200818188 九、發明說明 【發明所屬之技術領域】 本發明係有關高密度記錄媒體’光記錄媒體或光磁記 錄媒體（以下統稱「光記錄媒體」）用基板（光記錄媒體 基板）之製造方法。特別是有關資訊記錄層係使用有機色 素之追記型光記錄媒體基板或使用該基板之光記錄媒體之 製造方法。[Technical Field] The present invention relates to a method of manufacturing a substrate (optical recording medium substrate) for a high-density recording medium, an optical recording medium or a magneto-optical recording medium (hereinafter collectively referred to as "optical recording medium"). In particular, the information recording layer is a write-once optical recording medium substrate using an organic color or a method of manufacturing an optical recording medium using the substrate.
【先前技術】[Prior Art]
光記錄媒體係作爲低價格大容量之資訊記錄媒體，流 通著作用各種記錄方法之記錄媒體，且每年生產量增加中 。具體舉例如周知之 CD-ROM (Compact Disc read-only memory，唯讀光碟）、CD-DA ( Compact Disc-Digital Audio，精密光碟數字音頻）、V-CD ( Video-Compact Disc，影像光碟）、DVD-ROM ( Digital Versatile Disk-read-only memory ， 唯讀 數位影 音光碟 ） 、 DVD-video (The optical recording medium is a low-priced and large-capacity information recording medium, and it is a recording medium for various recording methods, and the annual production volume is increasing. Specifically, for example, a CD-ROM (Compact Disc read-only memory), a CD-DA (Compact Disc-Digital Audio), a V-CD (Video-Compact Disc), DVD-ROM (Digital Versatile Disk-read-only memory), DVD-video (DVD-video)
Digital Versatile Disk--video，數位影像光碟）、DVD-Audio (Digital VersatileDisk-video， 數位影 音光碟 ） 等 再生專用光記錄媒體，或CD-R (Compact Disc-Recorable ，光碟燒錄機)、DVD-R ( Digital Versatile Disk-Reeorable，數位多用途光碟）等追記型光記錄媒體，還 有 CD-RW ( CD- rewrit able) 、MO ( Magneto-optical Disk Drive) 、DVD-RAM ( DVD-Random Access Memory，隨 機存取記憶體）、DVD-RW ( DVD-rewritable) D VD + R W 200818188 等可覆寫型光記錄媒體等。 尤以追sS型先記錄媒體，隨者急速普及而低價格化， 而嚴加要求提升其信號特性與生產性，特別是，日趨受重 視之光記錄媒體用基板（光記錄媒體基板）之生產性。 光記錄媒體基板通常爲透明，其材料可使用熱可塑性 非晶質樹脂之聚碳酸酯樹脂、聚甲基丙烯酸甲酯樹脂、非 晶質聚烯烴樹脂等。其中就強度、耐熱性、尺寸安定性、 價格等層面而言，以聚碳酸酯最常使用。 聚碳酸酯樹脂之中，以芳香族二羥基化合物與碳酸二 酯經交酯化反應（交酯化法）而得之聚碳酸酯樹脂，由於 不使用如習知方法（界面法）所用之光氣氣體或有機溶劑 ，因而有對周邊環境負荷小之優點。此外，交酯化法較界 面法之製造步驟簡便化，而有可獲得安定品質之聚碳酸酯 樹脂之大優點。 再者，交酯化法由於可將反應所生成之副生成物苯酚 等作爲原料單體之製造原料使用，因而在產業上有利，且 有適應環境、安定品質、低價格等多項優點。因此，對使 用交酯化法所得之聚碳酸酯樹脂於光記錄媒體基板用樹脂 之硏究正盛行中，近年來以這種交酯化法製造之聚碳酸酯 樹脂（交酯化法聚碳酸酯樹脂）之使用正逐漸擴大中。 另一方面，交酯化法聚碳酸酯樹脂，特別是芳香族聚 碳酸酯樹脂，具有熔融黏度高、射出成形時流動性差之性 質。因此，若使用此交酯化法芳香族聚碳酸酯樹脂，射出 成形而成爲資訊信號的凹坑或槽溝（groove)之光記錄媒 200818188 體用基板時，會有凹坑、槽溝之轉錄性降低的情形。另外 ，該基板內部亦會發生歪斜而雙折射變大，成爲信號再生 錯誤之原因。 針對此類問題，可列舉如降低交酯化法芳香族聚碳酸 酯樹脂之黏度平均分子量而增加流動性之方法。但黏度平 均分子量的明顯降低會導致基板強度降低之問題。再者， 使用交酯化法芳香族聚碳酸酯樹脂所製造之射出成形樹脂 成形體，與以界面法所得之聚碳酸酯樹脂相較，會有易帶 電而成負極性之問題。 若光記錄媒體基板表面帶負電，則有空氣中之塵埃等 微粒子附著、追記型光記錄媒體之色素染性降低等問題。 對此，建議添加數種帶電防止劑之技術（例如參照專利文 獻1 )。 另一方面，在周知的光記錄媒體製造步驟中，亦提議 數個去除基板等帶電之方法。具體而言例如，提議由鑄模 取出後利用除電棒或靜電消除器（i〇nizer)使基板表面除 to之方法（例如梦照專利文獻2 )。另提議噴塗含有與基 板表面之帶電極性相反極性之離子的空氣來除電之方法（ 例如參照專利文獻3 )。再者亦提議將正極性之離子化空 氣噴塗至與基板表面平行方向之方法（例如參照專利文獻 4 ) 〇 專利文獻1:日本特開平11-279396號 專利文獻2:日本特開平7-57307號 專利文獻3:日本特開平ι〇-177744號 200818188 專利文獻4:日本特開2003-85835號 【發明內容】 發明所欲解決之課題 然而’如專利文獻i所記載，於聚碳酸酯中添加帶電 防止劑’會有聚碳酸酯樹脂之透明性降低，或在高溫、高 S度下長時間使用時樹脂容易分解之問題。另在專利文獻 2、3中，均未記載或暗示有關光記錄媒體製造方法之色 素的塗佈性改良，或有關交酯化法聚碳酸酯特有之帶負電 之課題。另在專利文獻4記載之方法中，有關光記錄媒體 製造中，塗佈後色素特性改良亦不足。 本發明之目的在提供光記錄媒體基板之製造方法及追 記型光記錄媒體之製造方法，特別是在交酯化法聚碳酸酯 樹脂所形成之光記錄媒體基板之製造方法中，抑制基板上 之資訊記錄層，尤其在設置追記型光記錄媒體之資訊記錄 層之色素層時的塗佈不良。 用以解決課題之手段 本發明者們首先在使用交酯化法聚碳酸酯樹脂之光記 錄媒體基板之製造方法中，詳細分析此光記錄媒體基板用 樹脂成形體之表面。其結果發現雖然表面大部分爲負帶電 ’但卻有局部性之正帶電部分，另發現此種正殘存電荷係 色素塗佈不良之原因。 另深入檢討自此種光記錄媒體基板用樹脂成形體表面 -8 - 200818188 去除正帶電之方法，結果發現藉由使具有特定以下平均分 子量的交酯化法聚碳酸酯樹脂所形成之光記錄媒體基板用 樹脂成形體表面，與離子產生器產生之正離子與負離子兩 者接觸，即可去除正帶電。 此外，發現除電時使用之離子產生器，若使用自一個 或數個電極針所形成之電極針部，周期性交互產生正離子 與負離子的離子產生器，更佳爲自一個電極針周期性交互 產生正離子與負離子的離子產生器，亦可去除正帶電而完 成本發明。 亦即本發明之重點係關於光記錄媒體之製造方法，其 特徵爲：使芳香族二羥基化合物與碳酸二酯經交酯化法所 得之黏度平均分子量2 5 000以下之芳香族聚碳酸酯樹脂成 形而得之光記錄媒體基板用樹脂成形體，與由具有周期性 交互產生正離子與負離子之電極針部的離子產生器所產生 之正離子及負離子接觸而製造光記錄媒體基板之方法，及 於經此得到之光記錄媒體基板上設置資訊記錄層而製造光 記錄媒體之方法。 發明之效果 依據本發明而得之由交酯化法聚碳酸酯樹脂所形成之 光記錄媒體基板，具有下列特徵：與以界面法得到之物係 同等水準地去除帶電、抑制色素塗佈不良等、良好地進行 資訊記錄層之形成。另外，本發明不僅在追記型光記錄媒 體基板之製造方法中有效，在ROM型光記錄媒體基板或 200818188 覆寫型（Rewritable )光記錄媒體基板之製造方法中亦有 效，更可期待各種光記錄媒體之信號特性及生產性良好。 再者，因爲利用交酯化法聚碳酸酯樹脂可輕易製造優 良特性之光記錄媒體基板，而可提供降低周遭環境之負荷 ，且品質安定、低價格之光記錄媒體基板、及光記錄媒體 發明實施之最佳形態Digital Versatile Disk--video, digital video disc), DVD-Audio (Digital Versatile Disk-video, digital video disc) and other dedicated optical recording media, or CD-R (Compact Disc-Recorable, CD-ROM burner), DVD- Write-once optical recording media such as R (Digital Versatile Disk-Reeorable), CD-RW (CD-rewrit able), MO ( Magneto-optical Disk Drive), DVD-RAM (DVD-Random Access Memory) , random access memory), DVD-RW (DVD-rewritable) D VD + RW 200818188 and other rewritable optical recording media. In particular, it pursues the sS-type recording medium, which is rapidly popularized and low-priced, and is strictly required to improve its signal characteristics and productivity, and in particular, the production of substrates (optical recording medium substrates) for optical recording media that are increasingly valued. Sex. The optical recording medium substrate is usually transparent, and a material thereof may be a polycarbonate resin of a thermoplastic amorphous resin, a polymethyl methacrylate resin, an amorphous polyolefin resin or the like. Among them, polycarbonate is most commonly used in terms of strength, heat resistance, dimensional stability, and price. Among the polycarbonate resins, a polycarbonate resin obtained by a transesterification reaction (lactification method) of an aromatic dihydroxy compound and a carbonic acid diester does not use light as in a conventional method (interface method). Gas or organic solvent has the advantage of having a small load on the surrounding environment. Further, the cross-esterification method is simpler than the manufacturing process of the interface method, and has the great advantage of obtaining a polycarbonate resin of a stable quality. Further, since the lactide method can be used as a raw material for producing a raw material phenol which is produced by the reaction, it is industrially advantageous, and has many advantages such as adaptability to the environment, stable quality, and low price. Therefore, in the past, the polycarbonate resin obtained by the lactide method has been popularized in the resin for optical recording medium substrates, and the polycarbonate resin produced by the lactide method in recent years (polyesterified polycarbonate) The use of ester resins is gradually expanding. On the other hand, the lactide-based polycarbonate resin, particularly the aromatic polycarbonate resin, has a high melt viscosity and poor fluidity at the time of injection molding. Therefore, when the aromatic polycarbonate resin of this cross-esterification method is used and the substrate for optical recording medium 200818188 which is formed into a pit or a groove of information signals is formed, there is a pit and groove transcription. Sexual reduction. In addition, the inside of the substrate is also skewed and the birefringence is increased, which causes a signal regeneration error. For such problems, a method of increasing the fluidity by lowering the viscosity average molecular weight of the aromatic polycarbonate resin