin (manufactured by Teijin Chemical Co., Ltd.: Paulite AD5 5 03, Tg = 145) was used. °C, refractive index nD = 1. 5 8 3 ) 99 parts by weight of the substituted cyclic olefin resin and 1 part by weight of the solidified resin particles as the diffusion particles, and a resin sheet D1 (thickness 1.0 mm) was produced in the same manner as in Example 1. In the same manner as in Example 1, except that the resin sheet D1 was used, and the temperature of the metal strip and the metal roller was set to 125 ° C, a light diffusion plate D 1 having a thickness of 1. mm was produced. The obtained light-diffusing sheet D1 was evaluated, and the results are shown in Table 1. [Comparative Example 1] A light diffusion plate a1 having a thickness of 0.5 mm was produced in the same manner as in Example 1 except that the amount of the cyclic olefin resin was changed to 100 parts by weight. • The obtained light diffusing plate a1 was evaluated, and the results are shown in Table 1. [Comparative Example 2] A resin sheet crucible 1 was produced in the same manner as in Example 1. Using the three rollers arranged in parallel (surface hard chrome plated, diameter 300 mm, surface roughness 0.1 s), the above resin sheet A1 was sandwiched between the above-mentioned rollers adjusted to 120 ° C, and taken up at a speed of 2.5 m / min. , a 1.0 mm thick light diffusing plate a2 was produced. The obtained light-diffusing sheet a2 was evaluated, and the results are shown in Table 1. -41 - 200837393 [Comparative Example 3] The diffusion particles used in Example 5 were changed to Examples. D1 (thickness: 1.0 mm) was produced in the same manner as in Example 5 except for the diffusion particles. A light diffusing plate d1 was produced in the same manner as in Example 5 except that the resin sheet D1 was used, and the metal strip and the metalness were set to be 1 35 °C. When the obtained light-diffusing sheet dl was evaluated, the result of the comparison was as follows: [Comparative Example 4] The amount of the cyclic olefin-based resin was changed to 98.8 by weight, and the amount of the particles was changed to an average particle diameter of 5 μm (product name: TECHPOLYMER ΜΒΧ-5, An I.0 mm plate el was produced in the same manner as in Example 1 except for the refractive index nD = parts by weight. The obtained light-diffusing sheet e 1 was evaluated, and the result was that the temperature of the resin sheet used as a roller was thick. In Table 1. Parts, manufactured by Diffusion Granules Co., Ltd., = 1.492) 1.2 Thick light is diffused in Table 1. -42 - 200837393
I撇 比較例4 13 oo o (N 1.515 1.492 0.023 〇 p <N OS 15±5 3900 m 1P-H f 1—^ CQ 比較例3 Q CN o 1.583 1.59 0.007 t p 00 oo Ο 75±5 1500 750 (N m 比較例2 Η < o 1.515 1.59 0.075 o CN ON Ο 85±5 1200 860 < 比較例1 1 i 1.515 1 1 o (N Os (Ν Ο 3800 m (N Η m 實施例5 r-H Q CN o 1.583 1.545 0.038 r-H p ON OO νο 1900 00 m < 實施例4 τ—H o (N o 1.531 1.492 0.039 1 i r-H o <N On (Ν r-H 3800 S < 實施例3 (N < rn 1.515 1.590 1 0.075 (Ν < oo o ON OO g ιτν 3680 (Ν 00 < 實施例2 r-H PQ (N 1.515 1.592 0.077 S s p 冢 3800 m (Ν Η < 實施例1 < 〇 1.515 1.590 0.078 \ < o (N 0's Ο 3750 m τ-Η < 樹脂組成物 s n 重量％ 樹脂 粒子 樹脂及粒子的折射率差的絕對値 樹脂薄片 光擴散板 mm i cd/m2 cd/m2 對比L 隱蔽性 平均粒徑 粒子添加量 折射率 厚度 全部光線透過率 霧度 殘留相位差 亮度(光軸平行） 亮度(光軸垂直） -43-I撇Comparative Example 4 13 oo o (N 1.515 1.492 0.023 〇p <N OS 15±5 3900 m 1P-H f 1—^ CQ Comparative Example 3 Q CN o 1.583 1.59 0.007 tp 00 oo Ο 75±5 1500 750 (N m Comparative Example 2 Η < o 1.515 1.59 0.075 o CN ON Ο 85±5 1200 860 < Comparative Example 1 1 i 1.515 1 1 o (N Os (Ν Ο 3800 m (N Η m Example 5 rH Q CN o 1.583 1.545 0.038 rH p ON OO νο 1900 00 m <Example 4 τ - H o (N o 1.531 1.492 0.039 1 i rH o < N On (Ν rH 3800 S < Example 3 (N < Rn 1.515 1.590 1 0.075 (Ν < oo o ON OO g ιτν 3680 (Ν 00 < Example 2 rH PQ (N 1.515 1.592 0.077 S sp 冢3800 m (Ν Η < Example 1 < 〇 1.515 1.590 0.078 \ < o (N 0's Ο 3750 m τ-Η < resin composition sn% by weight Resin particle resin and particle refractive index difference absolute 値 resin sheet light diffusing plate mm i cd/m2 cd/m2 contrast L concealment Average particle size Particle addition amount Refractive index Thickness Total light transmittance Haze Residual phase difference Brightness (optical axis parallel) Brightness (optical axis vertical) -43-