574249 五、發明説明（1 ) 發明所屬枝術領域 本發明係關於由含有脂環型構造的聚合物所構成，長光 程之黃指數小的成形體之製法。 習知技術 原冰片烯系樹脂等含有脂環型構造之聚合物，透明性、 耐熱性、低吸水性等均優。因此，含有脂環型構造之聚合 物，適合於光學透鏡、光碟等各種光學組件之成形材料。 近年來提倡含有脂環型構造的聚合物，作爲光學材料， 使用於各種用途’例如筆記型電腦、或汽車導航等所用液 晶顯示元件（LCD)之背面光用導光板或散光板。尤其是最 近隨著LCD的大型化’需要大型薄導光板，乃擬議最長 200mm以上之產品。大型且薄，而光路程長（例如最長 200mm以上）的光學組件成型時，通常必須提高成型溫度 。原冰片烯系樹脂由於流動性優，即使成形溫度高，也很 難因分解等發生銀條紋或發泡等之成形不良。 然而’在成形時受熱過程，所得成形品有目視不易辨別 程度的着色，有時亮度或色溫等諸特性會降低。因此，亟 需有不着色的大型薄光學組件。 在此狀況下，倡議原冰片烯系樹脂成形之際，可以減少 燒結、微孔隙、目視可辨別程度的着色之方法。例如，特 開平7-224155號公報揭不之成形方法，是在氧分壓 20mmHg(2kPa)以下的氣體氛圍，於溫度80°C以上，經一 定時間加熱乾燥而得九粒。特開平1 1 -28 725號公報揭示 之方法，是在樹脂供應到成形機之際，把裝該樹脂的容器 574249 五、發明説明（2 ) 減壓後，導入惰性氣體，將樹脂和惰性氣體供應至成形機。 蝥明所要解決之冃的 然而，上述公報所載方法均非關於可以防止大型薄成形 體的着色，尤其是光路程長，起初可確認透射率降低程度 的着色。 本發明之目的，在於提供一種成形體之製法，可製造長 光程的黃指數小之大型薄成形體。 解決目的之丰段 本發明人等發現，在含有脂環型構造的聚合物加熱熔化 成形之前，於特定氣體氛圍，在特定溫度範圍加熱，然後 保持聚合物在特定溫度範圍，移送到成形機之加熱筒，即 可得例如200mm左右的長光程中黃指數小的成形體。尤 其是發現，把加熱後的聚合物，於特定氣體氛圍下，保持 在特定溫度範圍’並移送至成形機的加熱筒，即可得長光 程中黃指數更加進一步降低之成形體。 即本發明成形體之製法，包含把含有脂環型構造的聚合 物，在氧分壓10kPa以下，且在比該聚合物的玻璃轉化溫 度低5〜60°C之溫度’加熱之步驟（加熱步驟）； 把該加熱後的聚合物，保持比該聚合物的玻璃轉化溫度 低5〜70°C之溫度，移送到成形機之步驟（移送步驟）；和 將該移送後之聚合物，在比該聚合物的玻璃轉化溫度高 50°C以上之溫度’加熱熔化成形之步驟（成形步驟）。 更好是把該加熱後的聚合物，不暴露於空氣氛圍氣體， 保持密閉狀態，移送至成形機。 -4- 574249 五、發明説明（3 ) 更好是該加熱後的聚合物，在氧分壓lOkPa以下，移送 至成形機。 更好是g亥加熱後的聚合物，使用氧濃度在1 0%以下的氣 體’壓送至成形機。 更好是該移送後的聚合物，在氧分壓lOkPa以下加熱熔 化成形。 發明具體例之細說明 含有脂環型構笱之聚g物 本發明可用之含有脂環型構造的聚合物，係在主鏈和/ 或側鏈含有含有脂環型構造，就機械強度、耐熱性等觀點 言’以在主鏈含有脂環型構造者爲佳。 脂環型構造有環烷構造、環烯構造等，就機械強度、耐 熱性等觀點言，以環烷構造爲佳。 構成脂環型構造的碳原子數，就機械強度、耐熱性、成 型加工性觀點言，通常在4〜3 0個範圍，以5〜2 0個爲佳 ，而以5〜1 5個更好。 具有脂環型構造的重複單位比例，可視使用目的適當選 擇’但通常在50重量％以上，以70重量％以上爲佳，而 以90重量％以上更好。具有脂環型構造的重複單位比例在 此範圍時，對透明性和耐熱性方面較佳。 此等含脂環型構造的聚合物具體例，有例如原冰片烯系 聚合物，單環之環烯烴系聚合物、環型共軛二烯系聚合物 、乙烯基脂環型烴系聚合物，及其加氫物，其中以原冰片 烯系聚合物、環型共軛二烯系聚合物、及其加氫物等爲佳， 五、發明説明（4 ) 就耐熱性、機械強度觀點言，以原冰片烯系聚合物更好。 原冰片烯系聚合物有例如特開平3- 14882號公報或特開 平3-1 22 137號公報等所揭示之已知聚合物，具體例有原 冰片烯系單體之開環聚合物及其加氫物，原冰片烯系單體 之加成聚合物，原冰片烯系單體與乙烯系化合物之加成聚 合物等。 原冰片烯系單體有例如雙環[2.2.1]-庚-2-烯（常用原冰片 烯）、5-甲基雙環[2·2·1]-庚-2-烯、5,5-二甲基雙環[2.2.1]-庚烯、5-乙基雙環[m]-庚·2_烯、丁基雙環[221]_ 庚烯、5-己基雙環[2.2.1]-庚-2-烯、5_辛基雙環[2.2.1]-庚烯、5-十八烷基雙環[2.2.1]-庚-2-烯、5-亞乙基雙環 [2·2·Π_庚-2-烯、5-亞甲基雙環[2.21]-庚_2-烯、5_乙烯基 雙環烯、5-丙烯基[2.21]_庚_2_烯、％甲氧基 羰基雙環[2.2.1]-庚-2-烯、5-氰基雙環[2.21]_庚-2_烯、5_ 基5-甲氧基羰基雙環[2.2.1]-庚_2·烯、5-甲氧基羰基雙 環[2·2·ι]·庚烯、5_乙氧基羰基雙環[m]•庚ι烯、5_ 甲基、乙氧基羰基雙環[2·2·1]_庚_2-稀， X壤[2.2.1]-庚-5-烯基-2-甲基丙酸酯、雙環[221]_庚_574249 V. Description of the invention (1) Field of invention The present invention relates to a method for forming a formed body composed of a polymer containing an alicyclic structure and having a small yellow index of long optical path. Conventional technology Polymers containing an alicyclic structure, such as original norbornene-based resins, are excellent in transparency, heat resistance, and low water absorption. Therefore, polymers containing alicyclic structures are suitable for molding materials for various optical components such as optical lenses and optical disks. In recent years, polymers containing alicyclic structures have been proposed as optical materials for various applications, such as light guide plates or diffuser plates for back light of liquid crystal display elements (LCDs) used in notebook computers and car navigation systems. Especially recently, with the increase in the size of LCD's, large and thin light guide plates are required, and products with a maximum length of 200 mm or more are proposed. When forming large and thin optical components with long optical paths (for example, up to 200mm or more), it is usually necessary to increase the molding temperature. Since the original norbornene-based resin has excellent fluidity, even if the molding temperature is high, it is difficult to cause defective molding such as silver streaks due to decomposition or the like. However, in the process of heating during molding, the resulting molded product is colored to a degree that is difficult to discern visually, and characteristics such as brightness and color temperature may be reduced. Therefore, there is a great need for large and thin optical components that are not colored. Under these circumstances, when proto-norbornene-based resins are being molded, a method that can reduce sintering, microvoids, and visually distinguishable coloring is recommended. For example, Japanese Unexamined Patent Publication No. 7-224155 discloses a molding method in which nine pellets are obtained by heating and drying at a temperature of 80 ° C or higher in a gas atmosphere with an oxygen partial pressure of 20 mmHg (2 kPa) or less. Japanese Patent Application Laid-Open No. 1 1-28 725 discloses a method in which a resin container 574249 is supplied when a resin is supplied to a molding machine. 