of the cross-esterification method can be mentioned. However, a significant decrease in the average molecular weight of the viscosity causes a problem of a decrease in the strength of the substrate. Further, the injection molded resin molded article produced by using the lactide-based aromatic polycarbonate resin has a problem that it is easily charged to have a negative polarity as compared with the polycarbonate resin obtained by the interfacial method. When the surface of the optical recording medium substrate is negatively charged, there are problems such as adhesion of fine particles such as dust in the air and deterioration of the dyeing property of the write-once optical recording medium. In this regard, it is recommended to add several kinds of anti-static agents (for example, refer to Patent Document 1). On the other hand, in the well-known optical recording medium manufacturing step, several methods of removing the substrate and the like are also proposed. Specifically, for example, a method of removing the surface of the substrate by a degaussing rod or a static eliminator after taking out the mold is proposed (for example, Dream Patent Document 2). It is also proposed to spray a method of removing air containing air having an opposite polarity to that of the surface of the substrate (for example, refer to Patent Document 3). Furthermore, it is also proposed to spray a positive ionized air to a direction parallel to the surface of the substrate (for example, refer to Patent Document 4). Patent Document 1: Japanese Patent Laid-Open No. Hei 11-279396 Patent Document 2: Japanese Patent Application No. Hei 7-57307 Patent Document 3: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. No. 2003-85835. The preventive agent 'has a problem that the transparency of the polycarbonate resin is lowered, or the resin is easily decomposed when used for a long period of time at a high temperature or a high S degree. Further, in Patent Documents 2 and 3, there is no description or suggestion of improvement in the coating property of the coloring matter relating to the method for producing an optical recording medium, or the problem of negative charging which is peculiar to the polycarbonate of the lactide-based method. Further, in the method described in Patent Document 4, in the production of an optical recording medium, improvement in dye properties after coating is also insufficient. An object of the present invention is to provide a method for producing an optical recording medium substrate and a method for producing a write-once optical recording medium, and more particularly to a method for producing an optical recording medium substrate formed by a lactide-based polycarbonate resin. The information recording layer is particularly poor in coating when the pigment layer of the information recording layer of the write-once optical recording medium is set. Means for Solving the Problem The inventors of the present invention first analyzed the surface of the resin molded article for an optical recording medium substrate in the method for producing an optical recording medium substrate using a polycarbonate resin. As a result, it was found that although the surface was mostly negatively charged, but there was a local positively charged portion, it was found that such a positive residual charge was poorly coated. Further, the method of removing the positive electrification from the surface of the resin molded body for an optical recording medium substrate -8 - 200818188 was examined in depth, and as a result, an optical recording medium formed by a lactide-based polycarbonate resin having a specific average molecular weight was found. The surface of the resin molded body for the substrate is brought into contact with both the positive ions and the negative ions generated by the ion generator to remove the positive charge. In addition, it has been found that an ion generator used in addition to electricity, if an electrode needle formed from one or several electrode needles is used, an ion generator that periodically generates positive ions and negative ions, preferably periodically interacts with an electrode needle. An ion generator that generates positive ions and negative ions can also be used to remove the positive charge to complete the present invention. That is, the focus of the present invention relates to a method for producing an optical recording medium, which is characterized in that an aromatic polycarbonate resin having a viscosity average molecular weight of 25,000 or less obtained by a lactide method of an aromatic dihydroxy compound and a carbonic acid diester is obtained. a method of manufacturing an optical recording medium substrate by forming a resin molded body for an optical recording medium substrate obtained by contact with positive ions and negative ions generated by an ion generator having an electrode needle portion which periodically generates positive ions and negative ions; and A method of manufacturing an optical recording medium by providing an information recording layer on an optical recording medium substrate obtained thereby. Advantageous Effects of Invention The optical recording medium substrate formed of the cross-esterification polycarbonate resin obtained according to the present invention has the following features: removal of charge at the same level as that obtained by the interface method, suppression of dye coating failure, etc. Good formation of the information recording layer. Further, the present invention is effective not only in the method of manufacturing a write-once optical recording medium substrate, but also in a method of manufacturing a ROM-type optical recording medium substrate or a 200818188 overprintable optical recording medium substrate, and it is expected that various optical recordings can be expected. The signal characteristics and productivity of the media are good. Further, since the optical recording medium substrate having excellent characteristics can be easily produced by using the cross-esterification polycarbonate resin, it is possible to provide an optical recording medium substrate which is stable in weight, low in price, and optical recording medium. Best form of implementation
