200940499 、六、發明說明： 【發明所屬之技術領域】 本發明係關於使用於半導體光阻、彩色光阻、LCD ( 液晶顯示裝置）用噴墨式印墨等之電子材料用途等要求高 純度之高沸點酯系溶劑及其之製造方法。 【先前技術】 利用醇類與酸的脫水反應之酯系溶劑之製造，通常係 在酸觸媒之存在下進行，而爲製造高純度之酯系溶劑通常 φ 係在反應結束後加以蒸餾精製。然而，在高沸點酯之情形 時，則在蒸餾時之熱劣化（酯之熱分解等）所引起之酸份 上升將成爲問題。在酸觸媒存在之系統中製品之熱分解顯 著，若欲有效率地製造高純度之酯系溶劑時，則必須移除 蒸餾前之酸觸媒。先前酸觸媒之移除方法，通常一直使用 以鹼金屬氫氧化物等實施中和之方法等（例如，引用文獻 1)。然而，此等方法則有爲中和所使用的鹼金屬成份將混 入於製品中之顧慮。因此，若欲在半導體光阻、彩色光阻 φ 、LCD用噴墨式印墨等之電子材料用途方面用作爲溶劑時 ，則必須採取在ppb (十億分率）等級下之金屬含量管理， 以致以先前的精製方法則不能充分對應於在電子材料用途 所要求之對於減少金屬含量或酸份之要求。 (專利文獻1)特開平第5-112489號公報。 【發明内容】 〔所欲解決之技術問題〕 本發明之目的係提供一種在要求高純度品質之電子材 200940499 料領域也可使用之鈉等之鹼金屬及酸份爲極低之高沸點酯 系溶劑、及其之有效率的工業製造方法。 〔解決問題之技術方法〕 本發明之發明人等爲解決如上所述之技術問題而經專 心硏究結果發現：即使將酯化反應粗液（esterification reaction crude)在蒸餾前不實施中和處理，而藉由在餾去 低沸點成份後，從蒸餾塔之側流管線（side-cut line)餾出 酯系溶劑，特別是藉由在蒸餾時以回流使低沸酸份濃縮於 塔頂部，而在此狀態下以側流法（side-cut method)將製品 餾出，藉此則可獲得酸份爲極低之製品，而且由於並未實 施中和處理，也可消除在先前的包括中和處理製程之製造 方法所成爲問題的混入鈉等之鹼金屬，因此可獲得鹼金屬 含量及酸份爲極低且爲高純度之高沸點酯系溶劑而達成本 發明。 亦即，本發明係提供一種酯系溶劑之製造方法，其係 將醇與羧酸在酸觸媒之存在下進行酯化反應所獲得之酯化 © 反應粗液使用蒸餾塔加以蒸餾精製之酯系溶劑之製造方法 ，而將該反應粗液不實施中和處理即供應至蒸餾精製，餾 去低沸點成份後，從設置於蒸餾塔中間部份之側流管線餾 出酯系溶劑。 可根據本發明之製造方法製造之酯系溶劑係包括在常 壓下沸點爲120至3 00°C之酯系溶劑。 在本發明之酯系溶劑之製造方法，用作爲原料來使用 之「醇」係包括：例如，環己醇、1，3·丁二醇、二丙二醇一 200940499 甲基醚、丙二醇、1，6-己二醇等；羧酸係可例示例如醋酸。 本發明之酯系溶劑之製造方法係藉由下列步驟來實施 。例如，在包括在內部可進行醇與羧酸反應之蒸餾釜（ distillation still)、連結於該蒸餾釜之蒸餾塔、設置於該 蒸餾塔中段部之側流管線、連結於該蒸餾塔塔頂部之傾析 器（decanter )及可調整該蒸餾塔塔頂部壓力之真空裝置之 設備中，在進行醇與羧酸之反應時，則以連結於蒸餾塔塔 頂部之傾析器將水層與有機層加以分離，並將水層移除至 Ο 系統外，同時將有機層回流至蒸餾塔塔頂部，同時進行酯 化反應，在進行所獲得之酯化反應粗液之蒸餾精製時，則 從蒸餾塔塔頂部移除低沸點成份後，加以回流並以在塔頂 部濃縮殘餘之低沸點成份的狀態下，從蒸餾塔側流管線餾 出酯系溶劑。 本發明又提供一種酯系溶劑之製造方法，其係將醇與 羧酸在酸觸媒之存在下進行酯化反應所獲得之酯化反應粗 液使用蒸餾塔加以蒸餾精製之酯系溶劑之製造方法，而將 ® 該反應粗液不實施中和處理即供應至蒸餾精製，餾去低沸 點成份後，從設置於蒸餾塔中間部份之側流管線餾出鈉含 量爲2重量ppb以下之酯系溶劑。 本發明更進一步提供一種包含鈉含量爲2重量ppb以 下之酯系溶劑之電子材料製造用溶劑組成物。 本發明又提供一種選自醋酸環己醇酯、1，3-二乙醯氧基 丁烷（亦即，二醋酸1，3 -丁二醇酯）、醋酸二丙二醇甲基 醚酯、二醋酸丙二醇酯、1,6-二乙醯氧基己烷（亦即，二醋 200940499 ' 酸1，6-己二醇酯），鈉含量爲2重量ppb以下，且酸份爲 0.008重量％以下之酯系溶劑。 〔發明之功效〕 若根據本發明，由於未實施酯化反應粗液之中和處理 ’在酯系溶劑中不至於發生由於中和處理的鈉等之鹼金屬 之混入。因此，可獲得鈉等之鹼金屬含量爲極少之酯系溶 劑。而且，經餾去酯化反應粗液中之低沸點成份後，則以 側流餾出製品，因此在蒸餾精製後之酯系溶劑中之酸份極 ® 少。 此外’由於未實施中和處理，精製作業簡易，可有效 率地製造鈉等之鹼金屬或酸成份等之雜質含量爲極少之酯 系溶劑。 【實施方式】 〔本發明之最佳實施形態〕 〔酯系溶劑之製造方法〕[Technical Field] The present invention relates to high-purity materials used for semiconductor materials such as semiconductor photoresists, color resists, and ink jet inks for LCDs (liquid crystal display devices). A high boiling point ester solvent and a method for producing the same. [Prior Art] The production of an ester solvent using a dehydration reaction of an alcohol and an acid is usually carried out in the presence of an acid catalyst, and in order to produce a high-purity ester solvent, φ is usually purified by distillation after completion of the reaction. However, in the case of a high-boiling ester, an increase in acidity caused by thermal deterioration (thermal decomposition of an ester, etc.) at the time of distillation becomes a problem. In the system in which the acid catalyst is present, the thermal decomposition of the product is remarkable. If it is desired to efficiently produce a high-purity ester solvent, the acid catalyst before distillation must be removed. In the prior art method of removing the acid catalyst, a method of neutralizing with an alkali metal hydroxide or the like is generally used (for example, cited Document 1). However, these methods have the concern that the alkali metal component used for neutralization will be incorporated into the article. Therefore, in order to use as a solvent for electronic materials such as semiconductor photoresist, color photoresist φ, and inkjet ink for LCD, it is necessary to manage metal content at a ppb (billionth fraction) level. As a result, previous purification methods do not adequately correspond to the requirements for reducing metal content or acidity required for use in electronic materials. (Patent Document 1) Japanese Laid-Open Patent Publication No. 5-112489. SUMMARY OF THE INVENTION [Technical Problem to be Solved] An object of the present invention is to provide an alkali metal having a low content of sodium and the like which is also usable in the field of electronic materials 200940499 requiring high purity quality, and an extremely low-boiling ester system. Solvents, and their efficient industrial manufacturing methods. [Technical method for solving the problem] The inventors of the present invention have found through intensive studies to solve the above-mentioned technical problems that even if the esterification reaction crude is not subjected to neutralization treatment before distillation, By distilling off the low-boiling component, the ester-based solvent is distilled off from the side-cut line of the distillation column, in particular by concentrating the low-boiling acid fraction at the top of the column by refluxing during distillation. In this state, the product is distilled off by a side-cut method, whereby an extremely low acid product can be obtained, and since neutralization treatment is not performed, the prior neutralization can be eliminated. In the production method of the treatment process, an alkali metal such as sodium is mixed, and thus the present invention can be obtained by obtaining a high-boiling ester solvent having an alkali metal content and an extremely low acidity and a high purity. That is, the present invention provides a method for producing an ester solvent which is obtained by esterification of an alcohol with a carboxylic acid in the presence of an acid catalyst. The esterification reaction crude solution is distilled and purified using a distillation column. In the production method of the solvent, the crude reaction liquid is supplied to the distillation purification without performing the neutralization treatment, and the low-boiling point component is distilled off, and then the ester-based solvent is distilled off from the side stream line provided in the intermediate portion of the distillation column. The ester solvent which can be produced according to the production method of the present invention includes an ester solvent having a boiling point of from 120 to 300 ° C under normal pressure. In the method for producing an ester solvent of the present invention, the "alcohol" used as a raw material includes, for example, cyclohexanol, 1,3-butanediol, dipropylene glycol-200940499 methyl ether, propylene glycol, 1,6. - hexanediol or the like; the carboxylic acid system is exemplified by acetic acid. The method for producing an ester solvent of the present invention is carried out by the following steps. For example, a distillation still including a reaction between an alcohol and a carboxylic acid, a distillation column connected to the distillation still, a side flow line provided in a middle portion of the distillation column, and a top