TWI588123B - Method for separating and recovering alkanediol monoalkyl ether, method for reusing photoresist composition waste liquid, and method for recovering photoresist composition treating liquid - Google Patents
Method for separating and recovering alkanediol monoalkyl ether, method for reusing photoresist composition waste liquid, and method for recovering photoresist composition treating liquid Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
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- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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Description
本發明係關於烷二醇單烷基醚之分離回收方法、光阻組成物處理廢液之再利用方法及光阻組成物處理液之回收方法。更詳言之,係關於自含有烷二醇單烷基醚及其對應之羧酸酯之溶劑混合物例如光阻組成物之處理廢液分離回收烷二醇單烷基醚之方法、光阻組成物處理廢液之再利用方法及光阻組成物處理液之回收方法。 The present invention relates to a method for separating and recovering an alkylene glycol monoalkyl ether, a method for recycling a photoresist composition treating waste liquid, and a method for recovering a photoresist composition treating liquid. More specifically, the method for separating and recovering an alkanediol monoalkyl ether from a solvent mixture containing a solvent mixture of an alkylene glycol monoalkyl ether and a corresponding carboxylate thereof, for example, a photoresist composition, and a photoresist composition Method for recycling material treatment waste liquid and method for recovering photoresist composition treatment liquid.
於半導體元件、液晶顯示元件、彩色濾光片等之製造步驟中,係使用利用以往液狀感光性組成物(本說明書中於以下亦稱為“阻劑”)之微影蝕刻技術。該液狀感光性組成物塗佈於半導體(矽基板等)、玻璃、樹脂(聚醯亞胺、聚酯等)等之基板上形成圖案時,有必要洗淨以去除附著於基板之端部或背面之液狀感光性組成物、或附著於用以塗佈液狀感光性組成物之裝置或構件表面之液狀感光性組成物。 In the manufacturing steps of a semiconductor element, a liquid crystal display element, a color filter, and the like, a lithography technique using a conventional liquid photosensitive composition (hereinafter also referred to as "resist" in the present specification) is used. When the liquid photosensitive composition is applied to a substrate such as a semiconductor (such as a ruthenium substrate), glass, or a resin (polyimine, polyester, or the like) to form a pattern, it is necessary to wash to remove the end portion attached to the substrate. Or a liquid photosensitive composition on the back surface or a liquid photosensitive composition attached to the surface of a device or member for applying a liquid photosensitive composition.
以溶解上述液狀感光性組成物之構成成分的 未硬化樹脂等為目的,已廣泛使用以烷二醇單烷基醚及與其對應之羧酸酯為主成分之各種溶劑混合物(參考專利文獻1及2)。該等因重複使用而洗淨能力慢慢降低,其性能劣化達到某程度時將作為廢溶劑排出。 To dissolve the constituents of the liquid photosensitive composition For the purpose of uncured resin or the like, various solvent mixtures containing an alkanediol monoalkyl ether and a corresponding carboxylate as a main component have been widely used (refer to Patent Documents 1 and 2). These washing powers are gradually reduced due to repeated use, and when the performance is deteriorated to a certain extent, they are discharged as waste solvents.
使用上述溶劑混合物洗淨液狀感光性組成物而產生之廢溶劑中,於原本溶劑混合物中所含之溶劑以外,亦會混入液狀感光性組成物之構成成分的樹脂、溶劑、其他添加劑。因此,基於近幾年備受矚目之環境問題對策、製造成本之減低等之觀點,強烈期望廢溶劑之再利用,亦即自廢溶劑分離回收有效成分並再利用。 In the waste solvent produced by washing the liquid photosensitive composition with the solvent mixture, a resin, a solvent, and other additives which are components of the liquid photosensitive composition are mixed in addition to the solvent contained in the original solvent mixture. Therefore, based on the environmental measures and the reduction of manufacturing costs that have been attracting attention in recent years, it is strongly desired to reuse the waste solvent, that is, to separate and recover the active ingredient from the waste solvent and reuse it.
自包含複數種成分之溶劑混合物分離回收溶劑成分之最代表性方法係使用蒸餾,於含特別多成分時,以蒸餾操作分離及純化廢溶劑中之各成分時,不僅步驟繁雜經濟上亦有困難。例如烷二醇單烷基醚與烷二醇單烷基醚單羧酸酯由於沸點比較接近,故難以以高純度且高回收率分離回收各者。且,由3種以上之溶劑混合物回收特定2成分(例如對應之烷二醇單烷基醚與烷二醇單烷基醚單羧酸酯)時,雖可分離沸點比相對較低之成分(烷二醇單烷基醚)更低之成分(低沸餾分)及沸點比相對較高之成分(烷二醇單烷基醚單羧酸酯)更高之成分(高沸餾分),但混合存在具有於2成分間之沸點之第3成分時難以僅分離第3成分。 The most representative method for separating and recovering solvent components from a solvent mixture containing a plurality of components is to use distillation. When a special component is contained, the components in the waste solvent are separated and purified by a distillation operation, which is not only complicated but also economically difficult. . For example, since the alkylene glycol monoalkyl ether and the alkylene glycol monoalkyl ether monocarboxylic acid ester are relatively close in boiling point, it is difficult to separate and recover each of them in high purity and high recovery. Further, when a specific two components (for example, a corresponding alkylene glycol monoalkyl ether and an alkylene glycol monoalkyl ether monocarboxylic acid ester) are recovered from three or more solvent mixtures, a component having a relatively low boiling point ratio can be separated ( Alkanediol monoalkyl ether) lower component (low boiling fraction) and higher boiling point component (alkane monoalkyl ether monocarboxylate) higher component (high boiling fraction), but mixed When the third component having a boiling point between the two components is present, it is difficult to separate only the third component.
專利文獻1中,作為光阻樹脂用醇/酯系溶劑之溶劑再利用方法,係揭示於由醇及與其對應之酯所成之 阻劑用溶劑中添加水進行酯之水解反應,使醇量比水解前更增加,接著使所得反應物料蒸餾純化。 In Patent Document 1, a solvent reuse method as an alcohol/ester solvent for a photoresist resin is disclosed in an alcohol and a corresponding ester thereof. The resist is added with water to carry out the hydrolysis reaction of the ester, so that the amount of the alcohol is increased more than before the hydrolysis, and then the obtained reaction material is distilled and purified.
專利文獻2中揭示使含有烷二醇單烷基醚(A成分)與A成分之乙酸酯(B成分)之溶劑混合物中之B成分進行酯交換反應而轉換成A成分,並蒸餾溶劑混合物而分離回收A成分。 Patent Document 2 discloses that a component B in a solvent mixture containing an alkylene glycol monoalkyl ether (component A) and an acetate (component B) of component A is subjected to a transesterification reaction to be converted into an component A, and a solvent mixture is distilled. The component A is separated and recovered.
[專利文獻1]日本特開2001-335535號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-335535
[專利文獻2]日本特開2005-247816號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-247816
專利文獻1中雖揭示藉由添加羧酸之醇的酯化反應或酯之水解,而可任意調整溶劑混合物中之酯/醇之比例,但實施例中,添加羧酸之酯化反應前或水解前之廢液中含有之作為目的之酯及醇以外之成分為0.3%之極微量,係在關於其他成分之共存幾乎不考慮之條件下實施者。亦即,專利文獻1中揭示僅控制實質上包含酯/醇之2成分之混合液中之兩者之混合比。於專利文獻2中,雖利用酯交換反應,但由於酯交換反應係平衡反應,故難以將B成分100%轉換為A成分,因此難以以高收率獲得。 Patent Document 1 discloses that the ratio of the ester/alcohol in the solvent mixture can be arbitrarily adjusted by the esterification reaction of the alcohol to which the carboxylic acid is added or the hydrolysis of the ester, but in the examples, before the esterification reaction of the carboxylic acid is added or The component other than the intended ester and the alcohol contained in the waste liquid before the hydrolysis is 0.3% in a very small amount, and is carried out under the condition that the coexistence of other components is hardly considered. That is, Patent Document 1 discloses that only the mixing ratio of two of the mixed liquids containing the two components of the ester/alcohol is controlled. In Patent Document 2, since the transesterification reaction is carried out, since the transesterification reaction is an equilibrium reaction, it is difficult to convert the B component to 100%, so that it is difficult to obtain it in a high yield.
本發明係鑒於上述情況,目的之一係提供以高純度且高收率自含有烷二醇單烷基醚及其對應之羧酸酯且包含其他溶劑之溶劑混合物分離回收烷二醇單烷基醚之方法。且目的之一係提供含有烷二醇單烷基醚及其對應之羧酸酯之光阻組成物之處理廢液之再利用方法及光阻組成物處理液之回收方法。 The present invention has been made in view of the above circumstances, and an object thereof is to provide separation and recovery of an alkylene glycol monoalkyl group from a solvent mixture containing an alkylene glycol monoalkyl ether and a corresponding carboxylate thereof and containing other solvents in high purity and high yield. The method of ether. One of the objects is to provide a method for recycling a treatment waste liquid containing a photoresist composition of an alkylene glycol monoalkyl ether and a corresponding carboxylate thereof, and a method for recovering a photoresist composition treatment liquid.