下文詳細說明本發明。 (芳香族聚碳酸酯） 使用於本發明之芳香族聚碳酸酯，係經芳香族二羥基 化合物與碳酸二酯所形成之交酯化法所得之芳香族聚碳酸 酯樹脂，亦稱爲交酯化法（或熔融法）芳香族聚碳酸酯樹 脂。其特性爲其黏度平均分子量（以下亦稱爲「Mv」） 在2 5 0 0 0以下。 若爲黏度平均分子量超過2 5 0 00之高分子量者，特別 是經由射出成形所得之光記錄媒體基板用樹脂成形體之雙 折射明顯增加。反之若黏度平均分子量過低，則會有不具 有作爲光記錄媒體基板用樹脂成形體或光記錄媒體基板之 充分強度的情形。 因此使用於本發明之交酯化法芳香族聚碳酸酯樹脂之 黏度平均分子量，尤以1 0000以上，特別是1 4000以上爲 佳。又此黏度平均分子量，尤以23000以下，特別是 -10 - 200818188 1 8000以下爲佳。 此外’本發明之黏度平均分子量係利用奧式（ Ostwald )黏度計，測量以二氯甲院爲溶劑之溶液於2〇°C 時之特性黏度（？7)，以斯涅耳（Schnel )黏度式（[;/ ] =1.23x1(T4mU3 )所計算之値。又，使用於本發明之交 酯化法芳香族聚碳酸酯樹脂，亦可爲倂用複數種聚碳酸酯 樹脂之.混合物，此時之黏度平均分子量係混合物全體所求 得之値。 使用於本發明之芳香族聚碳酸酯，係使用芳香族二羥 基化合物與碳酸二酯，在交酯化觸媒存在下，經交酯化反 應即可獲得。芳香族二羥基化合物，具體而言可例舉如雙 (4-羥基二苯基）甲烷、2,2-雙（4-羥基苯基）丙烷、 2,2-雙（4-羥基-3-甲基苯基）丙烷、2,2-雙（4-羥基-3-第 三丁基苯基）丙烷、2,2-雙（4-羥基- 3,5-二甲基苯基）丙 院、2,2 -雙（4·經基- 3,5 -二溴苯基）丙院、4,4 -雙（4 -經 基苯基）庚烷、1,1-雙（4-羥基苯基）環己烷、4,4，_二羥 基聯苯、3,3’，5,5’·四甲基_4,4、二羥基聯苯、雙（4_羥基 苯基）楓、雙（4 -經基苯基）硫醚、雙（4 -經基苯基）醚 、雙（4-羥基苯基）酮等。 其中，以使用2,2 -雙（4-羥基苯基）丙院（下文簡稱 爲「雙酸A」）爲佳。此等芳香族二羥基化合物可使用一 種，亦可二種以上（本文中，「二種以上」係指二種或二 種以上）以任何比例倂用。 碳酸二酯具體而言可例舉如碳酸二甲酯、碳酸二乙酯 -11 - 200818188 、碳酸二-第三丁酯等脂族碳酸酯；碳酸二苯酯及碳酸聯 苯酯苯酯（biphenylphenylcarbonate )等芳香族碳酸酯類 等。其中，以使用碳酸二苯酯爲佳，此等碳酸二酯可使用 一種，亦可二種以上以任何比例倂用。 本發明中所使用之芳香族聚碳酸酯係以交酯化法，特 別係以使用雙酚A作爲芳香族二羥基化合物，碳酸二苯 酯作爲碳酸二酯，藉由交酯化法而獲得者爲佳。 交酯化法中，原料之莫耳比係適當選擇而決定，惟若 過小，則所得芳香族聚碳酸酯樹脂之末端羥基含量增加， 聚合物之熱安定性有惡化之傾向。反之，若莫耳比過大， 則交酯化反應速度降低，欲製造所期望分子量之芳香族聚 碳酸酯有變困難之傾向。因此，原料之莫耳比爲例如，碳 酸二苯酯/雙酚A之莫耳比，一般爲1.001至1.3，其中以 1.02至1.2爲佳。 交酯化法中一般使用交酯化觸媒。交酯化觸媒可使用 周知之任意觸媒。其中，較佳者可例舉如鹼金屬化合物、 鹼土金屬化合物。亦可倂用輔助性的鹼性硼化合物、鹼性 磷化合物、鹼性銨化合物、胺系化合物等鹼性化合物等。 對芳香族二羥基化合物1莫耳，上述觸媒量一般使用 1x1 (Γ7至9x1 0_7莫耳。觸媒量若過少，則有難以獲得規定 之分子量，及難以獲得呈現末端羥基含量之聚碳酸酯樹脂 製造中所必要之聚合活性的傾向，反之若過多，則所得之 芳香族聚碳酸酯樹脂之色調變差，且有分歧增加，損及聚 合物成形性之傾向。因而，對芳香族二羥基化合物1莫耳 -12- 200818188 ，上述觸媒量係以1.5xl0·7至8xl0·7莫耳爲佳，2xl0·7至 7xl〇_7莫耳尤佳。 鹼金屬化合物可具體例舉如氫氧化鈉、氫氧化鉀、氫 氧化鋰、氫氧化鉋、碳酸氫鈉、碳酸氫鉀、碳酸氫鋰、碳 酸氫鉋、碳酸鈉、碳酸鉀、碳酸鋰、碳酸鉋、乙酸鈉、乙 酸鉀、乙酸鋰、乙酸鉋、硬脂酸鈉、硬脂酸鉀、硬脂酸鋰 、硬脂酸鉋、硼氫化鈉、硼氫化鉀、硼氫化鋰、硼氫化鉋 、苯基化硼鈉、苯基化硼鉀、苯基化硼鋰、苯基化硼鉋、 苯甲酸鈉、苯甲酸鉀、苯甲酸鋰、苯甲酸鉋、磷酸氫二鈉 、磷酸氫二鉀、磷酸氫二鋰、磷酸氫二鉋、苯基磷酸二鈉 、苯基磷酸二鉀、苯基磷酸二鋰、苯基磷酸二鉋；鈉、鉀 、鋰、絶之醇鹽，酚鹽；雙酚A之二鈉鹽、二鉀鹽、二 鋰鹽、二鉋鹽等。 鹼土金屬化合物可具體例舉如氫氧化鈣、氫氧化鋇、 氫氧化鎂、氫氧化緦、碳酸氫鈣、碳酸氫鋇、碳酸氫鎂、 碳酸氫緦、碳酸鈣、碳酸鋇、碳酸鎂、碳酸緦、乙酸鈣、 乙酸鋇、乙酸鎂、乙酸緦、硬脂酸鈣、硬脂酸鋇、硬脂酸 鎂、硬脂酸緦等。 鹼性硼化合物可具體例舉如四甲基硼、四乙基硼、四 丙基硼、四丁基硼、三甲基乙基硼、三甲基苯甲基硼、三 甲基苯基硼、三乙基甲基硼、三乙基苯甲基硼、三乙基苯 基硼、三丁基苯甲基硼、三丁基苯基硼、四苯基硼、苯甲 基三苯基硼、甲基三苯基硼、丁基三苯基硼等之鈉鹽、鉀 鹽、鋰鹽、鈣鹽、鋇鹽、鎂鹽、緦鹽等。 -13- 200818188 鹼性磷化合物可具體例舉如三乙基膦、三·正丙基膦 、三異丙基膦、三-正丁基膦、三苯基膦、三丁基膦、四 級鳞鹽等。 鹼性銨化合物可具體例舉如氫氧化四甲基銨、氫氧化 四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化三 甲基乙基銨、氫氧化三甲基苯甲基銨、氫氧化三甲基苯基 銨、氫氧化三乙基甲基銨、氫氧化三乙基苯甲基銨、氫氧 化三乙基苯基銨、氫氧化三丁基苯甲基銨、氫氧化三丁基 苯基銨、氫氧化四苯基銨、氫氧化苯甲基三苯基銨、氫氧 化甲基三苯基銨、氫氧化丁基三苯基銨等。 胺系化合物可具體例舉如4-胺基吡啶、2-胺基吡啶、 N，N-二甲基-4-胺基吡啶、4-二乙基胺基吡啶、2-羥基吡啶 、2-甲氧基吡啶、4-甲氧基吡啶、2-二甲胺基咪唑、2-二 甲氧基咪唑、咪唑、2-锍基咪唑、2-二甲基咪唑、胺基喹 咐等。 交酯化反應一般係以2階段以上之多階段步驟實施。 具體而言爲例如，第1階段之反應係於93至1.33kPa之 減壓下，於12〇至260°C，較佳於180至240°C反應0.1 至5小時，較佳爲〇· 1至3小時。繼之一邊提高反應系減 壓度，一邊提高反應溫度，而於最終爲133Pa以下之減壓 下，於240至320 °C之溫度進行縮聚反應之製造方法。 反應之形式可爲批式、連續式’亦可爲批式與連續式 組合之方式’所使用之裝置可爲槽型、管型或塔型等任一 種形式之反應器。 -14- 200818188 又，於本發明所使用之芳香族聚碳酸酯之製造時，於 反應後爲了使父酯化觸媒失活，亦可添加酸性化合物或其 前驅物，具體而言例如，磺酸化合物或其前驅物作爲失活 劑。此類觸媒失活劑以對-甲苯磺酸、對-甲苯磺酸甲酯、 對-甲苯磺酸丁酯等爲佳，該等可單獨使用，亦可2種以 上以任意比例使用。 對交酯化觸媒所使用之觸媒失活劑之量可適當選擇而 決定，具體而言例如，使用上述之酸性化合物或其前驅物 時，對縮聚反應中所使用之鹼性交酯化觸媒之中和量爲 0.1至50倍莫耳，其中以0.5至30倍莫耳爲佳。 添加觸媒失活劑之時期，只要在縮聚反應後即可，添 加方法亦無特別限制。視觸媒失活劑之性狀或所期望之條 件，可例舉如直接添加之方法、溶解於適當溶劑中再添加 之方法、使用顆粒狀或片狀母料之方法等。 本發明所使用之芳香族聚碳酸酯在不損及本發明效果 之範圍內亦可含有以往周知之任何樹脂添加劑，具體而言 例如安定劑、紫外線吸收劑、離型劑、著色劑等。 本發明之特點係如上述般，將由芳香族二羥基化合物 與碳酸二酯經由交酯化法而得之黏度平均分子量25000以 下之芳香族聚碳酸酯樹脂，射出成形而獲得光記錄媒體基 板用樹脂成形體。因此使該樹脂成形體與離子產生器產生 之正離子與負離子（以下亦簡稱爲「正離子與負離子」） 接觸而製造光記錄媒體基板。 -15- 200818188 (光記錄媒體基板用樹脂成形體之形成） 於本發明中，如上述使用芳香族聚碳酸酯樹脂之光記 錄媒體，例如CD-R或DVD-R等追記型光記錄媒體等之 基板製造方法，可使用以往周知之方法。具體而言可例舉 如，藉由將芳香族聚碳酸酯樹脂射出成形，而製造具有於 預定陰模（stamper )預先刻印之亞微粒子（submicron ) 大小之複數溝、凹坑或槽溝等凹凸形狀係轉印至該光記錄 媒體基板之表面，且該等凹凸形狀係同心圓狀配置之面（ 以下稱爲信號面）之圓盤狀光記錄媒體基板用樹脂成形體 〇 其中於本發中，此種藉由射出成形而製造光記錄媒體 基板用樹脂成形體之方法中，自射出成形鑄模剝離光記錄 媒體基板用樹脂成形體時，即使產生帶電亦可有效除電， 且其效果顯著。 (與離子產生器及與正離子和負離子之接觸） 本發明係使如此所得之光記錄媒體基板用樹脂成形體 與具有周期性交互產生正離子與負離子之電極針部的離子 產生器所產生之正離子與負離子接觸，而製造光記錄媒體 基板。此接觸時期只要是於該光記錄媒體基板用樹脂成形 體之信號面上形成資訊記錄層（以下，簡稱爲記錄層）、 反射膜、保護層、耐傷性、耐擦性層等之前即無特別限制 〇 其中’以於射出成形等樹脂成形製程後，於光記錄媒 -16- 200818188 體基板用樹脂成形體之冷卻台，使光記錄媒體基板用樹脂 成形體，同時與冷卻流體及正離子、負離子接觸之方法爲 佳。 因此冷卻流體可具體可例舉如空氣、氮氣等，這些流 體通常爲已去除微粒子經清淨化之流體，此種接觸亦以在 潔淨棚（clean booth，亦稱爲無塵室）內等清淨環境下進 行爲佳。具體而言例如，以在美國聯邦規格（FED規格， FED-STD-209E )之潔淨度等級1 0 0 0 0以下之條件下，與 離子產生器所產生之正離子及負離子接觸爲佳，其中以等 級1 000以下，特別是等級100以下爲佳。 同時與冷卻流體及正、負二種離子接觸之方法係隨意 的，並無特別限制。可具體例舉如，使以下吹方式大致供 給至冷卻台全體之冷卻用空氣等冷卻流體，以及正離子與 負離子同時接觸之方法。另外，也可同時使用經軟管等輸 送管將壓縮機所供給之冷卻流體供給至光記錄媒體基板用 樹脂成形體附近之冷卻流體。 其中，以將壓縮機供給之冷卻流體經軟管等輸送管導 入除電裝置內，作爲含有正負離子之冷卻流體，由除電裝 置排出口供給給光記錄媒體基板用樹脂成形體表面之方法 ，因除電效果高而較佳。此種除電裝置，可例舉如基恩斯 (KEYENCE)公司製的「SJ-R060」。 本發明中，相對於光記錄媒體基板用樹脂成形體，其 用於使正離子與負離子接觸之導入角度係隨意的，可適當 選擇而決定。其中，以在與光記錄媒體基板用樹脂成形體 -17- 200818188 之信號面略平行處導入正離子與負離子，並使其接觸爲佳 。此種正離子與負離子之導入，具體而言，可依下述方法 進行。 從射出成形機等樹脂成形機分離之光記錄媒體基板用 樹脂成形體，於潔淨棚內之冷卻台，基板表面係保持水平 方向或垂直方向。通常爲了使冷卻台之設置面積變小，基 板表面會保持垂直方向。於冷卻台上，對保持垂直之基板 表面，平行地自其上部同時導入冷卻流體及正離子與負離 子使其接觸。藉由此種方法，可一邊降低光記錄媒體基板 用樹脂成形體之「翹曲」，一邊有效率地除電。 本發明使用之離子產生器並無特別限制，只要具有周 期性交互產生正離子與負離子之電極針部者，即可自以往 周知之任一物品中適當選擇。離子產生器大致區分爲直流 方式（DC方式）與交流方式（AC方式）。 DC方式係持續掛上高電壓因而每單位時間之離子產 生量多，而自一個產生器，亦即自釋放出離子之一個電極 針僅產生正或負二者中之一種離子的方式。因此在使用 DC方式之離子產生器時，由於不助長正或負二者中之一 種離子量過多而帶電，因而離子平衡良好，可使用具有由 兩個以上電極針形成之電極針部，及具有周期性交互產生 正離子與負離子之電極針部之離子產生器。 另一方面，AC方式由於施加交流電壓於一個電極針 ，而由一個電極針釋放出正與負兩離子的方式。如此，可 去除正與負兩離子的帶電，且因離子平衡良好、助長帶電 -18- 200818188 之虞少，故令人滿意。又，由於AC方式一般而言每單位 時間之離子產生量比DC方式少且除電速度慢，因而可適 當增強施加電壓或增加使用之電極針數以進行除電。 AC方式有脈衝AC方式。脈衝AC方式係採用交互施 加直流電壓之方法，使施加電壓爲矩形波者。藉此比起採 用AC方式之交流電壓（正弦波），每單位時間之離子產 生量增多，因而正、負二種離子交互產生而使離子平衡良 好。 本發明使用之離子產生器，如上所述，可由以往周知 之任一物品中適當選擇而決定，但其中由於除電特性或電 極構造設計容易，而以使用脈衝AC方式之離子產生器爲 佳。使用脈衝AC方式作爲本發明使用之離子產生器時， 可具體例舉如，以使用複數個將該電極針大致排列於直線 上之電極棒爲佳。藉此，位於棒之長度方向的離子平衡良 好，且有效率地進行光記錄媒體基板用樹脂成形體之除電 〇 本發明使用之脈衝AC方式之離子產生器，可以適當 選擇決定離子產生時所要的輸出電壓，並使該離子朝向光 記錄媒體基板用樹脂成形體接觸時之冷卻流體之流量及壓 力、以及與樹脂成形體間之距離等，但一般而言，輸出電 壓爲1至20kv，脈衝波長爲1至100Hz，冷卻流體流量爲 1至l〇〇m3/min，冷卻流體壓力爲〇·〇1至IMPa，基板面 與離子產生器之距離爲0.1至lm，而如此之除電時間（ 與由離子產生器產生之正離子及負離子接觸之時間）爲1 -19- 200818188 秒至5分鐘。 本發明中，如上述般，使光記錄媒體基板用樹脂成形 體與離子產生器所產生之正離子與負離子接觸並進行除電 ，而獲得光記錄媒體基板。接著在信號面上，於資訊記錄 • 層（以下簡稱爲「記錄層」）或反射膜、保護層、耐傷性 - •耐擦性層，及DVD-R等之情形，在前述基板與反向面 之最外層再設置透明基板等而製造光記錄媒體。 0 本發明之光記錄媒體基板之製造方法可適用於製造用 於任意光記錄媒體之基板。光記錄媒體可具體例舉如於基 板上依序層壓色素記錄層、反射層、及保護層、耐擦性層 等之追記型光記錄媒體之CD - R。另可例舉如與CD— R 具有相同構成，並以記錄層爲內側，而貼合反射層上由保 護層形成之層壓體與透明基板（隔板）之追記型光記錄媒 體 DVD — R、DVD + R 〇 再者，記錄層可舉例如具有相變化型記錄層，且在光 φ 記錄媒體兩側具有基板之可覆寫型光記錄媒體DVD -以或 DVD + R。本發明之製造方法，尤以使用於記錄層使用色素 層之追§5型光sB錄媒體基板之製造方法效果顯著而令人滿 意。具體而θ ’可抑制基板上形成色素層時之色素塗佈不 ' 良，且良好地形成記錄層之效果顯著。 以下，以在記錄層使用色素層之追記型光記錄媒體爲 例，說明本光記錄媒體之製造方法。The invention is described in detail below. (Aromatic Polycarbonate) The aromatic polycarbonate used in the present invention is an aromatic polycarbonate resin obtained by a lactide method formed by an aromatic dihydroxy compound and a carbonic acid diester, and is also called a lactide. A method (or melt method) of an aromatic polycarbonate resin. Its characteristic is that its viscosity average molecular weight (hereinafter also referred to as "Mv") is below 2,500. In the case of a high molecular weight having a viscosity average molecular weight of more than 2,500, the birefringence of the resin molded article for an optical recording medium substrate obtained by injection molding is remarkably increased. On the other hand, if the viscosity average molecular weight is too low, there is a case where the resin molded body for an optical recording medium substrate or the optical recording medium substrate is not sufficiently strong. Therefore, the viscosity average molecular weight of the lactide-based aromatic polycarbonate resin used in the present invention is preferably 10,000 or more, particularly preferably 14,000 or more. Further, the viscosity average molecular weight is particularly preferably 23,000 or less, and particularly preferably -10 - 200818188 1 8000 or less. In addition, the viscosity average molecular weight of the present invention is measured by an Ostwald viscometer to measure the intrinsic viscosity (?7) of a solution of a solution of a dichlorocarbendron at 2 ° C, with a Schnel viscosity. The oxime calculated by the formula ([; / ] = 1.23x1 (T4mU3). Further, the aromatic polycarbonate resin used in the lactide method of the present invention may also be a mixture of a plurality of polycarbonate resins. The viscosity average molecular weight at this time is determined by the entire mixture. The aromatic polycarbonate used in the present invention is an aromatic dihydroxy compound and a carbonic acid diester, and a lactide is used in the presence of a lactide catalyst. The reaction can be obtained as an aromatic dihydroxy compound, and specifically, for example, bis(4-hydroxydiphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-dual ( 4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl Phenyl), propylene, 2,2-bis(4.ylamino-3,5-dibromophenyl)propyl, 4,4-bis(4-phenyl)heptane, 1,1- Bis(4-hydroxyphenyl)cyclohexane, 4 , 4,-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4,dihydroxybiphenyl, bis(4-hydroxyphenyl) maple, bis(4-cyanophenyl) ) thioether, bis(4-phenylphenyl)ether, bis(4-hydroxyphenyl) ketone, etc., wherein 2,2-bis(4-hydroxyphenyl)propene (hereinafter referred to as "double" is used. The acid A") is preferably used. These aromatic dihydroxy compounds may be used alone or in combination of two or more kinds (hereinafter, "two or more" means two or more kinds) in any ratio. Specific examples thereof include aliphatic carbonates such as dimethyl carbonate, diethyl carbonate-11 - 200818188, and di-tert-butyl carbonate; and aromas such as diphenyl carbonate and biphenylphenylcarbonate. A carbonate or the like is preferred. Among them, diphenyl carbonate is preferably used, and these diester carbonates may be used alone or in combination of two or more kinds. The aromatic polycarbonate used in the present invention is The lactide method, in particular, uses bisphenol A as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic acid diester by a lactide method. In the lactide method, the molar ratio of the raw material is determined by appropriate selection, but if it is too small, the terminal hydroxyl group content of the obtained aromatic polycarbonate resin increases, and the thermal stability of the polymer tends to deteriorate. On the other hand, if the molar ratio is too large, the rate of the transesterification reaction is lowered, and the aromatic polycarbonate to be produced having a desired molecular weight tends to be difficult. Therefore, the molar ratio of the raw material is, for example, diphenyl carbonate/double The molar ratio of phenol A is generally from 1.001 to 1.3, and preferably from 1.02 to 1.2. A lactide catalyst is generally used in the lactide method. The lactide catalyst can be any catalyst known in the art. Among them, preferred are, for example, an alkali metal compound or an alkaline earth metal compound. A basic compound such as an auxiliary basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound can also be used. For the aromatic dihydroxy compound 1 mole, the amount of the above catalyst is generally 1x1 (Γ7 to 9x1 0_7 moles. If the amount of the catalyst is too small, it is difficult to obtain a predetermined molecular weight, and it is difficult to obtain a polycarbonate exhibiting a terminal hydroxyl group content. When the polymerization activity required for the production of the resin tends to be too large, the color of the obtained aromatic polycarbonate resin is deteriorated, and the difference is increased, which tends to impair the polymer formability. Therefore, the aromatic dihydroxy group is preferred. Compound 1 Moel-12-200818188, the above catalyst amount is preferably 1.5xl0·7 to 8xl0·7 mole, and 2xl0·7 to 7xl〇_7 mole is particularly preferable. The alkali metal compound may specifically be exemplified as hydrogen. Sodium oxide, potassium hydroxide, lithium hydroxide, hydroxide planer, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, hydrogencarbonate planer, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid planer, sodium acetate, potassium acetate, acetic acid Lithium, acetic acid planer, sodium stearate, potassium stearate, lithium stearate, stearic acid planer, sodium borohydride, potassium borohydride, lithium borohydride, borohydride planer, sodium phenylhydride, phenylation Boron potassium, lithium phenyl boronate, phenylboride planer, Sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid planer, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dihydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, phenyl phosphate Dilithium, phenylphosphoric acid di-planar; sodium, potassium, lithium, absolute alkoxide, phenate; bisphenol A disodium salt, dipotassium salt, dilithium salt, di-planar salt, etc. Alkaline earth metal compound can be a specific example For example, calcium hydroxide, barium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, barium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, barium carbonate, calcium acetate, acetic acid Barium, magnesium acetate, barium acetate, calcium stearate, barium stearate, barium stearate, barium stearate, etc. The basic boron compound may specifically be exemplified by tetramethylboron, tetraethylboron, tetrapropylamine. Boron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenyl Boron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenyl a sodium salt, a potassium salt, a lithium salt, a calcium salt, a barium salt, a magnesium salt, a barium salt or the like of boron or the like. -13- 200818188 The basic phosphorus compound may specifically be exemplified by triethylphosphine or tri-n-propylphosphine. Triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt, etc. The basic ammonium compound may specifically be exemplified by tetramethylammonium hydroxide or tetraethyl hydroxide. Ammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylammonium hydroxide Ammonium, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, hydroxide Benzyltriphenylammonium, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, etc. The amine compound may specifically be exemplified by 4-aminopyridine, 2-aminopyridine, N, N. - dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-di Methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-dimethylimidazole, aminoquinoxaline and the like. The lactide reaction is generally carried out in a multistage step of two or more stages. Specifically, for example, the first stage reaction is carried out at a pressure of from 93 to 1.33 kPa under a reduced pressure of from 12 to 260 ° C, preferably from 180 to 240 ° C for from 0.1 to 5 hours, preferably 〇·1. Up to 3 hours. The production method of the polycondensation reaction is carried out at a temperature of 240 to 320 ° C under a reduced pressure of 133 Pa or less at the same time as the reaction temperature is increased while the reaction system is reduced in pressure. The reaction may be in the form of a batch, a continuous type or a combination