201219411 六、發明說明： 【發明所屬之技術領域】 本發日縣_-種高純度胺基亞甲基膦酸之製 ， 土亞甲基膦酸類為著名之配位於多種金屬 = 物之抗分解敎解各式各樣胁過氧化 【先前技術】 近?來於轉體產針，步购細微化魏，並主 潔度之提升、步驟簡略化為目的，削在作切 =過氧化氫水、氨水等中添加胺基亞甲基 S3 除去晶圓上之金屬的方法。 ； 几人ί基亞甲基膦酸的製造法，已知有於鹽酸酸性下，令，、松 是專胺 是Γ膦酸反應_胺基亞曱二‘ 万去考專利文獻1、非專利文獻1)。 適^半導體產業的石夕晶圓清洗液在其特性上 極力減少胺基亞甲基膦酸之未反應的原料、副; 料之選定等定為低階，而關於有機雜質，特 胺基亞甲基膦酸_留原料之中，特 而以添加至過氧化氫等之氧化劑為目的時，原:二 量，因胺基亞甲基膦酸之使用形態、添加量;異力^二而， 用時，宜為:。· 3麵町： 為G. 2重轉以下。以分離後的 重罝％以下，而較理想之樣態為G. 8重知以下牧用予且為1 曰之絲亞f基膦酸的精製方法，可舉出以再处 換樹脂精製的方法、藉由將轉反應蒸顧而變成縮U出的方法又。 201219411 定如固化後ί&Ξΐίϋ入不良溶劑而固化的方法，難於選 製效率低的缺點且，有產率及精 題。‘、、、勒祕之後的程序中亦存在處理性變得非常差的問 下精製時，由於曱崎於水的親和性大，於常壓、減壓 的蒸氣壓較甲較大，需要在系中添加水並=時 ^ ^的水’故?驗效率差。再者，加壓條件中，軸甲搭的 水大，但因為安全性低’所以需要對應於加壓之昂 方法之甲_低的 胺其2石油類的二f醇縮帽，故有減低大量的 月女基亞曱基膦酸之曱醛需要危險品設備的問題。 幻 [先前技術文獻] [專利文獻] [專利文獻1]美國專利3，288, 846號公報 [專利文獻2]日本特開2007-77040號公報 [非專利文獻] [非專利文獻 1]Journal 〇f 〇rganic Chemistry 第 31 卷 1603 頁 【發明内容】 [發明所欲解決的問題] ，本發明之目的在於解決先前技術之如前述的問題，將作為半 導體工業用途之石夕晶圓清洗液的成分使用的胺基亞曱基膦酸中之 未反應的甲醛，以產率佳，簡便的設#、簡單的操作且不產生危 險品而去除作為目的。 201219411 1 t [解決問題之技術手段] 本案發明人為了達成前述目的而進行仔細研究的結果發現： 高純度胺基亞曱基膦酸之製造方法中，將含有曱醛的粗胺^亞曱 基膦酸水溶液蒸餾之際，藉由設置於蒸餾中之粗胺基亞曱基膦酸， 水溶液添加預定量之水的步驟’而不會損失胺基亞曱基膦酸，且 可以高釜效率容易地去除甲醛，乃至達成本發明。 詳言之，本發明係關於一種高純度胺基亞曱基膦酸之製造方 法’包含：蒸餾步驟’使用批式蒸餾設，蒸餾水分濃度為35〜60 重量％的粗胺基亞曱基膦酸水溶液，且^亥粗胺基亞曱基膦酸水溶 液為包含胺基亞曱基膦酸、以及甲醛的水溶液；該蒸餾步驟具有 於蒸餾中添加水至蒸餾爸的步驟’且添加至該蒸餾釜之水的總 量，相對於粗胺基亞曱基膦酸水溶液之添加重量，至少定為0.5 倍量。 [對照先前技術之功效] 丨 根據本發明’不會損失胺基亞曱基膦酸，且可輕易以高蚤效 率安全地去除未反應的醛，並得到高純度胺基亞曱基膦酸，而發 ，細微化的半導體之碎晶圓清洗液的成分，以增加其機能為目的 等’同時添加過氧化氫水及氨水而可使用。 顯然以本發明之方法精製的胺基亞甲基膦酸，除了半導體關 連用途以外’若滿足其需要的規格亦可使用。 【實施方式】 〔粗胺基亞甲基膦酸水溶液〕 本發明所使用的粗胺基亞曱基膦酸水溶液，係為包含胺基亞 曱基^酸、曱醛、及水’且水之濃度為30〜65重量％的水溶液。 胺基亞甲基膦酸，較理想之樣態可舉出：胺基三亞曱基膦酸、 乙一胺四（亞甲基膦酸）、][，2—丙二胺四（亞曱基膦酸）、己二胺四 (亞曱基膦酸）、二乙三胺五（亞甲基膦酸)及該等之鹽、以及氧化 劑等。 ；201219411 VI. Description of the invention: [Technical field to which the invention belongs] This is a Japanese-made high-purity aminomethylene phosphonic acid system. The methylene phosphonic acid is a well-known compound located in various metals.敎 各 各 各 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 A method in which an aminomethylene S3 is added to ammonia, etc. to remove metal on the wafer. A few people, the production method of lysyl methylene phosphonic acid, known under the acidity of hydrochloric acid, let, pine is a specific amine is a phosphinic acid reaction _ amine amide ' two million to go to the patent document 1, non-patent Document 1). The Shixi wafer cleaning solution suitable for the semiconductor industry minimizes the unreacted raw materials and auxiliary materials of the aminomethylene phosphonic acid in its characteristics; the selection of the materials is determined to be low-order, and the organic impurities, the amine Among the methylphosphonic acid-retained raw materials, in particular, when it is added to an oxidizing agent such as hydrogen peroxide, the original amount is two, and the use form and amount of the aminomethylenephosphonic acid are different; When used, it should be: · 3 noodles: Repeat for G. 2 below. The method of purifying the sub-f-phosphonic acid of 1 曰 予 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重 重The method is further characterized by a method of steaming the reaction to reduce it. 201219411 It is difficult to select the low-efficiency defect and the yield and the problem if the curing method is cured after the curing. In the process of ',, and after the secret, there is also a problem that the handling is very poor. When the refining is in the water, the vapor pressure in the normal pressure and the reduced pressure is larger than that in the process. The water added in the system and the water at the time ^^ is poor. In addition, in the pressurized condition, the water of the shaft is large, but because of the low safety, it is required to correspond to the method of the pressurization method, the lower amine, and the second petroleum-based bis-alcoholic cap, so it is reduced. A large amount of furyl aldehydes of the genus thioglycolic acid requires the problem of dangerous goods equipment. [PRIOR ART DOCUMENT] [Patent Document 1] US Patent No. 3,288,846 [Patent Document 2] JP-A-2007-77040 [Non-Patent Document] [Non-Patent Document 1] Journal 〇 f 〇rganic Chemistry, Vol. 31, No. 1603 [Invention] [The problem to be solved by the invention] The object of the present invention is to solve the problems of the prior art as described above, and to use as a component of the Si Xi wafer cleaning liquid for the semiconductor industry. The unreacted formaldehyde in the aminophosphonium phosphonic acid used is desirably removed in a good yield, simple operation, simple operation, and no dangerous product. 