本發明人等欲解決上述課題而重複檢討之結果,發現將包含烷二醇單烷基醚(第一溶劑)、對應之羧酸酯的烷二醇單烷基醚羧酸酯(第二溶劑)、及其他溶劑(第三溶劑)之溶劑混合物中之第二溶劑藉由皂化而轉換成烷二醇單烷基醚(第一溶劑)後,藉由蒸餾,可效率良好地分離回收烷二醇單烷基醚(第一溶劑)。 As a result of repeated review, the inventors of the present invention have found that an alkylene glycol monoalkyl ether carboxylate (second solvent) containing an alkylene glycol monoalkyl ether (first solvent) and a corresponding carboxylic acid ester is found. And the second solvent in the solvent mixture of the other solvent (third solvent) is converted into the alkylene glycol monoalkyl ether (first solvent) by saponification, and the alkane can be efficiently separated and recovered by distillation. Alcohol monoalkyl ether (first solvent).
亦即,本發明包含以下之[1]~[15]之實施樣態。 That is, the present invention includes the following embodiments of [1] to [15].
[1]一種烷二醇單烷基醚之分離回收方法,其係自包含以下述通式(I)表示之第一溶劑、以下述通式(II)表示之第二溶劑、及與前述第一溶劑及第二溶劑不同之第三溶劑之第一溶劑混合物分離回收第一溶劑之方法,其特徵為包含下列步驟:藉由將鹼性化合物添加於前述第一溶劑混合物中使前述第二溶劑皂化而轉換成第一溶劑,而獲得第二溶劑混合物之第一步驟,與 蒸餾前述第二溶劑混合物而回收第一溶劑之第二步驟,【化1】R(OR’) n OH (I) [1] A method for separating and recovering an alkylene glycol monoalkyl ether, comprising a first solvent represented by the following general formula (I), a second solvent represented by the following general formula (II), and the aforementioned a method for separating and recovering a first solvent from a first solvent mixture of a solvent and a third solvent different from the second solvent, characterized by comprising the steps of: adding the basic compound to the first solvent mixture to form the second solvent a second step of saponification to convert to a first solvent, a second solvent mixture, and a second solvent mixture to recover the first solvent, [Chem. 1] R(OR') n OH (I)
【化2】 R(OR’) n OCOR” (II)[通式(I)及通式(II)中,R表示碳數1~4之烷基,R’表示碳數2~4之伸烷基,R”表示碳數1~2之烷基,通式(I)及通式(II)中之R及R’各為相同,n為1或2]。 [Chemical 2] R(OR') n OCOR" (II) [In the general formula (I) and the general formula (II), R represents an alkyl group having 1 to 4 carbon atoms, and R' represents a carbon number of 2 to 4 The alkyl group, R" represents an alkyl group having 1 to 2 carbon atoms, and in the general formula (I) and the general formula (II), R and R' are each the same, and n is 1 or 2].
[2]如[1]之烷二醇單烷基醚之分離回收方法,其中前述鹼性化合物係由氫氧化鈉、氫氧化鉀、氫氧化鈣及氫氧化銨所組成之群選出之至少一種氫氧化鹼性化合物。 [2] The method for separating and recovering an alkylene glycol monoalkyl ether according to [1], wherein the basic compound is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide. A basic compound of hydroxide.
[3]如[2]之烷二醇單烷基醚之分離回收方法,其中前述鹼性化合物為氫氧化鈉。 [3] The method for separating and recovering an alkanediol monoalkyl ether according to [2], wherein the basic compound is sodium hydroxide.
[4]如[1]~[3]中任一項之烷二醇單烷基醚之分離回收方法,其中前述第一溶劑為丙二醇單甲基醚,前述第二溶劑為丙二醇單甲基醚乙酸酯,前述第三溶劑為由環戊酮、環己酮及3-甲氧基丙酸甲酯所組成之群選出之至少一種。 [4] The method for separating and recovering an alkanediol monoalkyl ether according to any one of [1] to [3] wherein the first solvent is propylene glycol monomethyl ether, and the second solvent is propylene glycol monomethyl ether. The acetate, the third solvent is at least one selected from the group consisting of cyclopentanone, cyclohexanone and methyl 3-methoxypropionate.
[5]如[1]~[4]中任一項之烷二醇單烷基醚之分離回收方法,其中前述第一溶劑混合物係以包含前述第一溶劑及第二溶劑之混合溶劑處理光阻組成物而得之處理廢液。 [5] The method for separating and recovering an alkanediol monoalkyl ether according to any one of [1] to [4] wherein the first solvent mixture is treated with a mixed solvent comprising the first solvent and the second solvent. The waste liquid is treated by the composition.
[6]一種光阻組成物處理廢液之再利用方法,其特徵係具有下列步驟:使用包含以下述通式(I)表示之第一溶劑及以下述 通式(II)表示之第二溶劑之混合溶劑處理光阻組成物之第一步驟,回收由第一步驟生成之處理廢液之第二步驟,藉由將鹼性化合物添加於前述處理廢液中使前述處理廢液中之第二溶劑皂化轉換成第一溶劑之第三步驟,蒸餾前述第三步驟所得之溶劑混合物而回收第一溶劑之第四步驟,於前述第四步驟所回收之第一溶劑中添加新的第二溶劑再調製具有特定調配比之混合溶劑之第五步驟,【化3】R(OR’) n OH (I) [6] A method for recycling a photoresist composition treating waste liquid, which comprises the steps of: using a first solvent represented by the following general formula (I) and a second solvent represented by the following general formula (II); a first step of treating the photoresist composition by the mixed solvent, recovering the second step of treating the waste liquid generated by the first step, and adding the alkaline compound to the treatment waste liquid to make the second of the treatment waste liquid a third step of converting the solvent saponification into a first solvent, distilling the solvent mixture obtained in the third step to recover a first solvent, and adding a new second solvent to the first solvent recovered in the fourth step. The fifth step of preparing a mixed solvent having a specific mixing ratio, [Chemical 3] R(OR') n OH (I)
【化4】R(OR’) n OCOR” (II)[通式(I)及通式(II)中,R表示碳數1~4之烷基,R’表示碳數2~4之伸烷基,R”表示碳數1~2之烷基,且通式(I)及通式(II)中之R及R’各為相同,n為1或2]。 [Chemical 4] R(OR') n OCOR" (II) [In the general formula (I) and the general formula (II), R represents an alkyl group having 1 to 4 carbon atoms, and R' represents a carbon number of 2 to 4 The alkyl group, R" represents an alkyl group having 1 to 2 carbon atoms, and R and R' in the formula (I) and the formula (II) are each the same, and n is 1 or 2].
[7]如[6]之光阻組成物處理廢液之再利用方法,其中前述鹼性化合物係由氫氧化鈉、氫氧化鉀、氫氧化鈣及氫氧化銨所組成之群選出之至少一種氫氧化鹼性化合物。 [7] The method for recycling a photoresist composition treating waste liquid according to [6], wherein the basic compound is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide. A basic compound of hydroxide.
[8]如[7]之光阻組成物處理廢液之再利用方法,其中前述鹼性化合物為氫氧化鈉。 [8] The method for recycling a photoresist composition treating waste liquid according to [7], wherein the basic compound is sodium hydroxide.
[9]如[6]~[8]中任一項之光阻組成物處理廢液之再利用方法,其中前述第一溶劑為丙二醇單甲基醚,前述第二溶劑為丙二醇單甲基醚乙酸酯。 [9] The method for recycling a photoresist composition treating waste liquid according to any one of [6] to [8] wherein the first solvent is propylene glycol monomethyl ether, and the second solvent is propylene glycol monomethyl ether Acetate.
[10]如[6]~[9]中任一項之光阻組成物處理廢液之再利用方法,其中前述第三步驟後且第四步驟前,具有使前述處理廢液中所含之因皂化反應生成之固體成分分離之步驟。 [10] The method for recycling a photoresist composition treating waste liquid according to any one of [6] to [9], wherein, after the third step and before the fourth step, the method includes the The step of separating the solid components formed by the saponification reaction.
[11]一種光阻組成物處理液之再利用方法,其特徵為具有下列步驟,且重複實施下列第二步驟至第七步驟:使用者自製造業者購入以特定調配比例包含以下述通式(I)表示之第一溶劑及以下述通式(II)表示之第二溶劑之混合溶劑之第一步驟,使用者利用前述混合溶劑處理光阻組成物之第二步驟,製造業者或回收業者回收因第二步驟生成之處理廢液之第三步驟,製造業者或回收業者將鹼性化合物添加於前述處理廢液中而使前述處理廢液中之第二溶劑皂化而轉換成第一溶劑之第四步驟,製造業者或回收業者蒸餾前述第四步驟所得之溶劑混合物而回收第一溶劑之第五步驟,製造業者或回收業者將新的第二溶劑添加於前述第五步驟所回收之第一溶劑中再調製具有前述特定調配比之混合溶劑之第六步驟,與使用者自製造業者或回收業者購入再調製後之混合溶劑之第七步驟, 【化5】R(OR’) n OH (I) [11] A method for recycling a photoresist composition treatment liquid, which comprises the following steps, and repeats the following second to seventh steps: the user purchases from the manufacturer in a specific blending ratio to include the following formula ( I) the first step of the first solvent and the mixed solvent of the second solvent represented by the following formula (II), the second step of the user treating the photoresist composition with the mixed solvent, and the manufacturer or the recycler recycles In the third step of treating the waste liquid generated in the second step, the manufacturer or the recycler adds the alkaline compound to the treatment waste liquid to saponify the second solvent in the treatment waste liquid to be converted into the first solvent. a fourth step in which the manufacturer or the recycler distills the solvent mixture obtained in the fourth step to recover the first solvent, and the manufacturer or the recycler adds the new second solvent to the first solvent recovered in the fifth step. The sixth step of preparing a mixed solvent having the specific specific ratio described above, and purchasing a reconstituted mixed solvent from a manufacturer or a recycler Step seven, [Chemical Formula 5] R (OR ') n OH ( I)
【化6】R(OR’) n OCOR” (II)[通式(I)及通式(II)中,R表示碳數1~4之烷基,R’表示碳數2~4之伸烷基,R”表示碳數1~2之烷基,且通式(I)及通式(II)中之R及R’各為相同,n為1或2]。 [Chemical 6] R(OR') n OCOR" (II) [In the general formula (I) and the general formula (II), R represents an alkyl group having 1 to 4 carbon atoms, and R' represents a carbon number of 2 to 4 The alkyl group, R" represents an alkyl group having 1 to 2 carbon atoms, and R and R' in the formula (I) and the formula (II) are each the same, and n is 1 or 2].