of a batch and a continuous type. The apparatus used may be any one of a tank type, a tube type or a column type. Further, in the production of the aromatic polycarbonate used in the present invention, in order to inactivate the parent esterification catalyst after the reaction, an acidic compound or a precursor thereof may be added, specifically, for example, sulfonate. The acid compound or its precursor acts as a deactivating agent. Such a catalyst deactivating agent is preferably p-toluenesulfonic acid, methyl p-toluenesulfonate or butyl p-toluenesulfonate, and these may be used singly or in combination of two or more kinds in any ratio. The amount of the catalyst deactivator used for the lactide catalyst can be appropriately selected, and specifically, for example, when the above acidic compound or its precursor is used, the alkaline lactide touch used in the polycondensation reaction The median amount is from 0.1 to 50 moles, preferably from 0.5 to 30 moles. The period of adding the catalyst deactivator is not particularly limited as long as it is after the polycondensation reaction. The properties of the catalyst deactivator or the desired conditions may, for example, be a direct addition method, a method of dissolving in a suitable solvent, a method of using a pellet or a master batch, or the like. The aromatic polycarbonate used in the present invention may contain any conventional resin additives known in the range which does not impair the effects of the present invention, and specifically, for example, a stabilizer, an ultraviolet absorber, a release agent, a colorant and the like. According to the present invention, an aromatic polycarbonate resin having a viscosity average molecular weight of 25,000 or less obtained by a transesterification method of an aromatic dihydroxy compound and a carbonic acid diester is injection-molded to obtain a resin for an optical recording medium substrate. Shaped body. Therefore, the resin molded body is brought into contact with positive ions and negative ions (hereinafter also simply referred to as "positive ions and negative ions") generated by the ion generator to produce an optical recording medium substrate. -15-200818188 (Formation of a resin molded body for an optical recording medium substrate) In the present invention, an optical recording medium using an aromatic polycarbonate resin as described above, for example, a write-once optical recording medium such as CD-R or DVD-R As a method of manufacturing the substrate, a conventionally known method can be used. Specifically, for example, by molding an aromatic polycarbonate resin, a plurality of grooves, pits, grooves, and the like having a size of a submicron which is pre-marked in a predetermined stamper are produced. a resin molded body for a disk-shaped optical recording medium substrate in which the shape is transferred to the surface of the optical recording medium substrate, and the concave-convex shape is a concentrically arranged surface (hereinafter referred to as a signal surface). In the method of producing a resin molded article for an optical recording medium substrate by injection molding, when the resin molded article for an optical recording medium substrate is peeled off from the injection molding die, it is possible to effectively remove electricity even if charging occurs, and the effect is remarkable. (Contact with ion generator and with positive ions and negative ions) The present invention is produced by the resin molded body for an optical recording medium substrate thus obtained and an ion generator having an electrode needle portion which periodically generates positive ions and negative ions. The positive ions are in contact with the negative ions to produce an optical recording medium substrate. In the contact period, there is no special information before the formation of the information recording layer (hereinafter, simply referred to as a recording layer), the reflective film, the protective layer, the scratch resistance, the rubbing resistance layer, and the like on the signal surface of the resin molded article for an optical recording medium substrate. In the case of a resin molding process such as injection molding, the resin recording body of the optical recording medium substrate is used in a resin molding process for optical recording medium-16-200818188, and a resin molded body for an optical recording medium substrate is simultaneously provided with a cooling fluid and positive ions. The method of negative ion contact is preferred. Therefore, the cooling fluid may specifically be exemplified by air, nitrogen, etc., and these fluids are usually fluids from which the microparticles have been removed, and the contact is also cleaned in a clean booth (also known as a clean room). It is better to proceed below. Specifically, for example, it is preferable to contact positive ions and negative ions generated by the ion generator under the condition that the US federal specification (FED specification, FED-STD-209E) has a cleanliness level of 1 or less. It is preferably 1 or less, especially 100 or less. The method of contacting the cooling fluid and the positive and negative ions at the same time is arbitrary and is not particularly limited. For example, a cooling fluid such as cooling air that supplies the entire blowing method to the entire cooling stage, and a method in which positive ions and negative ions are simultaneously contacted can be specifically exemplified. In addition, the cooling fluid supplied to the vicinity of the resin molded body for an optical recording medium substrate may be supplied to the cooling fluid supplied from the compressor via a transfer tube such as a hose. In addition, the cooling fluid supplied from the compressor is introduced into the static eliminating device through a transfer pipe such as a hose, and is supplied as a cooling fluid containing positive and negative ions to the surface of the resin molded body for the optical recording medium substrate by the discharge port of the static eliminating device. The effect is high and better. Such a static elimination device may, for example, be "SJ-R060" manufactured by KEYENCE. In the present invention, the resin molded body for an optical recording medium substrate is used in an arbitrary manner for causing the introduction angle of the positive ions to contact with the negative ions, and can be appropriately selected and determined. In addition, it is preferable to introduce positive ions and negative ions in a direction slightly parallel to the signal surface of the resin molded body for optical recording medium substrate -17-200818188. The introduction of such positive ions and negative ions can be carried out in the following manner. The resin molded body for an optical recording medium substrate, which is separated from a resin molding machine such as an injection molding machine, is held in a horizontal direction or a vertical direction on