portion of the distillation column are connected In a decanter and an apparatus for adjusting the pressure of the top of the distillation column, in the reaction of the alcohol with the carboxylic acid, the water layer and the organic layer are separated by a decanter attached to the top of the distillation column. Separating and removing the aqueous layer to the outside of the system, and returning the organic layer to the top of the distillation column while performing the esterification reaction. When the distillation of the obtained esterification reaction is carried out, the distillation column is removed from the distillation column. After removing the low-boiling point component at the top of the column, the mixture was refluxed, and the ester solvent was distilled off from the side stream line of the distillation column while the residual low-boiling component was concentrated at the top of the column. Further, the present invention provides a process for producing an ester solvent which is obtained by subjecting an esterification reaction solution obtained by esterification reaction of an alcohol and a carboxylic acid in the presence of an acid catalyst to an ester solvent which is distilled and purified using a distillation column. In the method, the reaction crude liquid is supplied to the distillation refining without performing neutralization treatment, and after distilling off the low boiling point component, the ester having a sodium content of 2 wt ppb or less is distilled off from a side stream line disposed in the middle portion of the distillation column. Is a solvent. The present invention still further provides a solvent composition for producing an electronic material comprising an ester solvent having a sodium content of 2 wt ppb or less. The invention further provides a solvent selected from the group consisting of cyclohexyl acetate, 1,3-diethoxybutane (ie, 1,3 -butylene glycol diacetate), dipropylene glycol methyl ether acetate, diacetic acid Propylene glycol ester, 1,6-diethoxydecyl hexane (that is, diacetate 200940499 'acid 1,6-hexanediol ester), sodium content of 2 wt ppb or less, and acid component of 0.008 wt% or less Ester solvent. [Effect of the Invention] According to the present invention, the neutralization of the crude liquid such as sodium which is not neutralized by the neutralization treatment is not carried out in the esterification reaction. Therefore, an ester-based solvent having a very small alkali metal content such as sodium can be obtained. Further, after the low-boiling point component in the crude esterification reaction liquid is distilled off, the product is distilled off in a side stream, so that the acid fraction in the ester-based solvent after distillation purification is small. Further, since the neutralization treatment is not carried out, the purification operation is simple, and an ester-based solvent having an extremely low impurity content such as an alkali metal or an acid component such as sodium can be efficiently produced. [Embodiment] [Best Mode for Carrying Out the Invention] [Method for Producing Ester Solvent]
在下文中’則就本發明之酯系溶劑之製造方法視需要 ® 參閱圖式加以說明。第1圖係展示適合使用於本發明之酯 系溶劑製造方法之裝置（批式蒸餾裝置）之一實例示意圖 。若使用此等批式蒸餾裝置時，則可有效率地進行反應及 其之後的蒸餾精製。第1圖中，i係代表在內部可進行醇 與酸反應之蒸餾釜（在下文中，則稱爲「蒸餾釜」。），2 係代表蒸餾塔’ 3係代表真空裝置，4係代表傾析器，4-1 係代表傾析器內之水層，4-2係代表傾析器內之有機層。5 係代表栗’6及7係代表熱交換器（冷凝器）。圖中之A 200940499 至Η係分別代表管線。蒸餾釜1係以管線b與蒸餾塔2之 塔底部相連結。在蒸餾塔2之中段部則設置側流管線Η， 而在塔頂部則連結傾析器4及可用於調整蒸餾塔2內部之 壓力的真空裝置3。 〔酯化反應〕 在下文中，則以使用如第1圖所示之裝置（批式蒸餾 裝置）且以製造酯系溶劑之情形爲例，詳細地說明本發明 之酯系溶劑之製造方法。此外，在使用批式蒸餾裝置之情 Ο 形時’蒸餾塔2較佳爲使用理論段數爲5至50之蒸餾塔。 將作爲原料的醇、羧酸、及酸觸媒以及視需要將如後所述 之共沸溶劑等經由管線Α而供應至蒸餾釜1中進行酯化反 應。 如上所述之「醇」並無特殊的限制，其係包括··例如 ，環己醇、乙醇、丙醇、丁醇等之「脂肪族一醇類」；1，3-丁二醇、丙二醇、1，6-己二醇等之「脂肪族多元醇類」；乙 二醇一甲基醚、二甘醇一甲基醚、丙二醇一甲基醚、二丙 ® 二醇一甲基醚等之「二醇醚類」等。在此等之中，適合使 用在常壓下沸點爲120至3 00°C之醇，此等之醇係包括：例 如環己醇、1，3-丁二醇、二丙二醇一甲基醚、丙二醇、i，6_ 己二醇。 「羧酸」係包括：例如’甲酸、醋酸、丙酸、丁酸等 之「脂肪族飽和羧酸」；丙烯酸、甲基丙烯酸、巴豆酸等 之「脂肪族不飽和羧酸」：草酸、丙二酸、琥珀酸、戊二 酸、己二酸等之「多元羧酸」；苯甲酸、鄰苯二甲酸等之 200940499 ' 「芳香族羧酸」等。在此等之中，較佳爲使用醋酸、丙酸 、丁酸等之飽和脂肪族羧酸，特別是較佳爲醋酸。 此外，若採用環己醇作爲醇、採用醋酸作爲酸時，則 可獲得醋酸環己醇酯之酯系溶劑；若分別採用1,3-丁二醇 與醋酸時，則可獲得1,3-二乙醯氧基丁烷之酯系溶劑；若 分別採用二丙二醇一甲基醚與醋酸時，則可獲得醋酸二丙 二醇甲基醚酯之酯系溶劑；若分別採用丙二醇與醋酸時， 則可獲得二醋酸丙二醇酯之酯系溶劑；若分別採用1，6-己 〇 二醇與醋酸時，則可獲得1,6-二乙醯氧基己烷之酯系溶劑 〇 「酸觸媒」係可使用一般酯化反應所使用的習知或慣 用之任一種酸觸媒，雖然並無特殊的限制，但是可例示： 例如，硫酸等之「礦酸」：對-甲苯磺酸等之「有機酸（擴 酸）」；Bh等之「路以士酸」等。此外，在反應時，可添 加例如己烷、環己烷、苯、甲苯、二甲苯、醋酸丁醋、醋 酸異丁酯等之可與水共沸之成份（共沸溶劑）。 © 原料之混合比率並無特殊的限制，可適用—般使用醇 與羧酸之反應來製造酯系溶劑所使用的混合比率。例如， 酸係相對於醇約爲0.8至10倍莫耳，較佳爲可在約〇8至 5倍莫耳之範圍選擇。此外’酸觸媒之使用量係可例如相 對於酸爲在0.01至10重量％之範圍選擇。 反應溫度、壓力、時間等係並無特殊的限制，可根據 作爲原料的醇與酸之種類適當地設定。例如，原料醇使用 環己醇、1，3-丁二醇、二丙二醇一甲基醚、丙二醇、丨6_己 200940499 —醇等在常壓下之沸點爲120至300°C之醇，而原料酸係使 用醋酸時，則反應溫度較佳爲80至1801、反應時之壓力 爲1 kPa至常壓、反應時間爲約5至20小時。蒸餾鋈！係 使用可執行此等之溫度、壓力管理者即可。 此外’在進行反應時’則調整蒸飽塔2之塔頂部壓力 爲lkPa.A至常壓，較佳爲約40kPa.A(例如，35至45kPa.A 、特別是38至42 kPa.A) ’溫度爲80至20(TC，較佳爲 80至170 °C來進行。在酯化反應中飽出物係在第1圖中以 〇 虛線所表不之管線C中循環。在連結於蒸餾塔2之塔頂部 的傾析器4中，餾出液將被分離成含有由醋化反應進行所 產生之水的水層與由未反應原料及共沸溶劑所構成之有機 層。水層係由管線D抽取至系統外，同時有機層則以泵5 再度送至蒸餾塔2之塔頂部，以使有機層回流直至酯化反 應結束爲止。此外’根據水之形成停止，則可判斷爲酯化 反應爲已結束。 〔蒸餾精製〕 ® 在本發明雖然將經由如上述所獲得之酯化反應粗液不 實施中和處理即加以蒸餾精製來製造酯系溶劑，但是在蒸 餾塔2係在塔中段附近設置側流管線Η。設置側流管線Η 之位置係在除了塔頂部與塔底部以外的蒸餾塔2之中間部 份根據條件適當地設定，但是以理論段計則例如可設定爲 1/5至4/5，較佳爲1/4至3/4，特佳爲1/3至2/3。 在蒸餾精製時，首先則將殘留的未反應羧酸、未反應 醇及共沸溶劑等之低沸點成份，再加上在蒸餾中由於熱分 200940499 解等所產生的低沸點成份，從蒸餾塔2之塔頂部餾去。在 蒸飽精製時’蒸餾II 1之溫度及壓力係例如可分別在80至 180°C、1 kPa.A至常壓之範圍選擇。一般而言，在低沸點 成份中，沸點較低的成份（共沸溶劑、羧酸等）先餾出， 爾後沸點較髙的醇類餾出。因此，蒸餾開始初期係以低回 流比（reflux ratio)(例如，全餾出至5，較佳爲0.1至3 ’特佳爲0.2至1)進行蒸餾，而在醇類之餾出時，則提高 回流比（例如，0.5至20，較佳爲3至15，特佳爲8至12 Φ )進行蒸餾時，則可有效率地進行高精度蒸餾。此外，在 蒸餾精製時，則將蒸餾釜1內部溫度保持在特定溫度以下 (例如，180°C以下，較佳爲160°C以下，更佳爲15(TC以 下），且較佳爲以分段方式降低蒸餾塔2內部壓力。此外 ，所餾出的低沸點成份係可經由管線G移除，此外，可將 —部份以管線F回流至蒸餾塔2。 餾出酯化反應粗液中之大部份低沸點成份（例如，95 重量％以上，較佳爲99重量％以上）後，以回流濃縮殘留 e 於塔頂部之低沸點成份，並在此狀態下從設置於蒸餾塔之 中間部份的側流管線Η餾出酯系溶劑。在由側流管線Η餾 出酯系溶劑時，若殘留於蒸餾塔2的低沸點成份爲多時， 則有可能導致混入於酯系溶劑中之酸成份的量增加，使得 所獲得之酯系溶劑的純度不能達到吾所欲範圍之情況。此 外，殘留的低沸點成份之量過度減少是效率不佳，不利於 工業生產。 經餾出殘留醇，且酯化反應粗液中之低沸點成份濃度 -10- 200940499 達到如上所述之範圍時’則將殘留於酯化反應粗液中之低 沸點成份濃縮於蒸餾塔2塔頂部。此時之回流比較佳爲20 以上，更佳爲30以上，特佳爲全回流。在此狀態下，從側 流管線Η餾出經加以高度精製之酯系溶劑。此外，在側流 餾出時之分配比率（塔頂回流液量：側流液量）係例如在 10:1至1:5之範圍，較佳爲在5:1至1:3之範圍，特佳爲在 3:1至1:2之範圍中選擇。若分配比率係大於10:1時，則生 產效率降低、加熱蒸汽量增加，使得成本變高。若分配比 φ 率係小於1:5時，則製品品質（特別是酸份）易降低。此 外，從側流管線獲得高純度之酯系溶劑後，則可經由管線 I來移除殘留於蒸餾釜1之殘留份。 將藉由如上所述方式所獲得之酯系溶劑，亦即，藉由 將醇與羧酸在酸觸媒之存在下進行酯化反應所獲得之酯化 反應粗液，不實施中和處理即供應至蒸餾塔進行蒸餾精製 ，餾去低沸點成份後，從設置於蒸餾塔之中間部份的側流 管線餾出所獲得之酯系溶劑係鹼金屬含量爲2重量ppb以 © 下，特別是藉由調整塔底部之溫度或分配比率，則可將鹼 金屬含量控制在1重量PPb以下。此外’酸之含量則爲〇.〇1 重量％以下之極其微量，此爲與經由包括中和步驟之方法所 精製獲得之結果爲相同的水準。特別是在製造常壓沸點爲 220至250°C之1,3 -二乙醯氧基丁烷等之酯系溶劑時’該醋 系溶劑之酸份則爲0.005重量％以下；在製造醋酸環己醇醋 、醋酸二丙二醇甲基醚酯、二醋酸丙二醇酯等之常壓沸點 爲22(TC以下之酯系溶劑時，該酯系溶劑之酸份則爲0·001 200940499 ' 重量％以下。此外，本發明之酯系溶劑之製造方法係特 合於製造酯系溶劑之沸點爲高於作爲原料的醇之沸點 酸之沸點者。 〔電子材料製造用溶劑組成物〕 根據本發明所製造之酯系溶劑、及含有其作爲構 份之本發明之電子材料製造用溶劑組成物係適合用作 導體光阻、彩色光阻、彩色濾光片用噴墨式印墨、外 用樹脂組成物、光感應間隙材（photospacer )用光阻 〇 圖案用光阻等要求高品質之電子材料製造用溶劑，特 適合用作爲必須控制鈉等之金屬份爲1重量ppb以下 其微量的半導體光阻用溶劑。