201219411 1 t [Technical means for solving the problem] As a result of careful study in order to achieve the above object, the inventors of the present invention found that: in the method for producing high-purity aminomeridinophosphonic acid, a crude amine containing a furfural When the aqueous phosphonic acid solution is distilled, the step of adding a predetermined amount of water to the aqueous solution by using the crude amino-mercaptophosphonic acid in the distillation does not lose the amino-mercaptophosphonic acid, and the efficiency of the reaction can be high. The formaldehyde is removed to achieve the present invention. In particular, the present invention relates to a method for producing a high-purity aminomercaptophosphonic acid comprising: a distillation step of using a batch distillation apparatus to distill a crude aminophosphonium phosphine having a water concentration of 35 to 60% by weight. An aqueous acid solution, and the aqueous solution of crude amidophosphinic acid is an aqueous solution containing an amino-mercaptophosphonic acid and formaldehyde; the distillation step has a step of adding water to the distillation dad in the distillation and adding to the distillation The total amount of water in the kettle is at least 0.5 times the weight of the aqueous solution of the crude amino-mercaptophosphonic acid. [Comparative to the efficacy of the prior art] 丨 According to the present invention, 'the amino-mercaptophosphonic acid is not lost, and the unreacted aldehyde can be easily removed with high enthalpy efficiency, and a high-purity aminophosphonium phosphonic acid is obtained, The composition of the micro-wafer semiconductor wafer cleaning liquid can be used by adding hydrogen peroxide water and ammonia water for the purpose of increasing its function. It is apparent that the aminomethylenephosphonic acid purified by the method of the present invention can be used in addition to the semiconductor-related use. [Embodiment] [Aqueous solution of crude aminomethylenephosphonic acid] The aqueous solution of crude aminophosphonium phosphonic acid used in the present invention contains an aminomercapto acid, furfural, and water and water An aqueous solution having a concentration of 30 to 65% by weight. Aminomethylene phosphonic acid, preferably, is exemplified by: aminotrimethylenephosphonic acid, ethylamine tetrakis (methylene phosphonic acid), ][,2-propylenediaminetetrakis (phosphinium phosphine) Acid), hexamethylene diamine (m-decylphosphonic acid), diethylenetriamine penta (methylene phosphonic acid), salts thereof, and oxidizing agents. ;
I 本發明所使用的粗胺基亞甲基膦酸水溶液，需使用水之濃度 6 ⑧ 201219411 ^ 35〜60重量％的水溶液.。該水分濃度低於下限時，由於 亞τ基膦酸水溶液之鹽酸濃度‘ ΐϋίί膦，不理想。該水分濃度高於該範圍時， 甘\成釜劢率大幅受損，故較不理想。本發明中，胺美 ^巧之水的濃度於該範圍外時’需於該水溶液之“ 俾使其_範圍内，而以此為前提，藉由—邊““ 量的水…邊進行論，而得到高純度的胺基亞 使本剌之_麵f _酸水溶液巾的情濃度 =下述之粗絲亞？基膦_合成條件而增減，且本發明中並 限疋，但較理想之樣態為1〜12重量％，更理想之樣態為1〜9 5 wii本發明“有帽之粗胺基亞甲基膦酸水溶液 基亞甲基膦酸濃度並無_限定，但較理想之雜為1〇~5〇 直置％ 〇 (粗胺基亞曱基膦酸水溶液之製造） 本發明中，粗胺基亞甲基膦酸水溶液，宜於鹽酸酸性下 或是胺與甲醛、膦酸反應而得之。 將胺基亞甲基膦酸用於半導體產業用途的情況，不宜使用如 利^銹鋼等之有金屬成，之溶離龄備，而使用接液部為玻璃 襯袤（以下稱GL)等金屬成:分不會雜的攪拌機式反應爸較為理 :該⑶蚤事先令其成為Fe等金屬成分不會溶離的清淨化狀 態而使S。清淨化之方法有_稀魏、去軒水的清洗。 以下更5·體地說明製择順序較理想之一例。首先在GL釜中添 加鹽酸，接著添加亞鱗酸由於利用添加亞碟酸，藉由與鹽酸之 反應而吸熱，故進行加熱；，將溫度保持於5〜15t：。接著，將反應 溫度保持於15〜m：，-定速度添加氨或胺。由於本反應^ 放，，故需要散熱。胺添加I結束後，將反應液加熱至85~95t：為止。 接著將35〜50重量％的福馬林以—定速度供給*進行反應。反應 本身為放熱反應，而反應丨夜的溫度係管理成9〇〜1〇(rc。反應完成 201219411 後’冷卻至-溫為止並作為反應結束。產生的鹽酸蒸氣，根據利 用回流的防污染之觀點，通過噴射料而翻至系外，且盡可能 避免回流，以排放氣體處理設備處理。該等一系列的操作中，重 點為需要注t、科成絲。鱗謂造設躺魏清淨亦很重要。 =反應中，胺較理想之樣態可舉出：乙二胺、丨，2__丙二胺、 己二胺、二乙三胺等。亞磷酸，較理想之樣態為：利用 用N原子之3〜6倍莫耳；利驗時，該胺為—級胺的情況使用n ^子之2〜4倍莫耳，二級胺的情況使用N原子之1~2倍莫耳。在 胺為1分子中具有一級及二級之胺部位的情況，可使用對於先前 之一級、一級胺各別的使用量之總和。 該反應中，甲醛較理想之樣態為：利用氨時，使用N原子之 3〜9倍莫耳，·利用胺時，該胺為一級胺的情況使用N原子之2〜6 倍莫耳，二級胺的情況使用N原子之丨〜3倍莫耳。在胺為丨分子 中^有一級及二級之胺部位的情況，可使用對於先前之一級、二 級胺各別的使用量之總和。酸，較理想之樣態可舉出 、 磷酸、硝酸等之無機酸。 &瓜®夂 〔粗胺基亞甲基膦酸水溶液之蒸顧!〕 含^曱醛的粗胺基亞甲基膦酸水溶液，為了去除殘留的甲 醛，故藉由批式蒸餾設備而蒸餾◊在此粗胺基亞甲基膦酸水溶 ，，水的，度需為35〜60重量％，而水的濃度於該範圍外時，如 前述，在蒸餾前添加水，俾使其於該範菌内。 以下說明本發明所使用的批式蒸餾詨備。本發明的批式蓁餾 設備之一例，可舉出具備蒸餾釜與冷凝器的蒸餾設備。該等&餾 設備的材質係為玻璃製。 蒸餾溫度宜為90〜120〇C，而較理想之樣態為1〇〇〜。再 者，本發明中，由於藉由在蒸餾_的粗:胺基亞甲基膦酸水溶液添 加水，而可於常壓下將甲醛有效率地餾去，故不需要壓力調整所 品的设備改造費等’於安全面亦十分有利，且對於工業上非常有 益。 (水之添加） 201219411 *本發明中’在蒸餾中_加水至蒸德蚤十分重要。本發明中， 在蒸餾釜添加含有曱醛的麵胺基亞曱基膦酸水溶液，加熱蒸餾釜 而發成分自蒸餾塔餾出，將該等以冷凝器冷凝，並藉由超音 波流置，或渦流量計等之計數器而測定餾出量，而較理想之樣態 ，：在蒸餾中重複將配製成與該餾出量等量的水添加至蒸餾釜^ 操H。將配製成與雜出#等量的水添加至細辦，較理想之 樣態為一邊注意不令蒸餾釜内之粗胺基亞曱基膦酸水溶液的溫度 ^度地下降’ -邊迅速地添加。在此之「與顧出量等量」的「等 里」\其概念亦包含：不損及本發明效果之範圍的份量，而較理想 之樣，為館出量的0. 