a cooling stage in a clean booth. Usually, in order to make the installation area of the cooling stage small, the surface of the substrate will remain vertical. On the cooling stage, the surface of the substrate which is kept perpendicular is simultaneously introduced into the cooling fluid from the upper portion thereof in parallel with the positive ions and the negative ions. According to this method, it is possible to efficiently remove electricity while reducing the "warpage" of the resin molded body for an optical recording medium substrate. The ion generator used in the present invention is not particularly limited, and any one of the conventionally known articles can be appropriately selected as long as it has an electrode needle which periodically generates positive ions and negative ions. The ion generator is roughly classified into a direct current mode (DC mode) and an alternating current mode (AC mode). The DC mode continuously hangs a high voltage and thus generates a large amount of ions per unit time, and a single generator, that is, an electrode from which ions are released, produces only one of positive or negative ions. Therefore, when the DC type ion generator is used, since one of the positive or negative ones is not energized and charged, the ion balance is good, and an electrode needle having two or more electrode needles can be used, and An ion generator that periodically generates an electrode tip of a positive ion and a negative ion. On the other hand, the AC mode releases the positive and negative ions by one electrode needle by applying an alternating voltage to one electrode needle. In this way, the charging of the positive and negative ions can be removed, and it is satisfactory because the ion balance is good and the electrification is small -18-200818188. Further, since the AC mode generally has less ion generation per unit time than the DC mode and the static elimination rate is slow, it is possible to appropriately increase the applied voltage or increase the number of electrode pins used to perform the static elimination. The AC mode has a pulsed AC mode. The pulsed AC mode uses a method of applying a DC voltage alternately to make the applied voltage a rectangular wave. This results in an increase in the amount of ions per unit time compared to the AC voltage (sine wave) using AC mode, so that the positive and negative ions are alternately generated to make the ion balance good. The ion generator used in the present invention can be appropriately selected from any of the conventionally known articles as described above, but it is preferable to use a pulsed AC type ion generator because of the ease of electrical discharge characteristics or electrode structure design. When the pulsed AC method is used as the ion generator used in the present invention, it is preferable to use, for example, a plurality of electrode rods in which the electrode needles are arranged substantially in a straight line. Thereby, the ion balance in the longitudinal direction of the rod is good, and the resin molded body for the optical recording medium substrate is efficiently removed. The pulse AC type ion generator used in the present invention can be appropriately selected to determine the generation of ions. The output voltage and the flow rate and pressure of the cooling fluid when the ions are brought into contact with the resin molded body for the optical recording medium substrate, and the distance from the resin molded body, etc., but generally, the output voltage is 1 to 20 kV, and the pulse wavelength is The flow rate of the cooling fluid is 1 to 100 μm/min, the pressure of the cooling fluid is 〇·〇1 to IMPa, and the distance between the substrate surface and the ion generator is 0.1 to lm, and the time of the static elimination is The time between the positive and negative ions produced by the ion generator is 1 -19- 200818188 seconds to 5 minutes. In the present invention, the positive electrode and the negative ion generated by the resin molded body for an optical recording medium substrate and the ion generator are brought into contact with and neutralized to obtain an optical recording medium substrate. Then on the signal surface, in the information recording layer (hereinafter referred to as "recording layer") or reflective film, protective layer, scratch resistance - • rub resistance layer, and DVD-R, etc., in the above substrate and reverse An optical recording medium is produced by further providing a transparent substrate or the like on the outermost layer of the surface. The method for producing an optical recording medium substrate of the present invention can be applied to a substrate for use in any optical recording medium. The optical recording medium can be specifically exemplified by a CD-R of a write-once optical recording medium in which a dye recording layer, a reflective layer, a protective layer, and a rubbing resistant layer are sequentially laminated on a substrate. Further, a recordable optical recording medium DVD-R having the same configuration as that of the CD-R and having the recording layer as the inner side and the laminate formed of the protective layer on the reflective layer and the transparent substrate (separator) may be exemplified. Further, the recording layer may be, for example, a rewritable optical recording medium DVD- or DVD + R having a phase change type recording layer and having a substrate on both sides of the optical φ recording medium. The production method of the present invention is particularly satisfactory in that the method for producing a recording medium using a coloring layer of a recording layer using a dye layer is remarkable. Specifically, θ ′ can suppress the dye coating when the pigment layer is formed on the substrate, and the effect of forming the recording layer satisfactorily is remarkable. Hereinafter, a method of manufacturing the optical recording medium will be described by taking, as an example, a write-once optical recording medium using a pigment layer in a recording layer.