[12]如[11]之光阻組成物處理液之再利用方法,其中前述鹼性化合物係由氫氧化鈉、氫氧化鉀、氫氧化鈣及氫氧化銨所組成之群選出之至少一種氫氧化鹼性化合物。 [12] The method for recycling a photoresist composition treatment liquid according to [11], wherein the basic compound is at least one hydrogen selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide. Oxidizing basic compounds.
[13]如[12]之光阻組成物處理液之再利用方法,其中前述鹼性化合物為氫氧化鈉。 [13] The method for recycling a photoresist composition treatment liquid according to [12], wherein the basic compound is sodium hydroxide.
[14]如[11]~[13]中任一項之光阻組成物處理液之再利用方法,其中前述第一溶劑為丙二醇單甲基醚,前述第二溶劑為丙二醇單甲基醚乙酸酯。 [14] The method for recycling a photoresist composition treatment liquid according to any one of [11] to [13] wherein the first solvent is propylene glycol monomethyl ether, and the second solvent is propylene glycol monomethyl ether Acid ester.
[15]如[11]~[14]中任一項之光阻組成物處理液之再利用方法,其中前述第四步驟後且第五步驟前,具有使因皂化反應生成之前述處理廢液中所含固體成分分離之步驟。 [15] The method for recycling a photoresist composition treatment liquid according to any one of [11] to [14] wherein, after the fourth step and before the fifth step, the treatment waste liquid generated by the saponification reaction is formed The step of separating the solid components contained therein.
依據本發明,可以高純度且高收率自含有烷二醇單烷基醚及其對應之羧酸酯以及其他溶劑之溶劑混合物分離回收烷二醇單烷基醚。且可以高純度且高收率自含有烷二醇 單烷基醚及其對應之羧酸酯以及其他溶劑之光阻組成物之處理廢液分離回收烷二醇單烷基醚。因此,依據本發明,可再利用光阻組成物之處理廢液,而以低成本製造半導體元件、液晶顯示元件、彩色濾光片等。 According to the present invention, the alkanediol monoalkyl ether can be separated and recovered from a solvent mixture containing an alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and other solvents in high purity and high yield. And can be used in high purity and high yield from alkanediol The treatment waste liquid of the monoalkyl ether and its corresponding carboxylic acid ester and other solvent is used to separate and recover the alkanediol monoalkyl ether. Therefore, according to the present invention, the processing waste liquid of the photoresist composition can be reused, and a semiconductor element, a liquid crystal display element, a color filter, or the like can be manufactured at low cost.
10‧‧‧棚段塔式蒸餾裝置 10‧‧‧Schedule tower distillation unit
11‧‧‧回流頭 11‧‧‧Return head
12‧‧‧回流/餾出切換濾斗 12‧‧‧Reflow/distillation switching filter
13‧‧‧餾出活栓 13‧‧‧ Distillation stopcock
14‧‧‧接受器 14‧‧‧ Receiver
15‧‧‧溫度計 15‧‧‧ thermometer
A‧‧‧1L燒瓶 A‧‧1L flask
B‧‧‧精餾塔 B‧‧·Rectification Tower
圖1係實施例所用之蒸餾裝置之概略說明圖。 Fig. 1 is a schematic explanatory view of a distillation apparatus used in the examples.
針對本發明之烷二醇單烷基醚之分離回收方法、光阻組成物處理廢液之再利用方法及光阻組成物處理液之回收方法詳細加以說明,但本發明不限定於該等說明中所用之實施樣態。 The method for separating and recovering the alkanediol monoalkyl ether of the present invention, the method for recycling the photoresist composition treating waste liquid, and the method for recovering the photoresist composition treating liquid are described in detail, but the present invention is not limited to the description. The implementation form used in the process.
本發明之第一實施樣態係自包含烷二醇單烷基醚(第一溶劑)、烷二醇單烷基醚羧酸酯(第二溶劑)、及與烷二醇單烷基醚(第一溶劑)及烷二醇單烷基醚羧酸酯(第二溶劑)不同之溶劑(第三溶劑)之溶劑混合物(第一溶劑混合物),分離回收烷二醇單烷基醚(第一溶劑)之方法。其特徵為具有藉由將鹼性化合物添加於第一溶劑混合物中使第一溶劑混合物中之烷二醇單烷基醚羧酸酯皂化而轉換成烷二醇單烷基醚,而獲得第二溶劑混合物之第一步 驟,與蒸餾第二溶劑混合物而分離回收烷二醇單烷基醚之第二步驟。 The first embodiment of the present invention is derived from the inclusion of an alkanediol monoalkyl ether (first solvent), an alkanediol monoalkyl ether carboxylate (second solvent), and an alkylene glycol monoalkyl ether ( Solvent mixture (first solvent mixture) of a solvent (third solvent) different from the first solvent) and the alkylene glycol monoalkyl ether carboxylate (second solvent), and the alkane monoalkyl ether is separated and recovered (first Method of solvent). Characterized by the conversion of an alkanediol monoalkyl ether carboxylate in a first solvent mixture to an alkanediol monoalkyl ether by adding a basic compound to the first solvent mixture to obtain a second The first step of the solvent mixture The second step of separating and recovering the alkanediol monoalkyl ether from the distillation of the second solvent mixture.
第一實施樣態中成為分離回收處理對象之第一溶劑混合物包含以下述通式(I)表示之烷二醇單烷基醚(第一溶劑)與以下述通式(II)表示之第一溶劑之對應羧酸酯的烷二醇單烷基醚羧酸酯(第二溶劑),進而包含該等2種溶劑以外之至少1種溶劑(第三溶劑)。 The first solvent mixture to be subjected to the separation and recovery treatment in the first embodiment comprises an alkylene glycol monoalkyl ether (first solvent) represented by the following general formula (I) and the first one represented by the following general formula (II) The alkanediol monoalkyl ether carboxylate (second solvent) of the corresponding carboxylate of the solvent further contains at least one solvent (third solvent) other than the two solvents.
【化7】R(OR’) n OH (I) [Chemical 7] R(OR') n OH (I)
【化8】R(OR’) n OCOR” (II)[通式(I)及通式(II)中,R表示碳數1~4之烷基,R’表示碳數2~4之伸烷基,R”表示碳數1~2之烷基,通式(I)及通式(II)中之R及R’各為相同,n為1或2]。 [Chemical 8] R(OR') n OCOR" (II) [In the general formula (I) and the general formula (II), R represents an alkyl group having 1 to 4 carbon atoms, and R' represents a carbon number of 2 to 4 The alkyl group, R" represents an alkyl group having 1 to 2 carbon atoms, and in the general formula (I) and the general formula (II), R and R' are each the same, and n is 1 or 2].
第一溶劑混合物只要為含有如上述之分別以通式(I)及通式(II)表示之第一溶劑及第二溶劑作為必須成分,且含有該等2種溶劑以外之至少1種溶劑(第三溶劑)者,即無特別限制,本發明對於第三溶劑之沸點在第一溶劑之沸點與第二溶劑之沸點之間時特別有效。例如,將半導體元件、液晶顯示元件、彩色濾光片等之製造步驟中,作為光阻組成物之剝離用溶劑、洗淨用溶劑等使用之混合有機溶劑之廢溶劑作為分離回收之對象。 The first solvent mixture is an essential component containing the first solvent and the second solvent represented by the above formula (I) and the formula (II), and contains at least one solvent other than the two solvents ( The third solvent is not particularly limited, and the present invention is particularly effective for the boiling point of the third solvent between the boiling point of the first solvent and the boiling point of the second solvent. For example, in the production steps of a semiconductor element, a liquid crystal display element, a color filter, or the like, a waste solvent of a mixed organic solvent used as a solvent for stripping of a photoresist composition, a solvent for cleaning, or the like is used as a separation and recovery target.