5. Description of the invention (2) After the pressure is reduced, an inert gas is introduced and the resin and the inert gas are introduced. Supply to forming machine. However, none of the methods described in the above-mentioned bulletin is concerned with coloring that can prevent large and thin shaped bodies, especially with long light paths, and can initially confirm the degree of reduction in transmittance. An object of the present invention is to provide a method for manufacturing a compact, which can produce a large and thin compact having a long optical path and a small yellow index. The purpose of the solution is to find that before the polymer containing the alicyclic structure is heated and melted, it is heated in a specific gas atmosphere at a specific temperature range, and then the polymer is kept in a specific temperature range and transferred to the molding machine. By heating the barrel, for example, a compact having a small yellow index in a long optical path of about 200 mm can be obtained. In particular, it was found that by heating the polymer in a specific gas atmosphere at a specific temperature range 'and transferring it to the heating cylinder of the molding machine, a molded body with a further reduced yellow index in the long optical path can be obtained. That is, the method for producing a molded article of the present invention includes a step of heating a polymer containing an alicyclic structure at an oxygen partial pressure of 10 kPa or less and at a temperature 5 to 60 ° C lower than the glass transition temperature of the polymer (heating Step); the step of transferring the heated polymer to a forming machine (transfer step) at a temperature 5 to 70 ° C lower than the glass transition temperature of the polymer; and A step (molding step) of heating and melting forming at a temperature of 50 ° C or more higher than the glass transition temperature of the polymer. More preferably, the heated polymer is kept in a closed state without being exposed to the air atmosphere and transferred to a molding machine. -4- 574249 V. Description of the invention (3) More preferably, the heated polymer is transferred to a molding machine at an oxygen partial pressure of 10 kPa or less. More preferably, the polymer is heated to the molding machine using a gas' having an oxygen concentration of 10% or less. More preferably, the polymer after the transfer is heat-molded at an oxygen partial pressure of 10 kPa or less. Detailed description of specific examples of the invention Polymers containing alicyclic structure 笱 The polymers containing alicyclic structure which can be used in the present invention contain alicyclic structures in the main chain and / or side chains. From the viewpoint of sex, it is preferable to include an alicyclic structure in the main chain. The alicyclic structure includes a naphthene structure, a cycloolefin structure, and the like. From the viewpoints of mechanical strength and heat resistance, a naphthene structure is preferred. The number of carbon atoms constituting the alicyclic structure generally ranges from 4 to 30, preferably 5 to 20, and more preferably 5 to 15 from the viewpoints of mechanical strength, heat resistance, and moldability. . The proportion of the repeating unit having an alicyclic structure can be appropriately selected depending on the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more. When the proportion of the repeating unit having an alicyclic structure is within this range, it is preferable in terms of transparency and heat resistance. Specific examples of such alicyclic structure-containing polymers include, for example, orbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, and vinyl alicyclic hydrocarbon-based polymers. And its hydrogenated products, among which orthobornene-based polymers, cyclic conjugated diene-based polymers, and their hydrogenated materials are preferred. 5. Description of the Invention (4) In terms of heat resistance and mechanical strength, It is better to use the original norbornene-based polymer. The original norbornene-based polymers include known polymers disclosed in, for example, Japanese Unexamined Patent Publication No. 3-14882 or Japanese Unexamined Patent Publication No. 3-1 22 137, and specific examples include ring-opening polymers of original norbornene-based monomers and Hydrogenates, addition polymers of orbornene-based monomers, addition polymers of orthobornene-based monomers and vinyl compounds, and the like. Protobornene-based monomers include, for example, bicyclo [2.2.1] -hept-2-ene (common norbornene), 5-methylbicyclo [2 · 2 · 1] -hept-2-ene, 5,5- Dimethylbicyclo [2.2.1] -heptene, 5-ethylbicyclo [m] -hepta-2-ene, butylbicyclo [221] _heptene, 5-hexylbicyclo [2.2.1] -hept- 2-ene, 5-octylbicyclo [2.2.1] -heptene, 5-octadecylbicyclo [2.2.1] -hept-2-ene, 5-ethylenebicyclo [2 · 2 · Π_ Hept-2-ene, 5-methylenebicyclo [2.21] -hept-2-ene, 5-vinylbicycloene, 5-propenyl [2.21] _hept-2-ene,% methoxycarbonyl bicyclic [ 2.2.1] -hept-2-ene, 5-cyanobicyclo [2.21] _hept-2-ene, 5-yl 5-methoxycarbonylbicyclo [2.2.1] -hept-2-ene, 5-methyl Oxycarbonylbicyclo [2 · 2 · ι] · heptene, 5-ethoxycarbonylbicyclo [m] • heptene, 5-methyl, ethoxycarbonylbicyclo [2 · 2 · 1] _hept_2 -Dilute, X soil [2.2.1] -hept-5-enyl-2-methylpropionate, bicyclic [221] _hept_
5_烯基甲基辛酸酯、雙環—烯…，卜二羧酸酐 ' 甲甚鮮擐「2·2.11-_-9-條、c ,—_ ........5_alkenyl methyl octanoate, bicyclo-ene ..., dicarboxylic acid anhydride, methyl very fresh, "2.1.11 -_- 9-article, c, ---...