本發明之光記錄媒體之製造方法中所使用之光記錄媒 體基板通常厚度爲0.5至1.5mm，具體而言例如，CD - R -20- 200818188 方面可成形爲1.2mm、DVD— R方面可成形爲〇.6mm。成 形方法爲任意，但通常利用射出成形製造。此射出成形時 ’在信號面側形成溝與凹坑。以如此所得之光記錄媒體基 板用樹脂成形體，如前述般進行除電者作爲光記錄媒體基 板，在該基板上形成記錄層之色素層。 (記錄層之形成、色素之塗佈） 一般而言，在記錄層使用色素之追記型光記錄媒體之 製造方法中，將色素直接塗佈在基板信號面上，形成記錄 層。此色素之塗佈方法是任意的，可自以往周知之任意方 法中適當選擇而決定。通常，可例舉如：將有機色素溶解 於有機溶媒而得之色素溶液，以旋塗法塗佈使充滿於信號 面形成之溝槽的方法。 旋塗法一般可使用由塗佈液供料裝置（dispenser nozzle，供料噴嘴）、旋轉頭（80丨111161*11€&〇、飛散防止 壁、及排氣裝置等所構成，以往周知隻任意旋塗裝置進行 。具體而言，將光記錄媒體基板靜置於旋轉頭上，接著一 邊以驅動馬達使旋轉頭回轉，一邊從塗佈液供料裝置之噴 嘴供給塗佈液至該基板內周部之表面，以供給至離最內周 邊2至3mm內之位置爲佳。供給至基板上之塗佈液依離 心力呈現放射狀流延至外圍側，即可形成塗佈膜。 色素層之厚度可適當選擇決定，惟通常CD- R爲10 至 5000nm，DVD— R 爲 10 至 3000nm。 旋塗操作期間，自設置於飛散防止壁上方之開口部（ -21 - 200818188 氣體導入部）導入空氣等乾燥氣體，使該氣體流通於該塗 佈膜上，並由旋塗裝置下方排氣。藉由該氣體之流通，自 塗佈膜去除溶媒，塗佈膜即乾燥。另外必要時可將基板投 入稱爲烤箱之乾燥烘箱內以去除殘存溶媒，即可形成記錄 層。 追記型光記錄媒體記錄層之色素層所用之色素只要是 雷射光波長領域，具體而言例如於3 00至8 5 0nm吸收領 域之色素即可，並無限制，可適當選擇而決定。可具體例 舉如偶氮色素、花青苷色素、酞菁色素、莫鑰（ azulenium )色素、（S qualilium )色素、聚次甲基（ polymethine )、吡啶鏺色素、硫吡啶鍚色素、吲哚苯胺 (Indoaniline)色素、萘醌色素、蒽醌色素、三烯丙基甲 院色素、胺鑰（aminium)色素、二亞胺i翁（diiminium) 色素 '偶氮系配位子化合物與金屬所成之金屬螯合系色素 、金屬錯體等，以及該等之混合物。 其中，以偶氮系、花青苷（cyanine )系及酿菁系等 色素，由於可獲得信號感度優越，易溶解於溶劑，耐光性 良好’且高品質之追記型光記錄媒體而佳。 色素溶液所用之有機溶劑可適當選擇而決定，具體而 言可例舉如乙酸丁酯、乙酸賽璐蘇（cell〇s〇lve acetate) 等酯類；甲基乙基酮、環己酮、甲基異丁基酮等酮類；二 氯甲烷、1，2-二氯乙烷、氯仿等鹵化烴類；二甲基甲醯胺 等醯胺類；環己烷等烴類；四氫呋喃、乙基醚、二噚烷等 醚類；乙醇、正丙醇、異丙醇、正丁醇、二丙酮醇等醇類 -22- 200818188 ;2，2，3，3 -四氟丙醇等氟素系溶劑；乙二醇單甲基醚、乙 二醇單乙基醚、丙二醇單甲基醚等二醇醚類等。 考慮所使用之色素，該等溶劑可單獨使用，亦可適當 倂用2種以上。其中以使用2,2,3,3-四氟丙醇、八氟戊醇 、二丁基醚等氟素系溶劑爲佳。 然後於記錄層上設置反射層。反射層係將Ag、Au、 A1等金屬以濺鍍法等以往周知之方法設置即可。反射層 上可設置保護膜，亦可另設耐傷性層。C D -R之情況，係 形成單板，惟DVD-R之情況亦可於上述保護層上介由接 著劑層等，另外再貼合透明基板。 【實施方式】 實施例 下文以實施例更具體說明本發明，惟本發明於不超過 該要旨之範圍內並不限定於以下實施例。又，原料、除電 裝置係使用以下者。 1·交酯化法聚碳酸酯樹脂： 三菱工程塑料公司（ENGINEERING-PLASTICS CORP )製「NOVAREX M7020 AD2」（Mv : 1 6000 ) 2.除電裝置與冷卻條件等： 除電裝置（a):基恩斯（KEYENCE )公司製「SJ — R060」（脈衝AC方式）除電棒（於長度方向配置周期性 -23- 200818188 交互產生正、負二種離子之電極針者）。各條件 壓：7.0kv、脈衝波長：10Hz (矩形波）、空 4 0m3/分、空氣壓力：〇.2MPa、樹脂成形體（圓 成形體端部）與除電棒間之距離：0.3m、除電 秒。 除電裝置（b ) : Hugle Electronics 公司 _ 442」、雙直流（double DC)方式除電棒（於長 互配置僅產生正離子之電極針，與僅產生負離子 者）。各條件係輸出電壓：±6.0kv、空氣流量 、樹脂成形體（圓盤狀樹脂成形體端部）與除電 :0 · 3 m、除電時間：6 0秒。 3.冷卻條件等： 除電裝置（a ):使用（脈衝AC方式）時 媒體基板用樹脂成形體係於冷卻台（潔淨棚） 垂直靜置之狀態，往除電棒之長度方向水平移 生器係於潔淨棚內該樹脂成形體移動路徑之正 其長度方向之移動方向水平設置。然後冷卻空 給至除電棒，而自除電棒與正、負離子同時下 移動之光記錄媒體基板用樹脂成形體接觸。 除電裝置（b ):使用（雙DC方式）時 體基板用樹脂成形體亦係於潔淨棚內，以大致 狀態，往除電棒之長度方向水平移動。離子產 淨棚內該樹脂成形體移動路徑之正上方，沿者 係輸出電 氣流量： 盤狀樹脂 時間：60 吳 r Model 度方向交 之電極針 :40m3/分 棒之距離 ，光記錄 ，以大致 。離子產 方，沿者 於軟管供 而與水平 光記錄媒 直靜置之 器係於潔 淨棚內該 • 24- 200818188 樹脂成形體移動路徑之正上方，使長度方向沿者移動方向 水平設置’而使自潔淨棚上部供給之下吹冷卻空氣與自除 電棒產生之正、負離子同時與該樹脂成形體表面接觸。 ^ 實施例1、比較例1、2 : • 使用裝備有槽溝深度15〇nm、間距〇.74μ m之光記錄 媒體製造用鑄模（陰模）之射出成形機（住友重機公司製 馨 ，型式：s D 4 0 > ，於圓筒溫度3 8 0。〇、鑄模溫度1 2 8。(：、 成形遍期6 · 0秒之條件下，獲得厚度〇 . 6心m，直徑1 2 0 m m 之透明圓盤狀光記錄媒體基板用樹脂成形體。 繼之’自鑄模取出該樹脂成形體，於潔淨度等級 10000之室內冷卻並進行色素塗佈。首先，於該室內設置 之上部設有除電裝置之潔淨棚內（潔淨棚內之潔淨度爲等 級1 〇〇 )進行冷卻及除電，或不除電即進行冷卻，而製造 具有槽溝之光記錄媒體基板。 φ 接著使所得之光記錄媒體基板於200rpm回轉下，於 溝槽最內周起3mm內之內周部上，自噴嘴滴下偶氮系色 素（日本三菱化學媒體（Media)公司製：PDS-1861)之 ^ 八氟戊醇5%溶液。溶液滴下後，將基板之回轉數提高至 ' · 5000rpm，使供給至基板上之塗佈液呈放射狀流延至圓盤 狀基板外周側，形成充滿溝槽之塗佈液層。繼之，將設有 該塗佈液層之光記錄媒體基板投入保持於95 t之乾燥烘 箱內靜置1 5分鐘，去除殘存溶劑而形成色素記錄層。 對以上方法所得之設有色素記錄層之光記錄媒體基板 -25- 200818188 ，實施下列各項目之評估。結果示於表1。 (1 )有無明顯缺陷：以肉眼觀察於色素塗佈後之基 板上所形成之色素記錄層，以部分的色素成爲較薄部分爲 明顯缺陷，檢視其有無。 (2 )塗佈部內周之圓度（Roundness ):以肉眼觀察 於色素塗佈後之基板上所形成之色素記錄層內周部，檢視 圓形狀之部分有無紊亂。 [表1] 實施例1 比較例1 比較例2 除電裝置 (a) (b) 魅 j\w 明顯缺陷 ^frrr m >fnr 有 圓紊亂 Μ 有 有 CT' 由表1可知，本發明之光記錄媒體基板於色素塗佈時 無明顯缺陷，亦無圓紊亂之情況，判明適於作爲光記錄媒 體基板。但是，相同之交酯化法所得之聚碳酸酯樹脂製光 記錄媒體基板，即使將該基板用樹脂成形體以DC方式除 電機進行除電之情況（比較例〗）’亦由於圓紊亂而外觀 不良，因而判明不適於作爲記錄媒體基板。 再者，不除電之情況（比較例2)，由於會有圓紊亂 以及明顯缺陷存在，而影響信號特性因而可知不適於作爲 光記錄媒體基板。 -26-The optical recording medium substrate used in the method for producing an optical recording medium of the present invention has a thickness of usually 0.5 to 1.5 mm. Specifically, for example, the CD-R-20-200818188 can be formed into a shape of 1.2 mm, and the DVD-R can be formed. It is 6.6mm. The forming method is arbitrary, but it is usually manufactured by injection molding. At the time of this injection molding, grooves and pits are formed on the signal surface side. The resin molded article for an optical recording medium substrate thus obtained is subjected to a charge removing layer as an optical recording medium substrate as described above, and a dye layer of a recording layer is formed on the substrate. (Formation of Recording Layer and Application of Pigment) In general, in a method of producing a write-once optical recording medium using a dye in a recording layer, a dye is directly applied onto a signal surface of a substrate to form a recording layer. The method of applying the pigment is arbitrary, and can be appropriately selected from any conventionally known method. In general, a method in which a pigment solution obtained by dissolving an organic dye in an organic solvent is applied, and a method of filling a groove formed on a signal surface by spin coating is applied. The spin coating method can generally be composed of a coating liquid supply device (dispenser nozzle, a supply nozzle), a rotary head (80丨111161*11€&〇, a scattering prevention wall, and an exhaust device, etc., which has been known only recently. Specifically, the optical recording medium substrate is placed on the rotary head, and then the coating liquid is supplied from the nozzle of the coating liquid supply device to the substrate while the rotary head is rotated by the drive motor. The surface of the peripheral portion is preferably supplied to a position within 2 to 3 mm from the innermost periphery. The coating liquid supplied onto the substrate is radially cast to the peripheral side by centrifugal force to form a coating film. The CD-R is usually 10 to 5000 nm, and the DVD-R is 10 to 3000 nm. During the spin-coating operation, air is introduced from the opening (-21 - 200818188 gas introduction portion) provided above the scattering prevention wall. The gas is dried, the gas is circulated on the coating film, and is exhausted by the spin coating device. The solvent is removed from the coating film by the flow of the gas, and the coating film is dried. Cast The recording layer can be formed by removing the residual solvent in a drying oven called an oven. The pigment used in the pigment layer of the recording medium of the recordable optical recording medium is only in the field of laser light wavelength, specifically, for example, absorption in the range of 300 to 850 nm. The pigment in the field may be, and is not limited to, and may be appropriately selected and determined. Specific examples thereof include azo dye, anthocyanin pigment, phthalocyanine dye, azulenium pigment, (S qualilium) pigment, and polymethine. Polymethine, pyridinium pigment, thiopyridinium pigment, indoaniline pigment, naphthoquinone pigment, anthraquinone pigment, triallyl hospital pigment, aminium pigment, diimine i (diiminium) a metal chelate dye, a metal complex, or the like formed by a dye-azo-based ligand compound and a metal, and a mixture thereof. Among them, an azo-based, cyanine-based and brewed A pigment such as a phthalocyanine is excellent in signal sensitivity, is easily soluble in a solvent, and has good light resistance, and is preferably a high-quality write-once optical recording medium. The organic solvent used for the dye solution can be appropriately selected and determined. Specific examples thereof include esters such as butyl acetate and cell 〇 〇 ve ; acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; and dichloro a halogenated hydrocarbon such as methane, 1,2-dichloroethane or chloroform; a guanamine such as dimethylformamide; a hydrocarbon such as cyclohexane; an ether such as tetrahydrofuran, ethyl ether or dioxane; Alcohols such as n-propanol, isopropanol, n-butanol and diacetone alcohol-22-200818188; fluorinated solvents such as 2,2,3,3-tetrafluoropropanol; ethylene glycol monomethyl ether, B Glycol ethers such as diol monoethyl ether and propylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more kinds as appropriate. Among them, a fluorine-based solvent such as 2,2,3,3-tetrafluoropropanol, octafluoropentanol or dibutyl ether is preferably used. A reflective layer is then disposed on the recording layer. In the reflective layer, a metal such as Ag, Au, or A1 may be provided by a conventionally known method such as sputtering. A protective film may be disposed on the reflective layer, and a damage resistant layer may be additionally provided. In the case of C D -R, a single board is formed, but in the case of the DVD-R, the adhesive layer or the like may be applied to the protective layer, and the transparent substrate may be bonded. [Embodiment] The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples without departing from the scope of the invention. Further, the following materials are used for the raw material and the static elimination device. 