此外，本發明之電子材 造用溶劑組成物係視需要也可含有如上所述之酯系溶 外之溶劑。 《實施例》 在下文中，則以實施例更具體地說明本發明，但 發明並不受限於此等實施例。 Θ 在實施例1至5及比較例1至10係使用如第1圖 之批式蒸餾裝置來實施脫水酯化反應及精餾。此外， 塔之理論段數爲10段，側流管線之位置係以理論段計 從塔底起之第6段部位。 〔實施例1〕 將100重量份之環己醇、66重量份之醋酸、2重 之對-甲苯磺酸一水合物 （p-toluenesulfonic monohydrate) 、19重量份之醋酸異丁酯飼入蒸餾釜中 別適 及羧 成成 爲半 護膜 、VA 別是 之極 料製 劑以 是本 所示 蒸餾 則爲 量份 acid 。將 -12- 200940499 • 蒸餾塔塔頂部壓力減壓爲40 kPa.A，進行全回流。在餾出 液中開始產生水時，則將餾出液以傾析器加以液-液分離。 將有機層回流至塔頂部，水層則抽取至系統外。以水停止 產生時視爲脫水酯化反應結束，藉此則可獲得反應粗液。 將該反應粗液原封不動地以第1圖之裝置實施批式蒸 餾。從塔頂將醋酸異丁酯及醋酸加以蒸餾分離。此時，設 定回流比爲0.5，蒸餾釜溫度上限爲150°C，並以分段方式 將塔頂部壓力降低至2.7 kPa.A。 φ 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除環己醇。移除環己醇後，將塔頂部設定 爲全回流，並從側流管線餾出醋酸環己醇酯。此時，分配 比率（塔頂回流液量：側流液量）係設定爲3 : 2。 〔實施例2〕 將100重量份之1,3-丁二醇、147重量份之醋酸、4重 量份之對-甲苯磺酸一水合物、28重量份之醋酸異丁酯飼入 蒸餾釜中。將蒸餾塔塔頂部壓力減壓爲40 kPa.A，進行全 φ 回流。在餾出液中開始產生水時，則將餾出液以傾析器加 以液-液分離。將有機層回流至塔頂部，水層則抽取至系統 外。以水停止產生時視爲脫水酯化反應結束，藉此則可獲 得反應粗液。 將該反應粗液原封不動地以第1圖之裝置實施批式蒸 餾。從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此時，則 設定回流比爲0.5，蒸餾釜溫度上限爲150°C，並以分段方 式將塔頂部壓力降低至2.7 kPa.A。 200940499 餾出液中之醋酸異丁酯及醋酸濃度降低後 流比爲10，以移除1，3-丁二醇及一醋酸1,3-丁 除1，3-丁二醇及一醋酸1，3-丁二醇酯後，將塔 全回流，並從側流管線餾出1,3-二乙醯氧基丁 分配比率（塔頂回流液量：側流液量）係設定 〔實施例3〕 將100重量份之二丙二醇一甲基醚、45重 、1重量份之對-甲苯磺酸一水合物、16重量份 〇 酯飼入蒸餾釜中。將蒸餾塔塔頂部壓力減壓爲 進行全回流。在餾出液中開始產生水時，則將 析器加以液-液分離。將有機層回流至塔頂部， 至系統外。以水停止產生時視爲脫水酯化反應 則可獲得反應粗液。 將該反應粗液原封不動地以第1圖之裝置 餾。從塔頂將醋酸異丁酯及醋酸加以蒸餾分離 定回流比爲0.5，蒸餾釜溫度上限爲15(TC，並 Φ 將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後 流比爲10，以移除二丙二醇一甲基醚》移除二 基醚後’將塔頂部設定爲全回流，並從液相側 醋酸二丙二醇甲基醚酯。此時，分配比率（塔 :側流液量）係設定爲3:2。 〔實施例4〕 將100重量份之丙二醇、174重量份之醋面 ，則設定回 二醇酯。移 頂部設定爲 烷。此時， 爲 3 : 2。 量份之醋酸 之醋酸異丁 40 kPa.A * 餾出液以傾 水層則抽取 結束，藉此 實施批式蒸 。此時，設 以分段方式 ，則設定回 丙二醇一甲 流管線餾出 頂回流液量 ' 5重量份 -14- 200940499 * 之對-甲苯磺酸一水合物、31重量份之醋酸異丁酯飼 釜中。將蒸餾塔塔頂部壓力減壓爲40 kPa.A，進行 。在餾出液中開始產生水時，則將餾出液以傾析器文 液分離。將有機層回流至塔頂部，水層則抽取至系 以水停止產生時視爲脫水酯化反應結束，藉此則可 應粗液。 將該反應粗液原封不動地以第1圖之裝置實施 餾。從塔頂將醋酸異丁酯及醋酸加以蒸餾分離。此 Ο 定回流比爲0.5，蒸餾釜溫度上限爲150°c，並以分 將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則 流比爲10，以移除丙二醇及一醋酸丙二醇酯。移除 及一醋酸丙二醇酯後，將塔頂部設定爲全回流，並 管線餾出二醋酸丙二醇酯。此時，分配比率（塔頂 量：側流液量）係設定爲3 : 2。 〔實施例5〕 ® 將1〇〇重量份之1,6-己二醇、112重量份之醋麼 量份之對-甲苯磺酸一水合物、24重量份之醋酸異丁 蒸餾釜中。將蒸餾塔塔頂部壓力減壓爲40 kPa.A， 回流。在餾出液中開始產生水時，則將餾出液以傾 以液-液分離。將有機層回流至塔頂部，水層則抽取 外。以水停止產生時視爲脫水酯化反應結束，藉此 得反應粗液》 將該反應粗液原封不動地以第1圖之裝置實施 入蒸餾 全回流 口以液-統外。 獲得反 批式蒸 時，設 段方式 設定回 丙二醇 從側流 回流液 :、3重 酯飼入 進行全 析器加 至系統 則可獲 批式蒸 -15- 200940499 • 餾。從塔頂將醋酸異丁酯及醋酸加以蒸餾分離。此時’設 定回流比爲0.5，蒸餾釜溫度上限爲165°C ’並以分段方式 將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後’則設定回 流比爲10，以移除1，6-己二醇及一醋酸U6-己二醇酯。移 除1，6-己二醇及一醋酸1，6-己二醇酯後’將塔頂部設定爲 全回流，並從液相側流管線餾出1,6-二乙醯氧基己烷（亦 即，二醋酸1,6 -己二醇酯）。此時’分配比率（塔頂回流 〇 液量：側流液量）係設定爲3 :2。 〔比較例1〕 將以與實施例1相同的方式所合成之反應粗液移液至 與第1圖所示之批式蒸餾裝置另外設置之攪拌槽，並投入 0.6重量份之苛性鈉片（caustic soda flake)。然後，攪拌 5小時，以中和酸觸媒。 將中和完畢後之反應粗液再度移液至第1圖之批式蒸 餾裝置，並實施批式蒸餾。將蒸餾塔塔頂部壓力減壓爲40 © kPa.A，進行全回流。等待塔內在全回流狀態下穩定後，變 更回流比，從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此 時，則設定回流比爲0.5，蒸餾釜溫度上限爲150°C，並以 分段方式將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除環己醇。移除環己醇後’設定回流比爲 0.5，並從塔頂餾出醋酸環己醇酯。 〔比較例2〕 -16- 200940499 ' 將以與實施例2相同的方式所合成之反應粗液移液至 與第1圖所示之批式蒸餾裝置另外設置之攪拌槽，並投入 1.3重量份之苛性鈉片。然後，攪拌5小時’以中和酸觸媒 〇 將中和完畢後之反應粗液再度移液至第1圖之批式蒸 餾裝置，並實施批式蒸餾。將蒸餾塔塔頂部壓力減壓爲40 kPa.A，進行全回流。等待塔內在全回流狀態下穩定後，變 更回流比，從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此 φ 時，則設定回流比爲0.5，蒸餾釜溫度上限爲150°C ’並以 分段方式將塔頂部壓力降低至2.7 kPa·A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除1,3-丁二醇及一醋酸1，3-丁二醇酯。移 除1，3-丁二醇及一醋酸1,3-丁二醇酯後，則設定回流比爲 0.5，並從塔頂餾出1,3-二乙醯氧基丁烷。 〔比較例3〕 將以與實施例3相同的方式所合成之反應粗液移液至 〇 與第1圖所示之批式蒸餾裝置另外設置之攪拌槽，並投入 0.4重量份之苛性鈉片。然後，攪拌5小時，以中和酸觸媒 〇 將中和完畢後之反應粗液再度移液至第1圖之批式蒸 餾裝置，並實施批式蒸餾。將蒸餾塔塔頂部壓力減壓爲40 kPa. A，進行全回流。等待塔內在全回流狀態下穩定後，變 更回流比，從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此 時，則設定回流比爲〇. 5，蒸餾釜溫度上限爲1 5 0 °C ’並以 -17- .200940499 * 分段方式將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除二丙二醇一甲基醚。移除二丙二醇一甲 基醚後，則設定回流比爲0.5，並從塔頂餾出醋酸二丙二醇 甲基醚酯。 〔比較例4〕 將以與實施例4相同的方式所合成之反應粗液移液至 與第1圖所示之批式蒸餾裝置另外設置之攪拌槽，並投入 〇 1.6重量份之苛性鈉片。然後，攪拌5小時，以中和酸觸媒 〇 將中和完畢後之反應粗液再度移液至第1圖之批式蒸 餾裝置，並實施批式蒸餾。將蒸餾塔塔頂部壓力減壓爲40 kPa. A，進行全回流。等待塔內在全回流狀態下穩定後，變 更回流比，從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此 時，則設定回流比爲0.5，蒸餾釜溫度上限爲15(TC，並以 分段方式將塔頂部壓力降低至2.7 kPa.A。 © 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除丙二醇及一醋酸丙二醇酯。移除丙二醇 及一醋酸丙二醇酯後，則設定回流比爲0.5，並從塔頂餾出 二醋酸丙二醇酯。 〔比較例5〕 將以與實施例5相同的方式所合成之反應粗液移液至 與第1圖所示之批式蒸餾裝置另外設置之攪拌槽，並投入 1重量份之苛性鈉片。然後，攪拌5小時，以中和酸觸媒 -18- 200940499 將中和完畢後之反應粗液再度移液至第1圖之批式蒸 餾裝置，並實施批式蒸餾。將蒸餾塔塔頂部壓力減壓爲40 kPa.A，進行全回流。等待塔內在全回流狀態下穩定後，變 更回流比，從塔頂將醋酸異丁酯、醋酸加以蒸餾分離。此 時，則設定回流比爲0.5，蒸餾釜溫度上限爲165°C，並以 分段方式將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 〇 流比爲10，以移除1,6-己二醇及一醋酸1,6-己二醇酯。移 除1,6-己二醇及一醋酸1,6-己二醇酯後，則設定回流比爲 0.5，並從塔頂餾出1,6-二乙醯氧基己烷。 〔比較例6〕 將以與實施例1相同的方式所合成之反應粗液原封不 '動地以第1圖之裝置實施批式蒸餾。從塔頂將醋酸異丁酯 、醋酸加以蒸餾分離。此時，則設定回流比爲0.5，蒸餾釜 溫度上限爲150°C，並以分段方式將塔頂部壓力降低至2.7 kPa.A。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除環己醇。移除環己醇後，則設定回流比 爲0.5，並從塔頂餾出醋酸環己醇酯。 〔比較例7〕 將以與實施例2相同的方式所合成之反應粗液原封不 動地以第1圖之裝置實施批式蒸餾。從塔頂將醋酸異丁酯 、醋酸加以蒸餾分離。此時’則設定回流比爲0.5，蒸餾釜 -19- 200940499 ' 溫度上限爲150°C，並以分段方式將塔頂部壓力降低至2.7 kPa.A 。 餾出液中之醋酸異丁酯及醋酸濃度降低後’則設定回 流比爲10，以移除1,3 -丁二醇及一醋酸1，3 -丁二醇酯。移 除1,3 -丁二醇及一醋酸1，3· 丁二醇酯後，則設定回流比爲 0.5，並從塔頂餾出1，3-二乙醯氧基丁烷。 〔比較例8〕 將以與實施例3相同的方式所合成之反應粗液原封不 e 動地以第1圖之裝置實施批式蒸餾。從塔頂將醋酸異丁酯 、醋酸加以蒸餾分離。此時，則設定回流比爲0.5，蒸餾釜 溫度上限爲150°C，並以分段方式將塔頂部壓力降低至2.7 kPa.A 。 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除二丙二醇一甲基醚。移除二丙二醇一甲 基醚後，則設定回流比爲0.5,並從塔頂餾出醋酸二丙二醇 甲基醚酯。 © 〔比較例9〕 將以與實施例4相同的方式所合成之反應粗液原封不 動地以第1圖之裝置實施批式蒸餾。從塔頂將醋酸異丁酯 、醋酸加以蒸餾分離。此時，則設定回流比爲0.5，蒸餾釜 溫度上限爲150°C，並以分段方式將塔頂部壓力降低至2.7 kPa.A。 飽出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除丙二醇及一醋酸丙二醇酯。移除丙二醇 -20- 200940499 ' 及一醋酸丙二醇酯後，則設定回流比爲0.5,並從塔頂餾出 二醋酸丙二醇酯。 〔比較例10〕 將以與實施例5相同的方式所合成之反應粗液原封不 動地以第1圖之裝置實施批式蒸餾。從塔頂將醋酸異丁酯 、醋酸加以蒸餾分離。此時，則設定回流比爲0.5，蒸餾釜 溫度上限爲165 °C，並以分段方式將塔頂部壓力降低至2.7 kPa.A 〇 餾出液中之醋酸異丁酯及醋酸濃度降低後，則設定回 流比爲10，以移除1,6-己二醇及一醋酸1,6-己二醇酯。移 除1，6-己二醇及一醋酸1,6-己二醇酯後，則設定回流比爲 0.5，並從塔頂餾出1,6-二乙醯氧基己烷。 將藉由實施例及比較例所獲得之製品（酯系溶劑）之 Na含量及酸份以如下所述之方法測定。其結果係如表丨所 示。 (Na含量測定方法） © 使用ICP-MS ( Agilent HP-7500型）以標準添加法實施測定 〇 標準混合液係以異丙基醇（和光純藥工業股份有 司（Wako Pure Chemical Industries, Ltd.)電子材料用）將 SPEX公司製造之XSTC-22100ppm (含有23元素）稀釋爲 100倍來使用。 (酸份測定方法） 根據JIS K1 5 14之3.10準則進行測定。 -21- 200940499 表1Hereinafter, the method for producing the ester solvent of the present invention will be described with reference to the drawings as needed. Fig. 1 is a view showing an example of an apparatus (batch distillation apparatus) suitable for use in the method for producing an ester solvent of the present invention. When such a batch distillation apparatus is used, the reaction can be efficiently carried out and the subsequent purification can be carried out. In Fig. 1, i represents a distillation still in which an alcohol and an acid are reacted internally (hereinafter, referred to as "distillation"), and 2 represents a distillation column '3 is a vacuum device, and 4 is a decantation. The 4-1 series represents the water layer in the decanter, and the 4-2 series represents the organic layer in the decanter. The 5 series represents the pumps '6 and 7' represent the heat exchanger (condenser). In the figure, A 200940499 to the line represent the pipeline. The still 1 is connected to the bottom of the column of the distillation column 2 by a line b. A side stream line Η is provided in the middle portion of the distillation column 2, and a decanter 4 and a vacuum unit 3 which can be used to adjust the pressure inside the distillation column 2 are connected at the top of the column. [Esterification reaction] Hereinafter, a method for producing the ester solvent of the present invention will be described in detail by using a device (batch distillation apparatus) as shown in Fig. 1 and producing an ester solvent. Further, in the case of using a batch distillation apparatus, the distillation column 2 is preferably a distillation column having a theoretical number of 5 to 50. An alcohol, a carboxylic acid, and an acid catalyst as raw materials, and, if necessary, an azeotropic solvent or the like as described later are supplied to the distillation still 1 via a line to carry out an esterification reaction. The "alcohol" as described above is not particularly limited, and includes, for example, "aliphatic alcohols" such as cyclohexanol, ethanol, propanol, butanol, etc.; 1,3-butanediol, propylene glycol , "aliphatic polyols" such as 1,6-hexanediol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc. "Glycol ethers" and the like. Among these, it is suitable to use an alcohol having a boiling point of 120 to 300 ° C at normal pressure, and such alcohols include, for example, cyclohexanol, 1,3-butylene glycol, dipropylene glycol monomethyl ether, Propylene glycol, i, 6-hexanediol. The "carboxylic acid" includes, for example, "aliphatic saturated carboxylic acid" such as 'formic acid, acetic acid, propionic acid, butyric acid, and the like; "aliphatic unsaturated carboxylic acid" such as acrylic acid, methacrylic acid or crotonic acid: oxalic acid, C "Polycarboxylic acid" such as diacid, succinic acid, glutaric acid or adipic acid; 200940499 '"aromatic carboxylic acid" such as benzoic acid or phthalic acid. Among these, a saturated aliphatic carboxylic acid such as acetic acid, propionic acid or butyric acid is preferably used, and particularly preferably acetic acid. Further, when cyclohexanol is used as the alcohol and acetic acid is used as the acid, an ester solvent of cyclohexyl acetate can be obtained; if 1,3-butanediol and acetic acid are used, respectively, 1,3- An ester solvent of diethyl ethoxybutane; if dipropylene glycol monomethyl ether and acetic acid are used respectively, an ester solvent of dipropylene glycol methyl ether acetate can be obtained; if propylene glycol and acetic acid are used respectively, Obtaining an ester solvent of propylene glycol diacetate; if 1,6-hexanediol and acetic acid are used, respectively, an ester solvent of 1,6-diethoxymethoxyhexane can be obtained, and an "acid catalyst" system can be obtained. Any of the conventional or conventional acid catalysts used in the general esterification reaction may be used, and although it is not particularly limited, for example, "mineral acid" such as sulfuric acid: p-toluenesulfonic acid or the like "organic Acid (expanding acid); Bh et al. Further, at the time of the reaction, a component (azeotropic solvent) which can be azeotroped with water, such as hexane, cyclohexane, benzene, toluene, xylene, butyl acetate or isobutyl acetate, may be added. © The mixing ratio of the raw materials is not particularly limited, and the mixing ratio used for the ester solvent can be generally used by reacting an alcohol with a carboxylic acid. For example, the acid is about 0.8 to 10 moles relative to the alcohol, preferably from about 8 to 5 moles. Further, the amount of the acid catalyst used can be selected, for example, in the range of 0.01 to 10% by weight based on the acid. The reaction temperature, pressure, time, and the like are not particularly limited, and can be appropriately set depending on the type of the alcohol and the acid as the raw materials. For example, the raw material alcohol is an alcohol having a boiling point of 120 to 300 ° C under normal pressure using cyclohexanol, 1,3-butylene glycol, dipropylene glycol monomethyl ether, propylene glycol, 丨6_hex 200940499-alcohol, and the like. When the raw material acid is acetic acid, the reaction temperature is preferably from 80 to 1801, the pressure at the time of the reaction is from 1 kPa to the normal pressure, and the reaction time is from about 5 to 20 hours. Distillation! Use a temperature and pressure manager that can perform such a process. Further, when the reaction is carried out, the pressure at the top of the column of the steaming tower 2 is adjusted from 1 kPa.A to atmospheric pressure, preferably about 40 kPa.A (for example, 35 to 45 kPa.A, especially 38 to 42 kPa.A). 'The temperature is 80 to 20 (TC, preferably 80 to 170 ° C.) In the esterification reaction, the saturated system is circulated in the line C which is indicated by the dashed line in Fig. 1. It is connected to the distillation column. In the decanter 4 at the top of the tower, the distillate is separated into an aqueous layer containing water produced by the acetification reaction and an organic layer composed of unreacted raw materials and an azeotropic solvent. The line D is taken out of the system, and the organic layer is again sent to the top of the column of the distillation column 2 by the pump 5, so that the organic layer is refluxed until the end of the esterification reaction. Further, 'the esterification can be judged as esterification according to the formation of water. [Distillation and Purification] In the present invention, the esterification reaction crude solution obtained by the above-described above is subjected to a neutralization treatment, that is, it is subjected to distillation purification to produce an ester solvent, but the distillation column 2 is in the middle of the column. The side flow line Η is set nearby. The position of the side flow line Η is set in addition to the tower. The intermediate portion of the distillation column 2 other than the bottom portion of the column is appropriately set depending on the conditions, but may be set to, for example, 1/5 to 4/5, preferably 1/4 to 3/4, in a theoretical range, which is particularly preferable. It is 1/3 to 2/3. In the distillation purification, first, the low-boiling components such as residual unreacted carboxylic acid, unreacted alcohol, and azeotropic solvent are added, and in the distillation, the heat is divided into 200940499. The