[2·2·1μ 二羧基夸 醯亞胺 [2.2.ΐμ -6- 574249 五、發明説明（5 ) 雙環[2.2.1]-庚-2-烯， 三環[4.3.0.12,5]-癸-3，7-二烯（常用二環戊二烯）、三環 [4.3.0.12,5]-癸-3-烯、三環[4.4.0.12’5]-十一碳-3,7-二烯或 三環[4.4.0.12,5]-十二碳-3,8-二烯、三環[4.4.0.12’5]-十一 碳-3-烯、四環[7·4·0·11()，13·〇2,7]-十三碳-2,4,6-ll-四烯（亦 稱1,4-甲醇-:^^^-四氫莽:^四環^义力」11，14』3,8]-. 四碳-3,5,7，12-1 1-四烯（亦稱 1，4_甲醇- l，4,4a，5，l〇，l〇a-六氫 蒽）等不具有原冰片烷環之原冰片烯系單體， 四環[4.4.0.12,5·17’1G]-十二碳-2-烯（亦簡稱四環十二碳烯） ，8-甲基四環[4·4·0·12,5·17，1()]-十二碳-3-烯、8·乙基四環 [4.4.0.12,5.17，丨()]-十二碳-3-烯、8-亞甲基四環[4.4.0.12,5.17，10]-十二碳-3-烯、8-亞乙基四環[4·4·0·12’5·17’1()]-十二碳-3-烯 、8-乙烯基四環[4.4.0.12,5.17’1()]-十二碳-3-烯、8-丙烯基 四環[4.4.0.12,5.17，1G]-十二碳-3-烯、8-甲氧基羰基四環 [4·4.0·12,5·17，1()]-十二碳-3-烯、8-甲基-8-甲氧基羰基四環 [4·4·0·12,5·17，1()]-十二碳-3-烯、8-羥甲基四環[4·4·0·12’5.Γ’1()] -十二碳-3-烯、8-羧基四環[4·4·0·12’5·17’1()]-十二碳-3-烯、 8-環戊基四環[4.4.0.12’5.17，1。]-十二碳-3-烯、8-環己基四 環[4.4.0.12,5.17，1()]-十二碳-3-烯、8-環己烯基四環[4.4.0. 12,5.17，1()]-十二碳-3-嫌、8-苯基四環[4.4.0.12’5.17’1()]-十二 碳-3-烯、五環[6.5.1.13’6.02’7.09’13]-十五碳-3，10-二烯、五 環[7.4.0.13’6.11()，13.02’7]-十五碳-4，11-二烯等具有原冰片烷 環之原冰片烯系單體。 此等原冰片烯系單體可分別單獨或二種以上組合使用。 574249 五、發明説明（6 ) 在本發明中，除上述原冰片烯系單體之外，亦可用共聚 性單體。共聚性單體有例如乙烯、丙烯、1-丁烯、1-戊烯 、：1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊 烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、 4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛 烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、卜二十碳烯等C2〜C2Ga-烯烴；環丁烯、環戊 烯、環己烯、3,4-二甲基戊烯、3-甲基環己烯、2-(2-甲基 丁烯）-1-環己烯、環辛烯、3a,5,6,7a-四氫-4,7-甲醇-4,7-乙 醇-1H-茚等環烯烴；1，4-己二烯、4-甲基-1，4-己二烯、5-甲基-1,4-己二烯、1，7-辛二烯等非共軛二烯等等。 此等共聚性單體可分別單獨或二種以上組合使用。 上述單體之開環聚合，可用釕、铑、鈀、餓、銥、鉑等 金屬之鹵化物、硝酸鹽或乙醯丙酮化合物，還原劑構成的 觸媒系，以及鈦、釩、锆、鎢、鉬等金屬的鹵化物，和有 機錳化合物構成之觸媒系，作爲開環聚合觸媒，在溶劑中 或無溶劑，通常在-50至100°C的聚合溫度，0〜5MPa的 聚合壓力，進行開環聚合而得。 加氫原冰片嫌系聚合物可按照常法，將開環（共）聚合物 ，在加氫觸媒的存在下加氫之方法製得。 原冰片烯系單體與上述共聚性單體之加成共聚物，可利 用例如把單體成份在溶劑中或無溶劑，於鈦、锆、或釩， 和有機鋁化合物構成之觸媒系存在下，通常-50至1〇〇。〇 的聚合溫度’ 〇〜50MPa的聚合壓力，加以共聚合之方法 574249 五、發明説明（7 ) 製得。 單環之環烯烴系聚合物，有例如特開昭64-66216號公 報所揭不之環己儲、環庚儲、環辛儲等單環之環丨希煙系單 體的加成聚合物等。 環型共軛二烯系聚合物有例如特開平6-136057號公報 或特開平7-25 83 1 8號公報所載，由環戊二烯、環己二烯 等環型共軛二烯系單體，經1，2-或1,4-加成聚合所得聚合 物，及其加氫物等。 乙烯基脂環型烴系聚合物有例如特開昭5 1 -59989號公 報所載乙烯基環己基、乙烯基環己烷等乙烯基脂環型烴系 單體之聚合物及其加氫物，特開昭63-439 1 0、64- 1 706號 公報等所載苯乙烯、α-甲基苯乙烯等乙烯基芳族系單體 的聚合物在芳香環部份之加氫物等。關於此等乙烯基脂環 型烴系聚合物的主體配置，凡雜連、順聯、間規方式均可 ，例如利用二元顯示的間規方式，在0〜1 〇〇%均可用。 本發明可用之含脂環型構造的聚合物分子量，可視使用 目的適當選擇，惟以環己烷溶液（聚合物不溶解時則爲甲 苯溶液）的凝膠滲透層析法測得換算成聚異丙烯重量平均 分子量5000〜500000，更好是8000〜200000，最好1 0000 〜100000範圍時，對機械強度與成型加工性之高度平衡有 利。 本發明可用之含脂環型構造的聚合物玻璃轉化溫度（Tg) ，可視使用目的適當選擇，通常爲50〜300°c，以60〜 2〇〇°C爲佳，而以70〜180°C更好。 -9- 574249 五、發明説明（8 ) 本發明可用之含脂環型構造的聚合物，可視需要混配各 種混配劑。混配劑以一般塑膠所混配者即可，例如抗氧化 劑、熱安定劑、耐光安定劑等安定劑；紫外線吸收劑、抗 靜電劑、滑劑、可塑劑等。 尤其是爲了獲得透明性優良的成形體，宜混配抗氧化劑 。抗氧化劑有例如酚系抗老化劑、磷系抗老化劑、硫系抗 老化劑等。 酚系抗老化劑可用習知物，例如特開昭63-1 79953號或 特開平卜丨68643號公報所載2-三級丁基-6-(3-三級丁基-2-羥基-5-甲基苄基）-4-甲基苯基丙烯酸酯、2,4-二（三級戊 基）-6-(1-(3，5-二（三級戊基）-2-羥苯基）乙基）苯基丙烯酸酯 等丙烯酸酯系化合物；十八烷基-3-(3,5-二（三級丁基）-4-羥苯基）丙烯酯、2,2f-亞甲基雙（4-甲基-6-三級丁基酚）、 2,2’-伸乙基雙（4-甲基-6-三級丁基酚）、1，3,5-三甲基-2,4,6-參（3,5-二（三級丁基）-4-羥苄基）苯、肆（亞甲基-3·(3’，5’-二 (三級丁基）-4f-羥苯基丙酸酯）甲烷[即季戊四醇甲基肆（3-(3,5-二（三級丁基）-4-羥苯基丙酸酯））、硬脂基-(3，5-二 (三級丁基）-4-羥苯基）丙酸酯、3,9-雙[1，1-二甲基-2-[冷-(3-三級丁基-4-羥基-5-甲基苯基）丙醯氧基]乙基]-2,4,8,10-四唑螺[5.5]十一烷等烷基取代酚系化合物；6-(4-羥基-3, 5-二（三級丁基苯胺并）-2,4-雙辛基硫代-1，3,5-三哄、4-雙 辛硫代-1,3,5-三畊、2-辛基硫代-4,6-雙-(3,5-二（三級丁基） -4-氧基苯胺并）-1,3,5-三畊等含三哄基之酚系化合物等。 磷系抗老化劑只要是一般樹脂工業常用物，無特別限定。 -10- 574249 五、發明説明（9 ) 有例如三苯基亞磷酸酯、二苯基異癸基亞磷酸酯、苯基二 異癸基亞磷酸酯、參（壬苯基）亞磷酸酯、參（二壬苯基）亞 磷酸酯、參（2,4-二（三級丁基）苯基）亞磷酸酯、1〇-(3,5-二（ 三級丁基）-4-羥戊基）-9,10-二氫-9-噚-10-磷菲-10-氧化物 等單亞磷酸酯系化合物；4,4·-亞丁基雙（3-甲基-6-三級丁 基苯基二（十三烷基）亞磷酸酯）、4,4’-異亞丙基雙（苯基二 烷基（C12〜C15)亞磷酸酯）等二亞磷酸酯系化合物等。其中 以單亞磷酸酯系化合物爲佳，而以參（壬苯基）亞磷酸酯、 參（二壬苯基）亞磷酸酯、參（2,4-二（三級丁基）苯基）亞磷酸 酯等。 硫系抗老化劑有例如二月桂基3,3’·硫代二丙酸酯、二 肉豆蔻基3,3’-硫代二丙酸酯、二硬脂基3,3’-硫代二丙酸 酯、月桂基硬脂基3,3’-硫代二丙酸酯、異戊四醇肆-月 桂基硫代丙酸酯）、3,9-雙（2-十二烷基硫代乙基）-2,4,8，10-四噚螺[5.5]十一烷等。 其中以酚系抗老化劑爲佳，尤其是烷基取代之酚系抗老 化劑，即在芳香環上的羥基兩側碳上之氫被烷基所取代， 在長期耐熱性方面有利。 此等抗老化劑可單獨或二種以上組合使用，組合使用時 ，以酚系抗老化劑和磷系抗老化劑倂用爲佳，可得透明性 優良之成形體。 成形方法 本發明在將含脂環型構造的聚合物加熱後（加熱步驟）、 移送到成形機（移送步驟）、加熱熔化成形（成形步驟），製 -11- 574249 五、發明説明（10 ) 造成形體。 加熱步驟 含脂環型構造的聚合物，是在特定氣體氛圍下進行加熱 。此特定氣體氛圍，是氧分壓在lOkPa以下，以8kPa以 下爲佳，而以5kPa以下更好。此特定氣體氛圍可以例如 以氮、氬、氦、二氧化碳等惰性氣體排淨之方法、導入以 前述惰性氣體稀釋至氧分壓在前述範圍的稀釋空氣之方法 ，把空氣減壓之方法，及其組合方法（例如將惰性氣體稀 釋過的稀釋空氣減壓之方法等）等加以製作。在上述特定 氣體氛圍下，把聚合物加熱，以抑制聚合物內所吸收的氧 基，可充分降低最後所製成成形體之着色。 含脂環型構造的聚合物加熱，是在比該聚合物的Tg低 5〜60°C的溫度進行，以低5〜40°C爲佳，低10〜3(TC更 好。聚合物加熱溫度（T1)太低時，最後製成的成形體着色 降低效果不能充分發揮，加熱溫度太高時，聚合物在加熱 歷程中，會受到氧化劣化而着色。 含脂環型構造的聚合物加熱，可使用例如通常樹脂九粒 乾燥時所用熱風循環式棚型乾燥器、斜槽乾燥器、棚型真 空乾燥器、攪拌式真空乾燥器、攪拌式斜槽乾燥器、真空 式斜槽乾燥器等各種乾燥器。 移送步驟 加熱步驟後，聚合物移送是在保持溫度比該聚合物白勺 Tg低5〜70°C的溫度進行，以低5〜50°C爲佳’低〜 30°C更好。聚合物的移送溫度（T2)保持在前述溫度時’可 -12- 574249 五、發明説明（11 ) 防止加熱後的聚合物再度吸收氧，最後所製成的成形體着 色即可充分降低。 聚合物溫度要保持在設定溫度時，可在移送機構的配管 內用加熱器等，對加熱步驟後的聚合物進行再加熱。另外 ’加熱步驟後的聚合物可一同再加熱，亦可不進行再加熱 ’而在移送機構的配管繞以隔熱材料，使聚合物溫度短時 間內不會降低。 本發明在聚合物前述加熱溫度（Τ1)和移送溫度（T2)間之 溫度（T1-T2)，以在10°C以下爲佳，在5°C以下更好。加 熱溫度和移送溫度之溫差愈小，聚合物吸收氧愈少。 加熱後聚合物的移送，宜在特定氣體氛圍下進行。此特 定氣體氛圍，以氧分壓在l〇kPa以下爲佳，8kPa以下更好 ，而以5kPa以下最好。此特定氣體氛圍，可按前述加熱 步驟同樣方法製作。在上述特定氣體氛圍移送聚合物，可 進一步明顯抑制聚合物中吸收的氧量，最後製成的成形體 着色可更爲充分降低。 本發明以使用低氧濃度的氣體（例如惰性氣體）壓送加熱 後的聚合物爲佳。此時，氣體的氧濃度以10%以下爲佳， 8%以下更好，而以5%以下最好。 加熱步驟後，聚合物的移送，是經由上述各種乾燥器等 的加熱機構、後述成形機構，以及在密閉狀態連結之配管 等移送機構進行。 成形步驟 移送步驟後的聚合物加熱熔化成形’是在比該聚合物的 -13- 574249 五、發明説明（12 )[2 · 2 · 1μ dicarboxyquat imine [2.2.ΐμ -6- 574249 V. Description of the invention (5) Bicyclic [2.2.1] -hept-2-ene, tricyclic [4.3.0.12,5]- Dec-3,7-diene (commonly used dicyclopentadiene), tricyclo [4.3.0.12,5] -dec-3-ene, tricyclo [4.4.0.12'5] -undecyl-3,7 -Diene or tricyclic [4.4.0.12,5] -dodecane-3,8-diene, tricyclic [4.4.0.12'5] -undec-3-ene, tetracyclic [7 · 4 · 0 · 11 (), 13 · 〇2, 7] -Thirteen carbon-2,4,6-ll-tetraene (also known as 1,4-methanol-: ^^^-tetrahydromanganese: ^ tetracyclo ^ Yili "11,14" 3,8]-. Tetracarbon-3,5,7,12-1 1-Tetraene (also known as 1,4-methanol-1,4,4a, 5,10, l 〇a-hexahydroanthracene) and other norbornene-based monomers that do not have an original norbornane ring, tetracyclic [4.4.0.12, 5.17'1G] -dodec-2-ene (also referred to as tetracyclododeca) Carbene), 8-methyltetracycline [4 · 4 · 0 · 12,5 · 17,1 ()]-dodec-3-ene, 8 · ethyltetracyclo [4.4.0.12, 5.17, 丨()]-Dodec-3-ene, 8-methylenetetracycline [4.4.0.12, 5.17, 10] -Dodecane-3-ene, 8-ethylenetetracycline [4 · 4 · 0 · 12'5 · 17'1 ()]-dodec-3-ene, 8-vinyltetracycline [4.4.0.12,5.17'1 ()]-dodec-3-ene, 8-propenyl Four ring [4.4.0.12, 5.17, 1G] -dodec-3-ene, 8-methoxycarbonyl tetracyclo [4 · 4.0 · 12,5 · 17,1 ()]-dodec-3-ene, 8-methyl-8-methoxycarbonyl tetracyclo [4 · 4.0 · 12,5 · 17,1 ()]-dodec-3-ene, 8-hydroxymethyl tetracyclo [4 · 4 · 0 · 12'5.