5〜1.5倍之範圍，更理想之樣態為〇. 2 ，^圍’更加理想之樣態為G· 9〜1.1倍之麵，而最理想之樣 態無庸置疑為完全等量。 再者，該餾出量之測走可根據蒸餾設備的尺寸或冷凝器的能 2改變’可即時進行，亦可以30〜60分鐘技的間隔進行。在 ，餾爸添加的水’為了防#金屬污染而使用離子交換水較為理 4，但金屬之品質若穩定赤可使用蒸餾水。 本發明中，在蒸餾中添加至蒸餾釜之水的總量，至 胺基亞曱基膦酸水溶液之添加重量的0.5倍量。由於本發明^之 量至少定為G. 5倍4，故可得到高純度的胺基亞曱基膦酸。 日种_添加相當於細中讀出液量的水至蒸館蚤而 ’故於粗胺基亞!曱基膦酸水溶液之添加時不需要添加大 里的水，而於工業上非常秀利。 、，者，在蒸财添加至_水之總量的上限並I The aqueous solution of the crude aminomethylenephosphonic acid used in the present invention requires the use of a water concentration of 6 8 201219411 ^ 35 to 60% by weight of an aqueous solution. When the water concentration is lower than the lower limit, it is not preferable because the hydrochloric acid concentration of the aqueous solution of the zirconylphosphonic acid is '‘ίί phosphine. When the water concentration is higher than the range, the rate of sputum is greatly impaired, which is less desirable. In the present invention, when the concentration of the water of the amine is outside the range, it is required to be within the range of the aqueous solution, and on the premise of this, by "the amount of water" And obtaining a high-purity amino group to increase or decrease the concentration of the f f f _ acid aqueous solution of the = = = = = = = = , , , , , , , , , , , , , , , , , , , , The ideal state is 1 to 12% by weight, and more preferably 1 to 9 5 wii. The concentration of the methylene phosphonic acid in the aqueous solution of the capped crude aminomethylphosphonic acid is not limited, but Preferably, the mixture is 1〇~5〇 straight % 〇 (manufacture of aqueous solution of crude amino sulfinylphosphonic acid). In the present invention, the aqueous solution of crude aminomethylenephosphonic acid is preferably acidic under hydrochloric acid or amine and Formaldehyde and phosphonic acid are obtained by reaction. When the aminomethylenephosphonic acid is used in the semiconductor industry, it is not suitable to use a metal such as galvanized steel, which is available in the form of a metal, which is a metal lining (hereinafter referred to as GL). Into: a mixer-type reaction that is not mixed. Dad is more reasonable: (3) 蚤 beforehand, it is made into a clean state in which the metal component such as Fe does not dissolve, and S is made. The method of purifying and purifying is _ Wei Wei, go to Xuan Shui cleaning. The following is a more illustrative example of a preferred order of preparation. First, hydrochloric acid is added to the GL kettle, followed by the addition of squaric acid, which is heated by the reaction with hydrochloric acid by the addition of the sub-disk acid, and is heated; the temperature is maintained at 5 to 15 t:. Next, the reaction temperature is maintained at 15 to m:, and ammonia or an amine is added at a constant rate. Since this reaction is released, heat dissipation is required. After the end of the amine addition I, the reaction solution was heated to 85 to 95 t:. Next, 35 to 50% by weight of formalin is supplied at a constant rate to carry out the reaction. The reaction itself is an exothermic reaction, and the temperature at which the reaction stays up late is managed to be 9 〇 1 〇 (rc. After the reaction is completed in 201219411, it is cooled to -temperature and ends as a reaction. The generated hydrochloric acid vapor is based on the anti-pollution using reflux. The viewpoint is turned over to the outside by spraying the material, and avoiding the reflux as much as possible, and treating it with the exhaust gas treatment equipment. Among the series of operations, the focus is on the need to inject t, Kecheng silk. The scale is said to lay the Wei Qing. Very important. = In the reaction, the preferred form of the amine can be exemplified by ethylenediamine, hydrazine, 2_-propylenediamine, hexamethylenediamine, diethylenetriamine, etc. Phosphorous acid, the preferred state is: 3 to 6 times the molar amount of N atoms; in the case of the amine, the amine is 2 to 4 times the molar of n ^ 2, and the secondary amine is 1 to 2 times the molar of the N atom. In the case where the amine has a primary and secondary amine moiety in one molecule, the sum of the respective amounts used for the previous primary and primary amines can be used. In the reaction, the preferred form of formaldehyde is: when ammonia is used Using 3 to 9 moles of N atom, when using an amine, the amine is a primary amine In the case of using 2 to 6 moles of N atom, the case of secondary amine is 丨3 to 3 moles of N atom. In the case where