通式(I)及通式(II)中,R之具體例舉例為甲基、乙基、丙基、異丙基、正丁基、異丁基等之碳數 為1~4之烷基,R’之具體例舉例為伸乙基、三亞甲基、伸丙基、伸丁基等。通式(I)及通式(II)之R及R’分別為相同。通式(II)之R”為甲基或乙基。n為1或2。 In the general formula (I) and the general formula (II), specific examples of R are exemplified by carbon numbers of methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and the like. Specific examples of R' are an alkyl group of 1 to 4, and examples thereof include an ethyl group, a trimethylene group, a propyl group, a butyl group and the like. R and R' in the general formula (I) and the general formula (II) are the same. R" of the formula (II) is a methyl group or an ethyl group. n is 1 or 2.
通式(I)所示之第一溶劑之具體例舉例為例如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單乙基醚、丙二醇單甲基醚、二丙二醇單甲基醚等。通式(II)所示之第二溶劑可舉例為該等之乙酸酯或丙酸酯。 Specific examples of the first solvent represented by the formula (I) are exemplified by, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. The second solvent represented by the formula (II) can be exemplified by the acetate or propionate.
第一混合溶劑為第一溶劑與第二溶劑之混合物,舉例為包含乙二醇單甲基醚與乙二醇單甲基醚乙酸酯之混合液、包含乙二醇單乙基醚與乙二醇單乙基醚乙酸酯之混合液、包含乙二醇單丙基醚與乙二醇單丙基醚乙酸酯之混合液、包含乙二醇單丁基醚與乙二醇單丁基醚乙酸酯之混合液、包含二乙二醇單乙基醚與二乙二醇單乙基醚乙酸酯之混合液、包含丙二醇單甲基醚與丙二醇單甲基醚乙酸酯之混合液、包含二丙二醇單甲基醚與二丙二醇單甲基醚乙酸酯之混合液等。該等中,對於包含作為第一溶劑之丙二醇單甲基醚與作為第二溶劑之丙二醇單甲基醚乙酸酯之溶劑混合物可較好地應用本發明之分離回收方法。 The first mixed solvent is a mixture of the first solvent and the second solvent, and is exemplified by a mixture comprising ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate, comprising ethylene glycol monoethyl ether and a mixture of diol monoethyl ether acetate, comprising a mixture of ethylene glycol monopropyl ether and ethylene glycol monopropyl ether acetate, comprising ethylene glycol monobutyl ether and ethylene glycol monobutyl a mixture of ether ether acetate, comprising a mixture of diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetate, comprising propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate A mixed solution containing a mixture of dipropylene glycol monomethyl ether and dipropylene glycol monomethyl ether acetate. Among these, the separation and recovery method of the present invention can be preferably applied to a solvent mixture comprising propylene glycol monomethyl ether as the first solvent and propylene glycol monomethyl ether acetate as the second solvent.
第一溶劑混合物中之第一溶劑與第二溶劑之含有比例,只要自該等兩成分混合而成者,則無特別限制,但較好為第一溶劑與第二溶劑之質量換算之混合比(第一溶劑/第二溶劑)為1以上,更好為1.5以上,又更好為2以上。第二溶劑之含有比例較少時可使後述之第二 溶劑之皂化反應所需之鹼性化合物(氫氧化鈉等)之量減少,可使鹼性化合物於溶劑混合物中更均勻分散。較佳之第一溶劑混合物舉例為使用丙二醇單甲基醚/丙二醇單甲基醚乙酸酯=6.8/3.2~7.2/2.8(質量比),更好為丙二醇單甲基醚/丙二醇單甲基醚乙酸酯=6.9/3.1~7.1/2.9(質量比),最好為丙二醇單甲基醚/丙二醇單甲基醚乙酸酯=7/3(質量比)之混合溶劑處理光阻時所生成之光阻處理廢液。 The content ratio of the first solvent to the second solvent in the first solvent mixture is not particularly limited as long as it is a mixture of the two components, but is preferably a mixture ratio of the first solvent to the second solvent. The (first solvent/second solvent) is 1 or more, more preferably 1.5 or more, still more preferably 2 or more. When the content ratio of the second solvent is small, the second one described later can be made. The amount of the basic compound (sodium hydroxide or the like) required for the saponification reaction of the solvent is reduced, and the basic compound can be more uniformly dispersed in the solvent mixture. A preferred first solvent mixture is exemplified by the use of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 6.8 / 3.2 ~ 7.2 / 2.8 (mass ratio), more preferably propylene glycol monomethyl ether / propylene glycol monomethyl ether Acetate = 6.9 / 3.1 ~ 7.1 / 2.9 (mass ratio), preferably produced by treating a photoresist with a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio) The photoresist is used to treat the waste liquid.
第一溶劑混合物包含至少一種之第一溶劑及第二溶劑以外之第三溶劑。第一溶劑混合物為光阻組成物之剝離或洗淨所使用之廢液時,光阻組成物中所調配之溶劑稱為第三溶劑。作為第三溶劑具體例示為環戊酮、環己酮等酮類、乳酸乙酯、3-甲氧基丙酸甲酯等之酯類。第一溶劑混合物亦可含有溶劑以外之成分。光阻組成物之剝離或洗淨所使用之廢液中,一般含有源自光阻組成物之樹脂、添加劑(硬化劑、顏料等)等。 The first solvent mixture comprises at least one of a first solvent and a third solvent other than the second solvent. When the first solvent mixture is a waste liquid used for peeling or washing of the photoresist composition, the solvent to be formulated in the photoresist composition is referred to as a third solvent. Specific examples of the third solvent include ketones such as cyclopentanone and cyclohexanone, and esters such as ethyl lactate and methyl 3-methoxypropionate. The first solvent mixture may also contain components other than the solvent. The waste liquid used for the peeling or washing of the photoresist composition generally contains a resin derived from a photoresist composition, an additive (a curing agent, a pigment, etc.).
為了自第一溶劑混合物分離回收第一溶劑的烷二醇單烷基醚,於本發明之第一步驟中係應用皂化反應以使第一溶劑混合物中之第二溶劑轉換為第一溶劑。皂化反應可藉由添加鹼性化合物,較好為由氫氧化鈉、氫氧化鉀、氫氧化鈣及氫氧化銨所組成之群選出之至少一種氫氧化鹼性化合物而進行。作為一例,使用氫氧化鈉時之皂化反應係以下述反應式(III)表示。 In order to separate and recover the alkanediol monoalkyl ether of the first solvent from the first solvent mixture, a saponification reaction is applied in the first step of the invention to convert the second solvent in the first solvent mixture into the first solvent. The saponification reaction can be carried out by adding a basic compound, preferably at least one basic hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide. As an example, the saponification reaction using sodium hydroxide is represented by the following reaction formula (III).
【化9】R(OR’) n OCOR”+NaOH → R(OR’) n OH+R”COONa (III)反應式(III)中,R表示碳數1~4之烷基,R’表示碳數2~4之伸烷基,R”表示碳數1~2之烷基,n為1或2。 [Chemical 9] R(OR') n OCOR"+NaOH → R(OR') n OH+R"COONa (III) In the reaction formula (III), R represents an alkyl group having 1 to 4 carbon atoms, and R' represents The alkyl group having 2 to 4 carbon atoms, R" represents an alkyl group having 1 to 2 carbon atoms, and n is 1 or 2.
皂化反應中所用之鹼性化合物之量,對於第一溶劑混合物中所含之第二溶劑,為0.8~1.2莫耳當量,較好為0.9~1.1莫耳當量,更好為0.95~1.05莫耳當量。鹼性化合物之量少於0.8莫耳當量時,未轉換成第一溶劑之第二溶劑殘留量變多而使收率降低。鹼性化合物之量多於1.2莫耳當量時,不僅無助於皂化反應之量變多,且於第一溶劑混合物中均一分散方面亦不利。作為鹼性化合物使用氫氧化鈉、氫氧化鉀或氫氧化鈣時,由於該等氫氧化鹼性化合物對第一溶劑混合物之溶解度小,故而期望攪拌以使其均一分散。為了防止氫氧化鈉、氫氧化鉀或氫氧化鈣之沉降及使皂化反應順利進行,作為氫氧化鈉、氫氧化鉀或氫氧化鈣較好使用小粒徑者,例如使用顆粒狀者。氫氧化鈉或氫氧化鉀由於具有潮解性,故即使不添加水,亦包含微量之本身所吸收之水分。因此,即使不添加水而以固體狀態添加,亦可進行皂化反應。氫氧化鈣對於水之溶解度比氫氧化鈉及氫氧化鉀小,因此反應速度較慢。雖於後述,但含有環戊酮、環己酮等之酮系溶劑作為第三溶劑時,若使用氫氧化鈣化合物則引起該等酮系溶劑之二聚化(醇醛縮合反應),而生成更高沸點之二聚物。因此,例 如於欲回收之成分為丙二醇單甲基醚,酮系溶劑為具有與丙二醇單甲基醚之沸點(120℃)比較接近之沸點的環戊酮(131℃)時,生成與丙二醇單甲基醚之沸點差更大之酮系溶劑之二聚物(沸點>160℃),其容易與丙二醇單甲基醚分離。氫氧化甲與氫氧化鈉之反應性雖為相同程度,但比氫氧化鈉昂貴,氫氧化鈣雖為低成本但反應性差,因此較好使用氫氧化鈉。 The amount of the basic compound used in the saponification reaction is 0.8 to 1.2 mole equivalents, preferably 0.9 to 1.1 mole equivalents, more preferably 0.95 to 1.05 moles, for the second solvent contained in the first solvent mixture. equivalent. When the amount of the basic compound is less than 0.8 mol equivalent, the residual amount of the second solvent which is not converted into the first solvent is increased to lower the yield. When the amount of the basic compound is more than 1.2 mol equivalent, not only does it contribute to the amount of the saponification reaction, but it is also disadvantageous in terms of uniform dispersion in the first solvent mixture. When sodium hydroxide, potassium hydroxide or calcium hydroxide is used as the basic compound, since the solubility of the basic hydroxide compound to the first solvent mixture is small, stirring is desirably performed to uniformly disperse. In order to prevent sedimentation of sodium hydroxide, potassium hydroxide or calcium hydroxide and to smoothly carry out the saponification reaction, it is preferred to use a small particle diameter as sodium hydroxide, potassium hydroxide or calcium hydroxide, for example, a granular one. Since sodium hydroxide or potassium hydroxide is deliquescent, it contains a trace amount of water absorbed by itself even if water is not added. Therefore, the saponification reaction can be carried out even if it is added in a solid state without adding water. Calcium hydroxide has a lower solubility in water than sodium hydroxide and potassium hydroxide, so the reaction rate is slow. When a ketone solvent such as cyclopentanone or cyclohexanone is used as the third solvent, the use of a calcium hydroxide compound causes dimerization (aldol condensation reaction) of the ketone solvent to produce a ketone solvent. Higher boiling dimer. Therefore, for example If the component to be recovered is propylene glycol monomethyl ether, and the ketone solvent is cyclopentanone (131 ° C) having a boiling point close to the boiling point of propylene glycol monomethyl ether (120 ° C), it forms a monomethyl group with propylene glycol. A dimer of a ketone solvent having a larger difference in boiling point of ether (boiling point > 160 ° C), which is easily separated from propylene glycol monomethyl ether. Although the reactivity of the metal hydroxide and sodium hydroxide is the same, it is more expensive than sodium hydroxide, and calcium hydroxide is low in cost but poor in reactivity, so sodium hydroxide is preferably used.