resulting low-boiling component is distilled off from the top of the distillation column 2. The temperature and pressure system of the distillation II 1 can be selected, for example, in the range of 80 to 180 ° C, 1 kPa. A to atmospheric pressure, respectively. In general, among the low-boiling components, the components having a lower boiling point (azeotropic solvent, carboxylic acid, etc.) are first distilled off, and then the boiling point of the alcohol is distilled off. Therefore, the distillation is started at a low reflux ratio ( The reflux ratio (for example, total distillation to 5, preferably 0.1 to 3' is preferably 0.2 to 1) for distillation, and in the case of distillation of the alcohol, the reflux ratio is increased (for example, 0.5 to 20, When it is distilled from 3 to 15 and particularly preferably from 8 to 12 Φ), high-precision distillation can be efficiently performed. And maintaining the internal temperature of the still 1 below a specific temperature (for example, 180 ° C or less, preferably 160 ° C or less, more preferably 15 (TC or less), and preferably reducing the distillation column 2 in a sectional manner. The internal pressure. In addition, the distilled low-boiling component can be removed via line G. In addition, the portion can be refluxed to the distillation column 2 in line F. Distillation of most of the low boiling point in the crude esterification reaction After the component (for example, 95% by weight or more, preferably 99% by weight or more), the low-boiling component of the residual e at the top of the column is concentrated by reflux, and in this state, from the side flow line provided in the middle portion of the distillation column The ester solvent was distilled off. When the ester solvent is distilled off from the side stream line, if the low boiling point component remaining in the distillation column 2 is large, the amount of the acid component mixed in the ester solvent may increase, so that the obtained ester system is obtained. The purity of the solvent does not reach the range we want. In addition, excessive reduction of the amount of residual low-boiling components is inefficient and is not conducive to industrial production. When the residual alcohol is distilled off, and the concentration of the low-boiling component in the crude esterification reaction is -10 to 40,940,499, when the range as described above is reached, the low-boiling component remaining in the crude esterification reaction liquid is concentrated in the distillation tower 2 tower. top. The reflux at this time is preferably 20 or more, more preferably 30 or more, and particularly preferably full reflux. In this state, the highly purified ester solvent is distilled from the side stream. Further, the distribution ratio (the amount of overhead reflux liquid: the amount of side fluid) in the side stream distillation is, for example, in the range of 10:1 to 1:5, preferably in the range of 5:1 to 1:3. It is especially suitable for the range of 3:1 to 1:2. If the distribution ratio is more than 10:1, the production efficiency is lowered and the amount of heating steam is increased, so that the cost becomes high. If the distribution ratio φ ratio is less than 1:5, the product quality (especially the acid portion) is liable to lower. Further, after obtaining a high-purity ester solvent from the side stream line, the residual portion remaining in the distillation pot 1 can be removed via the line I. The ester-based solvent obtained as described above, that is, the crude esterification reaction obtained by esterification reaction of an alcohol with a carboxylic acid in the presence of an acid catalyst, is not subjected to neutralization treatment. After being supplied to a distillation column for distillation and purification, and distilling off the low-boiling point component, the ester-based solvent obtained by distilling off the side stream line provided in the middle portion of the distillation column has an alkali metal content of 2 wt ppb, especially borrowed The alkali metal content can be controlled to be less than 1 wt. PPb by adjusting the temperature or distribution ratio at the bottom of the column. Further, the 'acid content is an extremely small amount of 〇. 〇1% by weight or less, which is the same level as that obtained by the method of purification including the neutralization step. In particular, when an ester solvent such as 1,3-diethoxy oxybutane having a boiling point of 220 to 250 ° C is produced, the acid portion of the vinegar solvent is 0.005% by weight or less; When the normal pressure boiling point of hexanol vinegar, dipropylene glycol methyl ether acetate or propylene glycol diacetate is 22 (TC or less), the acid content of the ester solvent is 0.001 200940499 '% by weight or less. In addition, the method for producing the ester solvent of the present invention is specific to the boiling point of the boiling point acid of the alcohol as the raw material for producing the ester solvent. [Solvent composition for producing an electronic material] According to the present invention The ester solvent and the solvent composition for producing an electronic material of the present invention containing the component thereof are suitable for use as a conductor photoresist, a color resist, an ink jet ink for a color filter, a resin composition for external use, and light. In the case of a photoresist for a photo-resistance, a high-quality solvent for producing an electronic material is required, and it is particularly suitable as a solvent for semiconductor photoresist which has a metal component of 1 wt ppb or less. In addition The solvent composition for producing an electronic material of the present invention may contain an ester-based solvent as described above as needed. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not It is limited to these examples. Θ In Examples 1 to 5 and Comparative Examples 1 to 10, the dehydration esterification reaction and rectification were carried out using the batch distillation apparatus as shown in Fig. 1. In addition, the theoretical number of stages of the column was 10 In the section, the position of the side stream line is the sixth stage from the bottom of the column in the theoretical section. [Example 1] 100 parts by weight of cyclohexanol, 66 parts by weight of acetic acid, and 2 parts of p-toluenesulfonic acid. A monohydrate (p-toluenesulfonic monohydrate), 19 parts by weight of isobutyl acetate fed to a distillation pot, and a carboxylate to form a semi-film, VA is a very high-volume preparation. Acid -12- 200940499 • The pressure at the top of the distillation column is reduced to 40 kPa.A, and total reflux is carried out. When water is started to be produced in the distillate, the distillate is separated into a liquid-liquid by a decanter. The organic layer was refluxed to the top of the column and the aqueous layer was extracted outside the system. When the water is stopped, it is regarded as the end of the dehydration esterification reaction, whereby the reaction crude liquid can be obtained. The crude reaction liquid is subjected to batch distillation in the apparatus of Fig. 1 as it is. The isobutyl acetate and the acetic acid are topped from the top of the column. Distillation was carried out. At this time, the reflux ratio was set to 0.5, the upper limit of the distillation temperature was 150 ° C, and the pressure at the top of the column was reduced to 2.7 kPa.A in a segmented manner. φ Isobutyl acetate and acetic acid in the distillate After the concentration is lowered, the reflux ratio is set to 10 to remove cyclohexanol. After removing the cyclohexanol, the top of the column is set to total reflux, and the cyclohexyl acetate is distilled off from the side stream line. The ratio (the amount of reflux at the top of the column: the amount of side fluid) was set to 3:2. [Example 2] 100 parts by weight of 1,3-butylene glycol, 147 parts by weight of acetic acid, 4 parts by weight of p-toluenesulfonic acid monohydrate, and 28 parts by weight of isobutyl acetate were fed into a distillation still. . The pressure at the top of the distillation column was reduced to 40 kPa.A, and all φ was refluxed. When water is started to be produced in the distillate, the distillate is separated into a liquid-liquid by a decanter. The organic layer is refluxed to the top of the column and the aqueous layer is extracted outside the system. When the water is stopped, it is regarded as the end of the dehydration esterification reaction, whereby the reaction crude liquid can be obtained. The reaction crude liquid was subjected to batch distillation under the apparatus of Fig. 1 as it was. Isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 150 ° C, and the pressure at the top of the column was lowered to 2.7 kPa.A in a stepwise manner. 200940499 Distillate in the dibutyl acetate and acetic acid concentration decreased after the flow ratio of 10 to remove 1,3-butanediol and 1,3-butane 1,3-butane 1,3-butanediol and acetic acid 1 After the 3-butanediol ester, the column is completely refluxed, and the distribution ratio of the 1,3-diethoxylated butyl group is distilled off from the side stream line (the amount of the overhead reflux liquid: the amount of the side liquid) is set. 3] 100 parts by weight of dipropylene glycol monomethyl ether, 45 parts by weight, 1 part by weight of p-toluenesulfonic acid monohydrate, and 16 parts by weight of decyl ester were fed into a distillation pot. The pressure at the top of the distillation column was reduced to full reflux. When water is started to be produced in the distillate, the separator is liquid-liquid separated. The organic layer was refluxed to the top of the column to the outside of the system. When the water is stopped, it is regarded as a dehydration esterification reaction, and the reaction crude liquid can be obtained. The crude reaction solution was distilled as it is in the apparatus of Fig. 1 as it is. Isobutyl acetate and acetic acid were distilled from the top of the column to determine a reflux ratio of 0.5, and the upper limit of the distillation temperature was 15 (TC, and Φ reduced the pressure at the top of the column to 2.7 kPa. A. Isobutyl acetate in the distillate And after the acetic acid concentration is lowered, the flow ratio is 10 to remove the dipropylene glycol monomethyl ether. After removing the dialkyl ether, the top of the column is set to total reflux, and the dipropylene glycol methyl ether acetate is obtained from the liquid phase side. The distribution ratio (tower: side flow amount) was set to 3: 2. [Example 4] 100 parts by weight of propylene glycol and 174 parts by weight of vinegar surface were set to the glycol ester. The top of the shift was set to be an alkane. At this time, it is 3: 2. The acetic acid of acetic acid isobutyl 40 kPa. A * distillate is extracted with the pouring layer, and the batch steaming is carried out. At this time, the segmentation method is set. The amount of the top reflux liquid was distilled back to the propylene glycol-a-stream line, '5 parts by weight-14-200940499*, p-toluenesulfonic acid monohydrate, 31 parts by weight of isobutyl acetate, and the pressure at the top of the distillation column was reduced. The pressure is 40 kPa.A, and when the water starts to be produced in the distillate, the distillate is decanted. Separation of the liquid. The organic layer is refluxed to the top of the column, and the aqueous layer is extracted until the water is stopped. The dehydration and esterification reaction is considered to be completed, whereby the crude liquid can be used. The apparatus of the figure is subjected to distillation. The isobutyl acetate and acetic acid are separated and distilled from the top of the column. The reflux ratio is 0.5, the upper limit of the distillation temperature is 150 ° C, and the pressure at the top of the column is reduced to 2.7 kPa. After the concentration of isobutyl acetate and acetic acid in the distillate is lowered, the flow ratio is 10 to remove propylene glycol and propylene glycol acetate. After removing and propylene glycol acetate, the top of the column is set to full reflux, and The propylene glycol diacetate was distilled off from the line. At this time, the distribution ratio (top amount: side flow amount) was set to 3: 2. [Example 5] ® 1 part by weight of 1,6-hexanediol 112 parts by weight of vinegar in parts of p-toluenesulfonic acid monohydrate, 24 parts by weight in an isobutyl acetate still. The pressure at the top of the distillation column was reduced to 40 kPa. A, and refluxed. When water is started to be produced, the distillate is separated by liquid-liquid separation. The organic layer is returned. Flow to the top of the tower, the water layer is taken out. When the water stops, it is regarded as the end of the dehydration esterification reaction, thereby obtaining the reaction crude liquid. The reaction crude liquid is completely blocked by the apparatus of Fig. 1 into the distillation full reflux. When the anti-batch steaming is obtained, the propylene glycol is set back to the reflux liquid from the side stream, and the 3 heavy ester is fed to the system to obtain the full steamer to obtain the steaming -15- 200940499. The distillation was carried out by separating isobutyl acetate and acetic acid from the top of