Γ'1 ()] -Dodec-3-ene, 8-carboxytetracyclo [4 · 4 · 0 · 12'5 · 17'1 ()]-Dodecane-3 -Ene, 8-cyclopentyltetracyclo [4.4.0.12'5.17,1.]-Dodec-3-ene, 8-cyclohexyltetracyclo [4.4.0.12,5.17,1 ()]-dodecane -3-ene, 8-cyclohexenyl tetracyclo [4.4.0.12, 5.17, 1 ()]-dodecyl-3-phenyl, 8-phenyltetracycline [4.4.0.12'5.17'1 ( )]-Dodecane-3-ene, pentacyclic [6.5.1.13'6.02'7.09'13] -pentadeca-3,10-diene, pentacyclic [7.4.0.13'6.11 (), 13.02'7 ] -Pentacarbon-4,11-diene and other orthobornane-based monomers having orthobornane rings. These ortho-norbornene-based monomers can be used alone or in combination of two or more kinds. 574249 V. Description of the invention (6) In the present invention, in addition to the above-mentioned norbornene-based monomer, a copolymerizable monomer may be used. Examples of the copolymerizable monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene Ene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene C2 ~ C2Ga-olefins such as carbene, 1-octadecene, and icosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylpentene, 3-methylcyclohexene Ene, 2- (2-methylbutene) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methanol-4,7-ethanol-1H-indene, etc. Cyclic olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene and other non-conjugated dienes and many more. These copolymerizable monomers can be used alone or in combination of two or more kinds. For the ring-opening polymerization of the above monomers, halides, nitrates, or acetoacetone compounds of metals such as ruthenium, rhodium, palladium, iridium, and platinum can be used, and catalyst systems composed of reducing agents, and titanium, vanadium, zirconium, and tungsten A catalyst system composed of halides of metals such as molybdenum, molybdenum, and organic manganese compounds. As a ring-opening polymerization catalyst, in a solvent or without a solvent, usually at a polymerization temperature of -50 to 100 ° C, and a polymerization pressure of 0 to 5 MPa. , Obtained by ring-opening polymerization. Hydrogenated borneol polymer can be prepared by hydrogenation in the presence of a hydrogenation catalyst in accordance with a conventional method. The addition copolymer of the original norbornene-based monomer and the above-mentioned copolymerizable monomer may exist, for example, in a catalyst system composed of a monomer component in a solvent or without a solvent, titanium, zirconium, or vanadium, and an organic aluminum compound Down, usually -50 to 100. Polymerization temperature 〇 〇 ~ 50MPa polymerization pressure, the method of co-polymerization 574249 V. Invention description (7). Monocyclic cyclic olefin polymers include monocyclic rings such as cyclohexyl, cycloheptyl, cyclooctyl, etc., as disclosed in JP-A-64-66216, and addition polymers of Greek-smoke-based monomers. Wait. Cyclic conjugated diene polymers are disclosed in, for example, Japanese Unexamined Patent Publication No. 6-136057 or Japanese Unexamined Patent Publication No. 7-25 83 1 8. Cyclic conjugated diene-based polymers such as cyclopentadiene and cyclohexadiene are used. Monomers, polymers obtained by 1,2- or 1,4-addition polymerization, and hydrogenated products thereof. Examples of the vinyl alicyclic hydrocarbon-based polymer include polymers of vinyl alicyclic hydrocarbon-based monomers such as vinyl cyclohexyl and vinyl cyclohexane described in Japanese Patent Application Laid-Open No. 5 1-59989, and hydrogenated products thereof. Japanese Unexamined Patent Publication No. 63-439 1 0, 64-1 706 and the like, such as hydrogenated compounds of vinyl aromatic monomers such as styrene and α-methylstyrene, in the aromatic ring portion. Regarding the main configuration of these vinyl alicyclic hydrocarbon-based polymers, any of hetero-, cis-, and syndiotactic methods are acceptable. For example, the syndiotactic method using binary display can be used at 0 to 100%. The molecular weight of the alicyclic structure-containing polymer usable in the present invention can be appropriately selected according to the purpose of use, but is converted into polyisocyanate by gel permeation chromatography using a cyclohexane solution (toluene solution when the polymer is not dissolved). The weight average molecular weight of propylene is 5,000 to 500,000, more preferably 8,000 to 200,000, and most preferably 10,000 to 100,000, which is advantageous for a high balance between mechanical strength and molding processability. The glass transition temperature (Tg) of the alicyclic structure-containing polymer usable in the present invention may be appropriately selected depending on the purpose of use, usually 50 to 300 ° C, preferably 60 to 200 ° C, and 70 to 180 ° C is better. -9-574249 V. Description of the invention (8) The alicyclic structure-containing polymer usable in the present invention may be mixed with various