the amine is a hydrazine molecule, there are amines of primary and secondary, which can be used for the previous The sum of the respective amounts of the primary and secondary amines. The preferred form of the acid is a mineral acid such as phosphoric acid or nitric acid. & melon® 夂 [steamed aqueous solution of crude aminomethylenephosphonic acid Gu!] A crude amine-based methylene phosphonic acid aqueous solution containing furfural, in order to remove residual formaldehyde, is distilled by a batch distillation apparatus, and the crude amine-methylene phosphonic acid is water-soluble, water, The degree is required to be 35 to 60% by weight, and when the concentration of water is outside the range, water is added before the distillation, and the mixture is allowed to be in the bacteria as described above. The batch distillation apparatus used in the present invention will be described below. An example of the batch type retorting apparatus of the present invention includes a distillation apparatus including a distillation pot and a condenser. The material of the & distillation apparatus is made of glass. The distillation temperature is preferably 90 to 120 ° C, and is preferable. The state is 1〇〇~. Furthermore, in the present invention, due to the crude: amine group in the distillation_ The addition of water to the aqueous solution of phosphinic acid allows the formaldehyde to be efficiently distilled off under normal pressure, so that the equipment modification cost of the product is not required to be adjusted, and it is also advantageous in terms of safety surface, and is very industrially beneficial. [Addition of water] 201219411 * In the present invention, it is important to add water to steaming hydrazine in the distillation. In the present invention, an aqueous solution of a nonaminylphosphonium acid containing furfural is added to the distillation pot, and the distillation still is heated to form a component. Distilled from the distillation column, condensed by a condenser, and measured by a supersonic flow, or a counter of a vortex flowmeter, etc., and more preferably, it is repeatedly prepared in distillation. Adding the same amount of water as the amount of the distillate to the distillation kettle, H is added to the same amount as the mixed water, and it is preferable to pay attention to not to make the inside of the distillation pot thick. The temperature of the aqueous solution of the aminomeridenephosphonic acid is decreased by - while being rapidly added. 5〜1.5倍。 The amount of the amount of the library is 0. 5~1.5 times the amount of the library. The range, the more ideal form is 〇. 2, ^ circumference 'more ideal form is G · 9 ~ 1.1 times the face, and the most ideal form is undoubtedly completely equal. Further, the measurement of the amount of the distillate may be carried out immediately depending on the size of the distillation apparatus or the energy of the condenser, or may be carried out at intervals of 30 to 60 minutes. In the water added by the distiller, it is more reasonable to use ion-exchanged water for the purpose of preventing metal contamination. 4, if the quality of the metal is stable, distilled water can be used. In the present invention, the total amount of water added to the distillation pot in the distillation is 0.5 times the added weight of the aqueous solution of the aminomeridenephosphonic acid. Since the amount of the present invention is at least G. 5 times 4, a highly pure aminophosphonium phosphonic acid can be obtained. The Japanese type _ adds water equivalent to the amount of the liquid in the fine to the steaming 蚤. Therefore, it is not necessary to add the water in the addition of the aqueous solution of the crude amide thiolphosphonic acid, and it is very industrially advantageous. ,,,,,,,,,,,,,,,,,,,,,,