雖亦可使用氫氧化銨,但由於加熱時會以氨而揮發,故有不期望反應成為高溫之情況。氫氧化鹼性化合物亦可作為水溶液使用。作為水溶液使用時就朝溶劑混合物之均一混合之觀點而言較有利,但於後述之蒸餾步驟中欲分離回收之溶劑變成與水共沸,故就收率方面並不利。因此,水之添加較好抑制在必需之最低限度(例如氫氧化鈉作為水溶液使用時,係使用48質量%以上者)。 Ammonium hydroxide can also be used, but since it is volatilized by ammonia during heating, there is a case where the reaction is not expected to be high. The basic hydroxide compound can also be used as an aqueous solution. When it is used as an aqueous solution, it is advantageous from the viewpoint of uniform mixing of the solvent mixture, but the solvent to be separated and recovered in the distillation step described later becomes azeotroped with water, so that it is not advantageous in terms of yield. Therefore, the addition of water is preferably suppressed to a minimum necessary (for example, when sodium hydroxide is used as an aqueous solution, 48% by mass or more is used).
第一溶劑混合物為光阻組成物之處理廢液時,光阻組成物中有時含有以通式(II)表示之羧酸酯以外之羧酸酯,該等羧酸酯與通式(II)表示之羧酸酯同樣受到皂化反應而有消耗鹼性化合物之情況。因此,第一溶劑混合物中含有以通式(II)表示之羧酸酯以外之羧酸酯時,較好使用相對於第一溶劑混合物中所含之全部羧酸酯量在上述規定範圍之鹼性化合物。 When the first solvent mixture is a treatment waste liquid of the photoresist composition, the photoresist composition may contain a carboxylate other than the carboxylate represented by the formula (II), and the carboxylate and the formula (II) The carboxylic acid ester represented by the above is also subjected to a saponification reaction and consumes a basic compound. Therefore, when the first solvent mixture contains a carboxylic acid ester other than the carboxylic acid ester represented by the general formula (II), it is preferred to use a base having the above-mentioned specified range with respect to the total amount of the carboxylic acid ester contained in the first solvent mixture. Sex compounds.
皂化反應條件(溫度、時間、氛圍等)並未特別限制,但較好溫度為室溫至100℃之範圍,時間為1~10小時之範圍。反應氛圍亦未特別限制,在大氣下、 惰性氛圍(氮氣、氬氣等)下之任一者中進行均可,但於使用吸濕性較強之氫氧化鈉時,較好在濕度低之氛圍例如相對溼度為50%以下進行,更好於10~40%進行。 The saponification reaction conditions (temperature, time, atmosphere, etc.) are not particularly limited, but preferably the temperature is in the range of room temperature to 100 ° C, and the time is in the range of 1 to 10 hours. The reaction atmosphere is also not particularly limited, under the atmosphere, It can be carried out in any of an inert atmosphere (nitrogen, argon, etc.). However, when using a hygroscopically strong sodium hydroxide, it is preferred to carry out an atmosphere having a low humidity, for example, a relative humidity of 50% or less. Better than 10~40%.
第二步驟中,為了自皂化反應後所得之溶劑混合物(第二溶劑混合物)分離回收第一溶劑,而蒸餾第二溶劑混合物。第二溶劑混合物中包含皂化反應所生成之羧酸鹽。羧酸鹽由於幾乎不溶解於溶劑混合物(第二溶劑混合物)中,故羧酸鹽以包含於第二溶劑混合物中之狀態蒸餾時,羧酸鹽在蒸餾操作中析出而有污染蒸餾設備之情況。因此,蒸餾前較好設置使羧酸鹽分離之步驟。若可分離羧酸鹽,則分離步驟並未特別限制,可應用蒸發分離、過濾分離、離心分離等習知方法,但為使固形物(羧酸鹽)中所含之溶劑比例降低且有效地進行安定地排出,期望使用薄膜蒸發器。所謂薄膜蒸餾係藉由於圓筒之壁面形成溶液之薄膜而提高蒸發效率之蒸發器,舉例為例如神鋼環境解決股份有限公司之EXEVA(註冊商標)、木村化工機股份有限公司之強制擴販式蒸發器、櫻製作所股份有限公司之HIEVAOLATOR(註冊商標)等。薄膜蒸餾亦可在常壓下進行,但基於確保供給熱源之觀點等,較好在100~300torr左右之減壓下進行較有利。 In the second step, in order to separate and recover the first solvent from the solvent mixture (second solvent mixture) obtained after the saponification reaction, the second solvent mixture is distilled. The second solvent mixture contains a carboxylate formed by a saponification reaction. Since the carboxylate is hardly dissolved in the solvent mixture (second solvent mixture), when the carboxylate is distilled in a state of being contained in the second solvent mixture, the carboxylate is precipitated in the distillation operation and the contaminated distillation apparatus is present. . Therefore, it is preferred to provide a step of separating the carboxylate before distillation. If the carboxylate can be separated, the separation step is not particularly limited, and a conventional method such as evaporation separation, filtration separation, or centrifugal separation can be applied, but the ratio of the solvent contained in the solid matter (carboxylate) is lowered and effectively For safe discharge, it is desirable to use a thin film evaporator. The thin film distillation is an evaporator that increases the evaporation efficiency by forming a film of a solution on the wall surface of the cylinder, for example, EXEVA (registered trademark) of Kobelco Environmental Solutions Co., Ltd., and forced expansion evaporation of Kimura Chemical Machinery Co., Ltd. HIEVAOLATOR (registered trademark) of Sakura Manufacturing Co., Ltd., etc. The thin film distillation can also be carried out under normal pressure, but it is preferably carried out under a reduced pressure of about 100 to 300 torr based on the viewpoint of ensuring the supply of the heat source.
第一溶劑混合物為光阻組成物之處理廢液時,分離步驟中之處理廢液中含有之固體成分亦同時被分離。該等固體成分之分離亦可在第一溶劑混合物皂化反應前實施,但由於在皂化反應後有再度需要使生成之羧酸鹽 分離之步驟之情況,故在皂化反應後與羧酸鹽同時分離較有利。 When the first solvent mixture is a treatment waste liquid of the photoresist composition, the solid content contained in the treatment waste liquid in the separation step is also simultaneously separated. Separation of the solid components may also be carried out before the saponification reaction of the first solvent mixture, but since the saponification reaction is again required to form the formed carboxylate In the case of the separation step, it is advantageous to simultaneously separate the carboxylate after the saponification reaction.
第二溶劑混合物之蒸餾方法及蒸餾裝置並未特別限制,例如作為蒸餾方法可應用常壓蒸餾、減壓蒸餾等之過去以來已知之任何方法,蒸餾裝置亦可應用連續式、批式等之習知各種蒸餾裝置之任何者。 The distillation method and the distillation apparatus of the second solvent mixture are not particularly limited. For example, any method known in the art such as atmospheric distillation or vacuum distillation can be applied as the distillation method, and the distillation apparatus can also be applied to a continuous type, a batch type, or the like. Any of a variety of distillation devices are known.