compounding agents as required. The compounding agents can be those mixed with general plastics, such as stabilizers such as antioxidants, heat stabilizers, and light stabilizers; ultraviolet absorbers, antistatic agents, slip agents, and plasticizers. In particular, in order to obtain a molded body having excellent transparency, it is advisable to mix antioxidants. Examples of the antioxidant include phenol-based anti-aging agents, phosphorus-based anti-aging agents, and sulfur-based anti-aging agents. As the phenolic anti-aging agent, conventional substances can be used, for example, 2-Tributyl-6- (3-Tributyl-2-hydroxy- 5-methylbenzyl) -4-methylphenylacrylate, 2,4-bis (tertiary pentyl) -6- (1- (3,5-bis (tertiary pentyl) -2-hydroxy Acrylic compounds such as phenyl) ethyl) phenyl acrylate; octadecyl-3- (3,5-di (tertiary butyl) -4-hydroxyphenyl) propene, 2,2f- Methyl bis (4-methyl-6-tertiary butylphenol), 2,2'-ethylidene bis (4-methyl-6-tertiary butylphenol), 1,3,5-trimethyl -2,4,6-ginseng (3,5-bis (tertiary butyl) -4-hydroxybenzyl) benzene, methane (methylene-3 · (3 ', 5'-bis (tertiary butyl) ) -4f-hydroxyphenylpropionate) methane [ie pentaerythritol methyl ester (3- (3,5-bis (tertiarybutyl) -4-hydroxyphenylpropionate)), stearyl- (3,5-bis (tertiarybutyl) -4-hydroxyphenyl) propionate, 3,9-bis [1,1-dimethyl-2- [cold- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propanyloxy] ethyl] -2,4,8,10-tetrazolospiro [5.5] undecane and other alkyl-substituted phenolic compounds; 6- (4- Hydroxy-3,5-di (tertiary butane Phenylanilide) -2,4-bisoctylthio-1,3,5-trioxine, 4-bisoctylthio-1,3,5-three farming, 2-octylthio-4,6 -Bis- (3,5-bis (tertiary butyl) -4-oxyanilide) -1,3,5-trigenol and other phenolic compounds containing trioxo groups. As long as the phosphorus anti-aging agent is General resin industry commonly used products, without particular limitation. -10- 574249 V. Description of the invention (9) There are, for example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, Ginseng (nonylphenyl) phosphite, Ginseng (dinonyl) phosphite, Ginseng (2,4-bis (tertiary butyl) phenyl) phosphite, 10- (3,5-di (Tertiary butyl) -4-hydroxypentyl) -9,10-dihydro-9-fluorene-10-phosphophenanthrene-10-oxide and other monophosphite compounds; 4,4 · -butylenebis (3-methyl-6-tert-butylphenyl di (tridecyl) phosphite), 4,4'-isopropylidene bis (phenyl dialkyl (C12 ~ C15) phosphite ) And other diphosphite-based compounds, etc. Among them, monophosphite-based compounds are preferred, and ginseng (nonylphenyl) phosphite, ginseng (dinonylphenyl) phosphite, and ginseng (2,4- two Tertiary butyl) phenyl) phosphite, etc. Sulfur-based anti-aging agents include, for example, dilauryl 3,3 '· thiodipropionate, dimyristoyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, lauryl stearate 3,3'-thiodipropionate, isopentaerythritol-lauryl thiopropionate), 3 , 9-bis (2-dodecylthioethyl) -2,4,8,10-tetrahydrospiro [5.5] undecane and the like. Among them, phenol-based anti-aging agents are preferred, especially alkyl-substituted phenol-based anti-aging agents, that is, hydrogens on the carbon on both sides of the hydroxyl group on the aromatic ring are replaced by alkyl groups, which is advantageous in terms of long-term heat resistance. These anti-aging agents can be used singly or in combination of two or more. When used in combination, a phenol-based anti-aging agent and a phosphorus-based anti-aging agent are preferably used, and a molded body having excellent transparency can be obtained. Molding method After heating the polymer containing the alicyclic structure (heating step), the method is transferred to a molding machine (transfer step), and the heat-melting molding (molding step) is performed. -11-574249 V. Description of the invention (10) Result in shape. Heating step The polymer with alicyclic structure is heated under a specific gas atmosphere. In this specific gas atmosphere, the oxygen partial pressure is below 10 kPa, preferably below 8 kPa, and more preferably below 5 kPa. This specific gas atmosphere can be, for example, a method of purging with inert gas such as nitrogen, argon, helium, carbon dioxide, a method of introducing dilute air diluted with the aforementioned inert gas to an oxygen partial pressure within the aforementioned range, a method of decompressing the air, and It is produced by a combination method (for example, a method of decompressing a dilution air diluted with an inert gas). Under the specific gas atmosphere described above, the polymer is heated to suppress the oxygen groups absorbed in the polymer, which can sufficiently reduce the coloration of the final formed body. Polymer heating with alicyclic structure is performed at a temperature of 5 to 60 ° C lower than the Tg of the polymer, preferably 5 to 40 ° C lower, and 10 to 3 (TC better. Polymer heating When the temperature (T1) is too low, the effect of reducing the coloration of the final formed body cannot be fully exerted, and when the heating temperature is too high, the polymer will be colored by oxidative degradation during the heating process. Polymers with alicyclic structure are heated You can use, for example, the hot air circulation type shed dryer, chute dryer, shed vacuum dryer, agitated vacuum dryer, agitated chute dryer, vacuum chute dryer, etc. that