二ίΐ理ί之樣態至多為粗胺基亞曱基膦酸水溶液之添加重量 ，^倍量。由於水的總量;至多定為2倍量，故可添加粗 J科酸水驗至蒸餾設備财效容積為止，而敎業上J 且’相較於在粗胺基亞甲基膦酸水溶液之添加時，添加大 ^的水而蒸_情況’即丨令添加的水總量少亦可有效率地德去甲 根據前述之觀點，，發明中添加之水的總量，較理想之樣態 201219411 為粗胺，亞甲基膦酸水溶液之添加重量的OH. 5倍量，而更理 想之樣態為G.5~1.2 .倍1：，更加理想之樣態為Q.5〜1()5倍量。 本發明中，於前述之鹽_性下’將氨或胺與情、膦酸反 應而得到粗胺基亞曱基膦酸水溶液時，餘水溶液係包含趟酸。此 a^ ,，粗胺基亞曰曱基膦酸水溶液中之鹽酸_濃度，較理想之樣態通 吊為6〜10重量％左右，*更理想之樣態為7〜8重魏左右。 粗絲亞甲基膦酸水溶液中包含鹽故的情況中，.當蒸顧爸中 之鹽酸的濃度過糾’係藉由高濃度_酸氣黏腐^備，另 -方面’舰的濃度過稀時，會析“红危#。但是，根據如 本發明在蒸齡添加水，即令於粗絲基膦酸水溶液包含如 情況中，由於亦可將驗爸中之鹽酸的濃度定為適 樣態為7〜8重量％之範圍内，故可輕易地，而且右ϋ之 =田，操作且不產生危險品而去除甲 二』 胺基亞曱基膦酸。 τ』门、w又w 〔精製步驟（鹽酸之去除）〕 丨 胺將氨或胺與㈣、膦酸反應而得到粗 舻水浴液時，如前述而蒸餾精製後的胺基亞甲基膦 酸的精製步驟較為理奴。只要去除鹽酸，便可 亞甲基膦酸水溶液使用。鹽酸之 g ==透析等之方法。再者:，若追求更進-步= 法之ϋ等。σ實施湘再結晶H謂之固化、湘離子交換 〔高純度胺基亞曱基膦酸〕 的本ΐΐίΐ造方法而得到触基亞甲基膦酸，係為充分 量^為Γ 25 顧後的胺基亞甲基膦酸水溶液中之帽的含 ίί酸Ιί減率（減率=(蒸餾後之水溶液中的甲亞甲。 液中的甲醛)_，可定為m以上、98%以上二 201219411 [實施例] 以下根據實施例詳細地說明本發明，但本發明並非限制於實 施例。再者，實施例、比較例中之含胺基亞甲基膦酸液中的甲醛 濃度分析，係藉由乙醯丙啊之吸光光度分析而實施，而餾出液中 f甲醛濃度係藉由利用硫作硫酸鈉水溶液之滴定而實施，氯化物 》辰度係藉由利用石肖酸銀水溶液之滴定而實施，二乙:r胺$巧审其 膦酸係藉由氯化鋅滴定而實施。貫&乙-胺五亞甲基 參考例1 t 在附有冷凝器、攪拌轉、夾套的lm3GL爸添加36重量％鹽酸 240kg。接著’花費約30分鐘投入亞磷酸175kg。由於投入中之吸 熱，故於夾套加入水蒸氣v將釜溫度保持於5〜1〇<t。接著，於夾 套加入冷卻水，一邊將反應溫度調節至15〜2〇。〇，一邊將二乙三胺 (DETA)30kg藉由定量泵而花費！小時投入後，並於丨5〜2〇^進^ 1 小時反應。之後，藉由水蒸氣而加溫至9〇。〇為止後，花費2小時 令50重量％福馬林2〇〇kg反應。此期間之反應溫度係維持於卯〜的 °C。福馬林投入結束後，於9〇〜95X：保持1小時。 實施例1 ’ 使用以參考例丨製造的二乙三胺五亞甲基膦酸，在難蒼添 加粗一乙二胺五亞甲基膦酸水溶液5〇〇g(二乙三胺五亞 重H情濃，3重量％，水分濃度42. 8 “％)， 義中为舌’並於大氣壓下進行蒸顧。在分離器餾出 的顧出液重1母保存lGGg即添加與館出液重量等重量的離 °在_添加之離子交換水的總添加量達 二 之ίΐ與燒瓶之浸潰，並繼續蒸鶴至分 ΐ = 在蒸餾中添加之離子交換水的 g為粗二乙三胺五亞甲細酸水额之添加重量（5_的〇·6 二f^_水;容液中的甲錢度為 實施例2 201219411 :胳中添加之離子交換水的總量定為500g(粗二乙 之添加重量的i倍量）峰倾實施例 酿、農^為oH。蒸顧後之二乙三胺五亞甲基鱗酸水溶液中的曱 备濃度為0.020重量％(甲搭減率99 8% 比較例1 ' 、、容液器，在1L燒瓶添加粗二乙三胺五亞曱基膦酸水 二胺五亞甲基膦酸卿.3娜，甲醛濃度8. 3 ^ 刀戚度42.8重量％)、離子交換水50吆(粗二乙三胺五 瓶，i於ίίί液之ί加重量的,1倍量j，於12(rc的油浴浸潰燒 蒸顧至餾皱添加料交換水，繼續 重胺ifψ基膦酸水㈣中的情濃度為L 23 比較例2 、、六、、乂，蒸？器，在1[燒瓶添加粗二乙三胺五亞曱基膦酸水 ί:。/ \一乙二胺五亞甲基膦酉曼濃度加‘ 3重量％，曱酸濃度6. 9 重置^ ’水分濃度43. 7重量％)、離子交換水5〇g(粗二乙三胺五 ”溶液之添加重量的〇. 33倍量)，於i腕的油浴浸潰 大氣壓下進行蒸顧。在蒸顧中不添加離子交換水，繼 續蒸，至餾出液達到與添加的離子交換水近似等量為止。 番曰乙三胺五亞甲基膦酸水溶液巾的帽濃度為2. 60 重虿％(甲醛減率62. 3%)。 比較例3 除了將離子交換水的添加量定為100g(粗二乙三胺五亞甲基 膦酸水溶液之添加重量的G· 67倍量）以外，係與比較例2相同而 進行蒸餾。 蒸餾後之二乙三胺五亞甲基膦酸水溶液中的甲醛濃度 7〇 重量％(甲醛減率75.4%)。 · 比較例4 除了將離子交換水的添加量定為2(J〇g(粗二乙三胺五亞甲基 201219411 添加重制K33倍量）叫,比_相同而 重甲基麟酸水溶液中的甲醛濃度為0.50 比較例5 除了將離子交換水_加量定 添加《的…辟)《外^ϊίί 重量=ψ基騎键中的瓣度為⑽ 參考例2 在1气冷凝擾摔械、夹套的llfl3GL爸添加36重量％鹽酸 花㈣3g分鐘投人亞顧丨娜。由於投入中之吸 二，故於炎套加人水威，丨將爸溫度保持於5〜l(rc。接著，於爽 ，加入冷卻.水…邊將反應溫度調節至15〜2(rc，—邊將二乙三胺 (DETA)30kg藉由定量栗而花費i小時投入後，胁15〜耽進了于i 小時反應曰。之後’藉由水蒸氣而加溫至9〇。〇為止後，花費2小時 令35。重置％福馬林25〇kg反應。此期間之反應溫度係維持於 90〜95°C。福馬林投入結束後，於卯〜邪它保持丨小時。 實施例3 ，用?參考例2製造的二乙三胺五亞甲基膦酸，在蒸顧蒼添 加粗一乙二胺五亞甲基膦酸水溶液787kg(二乙三胺五亞曱基膦酸 濃度21.1重量％，曱醛濃度4. 3重量％，水分濃度54. 3重量％)， f蒸餾釜^夾套供給表壓〇· 2〜〇· 3MPa的蒸氣，並於大氣壓下進行 蒸餾。自蒸餾塔餾出揮發成分，以冷凝器冷卻，並將該餾出液量 以計數器（渦流量計）自動f量。將作為輸入該計量值之通過計數 器之餾出液量之0· 95〜1. 05倍的離子交換水，利用計數器（渦流量 計）自動添加至蒸餾釜。在蒸餾中添加之離子交換水的總量達到粗 二乙三胺五亞甲基膦酸水溶液之添加量（787kg)之0. 59倍的 462kg時，停止離子交換水之添加與蒸氣之供給，並繼續蒸餾至餾 13 201219411 出液不會餾出為止。 蒸館後之二乙三胺五亞甲基膦酸水溶液中的曱酸濃度為 重量％(曱醛減率97· 0%)。 “' · 實施例4 除了將蒸顧中添加之離子交換水的總量定為(粗二乙三 胺五亞甲基载水溶液之添加重量的Q. 95倍量） ^ 例3相同而進行蒸餾。 ； 蒸館後之一乙二胺五亞曱基膦酸水溶液中的甲駿濃度為 0 008重量％(曱醛減率99. 8%)。 比較例6 除了將蒸餾中添加之離子交換水的i悤量定為174kg(粗二乙三 胺五亞甲基膦酸水溶液之添加重量的〇. 22倍量）以外，係與7 例3相同而進行蒸餾。 …、 & θ if後之二乙三胺五亞甲基膦酸水溶液中的曱醛濃度為1.10 重(甲憋減率74. 4%)。 參考例3 在附有攪拌機、夾套的lm3GL釜添如35重量％酿酸240L。接 著’花費約30分鐘投入亞碟酸250kg由於投入狐故ί 夾套加入水蒸氣，將釜溫度保持於5~urc。接著，於夾套加入冷 卻水三一邊將反應溫度調節至15〜2(TC : —邊將1，2一丙二胺46kg 藉由定量泵而花費1小時投入後，並於:15〜20t進行1小時反應。 之後，，由水蒸氣而加溫至90〇c為止後，投入37重量％福馬林 。2801、’_花費2小時令其反應。此期間之反應溫度係維持於卵〜的 C。福馬林投入結束後，於90〜95°C保持1小時。 實施例5 使用以參考例3製造的丙二胺四韭甲基膦酸，在蒸餾爸添加 粗丙二胺四亞甲基膦酸水溶液976kg(丙二胺四亞甲基膦酸濃度 28. 8重量％，曱醛濃度4. 〇重量％，水分濃度52. 4重量％)，在 蒸餾釜之夾套供給表壓〇· 2〜0. 3MPa的蒸氣，並於大氣壓下進行蒸 餾。自蒸餾塔餾出揮發成分，以冷凝器冷卻，並將該餾出液量以 201219411 §十數器（渴流量計）自動計暈。將作為輸入該計量值之通過計數器 之餾出液量之0.95〜1.05倍的離子交換水，利用計數器（渦流量計) 添加至蒸餾釜。在蒸餾中添加之離子交換水的總量達到粗丙 二胺=亞曱基膦酸水溶液之添加量（976吆)之〇. 61倍的595kg 時’停止離子交換水之添加與蒸氣之供給，並繼續蒸餾至餾出液 不會德出為止。 洛館後之丙二胺四亞甲基膦酸水溶液中的曱醛濃度為〇. 〇55 重量％(甲醛減率98.6%) ? 實施例6 ： ’除了將蒸餾中添加之離子交換水的總量定為910kg(粗丙二胺 四亞曱基膦酸水溶液之添加重量的0.93倍量）以外，係與實施例5 相同而進行蒸餾。 蒸鶴後之丙二胺四亞曱基膦酸水溶液中的曱醛濃度為〇 〇〇6 重量％(甲醛減率99.9%) ό 比較例7 除了將蒸餾中添加之離子交換水的總量定為31 〇kg(粗丙二胺 四亞曱基膦酸水溶液之添加重量的〇 32倍量）以外，係與實施例5 相同而進行蒸餾。 曰蒸餾後之丙二胺四亞甲基膦酸水溶液中的曱醛濃度為〇. 43重 夏％(曱醛減率89.3%)。： [產業上利用性] 2據本發明，可進行高純度胺基亞曱基膦酸之製造，將胺基 土膦酸中之未反應的甲醛，以產率佳，簡便的設備、簡單的 知作且不產生危險品而去除。 【圖式簡單說明】 無 【主要元件符號說明】 無 15The state of the two is at most the weight of the aqueous solution of the crude amine sulfhydrylphosphonic acid. Since the total amount of water; at most twice the amount, it is possible to add the crude J-acid water to the volume of the distillation equipment, and the industry is J and 'compared with the aqueous solution of the crude amino-methylene phosphonic acid. When adding, adding a large amount of water and steaming _ the situation 'that is, the amount of water added is small, and the amount of water added can be efficiently. According to the above viewpoint, the total amount of water added in the invention is preferable. State 201219411 is the weight of the crude amine, methylene phosphonic acid aqueous solution added OH. 5 times the amount, and more ideally the state is G.5~1.2. 