1. Polyesterification polycarbonate resin: "NOVAREX M7020 AD2" manufactured by ENGINEERING-PLASTICS CORP (Mv: 1 6000) 2. Static elimination device and cooling conditions, etc.: Removal device (a): Keynes ( KEYENCE) "SJ-R060" (pulse AC method) power-removing bar (the periodicity of the length direction -23-200818188 alternately produces the positive and negative electrode electrodes). Each conditional pressure: 7.0 kV, pulse wavelength: 10 Hz (rectangular wave), empty 40 m3/min, air pressure: 〇. 2 MPa, distance between resin molded body (end of round shaped body) and static elimination rod: 0.3 m, static elimination seconds . De-energizing device (b): Hugle Electronics _ 442", double DC (double DC) type de-energizing rod (electrode needles that only produce positive ions in long mutual configuration, and those that only generate negative ions). The output voltage of each condition was ±6.0 kV, the air flow rate, the resin molded body (end of the disk-shaped resin molded body), and the static elimination: 0 · 3 m, and the static elimination time: 60 seconds. 3. Cooling conditions, etc.: In addition to the electric device (a): When the (pulse AC method) is used, the resin molding system for the dielectric substrate is placed in a state where the cooling stage (clean shed) is vertically placed, and the horizontal transfer unit is attached to the length of the static elimination rod. The moving direction of the moving path of the resin molded body in the clean booth is horizontally set in the longitudinal direction. Then, the heat-dissipating rod is cooled, and the optical recording medium substrate is moved in contact with the positive and negative ions. In addition to the electric device (b), the resin molded body for the bulk substrate is also used in the clean room, and is horizontally moved in the longitudinal direction of the static eliminating bar in a substantially state. In the ion production shed, the resin molding body moves directly above the moving path, and the electrical flow is output along the system: Disk resin time: 60 ng r Model degree direction electrode needle: 40 m3 / minute rod distance, light recording, to approximate . In the ion production side, the device is placed in the hose and the horizontal optical recording medium is placed in the clean booth. 24-200818188 The resin molding body is directly above the moving path, so that the length direction is horizontally set along the moving direction. The positive and negative ions generated by the blowing of the cooling air from the upper portion of the clean booth and the self-removing rod are simultaneously brought into contact with the surface of the resin molded body. ^Example 1, Comparative Example 1, 2: • Injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd.), which is equipped with a mold (female mold) for optical recording medium production with a groove depth of 15 〇 nm and a pitch of 74.74 μm. : s D 4 0 > , at a cylinder temperature of 380 〇, a mold temperature of 1 2 8 (:, a forming period of 6 · 0 seconds, obtaining a thickness 〇. 6 hearts m, diameter 1 2 0 a resin molded body for a transparent disc-shaped optical recording medium substrate of mm. The resin molded body is taken out from the mold, and is cooled in a room having a cleanliness level of 10,000 to perform dye coating. First, an upper portion of the chamber is provided. In the clean shed of the static elimination device (the cleanliness in the clean shed is level 1 〇〇), cooling or de-energization is performed, or cooling is performed without removing electricity, and an optical recording medium substrate having grooves is manufactured. φ Next, the obtained optical recording medium is used. The substrate was rotated at 200 rpm, and an azo-based pigment (manufactured by Mitsubishi Chemical Corporation, Japan: PDS-1861) was dropped from the nozzle on the inner peripheral portion within 3 mm from the innermost circumference of the groove. % solution. After the solution is dropped, the number of revolutions of the substrate Increasing to 5000 rpm, the coating liquid supplied onto the substrate is radially cast to the outer peripheral side of the disk-shaped substrate to form a coating liquid layer filled with the groove. Then, the light of the coating liquid layer is provided. The recording medium substrate was placed in a drying oven maintained at 95 t for 15 minutes, and the residual solvent was removed to form a dye recording layer. The optical recording medium substrate 25-200818188 provided with the dye recording layer obtained by the above method was subjected to the following The results of the evaluation are shown in Table 1. (1) Whether there are obvious defects: The pigment recording layer formed on the substrate after the pigment coating is observed with the naked eye, and some of the pigments become thin defects as obvious defects, and the presence or absence of the pigment is examined. (2) Roundness of the inner circumference of the coating portion: The inner peripheral portion of the dye recording layer formed on the substrate after the dye coating was visually observed, and the portion of the circular shape was examined for the disorder. [Table 1] Example 1 Comparison Example 1 Comparative Example 2 De-energizing device (a) (b) Charm j\w Obvious defect ^frrr m > fnr Rounded disorder Μ There is CT' As can be seen from Table 1, the optical recording medium substrate of the present invention is coated with a pigment No obvious In the case where there is no rounding disorder, it is found to be suitable as an optical recording medium substrate. However, the polycarbonate resin optical recording medium substrate obtained by the same lactide method is divided by the DC resin method. In the case where the motor was de-energized (Comparative Example), the appearance was poor due to the disorder of the circle, and it was found that it was not suitable as a recording medium substrate. Further, in the case where the power was not removed (Comparative Example 2), there was a round disorder and a significant defect. However, it affects the signal characteristics and thus is not suitable as an optical recording medium substrate. -26-