藉由蒸餾操作將比第一溶劑之沸點低之成分(低沸餾物)餾除後,回收第一溶劑。蒸餾包含第一溶劑及第二溶劑之第一溶劑混合物時,難以分離具有第一溶劑與第二溶劑之中間沸點之第三溶劑,但本發明中藉由皂化反應將第二溶劑轉換成第一溶劑而可自第三溶劑分離回收。第一溶劑藉由蒸餾而分離回收時之條件並無特別限制,但較好在第一溶劑之沸點左右之溫度,回流10分鐘~2小時左右後,蒸餾第一溶劑並單離。藉由此種操作可回收純度高的第一溶劑。如前述第三溶劑為具有與第一溶劑沸點接近之沸點的酮系溶劑時,由於第一溶劑混合物之皂化反應時酮系溶劑因醛醇縮合而二聚化,而生成與第一溶劑之沸點差更大之二聚化物,故可容易地以高純度分離回收第一溶劑。 After the component (lower boiling) having a lower boiling point than the first solvent is distilled off by a distillation operation, the first solvent is recovered. When the first solvent mixture comprising the first solvent and the second solvent is distilled, it is difficult to separate the third solvent having the intermediate boiling point of the first solvent and the second solvent, but in the present invention, the second solvent is converted into the first by the saponification reaction. The solvent can be separated and recovered from the third solvent. The conditions for separating and recovering the first solvent by distillation are not particularly limited, but it is preferably at a temperature of about the boiling point of the first solvent, and after refluxing for about 10 minutes to 2 hours, the first solvent is distilled and separated. By this operation, the first solvent having a high purity can be recovered. When the third solvent is a ketone solvent having a boiling point close to the boiling point of the first solvent, the ketone solvent is dimerized by aldol condensation due to the saponification reaction of the first solvent mixture to form a boiling point with the first solvent. Since the dimer is larger, the first solvent can be easily separated and recovered in high purity.
依據本發明之第一樣態,可有效率地自含有烷二醇單烷基醚及其對應之羧酸酯以及至少一種其他溶劑之溶劑混合物分離回收純度高的烷二醇單烷基醚。 According to the first aspect of the present invention, an alkane monoalkyl ether having a high purity can be efficiently separated and recovered from a solvent mixture containing an alkylene glycol monoalkyl ether and its corresponding carboxylate and at least one other solvent.
本發明之第二實施樣態係使用含有烷二醇單烷基醚(第一溶劑)及第一溶劑之對應羧酸酯的烷二醇單烷基醚羧酸酯(第二溶劑)之混合溶劑處理光阻組成物之廢液之再利用方法。第二實施樣態中使用之廢液與第一實施樣態中說明之光阻組成物之處理廢液同等。因此,第二實施樣態之第三步驟及第四步驟由於各與第一實施樣態之第一步驟及第二步驟對應,故省略說明。 A second embodiment of the present invention uses a mixture of an alkylene glycol monoalkyl ether carboxylate (second solvent) containing an alkylene glycol monoalkyl ether (first solvent) and a corresponding carboxylate of the first solvent. A method of recycling a waste liquid of a solvent-treated photoresist composition. The waste liquid used in the second embodiment is equivalent to the treatment waste liquid of the photoresist composition described in the first embodiment. Therefore, since the third step and the fourth step of the second embodiment correspond to the first step and the second step of the first embodiment, the description is omitted.
第二實施樣態中之第一步驟係以包含以通式(I)及通式(II)表示之溶劑之混合溶劑例如光阻組成物之剝離用溶劑、洗淨用溶劑等處理例如洗淨或清洗光阻組成物之步驟。更具體而言,係於半導體元件、液晶顯示元件、彩色濾光片等之製造步驟中,將附著於半導體基板或玻璃基板之不需要之光阻組成物或附著於將光阻組成物朝前述基板之塗佈裝置之噴嘴、配管等之光阻組成物去除之步驟。光阻組成物之剝離用溶劑及洗淨用溶劑通常實質上不含有以通式(I)及通式(II)表示之溶劑以外之第三溶劑。此處所謂“實質上不含有”意指非刻意添加第三溶劑,但在滿足光阻組成物之剝離用溶劑及洗淨用溶劑之製品規格之範圍內含有雜質時除外。 The first step in the second embodiment is a treatment comprising a solvent mixture of a solvent represented by the general formula (I) and the general formula (II), for example, a solvent for a release of a photoresist composition, a solvent for cleaning, or the like, for example, washing. Or the step of cleaning the photoresist composition. More specifically, in a manufacturing step of a semiconductor element, a liquid crystal display element, a color filter or the like, an unnecessary photoresist composition adhering to a semiconductor substrate or a glass substrate or attached to the photoresist composition is applied to the foregoing The step of removing the photoresist composition of the nozzle, the pipe, or the like of the coating device of the substrate. The solvent for the release of the photoresist composition and the solvent for cleaning generally do not substantially contain the third solvent other than the solvent represented by the general formula (I) and the general formula (II). The term "substantially not contained" as used herein means that the third solvent is not intentionally added, except when the impurities are contained within the range of the product specifications for the solvent for the release of the photoresist composition and the solvent for the cleaning.
第二實施樣態之第二步驟係回收包含第一步驟所生成之光阻組成物之處理廢液之步驟。所回收之廢液中包含以通式(I)及通式(II)表示之溶劑以外之成分,亦即光阻組成物中所含之溶劑、樹脂、顏料等之固體成分、其他添加劑成分。 The second step of the second embodiment is a step of recovering the treatment waste liquid comprising the photoresist composition produced in the first step. The recovered waste liquid contains components other than the solvent represented by the general formula (I) and the general formula (II), that is, a solid component such as a solvent, a resin, or a pigment contained in the photoresist composition, and other additive components.
第二實施樣態之第五步驟係藉由於第四步驟所分離回收之第一溶劑中添加新的第二溶劑,而再調製具有於成為目的用途所期望之特定調配比之混合溶劑之步驟。作為一例舉例為添加特定量之第二溶劑以成為與第一步驟所用之光阻組成物之剝離用溶劑或洗淨用溶劑同等之組成,但亦可調整為其他用途所使用之調配比之不同組成。 The fifth step of the second embodiment is a step of re-modulating a mixed solvent having a specific compounding ratio desired for the intended use by adding a new second solvent to the first solvent separated by the fourth step. As an example, a specific amount of the second solvent is added so as to be equivalent to the solvent for peeling or the solvent for cleaning of the photoresist composition used in the first step, but it may be adjusted to be different in the blending ratio used for other uses. composition.
依據本發明之第二實施樣態,藉由有效率地自處理光阻組成物之廢液中回收純度高的第一溶劑,添加特定量之新第二溶劑,而可再調製光阻組成物之剝離用溶劑、洗淨用溶劑等,亦即可有效再利用處理廢液。依據該樣態,相較於藉由直接蒸餾處理廢液(溶劑混合物)而分離去除較第一溶劑之低沸點餾分及較第二溶劑之高沸點餾分之以往方法,可以低成本獲得高純度之混合溶劑。 According to the second embodiment of the present invention, the photoresist can be re-modulated by efficiently recovering the first solvent having a high purity from the waste liquid of the photoresist composition and adding a specific amount of the new second solvent. The solvent for peeling, the solvent for washing, and the like can also effectively reuse the waste liquid. According to this aspect, the high-purity can be obtained at a low cost compared to the conventional method of separating and removing the lower boiling fraction of the first solvent and the higher boiling fraction of the second solvent by directly distilling the waste liquid (solvent mixture). Mixed solvent.
第三實施樣態係光阻組成物處理液之回收方法。關於自光阻組成物處理廢液回收第一溶劑及添加新的第二溶劑而再調製具有特定調配比之混合溶劑例如光阻組成物之剝離用溶劑或洗淨用溶劑由於與第二實施樣態同等,故省略重複說明。 The third embodiment is a method for recovering a photoresist composition treatment liquid. Regarding the solvent for removing the first solvent from the photoresist composition treatment waste liquid and adding a new second solvent, and preparing a solvent having a specific compounding ratio such as a photoresist composition, or a solvent for cleaning, as in the second embodiment The states are the same, so the repeated description is omitted.
於將光阻組成物處理廢液作為光阻組成物處理液再利用時,使用者亦可進行如上述之處理廢液之回收處理(第三步驟)、反應處理(第四步驟)、蒸餾處理 (第五步驟)等,但較好溶劑之製造業者或回收業者自複數個使用者回收並進行統一處理。尤其溶劑之製造業者進行處理時,可於處理廢液而分離回收之第一溶劑中調配新製造之第二溶劑,以滿足光阻組成物處理液之規格之方式再調製混合溶液。第三實施樣態中,使用者自製造業者購入光阻組成物處理液(第一步驟),使用者進行光阻組成物之處理(第二步驟)後,製造業者或回收業者實施第三至第六步驟,使用者自製造業者或回收業者購入再調製之混合溶劑(第七步驟),之後重複實施第二至第七步驟。 When the photoresist composition treatment waste liquid is reused as the photoresist composition treatment liquid, the user can also perform the recovery treatment (third step), the reaction treatment (fourth step), and the distillation treatment of the treatment waste liquid as described above. (Fifth step), etc., but the manufacturer or recycler of the better solvent is recovered and processed by a plurality of users. In particular, when the solvent manufacturer performs the treatment, the newly prepared second solvent may be blended in the first solvent separated and recovered by treating the waste liquid to prepare the mixed solution in such a manner as to satisfy the specifications of the photoresist composition treatment liquid. In the third embodiment, the user purchases the photoresist composition treatment liquid from the manufacturer (first step), and after the user performs the treatment of the photoresist composition (the second step), the manufacturer or the recycler implements the third to In the sixth step, the user purchases the reconditioned mixed solvent from the manufacturer or the recycler (seventh step), and then repeats the second to seventh steps.