are usually used when drying nine pellets of resin. Various dryers. Transfer step After the heating step, the polymer transfer is performed at a temperature that is 5 to 70 ° C lower than the polymer's Tg, preferably 5 to 50 ° C lower, and lower to 30 ° C. Good. When the polymer transfer temperature (T2) is maintained at the aforementioned temperature, 'may-12-574249' V. Description of the invention (11) Prevent the heated polymer from absorbing oxygen again, and the color of the final formed body can be sufficiently reduced The polymer temperature should be maintained at the set temperature In this case, the heater after the heating step can be used to reheat the polymer in the piping of the transfer mechanism. In addition, the polymer after the heating step can be reheated together or without reheating. Wrap a heat-insulating material so that the polymer temperature does not decrease for a short time. The temperature (T1-T2) between the aforementioned heating temperature (T1) and transfer temperature (T2) of the polymer is below 10 ° C as It is better to be below 5 ° C. The smaller the temperature difference between the heating temperature and the transfer temperature, the less the polymer absorbs oxygen. The polymer transfer after heating should be performed in a specific gas atmosphere. This specific gas atmosphere is divided by oxygen. The pressure is preferably below 10 kPa, more preferably below 8 kPa, and most preferably below 5 kPa. This specific gas atmosphere can be produced in the same way as the aforementioned heating step. Transferring the polymer in the above specific gas atmosphere can further significantly inhibit the polymer The amount of oxygen absorbed in the medium can be more fully reduced in the color of the final formed body. In the present invention, it is preferable to use a low oxygen concentration gas (such as an inert gas) to pressure-feed the heated polymer. In this case, the oxygen concentration of the gas is preferably 10% or less, more preferably 8% or less, and most preferably 5% or less. After the heating step, the polymer is transferred through the above-mentioned various dryers and other heating mechanisms, and a molding mechanism described later. And the transfer mechanism such as piping connected in a closed state. The forming step The polymer after the transfer step is heated and melted to form the polymer. -13- 574249 V. Description of the invention (12)
Tg高50°C以上的溫度，更好是高100〜230°C的溫度，最 好是高120〜210°C的溫度進行。聚合物的成形溫度（T3)在 前述溫度時，可充分確保聚合物的流動性，防止發生成形 不良。 移送步驟後的聚合物加熱熔化成形，宜在特定氣體氛圍 下進行。此特定氣體氛圍，以氧分壓在1 OkPa以下爲佳， 8kPa以下更好，5kPa以下尤佳。此特定氣體氛圍，可和 前述加熱步驟的同樣方法製作。聚合物在上述特定氣體氛 圍加熱熔化成形，最後製成的成形體着色可充分降低。 移送步驟後，聚合物的加熱熔化成形，可使用例如擠出 成形、擠出壓縮成形、壓出成形、加壓成形、擠壓吹氣成 形、直接吹氣成形等各種成形機。 成形體 經過上述步驟後，長光程上的黃指數（ΛΥΙ)小（例如在光 程長度200mm時，Z\YI2⑽在25以下，以20以下爲佳， 又以1 8以下更好），可由含脂環型構造的聚合物製得透明 性（色調）優異的成形體。 黃指數（ΛΥΙ)表示黃色度，ΛΥΙ以長光程色差計測定。 只要△ ΥΙ小，成形體的形狀並無特限制，例如板狀、碟 狀、圓柱狀、筒狀、桿狀等各種形狀。 本發明方法適於製造例如LCD背面光用之導光板，散 光片、大型透鏡（例如涅耳透鏡、雙凸透鏡、FQ透鏡等）光 導、或光織寺成形體之製造’尤指對亮度或色度均優的大 型薄LCD用導光板製造有效。 -14- 574249 五、發明説明（13 ) 實施例 茲以實施例和比較例具體說明本發明如下，惟本發明範 圍不受此等例之限制。 此等例中「份」如未特別指明，均爲重量基準。各種物 體之測定法如下。 (1) Tg是利用差示掃描熱量計（DSC法）測量。 (2) 分子量若未特別指明，係以環己烷爲溶劑，藉凝膠 滲透層析法（GPC)測量，作爲聚異丙烯換算値。 (3) 長光程的黃指數（△ YI2()())，使用長光程色差計（日本 電色工業公司製ASΑ-300Α)測量。其値在18以下時評爲 ◎，：18至20時爲〇，20至25時爲△，25以上時爲X。 (4) 導光板的亮度和色度，是在使用導光板組合背面光 單位後，把發光面積縱橫分別三等分區域的各中心點（9點） ，於垂直上方60cm位置，使用色彩亮度計（多普空（音譯） 公司製BM-7)測量，將9點平均作爲平均亮度。測定色度 的X座標、y座標。 實施例1 九粒（聚合物）之製浩 在氮氣氛圍下，取二環戊二烯（DCP)85份和8-乙基四環 十二院（E T D) 1 5分組成的混合單體1 0 0份，溶於脫水的環 己烷250份，添加分子量調節劑1-己烯1.8份，以公知的 複分解開環聚合觸媒加以聚合。其次，以公知方法加氫， 得DCP/ETD開環共聚物之加氫物。聚合物中的各原冰片 烯類之共聚合比率，係由聚合後的溶液中殘留的原冰片嫌 -15- 574249 五、發明説明（14 ) 系類組成（利用氣體層析法）算出，大約等於DCP/ETD = 8 5/15。此DCP/ETD開環聚合物之加氫物，重量平均分子 量（Mw)爲 3 1 000，加氫率爲 99.9%，Tg 爲 100t。 於所得開環聚合物之加氫物1 00份，添加抗老化劑（吉 富製藥公司製品特米若庫司TT)0.5份，軟質聚合物（旭化 成公司製品，他付鐵克Η1 052)0.02份，以雙軸混練機（東 芝機械公司製品，ΤΕΜ-35Β，螺桿徑37mm，L/D = 32，螺 桿轉數250rpm，樹脂溫度24(TC，進料率10kg/hr)，加以 混練壓出、製粒，即得聚合物九粒。 成形裝置 ' 在本實施例中使用之成形裝置，作爲加熱機構的氮氣排 淨式真空乾燥器（松井製造公司製品，商品號HDII-100)， 經由移送機構之配管，連接到作爲成形機構之側面流道模 型方式擠出成形機（東芝機械公司製品，IS450)之斜槽。 導光板之成形 所得九粒，放入本實施例所用成形裝置的氮氣排淨式真 空乾燥器，於氮氣氛圍下（氧分壓在0.1 kPa以下），在溫度 80°C加熱乾燥4小時（加熱步驟）。乾燥器內的氣體氛圍是 先將該乾燥器內減壓，再從連接於該乾燥器的氮氣管路吹 入氮氣，如此重複操作三次（氮氣排淨），使氧分壓在 0.1 kPa 以下。 其次，把加熱後的九粒，在配管內壓送，通至擠出成形 機斜槽之加熱管筒部內（移送步驟）。配管內部保持藉氮氣 排淨所產生氮氣氛圍下（氧分壓在0.1 kPa以下），和溫度 -16- 574249 五、發明説明（15 ) 8〇°C。使用溫度80°C的氮壓送。 移送後的九粒，在氮氣排淨產生的氮氣氛圍下（氧分壓 O.lkPa以下），於樹脂溫度28(TC擠出成形（成形步驟）。 結果，得橫2 1 8mmx縱280mm，厚度則在橫向從2.5mm 到0.9mm，逐漸減薄之導光板（成形體）。 把所得導光板切斷，測量光路徑200mm的AYhoo，爲 15.5。 在所得導光板的單面，利用網版印刷印出從厚側向薄側 逐漸加大的複數白色圓點圖案。使用上述印成圖案的導光 板，利用下述方法製成背面光單位，測量表面平均亮度和 色度。單位製成時，使用冷陰極間爲光源，藉光源用反射 器，於形成圓點圖案的面安裝反射片，在相反面（出光面） 配置散光片。結果載於表1。 實施例2 除加熱後的九粒移送，在利用氮氣排淨產生的氮氣氛圍 下（氧分壓5kPa)進行外，和實施例1同樣形成導光板。所 得導光板的AYhoo爲19.0。再利用實施例1同樣方法製 成背面光單位，測量表面平均亮度和色度。結果載於表1。 實施例3 除加熱後的九粒移送，在利用氮氣排淨產生的氮氣氛圍 下（氧分壓20kPa)進行外，和實施例1同樣形成導光板。 所得導光板的AYhoo爲22.3。再利用實施例1同樣方法 製成背面光單位，測量表面平均亮度和色度。結果載於表 -17- 574249 五、發明説明（16) 比較例1 除加熱後的九粒移送，在利用氮氣排淨產生的氮氣氛圍 下（氧分壓2〇kPa)，並在冷卻到25t的溫度進行外，和實 施例1同樣形成導光板。所得導光板的ΛΥΐ2㈣爲26.8。 再利用實施例1同樣方法製成背面光單位，測量表面平均 亮度和色度。結果載於表i。 -18- 574249 五、發明説明（1) 平均色度 y座標 0.325 0.370 0.389 寸 Ο X座標 0.283 ： 0.3 13 寸 m 〇 0.366 平均 亮度 (cd/cm2) 1- 1650 1440 1230 940 Δ YI2〇„ (0)(15.5) 0(19.0) 1- Δ(22.3) x(26.8) 成形步驟 氧分壓 (k Pa) K- 〇 0. 