1 :, more ideal form is Q.5~1 () 5 times the amount. In the present invention, when an ammonia or an amine is reacted with an acid or a phosphonic acid to obtain an aqueous solution of a crude amino-mercaptophosphonic acid under the above-mentioned salt properties, the residual aqueous solution contains citric acid. The concentration of hydrochloric acid _ in the aqueous solution of the crude amine sulfhydrylphosphonic acid is preferably about 6 to 10% by weight, and more preferably about 7 to 8 angstroms. In the case where the crude methylene phosphonic acid aqueous solution contains a salt, when the concentration of the hydrochloric acid in the steaming father is overcorrected, the concentration of the ship is increased by the high concentration of acid gas. When it is thin, it will analyze "Red Danger #. However, according to the present invention, adding water at the steaming age, that is, in the case of containing a crude aqueous solution of phosphonic acid, as in the case, the concentration of hydrochloric acid in the test dad can also be determined as appropriate. The state is in the range of 7 to 8 wt%, so that it can be easily and right-handed, and the operation is carried out without the generation of dangerous goods to remove the dimethyl hydrazide-phosphonic acid. τ 』 gate, w and w 〔 Purification step (removal of hydrochloric acid)] When the guanamine reacts ammonia or an amine with (4) or phosphonic acid to obtain a crude water bath, the purification step of the aminomethylene phosphonic acid distilled and purified as described above is relatively simple. The hydrochloric acid can be removed, and the methylene phosphonic acid aqueous solution can be used. The hydrochloric acid g == dialysis method, etc. Further, if the pursuit of further step-step = method, etc., σ implementation of Hunan recrystallization H is the solidification, Xiang The contact group methylene phosphonic acid is obtained by a method of ion exchange (high purity amino sulfinylphosphonic acid) Is a sufficient amount of 帽 25 顾 的 的 的 的 的 胺 胺 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 帽 胺 胺 胺It can be set to m or more and 98% or more. 201219411 [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. Further, the amine-containing groups of the examples and comparative examples are contained. The concentration analysis of formaldehyde in the phosphinic acid solution was carried out by the spectrophotometric analysis of acetonitrile, and the concentration of f-formaldehyde in the distillate was carried out by titration with sodium sulphate as an aqueous solution of sodium sulphate. The degree is carried out by titration with an aqueous solution of silver sulfate, and the diamine:ramine is judged to be carried out by titration of zinc chloride. The & ethylamine pentamethylene reference example 1 t In the lm3GL dad with condenser, stirring and jacket, add 240kg of 36% hydrochloric acid hydrochloric acid. Then, it takes about 30 minutes to put 175kg of phosphorous acid. Because of the heat absorption in the input, the steam is added to the jacket to keep the temperature of the kettle. At 5~1〇<t. Then, add cooling water to the jacket, and then reverse The temperature should be adjusted to 15~2 〇. 〇, while diethylenetriamine (DETA) 30kg is spent by the metering pump! After the hour is put in, and the reaction is carried out at 丨5~2〇^ for 1 hour. The water vapor was heated to 9 Torr. After that, it took 2 hours to react 50% by weight of formalin 2 〇〇 kg. The reaction temperature during this period was maintained at ° ° ° C. After the completion of the formalin, at 9 〇~95X: kept for 1 hour. Example 1 ' Using diethyl triamine penta methylene phosphonic acid manufactured by reference example, adding 5 g of crude ethylenediamine penta methylene phosphonic acid solution to Dangdang (Diethylenetriamine, hexahydrate, heavy H, 3% by weight, water concentration 42.8 "%", Yizhong is the tongue' and steamed under atmospheric pressure. The weight of the effluent distilled in the separator is 1 gg, that is, the weight of the effluent is added to the weight of the effluent, and the total amount of the ion-exchanged water added is increased by two immersed in the flask, and the steaming crane is continued. To the ΐ = g of ion-exchanged water added in the distillation is the added weight of the crude diethylenetriamine penta methylene acid water (5 _ 〇 · 6 two f ^ _ water; the amount of money in the liquid For the example 2 201219411: the total amount of ion-exchanged water added to the stalk is set to 500g (i times the weight of the added weight of the crude bis). The peak is poured into the example, and the agricultural product is oH. The concentration of the preparation in the aqueous solution of methylene quaternary acid was 0.020% by weight (the rate of substitution was 99 8%. Comparative Example 1 ', the liquid container, and the crude diethylenetriamine pentadecylphosphonic acid was added to the 1 L flask. Diamine penta methylene phosphonic acid Qing. 3 Na, formaldehyde concentration 8. 