依據本發明之第三實施樣態,由於反覆進行製造業者或回收業者對使用者所使用之光阻組成物處理廢液進行回收及再生處理,及使用者使用經再生之光阻組成物處理液之循環,故對環境之負荷小,可以低成本有效率地回收光阻組成物用處理液。 According to the third embodiment of the present invention, the manufacturer or the recycling company repeatedly recycles and regenerates the photoresist composition treatment waste liquid used by the user, and the user uses the regenerated photoresist composition treatment liquid. Since the cycle is small, the load on the environment is small, and the treatment liquid for the photoresist composition can be efficiently and efficiently recovered.
以下,藉由實施例更具體說明本發明。又,本發明不限定於實施例之記載內容。且,本發明中,於以下實施例以外,進而於上述具體描述以外,在不脫離本發明主旨之範圍內,基於本技藝者之知識,可進行各種變更、修正、改良等。 Hereinafter, the present invention will be more specifically described by way of examples. Further, the present invention is not limited to the contents described in the examples. In addition to the above-described embodiments, various changes, modifications, improvements, and the like may be made without departing from the spirit and scope of the invention.
作為包含烷二醇單烷基醚(第一溶劑)及其對應之羧 酸酯(第二溶劑)以及其他溶劑(第三溶劑)之溶劑混合物,係準備包含下述表1所示組成之丙二醇單甲基醚(PGME)、丙二醇單甲基醚乙酸酯(PGMEA)及其他溶劑之溶劑混合物(第一溶劑混合物)。 As an alkylene glycol monoalkyl ether (first solvent) and its corresponding carboxylic acid A solvent mixture of an acid ester (second solvent) and another solvent (third solvent) is prepared by including propylene glycol monomethyl ether (PGME) or propylene glycol monomethyl ether acetate (PGMEA) having the composition shown in Table 1 below. And a solvent mixture of other solvents (first solvent mixture).
MeOH:甲醇 MeOH: methanol
EtOH:乙醇 EtOH: ethanol
PGME:丙二醇單甲基醚 PGME: propylene glycol monomethyl ether
PGMEA:丙二醇單甲基醚乙酸酯 PGMEA: propylene glycol monomethyl ether acetate
MMP:3-甲氧基丙酸甲酯 MMP: methyl 3-methoxypropionate
EL:乳酸乙酯 EL: ethyl lactate
CYP:環戊酮 CYP: cyclopentanone
蒸餾之回收率(%)=(蒸餾之回收液量)/(溶劑混合物之量)×100 Recovery by distillation (%) = (amount of recovered liquid by distillation) / (amount of solvent mixture) × 100
PGME回收率(%)=(回收之PGME量)/(溶劑混合物中之PGME量+PGMEA量)×100 PGME recovery rate (%) = (recovered PGME amount) / (PGME amount in solvent mixture + PGMEA amount) × 100
實施具有表1中記載之組成之溶劑混合物(第一溶劑混合物)之皂化反應。具體而言,於具備回流冷卻器及攪拌裝置之容量1升之三頸燒瓶中饋入793g之具有表1記載之組成的溶劑混合物(第一溶劑混合物)及 94g氫氧化鈉。對內部邊吹入氮氣邊於常壓加熱至80℃後保持3小時進行皂化反應。反應後之溶劑混合物(第二溶劑混合物)放冷至室溫後,以蒸發器進行用以與固形分(乙酸鈉)分離之單蒸餾後,再度進行用以獲得目的物(PGME)之蒸餾。 A saponification reaction of a solvent mixture (first solvent mixture) having the composition described in Table 1 was carried out. Specifically, 793 g of a solvent mixture (first solvent mixture) having the composition shown in Table 1 was fed into a three-necked flask having a volume of 1 liter equipped with a reflux condenser and a stirring device. 94 g of sodium hydroxide. The internal side was blown with nitrogen gas and heated at 80 ° C under normal pressure for 3 hours to carry out a saponification reaction. After the reaction, the solvent mixture (second solvent mixture) was allowed to cool to room temperature, and subjected to a single distillation for separation from a solid component (sodium acetate) by an evaporator, and then used again to obtain a distillation of the target product (PGME).
作為蒸餾裝置係使用圖1所示之棚段塔式(Oldershaw)蒸餾裝置10。圖1中,A係具備溫度計15之1L燒瓶,B係理論段數為20段之精餾塔。升至塔頂之蒸氣在回流頭11內凝縮,以電磁閥操作之回流/餾出切換濾斗12作成可調整回流比之構成。且於餾出側配置餾出活栓13,於其前端準備接受器14。使上述所得之單蒸餾回收液流入燒瓶A內,2小時加熱回流後,分餾出餾出物。 As the distillation apparatus, the Oldershaw distillation apparatus 10 shown in Fig. 1 was used. In Fig. 1, A is provided with a 1 L flask of a thermometer 15, and B is a rectification column having a theoretical number of 20 stages. The vapor rising to the top of the column is condensed in the reflux head 11, and the reflux/distillation switching bucket 12 operated by the solenoid valve is configured to adjust the reflux ratio. The distillate stopper 13 is placed on the distillation side, and the receiver 14 is prepared at the tip end. The single-distilled recovered liquid obtained above was poured into the flask A, heated under reflux for 2 hours, and the distillate was fractionated.
上述表1中記載之溶劑混合物、單蒸餾回收液及蒸餾回收液以氣相層析(GC)分析之結果示於表1。表1中,單蒸餾回收液中之所謂蒸餾之回收率係單蒸餾回收液之質量相對於所使用之原本溶劑混合物(第一溶劑混合物)之質量的比例,單蒸餾回收液中之所謂PGME回收率係單蒸餾回收液中之PGME質量相對於所使用之原本溶劑混合物(第一溶劑混合物)中之PGME質量與PGMEA質量之和的比例。蒸餾回收液中之所謂蒸餾之回收率係最終蒸餾回收液之質量相對於所使用之原本溶劑混合物(第一溶劑混合物)之質量的比例,蒸餾回收液中之所謂PGME回收率係最終蒸餾回收液中之PGME質量相對於所 使用之原本溶劑混合物(第一溶劑混合物)中之PGME質量與PGMEA質量之和的比例。 The solvent mixture, the single distillation recovery liquid, and the distillation recovery liquid described in Table 1 above were analyzed by gas chromatography (GC). Table 1 shows the results. In Table 1, the so-called distillation recovery rate in the single-distillation recovery liquid is the ratio of the mass of the single-distillation recovery liquid to the mass of the original solvent mixture (first solvent mixture) used, and the so-called PGME recovery in the single-distillation recovery liquid. The ratio is the ratio of the mass of PGME in the single distillation recovery liquid to the sum of the mass of PGME and the mass of PGMEA in the original solvent mixture (first solvent mixture) used. The so-called distillation recovery rate in the distillation recovery liquid is the ratio of the mass of the final distillation recovery liquid to the mass of the original solvent mixture (first solvent mixture) used, and the so-called PGME recovery rate in the distillation recovery liquid is the final distillation recovery liquid. PGME quality in the middle The ratio of the mass of PGME to the mass of PGMEA in the original solvent mixture (first solvent mixture) used.
氣相層析(GC)之測定條件如下。 The measurement conditions of gas chromatography (GC) are as follows.
裝置:GC-14B(島津製作所製) Device: GC-14B (made by Shimadzu Corporation)
管柱:毛細管管柱(CBP1-M50-025) Column: capillary column (CBP1-M50-025)
固定相液體:甲基聚矽氧 Stationary phase liquid: methyl polyoxyl
固定相液體厚:0.25μm Stationary phase liquid thickness: 0.25μm
管柱材質:超高純度氧化矽 Column material: ultra high purity bismuth oxide
管柱內徑:0.22mm Column inner diameter: 0.22mm
管柱長:50m Column length: 50m
載氣:氦氣 Carrier gas: helium
流速:2mL/分鐘 Flow rate: 2mL/min
壓力:150kPa Pressure: 150kPa
檢測器:氫焰離子化檢測器(FID) Detector: Hydrogen Flame Ionization Detector (FID)
氫氣壓:50kPa Hydrogen pressure: 50kPa
空氣壓:50kPa Air pressure: 50kPa
管柱溫度:50℃(保持1分鐘)→5℃/分鐘升溫→145℃(保持5分鐘) Column temperature: 50 ° C (for 1 minute) → 5 ° C / min for temperature → 145 ° C (for 5 minutes)
注入口溫度:200℃ Injection inlet temperature: 200 ° C
檢測器溫度:200℃ Detector temperature: 200 ° C
試料量:0.2μL(分裂比1/50) Sample volume: 0.2 μ L (split ratio of 1/50)
指定感度:10-2 Specify sensitivity: 10 -2
定量方法:修正面積百分率法 Quantitative method: corrected area percentage method
於實施例1之溶劑混合物714g中添加水65g所得之溶劑混合物,使用與實施例1同樣之蒸餾裝置,進行21小時之加熱回流後,分餾出餾出物,算出其回收率,並且以氣相層析確認餾出物純度。氣相層析之測定條件與實施例1之情況相同。所得之回收率及純度示於表2。PGME回收率係由以下式算出。上述水之添加量65g係考慮可使溶劑混合物中之第三成分(MMP及CYP)作為最低共沸混合物(共沸混合物之沸點及共沸溫度在沸點曲線上取最小值時之混合物)予以去除及使PGME之損失抑制在最小限度而決定。本比較例由於與實施例1不同不副產生乙酸鈉,故並無相當於實施例1之單蒸餾之步驟。 65 g of the obtained solvent mixture was added to 714 g of the solvent mixture of Example 1, and the mixture was heated and refluxed for 21 hours using the same distillation apparatus as in Example 1, and the distillate was fractionally distilled to calculate the recovery rate and the gas phase. The purity of the distillate was confirmed by chromatography. The measurement conditions of the gas chromatography were the same as those in the case of Example 1. The recovery and purity obtained are shown in Table 2. The PGME recovery rate was calculated by the following formula. The above-mentioned amount of water added is 65 g, and it is considered that the third component (MMP and CYP) in the solvent mixture can be removed as the lowest azeotrope (the mixture of the boiling point of the azeotrope and the azeotropic temperature on the boiling point curve). And it is determined to minimize the loss of PGME. In this comparative example, since sodium acetate was not produced in the same manner as in Example 1, there was no step corresponding to the single distillation of Example 1.