1以下 K- 〇 0.1以下 成形溫度 (°C ) 280 280 280 280 1 移送步驟 氧分壓 (kPa) K- Ξί 〇 iT) 〇 <N 移送溫度 (°C ) 〇 00 〇 〇〇 Ο 00 <N 加熱步驟 氧分壓 (k P a) zs 〇 〇 1 0.1以下 〇. 1以下 加熱溫度 α) 〇 00 〇 00 ο 00 Ο 00 聚合物 S Ρ 100 100 I 100 1_ 1 I loo 1 組成 DCP/ETD = 85/1 5 DCP/ETD = 85/1 5 1 DCP/ETD = 85/1 5 DCP/ETD = 85/1 5 實施例1 實施例2 實施例3 實施例4 574249 五、發明説明（18) 如表1所示，使用本發明方法所處理的聚合物九粒之實 施例1-.3，成形品的△ YI2G()均小於25，平均亮度和色度均 佳。相對地，比較例1中，成形品的△ Yhoo大於26·8 ’ 平均亮度和色度均劣。 發明效果 如上所述，按照本發明，可提供一種成形體之製法’得 以製造長光程的黃指數小之大型薄成形體。 -20-The temperature of Tg is higher than 50 ° C, more preferably from 100 to 230 ° C, and most preferably from 120 to 210 ° C. When the polymer forming temperature (T3) is at the above-mentioned temperature, the fluidity of the polymer can be sufficiently ensured, and formation failures can be prevented. After the transfer step, the polymer is melt-molded and formed under a specific gas atmosphere. The specific gas atmosphere is preferably an oxygen partial pressure below 1 OkPa, more preferably below 8 kPa, and even more preferably below 5 kPa. This specific gas atmosphere can be produced in the same manner as in the aforementioned heating step. The polymer is melt-molded under the above-mentioned specific gas atmosphere, and the color of the final formed body can be sufficiently reduced. After the transfer step, the polymer is melt-molded by heating, and various molding machines such as extrusion molding, extrusion compression molding, extrusion molding, pressure molding, extrusion blow molding, and direct blow molding can be used. After the above steps, the yellow index (ΛΥΙ) of the long optical path is small (for example, when the optical path length is 200mm, Z \ YI2⑽ is below 25, preferably below 20, and even below 18 is better). A polymer having an alicyclic structure provides a molded body having excellent transparency (hue). The yellow index (ΛΥΙ) indicates yellowness, and ΔΥΙ is measured by a long optical path colorimeter. The shape of the molded body is not particularly limited as long as ΔΥΙ is small, and various shapes such as a plate shape, a dish shape, a cylindrical shape, a cylindrical shape, a rod shape, and the like are not particularly limited. The method of the present invention is suitable for manufacturing, for example, a light guide plate for LCD back light, a light diffusion sheet, a large lens (such as a Neel lens, a lenticular lens, an FQ lens, etc.), a light guide, or a light-woven temple formed body, especially for brightness or color. It is effective to manufacture light guide plates for large and thin LCDs with excellent uniformity. -14- 574249 V. Description of the Invention (13) Examples The present invention is specifically described below by way of examples and comparative examples, but the scope of the present invention is not limited by these examples. In these examples, "parts" are based on weight unless otherwise specified. The measurement methods for various objects are as follows. (1) Tg is measured using a differential scanning calorimeter (DSC method). (2) Unless otherwise specified, the molecular weight is measured by gel permeation chromatography (GPC) with cyclohexane as the solvent, and is used as the polyisopropene equivalent. (3) The yellow index (ΔYI2 () ()) of the long optical path is measured using a long optical path colorimeter (ASAA-300A, manufactured by Nippon Denshoku Industries Co., Ltd.). Its 値 is rated as ◎ when it is 18 or less, 0 when it is 18 to 20, △ when it is 20 to 25, and X when it is 25 or more. (4) The brightness and chromaticity of the light guide plate are after the light guide plate is used to combine the back light units, the center point (9 points) of the light emitting area is divided into three equal areas vertically and horizontally, and 60 cm above the vertical position, using a color luminance meter (BM-7, manufactured by Doppler Co., Ltd.). The 9 points are averaged as the average brightness. X-coordinate and y-coordinate of chromaticity. Example 1 The production of nine capsules (polymer). Under a nitrogen atmosphere, 85 parts of dicyclopentadiene (DCP) and 8-ethyltetracyclododecane (ETD) 1 were mixed. 5 mixed monomers 1 0 parts, 250 parts dissolved in dehydrated cyclohexane, 1.8 parts of molecular weight modifier 1-hexene was added, and polymerization was performed using a known metathesis ring-opening polymerization catalyst. Next, hydrogenation is performed by a known method to obtain a hydrogenated product of the DCP / ETD ring-opening copolymer. The copolymerization ratio of each original norbornene in the polymer is calculated from the original borneol remaining in the polymerized solution. -15-574249 V. Description of the invention (14) The composition of the series (using gas chromatography) is calculated. Approximately Equal to DCP / ETD = 8 5/15. The hydrogenated product of this DCP / ETD ring-opening polymer has a weight average molecular weight (Mw) of 3 1 000, a hydrogenation rate of 99.9%, and a Tg of 100t. To 100 parts of the hydrogenated product of the obtained ring-opened polymer, add 0.5 part of an anti-aging agent (product of JIFU Pharmaceutical Co., Ltd. TT), and 0.02 part of soft polymer (product of Asahi Kasei Co., Ltd., he pays Tieke 1 052), Using a twin-shaft kneading machine (product of Toshiba Machinery Co., Ltd., TEM-35B, screw diameter 37mm, L / D = 32, screw revolutions 250rpm, resin temperature 24 (TC, feed rate 10kg / hr), kneading, extrusion and granulation Nine pellets of polymer are obtained. Molding