3 ^ Knife degree 42.8% by weight), ion exchange water 50 吆 (5 parts of crude diethylene triamine, i ί ί ί 加 加, 1 times the amount of j, in 12 (rc oil bath dipping steam to take care of the wrinkle additive exchange water, continue the concentration of heavy amine if decylphosphonic acid water (4) is L 23 Comparative Example 2, 6, Hey, steam , in a flask [addition of crude diethylenetriamine pentadecylphosphonic acid water ί:. / \-ethylenediamine penta methylene phosphine 酉man concentration plus '3 wt%, tannic acid concentration 6.9 weight ^ 'water concentration 43.7 wt%), ion exchange water 5 〇 g (crude diethylene triamine five) solution added weight of 〇. 33 times the amount), steamed in the i-bath oil bath impregnation at atmospheric pressure Gu. In the steaming, no ion-exchanged water is added, and the steaming is continued until the distillate reaches approximately the same amount as the added ion-exchanged water. The cap concentration of the panaxanthin triamine penta methylene phosphonic acid aqueous solution towel is 2. 60% by weight (formaldehyde reduction rate 62.3%). Comparative Example 3 except that the amount of ion-exchanged water added was set to 100 g (G·67 times the added weight of the crude diethylenetriamine pentamethylenephosphonic acid aqueous solution) The distillation was carried out in the same manner as in Comparative Example 2. The concentration of formaldehyde in the aqueous solution of diethylenetriamine pentamethylenephosphonic acid after distillation was 7% by weight (formaldehyde reduction rate: 75.4%). The amount of exchanged water is set to 2 (J〇g (crude diethylenetriamine pentamethylene 201219411 added reconstituted K33 times), which is the same as _ the same as heavy methyl linonic acid water soluble The concentration of formaldehyde in the sample is 0.50. Comparative Example 5 In addition to the addition of ion-exchanged water, the addition of the ion-exchanged water is added to the outer diameter of the ϊ 骑 ί ί ψ ψ ψ ψ ψ 骑 骑 骑 在 在 在 在 在 在 在 在 在 在 在 在The jacket of llfl3GL dad added 36% by weight of HCl flower (four) 3g minutes to vote for A Gu Na. Because of the investment in the second, so in the Yan set plus water, the father to maintain the temperature of 5 ~ l (rc. Then, Cool, add cooling, water... while adjusting the reaction temperature to 15~2 (rc, - while diethylenetriamine (DETA) 30kg is taken by the metering of the chestnut for an hour, the threat 15~ broke into the hour Reaction 曰. After that, it was heated to 9 藉 by steam. After that, it takes 2 hours to order 35. Reset the % Famamarin 25 〇 kg reaction. The reaction temperature during this period was maintained at 90 to 95 °C. After the end of the formalin, Yu Yu ~ evil it keeps for hours. Example 3, using diethyldiamine penta methylene phosphonic acid produced in Reference Example 2, adding 787 kg of a solution of crude ethylenediamine penta methylene phosphonic acid to distillate, and diethylenetriamine pentadecylphosphine. The acid concentration was 21.1% by weight, the furfural concentration was 4.3% by weight, the water concentration was 54.3% by weight, and the f distillation kettle was supplied with a vapor of 2 MPa·3 MPa and distilled under atmospheric pressure. The volatile component was distilled off from the distillation column, cooled by a condenser, and the amount of the distillate was automatically counted by a counter (vortex flowmeter). The ion exchange water, which is 0. 95 to 1. 05 times the amount of the distillate passing through the counter, is automatically added to the distillation pot by a counter (vortex flow meter). When the total amount of the ion-exchanged water added in the distillation reaches the amount of the crude diethylenetriamine pentamethylenephosphonic acid aqueous solution (787 kg) of 5.9 kg, the addition of the ion-exchanged water and the supply of the vapor are stopped. And continue to distill to distillation 13 201219411 The liquid will not be distilled. The concentration of citric acid in the aqueous solution of diethylenetriamine pentamethylenephosphonic acid after steaming was % by weight (furfural reduction rate: 97. 