PGME回收率(%)=(回收之PGME量)/(溶劑混合物中之PGME量+PGMEA量)×100 PGME recovery rate (%) = (recovered PGME amount) / (PGME amount in solvent mixture + PGMEA amount) × 100
於對實施例1之溶劑混合物700g中添加甲醇138g所得之溶劑混合物中,添加約0.8g之甲氧化鈉作為觸媒(溶劑混合物中之PGMEA之0.01倍莫耳),直至成為平衡之前,於常壓、70℃加熱反應190分鐘後,使用與比較例1同樣之蒸餾裝置,加熱回流2小時後,分餾餾出物,算出其回收率,且以氣相層析確認餾出物純度。所得回收率及純度示於表2。甲醇之添加量138g係考慮酯交換反應之轉化率與基於隨後分離製程之能量成本所決定者,相 當於溶劑混合物中之PGMEA之3倍莫耳量。以上述條件達平衡時係以經時取樣並以氣相層析檢測組成成為一定而確認。本比較例亦無相當於實施例1中之單蒸餾之步驟。 To the solvent mixture obtained by adding 138 g of methanol to 700 g of the solvent mixture of Example 1, about 0.8 g of sodium methoxide was added as a catalyst (0.01 times of PGMEA in the solvent mixture) until it became equilibrated. After heating and reacting at 70 ° C for 190 minutes, the mixture was heated under reflux for 2 hours using a distillation apparatus similar to that of Comparative Example 1, and then the fraction was fractionated, and the recovery was calculated, and the purity of the distillate was confirmed by gas chromatography. The recovery and purity obtained are shown in Table 2. The amount of methanol added 138g is determined by considering the conversion rate of the transesterification reaction and the energy cost based on the subsequent separation process. 3 times the molar amount of PGMEA in the solvent mixture. When the above conditions were reached, the equilibrium was confirmed by sampling with time and detecting the composition by gas chromatography. This comparative example also does not have the same step as the single distillation in Example 1.
實施例1之溶劑混合物不實施皂化反應,而使用蒸餾裝置加熱回流2小時後,分餾餾出物,算出其回收率且以氣相層析確認餾出物純度。所得回收率及純度示於表2。本比較例亦無相當於實施例1中之單蒸餾之步驟。 The solvent mixture of Example 1 was not subjected to a saponification reaction, and was heated and refluxed for 2 hours using a distillation apparatus, and then the distillate was fractionated, the recovery was calculated, and the purity of the distillate was confirmed by gas chromatography. The recovery and purity obtained are shown in Table 2. This comparative example also does not have the same step as the single distillation in Example 1.
將僅含丙二醇單甲基醚與丙二醇單甲基醚乙酸酯700g作為溶劑混合物,於其中添加氫氧化鈉33g及水14g,在常壓進行120℃、4小時水解反應,隨後,使用蒸餾裝置,加熱回流21小時後,分餾餾出物,算出其回收率。本比較例亦無相當於實施例1中之單蒸餾之步驟。 700 g of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate were used as a solvent mixture, and 33 g of sodium hydroxide and 14 g of water were added thereto, and hydrolysis reaction was carried out at normal pressure at 120 ° C for 4 hours, followed by using a distillation apparatus. After heating under reflux for 21 hours, the distillate was fractionated to calculate the recovery. This comparative example also does not have the same step as the single distillation in Example 1.
以上結果彙總示於表2。如由表2之結果所了解,於溶劑混合物中添加水進行蒸餾之比較例1,作為純度99.5%以上之高純度品的丙二醇單甲基醚(PGME)之回收率為58%,相對於此,可知實施例1中,作為純度99.5%以上之高純度品的丙二醇單甲基醚(PGME)之回收率高於比較例1。 The above results are summarized in Table 2. As is understood from the results of Table 2, in Comparative Example 1 in which water was added to the solvent mixture for distillation, the recovery rate of propylene glycol monomethyl ether (PGME) as a high purity product having a purity of 99.5% or more was 58%. It is understood that the recovery rate of propylene glycol monomethyl ether (PGME) as a high purity product having a purity of 99.5% or more is higher than that of Comparative Example 1.
於溶劑混合物中添加甲醇進行酯交換反應之比較例2,作為純度99.5%以上之高純度品的丙二醇單甲 基醚(PGME)之回收率,由於環戊酮等之雜質接近PGME之沸點,故為73%,相對於此,可知實施例1中,作為純度99.5%以上之高純度品的PGME之回收率高於比較例2。 Comparative Example 2 in which methanol was added to a solvent mixture for transesterification, and propylene glycol monomethyl as a high purity product having a purity of 99.5% or more The recovery rate of the PGME is 3% by weight, and since the impurity of cyclopentanone is close to the boiling point of PGME, it is 73%. In contrast, the recovery rate of PGME as a high purity product having a purity of 99.5% or more in Example 1 is known. Higher than Comparative Example 2.
於不進行皂化反應而僅進行蒸餾之比較例3中,作為純度99.5%以上之高純度品的丙二醇單甲基醚(PGME)之回收率為44%,可知相較於實施例1顯著劣化。 In Comparative Example 3 in which only the distillation was carried out without performing the saponification reaction, the recovery rate of propylene glycol monomethyl ether (PGME) as a high-purity product having a purity of 99.5% or more was 44%, which was found to be significantly deteriorated compared with Example 1.
比較例4雖顯示以高收率獲得高純度品,但係溶劑混合物中不含有丙二醇單甲基醚(PGME)及丙二醇單甲基醚乙酸酯(PGMEA)以外之其他雜質之情況的結果,對於自其他雜質分離PGME之PGME分離溶液性未有任何見解。 In Comparative Example 4, a high-purity product was obtained in a high yield, but the solvent mixture did not contain propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA). There is no insight into the separation of solution properties of PGME from PGME from other impurities.
MeOH:甲醇 MeOH: methanol
EtOH:乙醇 EtOH: ethanol
PGME:丙二醇單甲基醚 PGME: propylene glycol monomethyl ether
PGMEA:丙二醇單甲基醚乙酸酯 PGMEA: propylene glycol monomethyl ether acetate
MMP:3-甲氧基丙酸甲酯 MMP: methyl 3-methoxypropionate
EL:乳酸乙酯 EL: ethyl lactate
CYP:環戊酮 CYP: cyclopentanone
ML:乳酸甲酯 ML: Methyl lactate
MA:乙酸甲酯 MA: methyl acetate
1)溶劑混合物之組成比,係以「實施例1:表1」所示者為基礎所合計。此外,比較例1中係加上添加水而計算,比較例2中係加上添加甲醇量而計算。 1) The composition ratio of the solvent mixture is based on the results shown in "Example 1: Table 1". Further, in Comparative Example 1, calculation was carried out by adding water, and in Comparative Example 2, the amount of methanol added was calculated.
依據本發明,可自包含烷二醇單烷基醚及其對應之羧酸酯及其他溶劑之溶劑混合物以高純度且高收率分離回收烷二醇單烷基醚。本發明可有效作為光阻組成物之處理廢液之再利用方法,可以低成本製造半導體元件、液晶顯示元件、彩色濾光片等。 According to the present invention, the alkanediol monoalkyl ether can be isolated and recovered in high purity and high yield from a solvent mixture comprising an alkanediol monoalkyl ether and its corresponding carboxylic acid ester and other solvents. The present invention can be effectively used as a method for recycling a treatment waste liquid of a photoresist composition, and can manufacture a semiconductor element, a liquid crystal display element, a color filter, and the like at low cost.
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JP2005247816A (en) * | 2004-03-08 | 2005-09-15 | Sanwa Yuka Kogyo Kk | Method for separating and recovering alkylene glycol monoalkyl ether |
TW200720861A (en) * | 2005-07-19 | 2007-06-01 | Showa Denko Kk | Removing solution for photosensitive composition |
TW201034765A (en) * | 2009-03-31 | 2010-10-01 | Tokyo Ohka Kogyo Co Ltd | Regenerated photoresist and manufacturing method of regenerated photoresist |
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