the column. At this time, 'the reflux ratio was set to 0.5, the upper limit of the distillation temperature was 165 ° C ' and the pressure at the top of the column was reduced to 2.7 kPa. After the isobutyl acetate and the acetic acid concentration in the distillate were lowered, the reflux ratio was set to 10 to remove 1,6-hexanediol and U6-hexanediol monoacetate. After removing 1,6-hexanediol and 1,6-hexanediol acetate, the top of the column was set to total reflux, and 1,6-diethoxycarbonylhexane was distilled off from the liquid phase side stream line. (ie, 1,6-hexanediol diacetate). At this time, the 'distribution ratio (the amount of overhead reflux 〇 liquid: the amount of side fluid) was set to 3:2. [Comparative Example 1] The reaction crude liquid synthesized in the same manner as in Example 1 was pipetted to a stirring tank separately provided from the batch distillation apparatus shown in Fig. 1, and 0.6 parts by weight of caustic soda tablets were charged. Caustic soda flake). Then, it was stirred for 5 hours to neutralize the acid catalyst. The crude reaction liquid after the completion of the neutralization was again pipetted to the batch distillation apparatus of Fig. 1, and batch distillation was carried out. The pressure at the top of the distillation column was reduced to 40 kPa.A, and total reflux was performed. After the column was stabilized under full reflux, the reflux ratio was changed, and isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 150 ° C, and the pressure at the top of the column was reduced to 2.7 kPa.A in a sectional manner. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, a reflux ratio of 10 was set to remove cyclohexanol. After the cyclohexanol was removed, the reflux ratio was set to 0.5, and cyclohexanol acetate was distilled off from the top. [Comparative Example 2] -16-200940499 ' The reaction crude liquid synthesized in the same manner as in Example 2 was pipetted to a stirring tank additionally provided in the batch distillation apparatus shown in Fig. 1, and 1.3 parts by weight was charged. Caustic sodium tablets. Then, the mixture was stirred for 5 hours to neutralize the acid catalyst. The crude reaction liquid after the completion of the neutralization was again pipetted to the batch distillation apparatus of Fig. 1, and batch distillation was carried out. The pressure at the top of the distillation column was reduced to 40 kPa.A, and total reflux was performed. After the column was stabilized under full reflux, the reflux ratio was changed, and isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this φ, the reflux ratio was set to 0.5, the upper limit of the still temperature was 150 °C', and the pressure at the top of the column was reduced to 2.7 kPa·A in a segmented manner. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, a reflux ratio of 10 was set to remove 1,3-butanediol and 1,3-butylene glycol acetate. After removing 1,3-butanediol and 1,3-butylene glycol acetate, the reflux ratio was set to 0.5, and 1,3-diethoxyoxybutane was distilled off from the top. [Comparative Example 3] The reaction crude liquid synthesized in the same manner as in Example 3 was pipetted to a stirring tank additionally provided in the batch distillation apparatus shown in Fig. 1, and 0.4 parts by weight of caustic soda tablets were charged. . Then, the mixture was stirred for 5 hours to neutralize the acid catalyst. The crude reaction liquid after the completion of the neutralization was again pipetted to the batch distillation apparatus of Fig. 1, and batch distillation was carried out. The pressure at the top of the distillation column was reduced to 40 kPa. A, and total reflux was performed. After the column was stabilized under full reflux, the reflux ratio was changed, and isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 〇. 5, the upper limit of the still temperature was 150 ° C ' and the pressure at the top of the column was reduced to 2.7 kPa.A in a -17-.200940499 * segmentation manner. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, a reflux ratio of 10 was set to remove dipropylene glycol monomethyl ether. After the dipropylene glycol monomethyl ether was removed, a reflux ratio of 0.5 was set, and dipropylene glycol methyl ether acetate was distilled off from the top. [Comparative Example 4] The reaction crude liquid synthesized in the same manner as in Example 4 was pipetted to a stirring tank separately provided in the batch distillation apparatus shown in Fig. 1, and 1.6 parts by weight of caustic soda tablets were put into the crucible. . Then, the mixture was stirred for 5 hours to neutralize the acid catalyst. The crude reaction liquid after the completion of the neutralization was again pipetted to the batch distillation apparatus of Fig. 1, and batch distillation was carried out. The pressure at the top of the distillation column was reduced to 40 kPa. A, and total reflux was performed. After the column was stabilized under full reflux, the reflux ratio was changed, and isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 15 (TC, and the pressure at the top of the column was reduced to 2.7 kPa.A in a segmented manner. © Isobutyl acetate and the concentration of acetic acid in the distillate were lowered. Then, the reflux ratio was set to 10 to remove propylene glycol and propylene glycol acetate. After removing propylene glycol and propylene glycol acetate, the reflux ratio was set to 0.5, and propylene glycol diacetate was distilled off from the top. [Comparative Example 5 The reaction crude liquid synthesized in the same manner as in Example 5 was pipetted to a stirring tank separately provided from the batch distillation apparatus shown in Fig. 1, and 1 part by weight of caustic soda tablets was charged. Then, stirring was carried out. In the hour, neutralize the acid catalyst -18- 200940499. The crude reaction solution after the neutralization is again pipetted to the batch distillation apparatus of Fig. 1 and perform batch distillation. The pressure at the top of the distillation column is reduced to 40. kPa.A, total reflux is performed. After the column is stabilized in the state of total reflux, the reflux ratio is changed, and isobutyl acetate and acetic acid are separated and distilled from the top of the column. At this time, the reflux ratio is set to 0.5, and the upper limit of the distillation temperature is set. 165 ° C, and segmented The pressure at the top of the column was lowered to 2.7 kPa. A. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, the reflux ratio was set to 10 to remove 1,6-hexanediol and monoacetic acid 1. 