0%). "' Example 4 except that the total amount of ion-exchanged water added in the steaming was determined to be (the amount of Q. 95 times the added weight of the crude diethylenetriamine pentamethylene aqueous solution). The concentration of methine in an aqueous solution of ethylenediamine pentadecylphosphonic acid after evaporation was 008% by weight (furfural reduction rate of 99.8%). Comparative Example 6 In addition to ion exchange water added in distillation Distillation was carried out in the same manner as in the case of 7 cases, except that the amount of i悤 was 174 kg (the amount of the added weight of the aqueous solution of the crude diethylenetriamine pentamethylenephosphonic acid solution was 22 times). ..., & θ if The concentration of furfural in the aqueous solution of diethylenetriamine pentamethylenephosphonic acid was 1.10 (the rate of formazan reduction was 74.4%). Reference Example 3 Adding 35% by weight of the lm3GL in a mixer with a stirrer and a jacket 240L. Then, it takes about 30 minutes to put 250 kg of sub-disc acid. Since the steam is put into the jacket, the temperature of the kettle is maintained at 5 urc. Then, the reaction temperature is adjusted to 15 by adding cooling water to the jacket. 〜2 (TC: - 46 kg of 1,2-propylenediamine was charged by a metering pump for 1 hour, and the reaction was carried out for 1 hour at 15 to 20 t. Thereafter, after heating to 90 〇c by steam, 37% by weight of formalin was added. 2801, '_ took 2 hours to react. The reaction temperature during this period was maintained at egg ~ C. Formalin input After completion, it was kept at 90 to 95 ° C for 1 hour. Example 5 Using propylenediamine tetramethylphosphonic acid produced in Reference Example 3, 976 kg of a crude propylenediamine tetramethylenephosphonic acid solution was added to the distillation dad ( 5MPa。 The propylene diamine tetramethylene phosphonic acid concentration of 28. 8wt%, furfural concentration of 4. 〇% by weight, water concentration of 52.4% by weight, in the distillation tank of the jacket supply gauge pressure 〇 2~0. 3MPa The vapor is distilled at atmospheric pressure. The volatile component is distilled from the distillation column, cooled by a condenser, and the amount of the distillate is automatically counted by the 201219411 § tens of meters (thirsty flow meter). The ion-exchanged water having a value of 0.95 to 1.05 times the amount of the distillate passing through the counter is added to the distillation pot by a counter (vortex flowmeter). The total amount of ion-exchanged water added in the distillation reaches crude propylenediamine = Aa Addition amount of phosphinic acid aqueous solution (976 吆) 61. 61 times 595kg when 'stop The addition of ion exchange water and the supply of steam, and continue to distill until the distillate does not come out. The concentration of furfural in the aqueous solution of propylenediamine tetramethylenephosphonic acid after Luoguan is 〇. 〇55 wt% ( Formaldehyde reduction rate 98.6%) ? Example 6: 'In addition to the total amount of ion-exchanged water added in the distillation was 910 kg (0.93 times the added weight of the crude propylenediamine tetramethylenephosphonic acid aqueous solution), Distillation was carried out in the same manner as in Example 5. The concentration of furfural in the aqueous solution of propylenediamine tetradecylphosphonic acid after steaming was 〇〇〇6 wt% (formaldehyde reduction rate 99.9%) ό Comparative Example 7 In addition to distillation The distillation was carried out in the same manner as in Example 5 except that the total amount of the ion-exchanged water to be added was 31 〇kg (amount of 〇32 times the added weight of the crude propylenediamine tetramethylenephosphonic acid aqueous solution). The concentration of furfural in the aqueous solution of propylenediamine tetramethylenephosphonic acid after the distillation of hydrazine was 〇 43 weight% (the formaldehyde reduction rate was 89.3%). [Industrial Applicability] 2 According to the present invention, the production of high-purity aminopyrylenephosphonic acid can be carried out, and the unreacted formaldehyde in the amine phosphonic acid can be obtained in a simple yield, simple equipment, and simple Know and do not produce dangerous goods and remove them. [Simple description of the diagram] None [Key component symbol description] None 15
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