device The molding device used in this example is a nitrogen purging vacuum dryer (product of Matsui Manufacturing Co., Ltd. HDII-100) as a heating mechanism, and is piped through the transfer mechanism. , Connected to the chute of a side flow channel model extrusion molding machine (product of Toshiba Machinery Co., Ltd., IS450) as a molding mechanism. Nine pellets obtained from the molding of the light guide plate were put into the nitrogen exhaust vacuum of the molding device used in this embodiment. The dryer is heated and dried in a nitrogen atmosphere (oxygen partial pressure below 0.1 kPa) at a temperature of 80 ° C for 4 hours (heating step). The gas atmosphere in the dryer is first decompressed in the dryer and then connected from to Nitrogen is blown into the nitrogen line of the dryer, and the operation is repeated three times (nitrogen purging) so that the partial pressure of oxygen is below 0.1 kPa. Next, the heated nine pellets are pressure-fed in a pipe and passed to extrusion molding. Inside the heating tube of the machine chute (transfer step). The inside of the piping is kept under a nitrogen atmosphere (the oxygen partial pressure is below 0.1 kPa) and the temperature is -16-574249. V. Description of the invention (15) 8 ° C. Nitrogen pressure feeding at a temperature of 80 ° C. Nine pellets after the transfer, at a resin temperature of 28 (TC extrusion molding (molding step) under a nitrogen atmosphere (oxygen partial pressure O.lkPa or less) generated by nitrogen purging. As a result, a light guide plate (shaped body) having a thickness of 2 18 mm x 280 mm in length and a thickness from 2.5 mm to 0.9 mm in the horizontal direction was gradually thinned. The obtained light guide plate was cut and the AYhoo measuring 200 mm of the light path was 15.5 . On one side of the obtained light guide plate, a plurality of white dot patterns that gradually increase from the thick side to the thin side are printed by screen printing. Using the printed light guide plate described above, a back light unit is prepared by the following method. Measure the average surface brightness and color. Units At the time of completion, a cold cathode is used as the light source, and a reflector is used for the light source. A reflector is installed on the surface forming the dot pattern, and a diffuser is arranged on the opposite surface (light emitting surface). The results are shown in Table 1. Example 2 After heating Nine grains were transferred under the nitrogen atmosphere (oxygen partial pressure 5 kPa) generated by nitrogen purging, and a light guide plate was formed in the same manner as in Example 1. The AYhoo of the obtained light guide plate was 19.0. It was made by the same method as in Example 1 Back light unit, the average surface brightness and chromaticity were measured. The results are shown in Table 1. Example 3 Except for the transfer of nine pellets after heating, it was carried out under a nitrogen atmosphere (oxygen partial pressure 20kPa) generated by nitrogen purging, and In Example 1, a light guide plate was also formed. The AYhoo of the obtained light guide plate was 22.3. The same method as in Example 1 was used again to make a back light unit, and the average surface brightness and chromaticity were measured. The results are shown in Table-17-574249. V. Description of the invention (16) Comparative example 1 In addition to the nine pellets transferred after heating, under a nitrogen atmosphere (oxygen partial pressure 20kPa) generated by nitrogen purging, and cooled to 25t A light guide plate was formed in the same manner as in Example 1 except that the temperature was changed. The ΛΥΐ2㈣ of the obtained light guide plate was 26.8. The same method as in Example 1 was used to make a back light unit, and the average surface brightness and chromaticity were measured. The results are shown in Table i. -18- 574249 V. Description of the invention (1) Average chromaticity y coordinate 0.325 0.370 0.389 inch 〇 X coordinate 0.283: 0.3 13 inch m 〇 0.366 average brightness (cd / cm2) 1- 1650 1440 1230 940 Δ YI2〇 „(0 ) (15.5) 0 (19.0) 1- Δ (22.3) x (26.8) Oxygen partial pressure in forming step (k Pa) K- 〇0.1 or less K- 〇0.1 or less Forming temperature (° C) 280 280 280 280 1 Oxygen partial pressure in transfer step (kPa) K-Ξί 〇iT) 〇 < N Transfer temperature (° C) 〇00 〇〇〇〇00 00 < N Oxygen partial pressure in heating step (k P a) zs 〇〇1 0.1 or less 〇1 heating temperature below α) 〇00 〇00 ο 00 〇 00 Polymer SP 100 100 I 100 1_ 1 I loo 1 Composition DCP / ETD = 85/1 5 DCP / ETD = 85/1 5 1 DCP / ETD = 85/1 5 DCP / ETD = 85/1 5 Example 1 Example 2 Example 3 Example 4 574249 V. Description of the invention (18) As shown in Table 1, nine particles of polymer treated by the method of the present invention In Example 1-.3, the △ YI2G () of the molded products were all less than 25, and the average brightness and chromaticity were good. In contrast, in Comparative Example 1, the △ Yhoo of the molded products was greater than 26 · 8 ′, the average brightness and chromaticity Inferior. Fruit described above, according to the present invention, there is provided a manufacturing method of the molded 'obtained in the manufacture of small yellow index of the optical path length of the large thin molded article. -20-