6-hexanediol ester. After removing 1,6-hexanediol and 1,6-hexanediol acetate, the reflux ratio is set to 0.5, and 1,6-diethyloxane is distilled off from the top. [Comparative Example 6] The crude reaction liquid synthesized in the same manner as in Example 1 was subjected to batch distillation without the operation of the apparatus of Fig. 1. Isobutyl acetate and acetic acid were topped from the top of the column. Distillation was carried out. At this time, the reflux ratio was set to 0.5, the upper limit of the distillation temperature was 150 ° C, and the pressure at the top of the column was reduced to 2.7 kPa.A in a stepwise manner. Isobutyl acetate and acetic acid in the distillate After the concentration was lowered, the reflux ratio was set to 10 to remove cyclohexanol. After the cyclohexanol was removed, the reflux ratio was set to 0.5, and cyclohexanol acetate was distilled off from the top. [Comparative Example 7] The crude reaction liquid synthesized in the same manner as in Example 2 was subjected to batch distillation as in the apparatus of Fig. 1. The isobutyl acetate and acetic acid were topped from the top of the column. Distillation separation. At this time, 'the reflux ratio is set to 0.5, the distillation tank -19-200940499' The upper temperature limit is 150 ° C, and the pressure at the top of the column is reduced to 2.7 kPa.A in a segmented manner. The acetic acid in the distillate After the concentration of butyl ester and acetic acid is lowered, 'the reflux ratio is set to 10 to remove 1,3 -butanediol and 1,3-butanediol monoacetate. Remove 1,3 -butanediol and monoacetic acid 1 After the addition of the butanediol ester, the reflux ratio was set to 0.5, and 1,3-diethoxyoxybutane was distilled off from the top. [Comparative Example 8] The same procedure as in Example 3 was carried out. The reaction crude liquid was not subjected to batch distillation in the apparatus of Fig. 1. Isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 150 ° C, and the pressure at the top of the column was lowered to 2.7 kPa.A in a sectional manner. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, a reflux ratio of 10 was set to remove dipropylene glycol monomethyl ether. After the dipropylene glycol monomethyl ether was removed, a reflux ratio of 0.5 was set, and dipropylene glycol methyl ether acetate was distilled off from the top. © [Comparative Example 9] The crude reaction liquid synthesized in the same manner as in Example 4 was subjected to batch distillation in the apparatus of Fig. 1 as it is. Isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 150 ° C, and the pressure at the top of the column was lowered to 2.7 kPa. After the isobutyl acetate and the acetic acid concentration in the solution were lowered, a reflux ratio of 10 was set to remove propylene glycol and propylene glycol acetate. After removing propylene glycol -20- 200940499 ' and a propylene glycol acetate, the reflux ratio was set to 0.5, and propylene glycol diacetate was distilled off from the top. [Comparative Example 10] The crude reaction liquid synthesized in the same manner as in Example 5 was subjected to batch distillation in the apparatus of Fig. 1 as it was. Isobutyl acetate and acetic acid were separated by distillation from the top of the column. At this time, the reflux ratio was set to 0.5, the upper limit of the still temperature was 165 ° C, and the pressure at the top of the column was reduced to 2.7 kPa in a stepwise manner. After the concentration of isobutyl acetate and acetic acid in the distillate was lowered, Then, a reflux ratio of 10 was set to remove 1,6-hexanediol and 1,6-hexanediol monoacetate. After removing 1,6-hexanediol and 1,6-hexanediol monoacetate, the reflux ratio was set to 0.5, and 1,6-diethoxydecane was distilled off from the top. The Na content and the acid portion of the product (ester solvent) obtained by the examples and the comparative examples were measured by the following methods. The results are shown in the table. (Method for determining Na content) © ICP-MS (Agilent HP-7500 type) was measured by standard addition method. Standard mixture was isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) For electronic materials, XSTC-22100ppm (containing 23 elements) manufactured by SPEX is diluted to 100 times. (Method for measuring acid content) The measurement was carried out in accordance with JIS K1 5 14 3.10. -21- 200940499 Table 1
Na含量 (ppb) 驗 (wt%) Na含量 (ppb) 驗 (wt%) Na雜 (PPb) 酸份 (wt%) 實施例1 0.5 0.001 比額1 5 0.002 比較例6 0.5 0.008 實施例2 0.3 0.005 比較例2 4 0.005 比較例7 0.5 0.02 實施例3 0.7 0.0004 比較例3 3.5 0.0005 比較例8 0.7 0.0012 資施例4 0.5 0.001 比較例4 2 0.001 比較例9 0.2 0.01 實施例5 0.4 0.004 mm 5 4 0.006 比較例1〇 0.4 0,16 Φ 如表1之測定結果所示，藉由實施例1至5所獲得之 酯系溶劑，由於不實施中和處理即供應至蒸餾精製，餾去 低沸點成份後，則從設置於蒸餾塔中間部份之側流管線餾 出，因此Na含量及酸份皆爲極低的濃度。與此相對，藉由 比較例1至5所獲得之酯系溶劑，由於其係實施中和處理 ，結果導致殘留Na含量爲高濃度，而從蒸餾塔塔頂部餾出 酯系溶劑之比較例6至10，則其酸份爲高値。 【圖式簡單說明】 φ 第1圖係展示可使用於實施本發明之酯系溶劑之製造 方法的裝置（批式蒸餾裝置）一實例示意圖。 【主要元件符號說明】 1 在內部可進行醇與酸反應之蒸餾釜 2 蒸餾塔 3 真空裝置 4 傾析器 4-1 傾析器內之水層 -22- 200940499 4-2 傾 析 器 內之有機層 5 泵 6 熱 交 換 器 7 熱 交 換 器 A~I 管 線Na content (ppb) test (wt%) Na content (ppb) test (wt%) Na (PPb) acid fraction (wt%) Example 1 0.5 0.001 Ratio 1 5 0.002 Comparative Example 6 0.5 0.008 Example 2 0.3 0.005 Comparative Example 2 4 0.005 Comparative Example 7 0.5 0.02 Example 3 0.7 0.0004 Comparative Example 3 3.5 0.0005 Comparative Example 8 0.7 0.0012 Example 4 0.5 0.001 Comparative Example 4 2 0.001 Comparative Example 9 0.2 0.01 Example 5 0.4 0.004 mm 5 4 0.006 Comparative Example 1〇0.4 0,16 Φ As shown in the measurement results of Table 1, the ester-based solvent obtained in Examples 1 to 5 was supplied to the distillation purification without performing the neutralization treatment, and the low-boiling component was distilled off. Thereafter, it is distilled from a side stream line provided in the middle portion of the distillation column, so that both the Na content and the acid portion are extremely low concentrations. On the other hand, in the ester-based solvent obtained in Comparative Examples 1 to 5, since the neutralization treatment was carried out, the residual Na content was high, and the ester solvent was distilled off from the top of the distillation column. To 10, the acidity is high. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a device (batch distillation apparatus) which can be used for carrying out the production method of the ester solvent of the present invention. [Main component symbol description] 1 Distillation tank in which alcohol and acid can be reacted internally 2 Distillation column 3 Vacuum device 4 Decanter 4-1 Water layer in decanter-22- 200940499 4-2 In the decanter Organic layer 5 pump 6 heat exchanger 7 heat exchanger A~I pipeline
-23--twenty three-