200835668 九、發明說明 【發明所屬之技術領域】 本發明係關於一種操作含1，1，1，3,3-五氟丁烷的組成 物之方法，該組成物特別呈液體或蒸氣形式，例如，作爲 溶劑、作爲冷藏劑、作爲可噴灑組成物的推進劑/溶劑、 或作爲固體表面的清潔及/或乾燥劑，如用於去除電子部 件的助熔劑或將金屬除脂，或用於在文件、印刷機或複印 機中固定調色劑。 【先前技術】 完全鹵化的氯氟化碳氫化合物（CFC )，特別是 1，1，2-三氯-1，2,2-三氟乙烷（CFC-1 13 )，廣用於工業中作 爲溶劑用於各種表面的除脂和清潔，特別是複雜形狀而難 以清潔的固體組件。除了彼等在電子器件中用於清潔焊接 助熔劑以移除黏附在印刷電路上的浸漬助熔劑之外，彼等 也慣常地用於去除金屬組件的油脂或清潔高品質及高精密 度的機械組件。於此等各種應用中，CFC-1 13最常與其他 有機溶劑結合使用，較佳地係呈在氣相和液相中都具有實 質相同組成的共沸或假共沸組成物之形式，使彼等能容易 地於回流下使用。 基於CFC-1 13的組成物也慣常地用爲乾燥劑，以移除 吸附在固體組件表面上的水。 不過，CFC-1 13，及其他完全鹵化地氟氯烷類，被懷 疑牽涉到平流層臭氧層的破壞中，且因此之故，必須鑑別 -5 - 200835668 出替代物。時常地，此等替代物爲以氫氟碳化合物爲基者 。此等由碳、氫和氟組成的化合物皆爲臭氧友善者。於此 等化合物中，1，1，1，3,3·五氟丁烷（HFC-3 65mfc)經鑑定 爲特別有用的化合物。其可用爲，例如溶劑、用於製造發 泡體之發泡劑，或冷藏劑。其也可用來，例如，清潔表面 〇 EP專利申請案ΕΡ-Α-0 653484揭示包含1，1，153,3-五 氟丁烷，反-1，2-二氯乙烯和隨意地具有1至3個碳原子的 醇之組成物。反-1，2-二氯乙烯和具有1至3碳原子的醇兩 者本身都是可燃者。 美國專利5,7 1 4,298揭示包含HFC-3 65mfc及反-1，2- 二氯-乙烯的調色劑固定劑。該專利的表II中述及一種由 70重量％ HFC-365mfc和30重量％反-1，2-二氯-乙烯組成 的混合物，不具有在-3 0°C至+40 °C範圍內的密閉杯閃點。 因此之故，該1996年所作的陳述，不排除閃點以較在該 例中檢驗過者更高溫度存在之可能性；尤其是若考慮到， 在相信HFC-3 65mfc係不可燃者之該時下，後來其經認爲 是可燃者（參見，例如，US 6080799 )，即使其因爲其需 要高點燃能量而僅可困難地點燃。 ΕΡ-Α-0 6 1 8288揭示包含HFC-365mfc和乙醇的組成 物，其適合作爲清潔劑或去脂劑。 若1，1，1，3,3-五氟丁烷，於其使用中的至少一個步驟 中’不需要在操作可燃產物所需條件下操作，將是非常有 利者。 -6 - 200835668 【發明內容】 本發明提供一種此等方法。本發明使用包含1,1，1，3， 3-五氟丁烷和反-1，2·二氯乙烯（TDCE)的不可燃組成物 之方法包括至少一個該組成物不在操作可燃組成物所需條 件下操作的步驟。 術語Μ步驟’’於本發明中較佳地係表在將HFC-3 65mfe 和TDCE (隨意地也與安定劑）混合且處置其TDCE的組 成物之後的一獨特步驟。當然，本發明方法可包括該組成 物不在操作可燃組成物所需條件下操作的二或更多或甚至 實質地所有步驟。根據本發明的一步驟爲，例如，在混合 之後將該組成物轉移到運送或貯存所用的容器之內，可能 的其純化步驟（如於再使用槪念中者），在將該組成物完 全或部分轉移到其他容器後，到使用點或採取檢驗樣品時 打開容器的第一步驟，將組成物施加到要處理的物件，或 於使用之後再收集該組成物。 術語”可燃”意表根據任何適用的標準，例如，根據 Pensky-Martens (密閉杯檢驗）之 A S TM D 93 - 94，JIS Κ2265- 1 996，且較佳地於DIN/EN/ISO 1 3 73 6中所定義者 而測定之任何燃燒性。燃燒性爲一物質在燃原存在中可進 行自傳播反應的條件下於空氣中形成一混合物之能力。 術語’’條件”包括預期警告大眾有燃燒危險存在之措施 。此等措施通告使用該組成物的人技術指示使得操作該組 成物的方式要能防止或至少減低燃燒風險及減低爆炸危險 -7- 200835668 ，及告知預期警告大眾針對在操作該 HFC-3 65mfc和 TDCE的組成物之至少一個步驟中省略掉的潛在燃燒危險 性之措施。該等措施包括’例如’在例如運送組成物的步 驟中或在貯存該組成物的步驟中，對容器加上裝有可燃產 品之標示。術語’’標示”預期包括直接附加在容器上的標記 ，不過也包括附加在此等容器所用運送工具，如陸路油罐 車或鐵道貨運列車，之上的標記。術語”容器”包括大型容 器，例如，經設計供等於或大於1 〇公噸的容量所用者， 尤其是供20公噸的物質所用的ISO容器或陸路油罐車。 術語”容器’’也包括具有中等容量者，例如，具有等於或大 於1 〇公斤的容量者。例如，包括容量爲5加侖、6 0公斤 或240公斤的容器。術語”容器"也包括具有小容量者，例 如具有1 0公斤以下的容器。雖然在貯存，運送或大規模 工業應用中，可能時常用到大型容器，不過零售商可能用 到具有較小容積的容器來貯存及/或分銷，例如用於某些 機器中的組成物應用，如在清潔電子部件所用裝置中，用 在複印機或印刷機中供調色劑固定所用，或用於清潔及去 除金屬的油脂。 操作可燃產品所需但在本發明至少一個操作步驟中省 略的"條件”一詞也包括對燃燒危險的主動預防措施。此等 在本發明至少一個操作步驟中可能省略的措施包括在操作 中，例如，混合物的貯存，運送或應用中，在HFC-3 6 5mfc組成物上方氣體空間中，加上惰性氣體，諸如氮 氣或氬氣；在組成物操作中排除氧氣；或經由施用加壓條 -8- 200835668 件以防止氧氣或空氣進入液體混合物上方的氣體空間內； 或加裝可防止電花形成所用的工具，例如，經由接地。 本發明一較佳具體實例係關於在沒有標示出裝有可燃 產品的容器內運送該組成物。此運送包括在短距離間的運 送，如在房間或工廠內，或在較長距離內的運送，如在城 市、國家或甚至從一洲到另一洲的運送，如分別經由手、 汽車、火車、船、飛機、或適合運送容器的其他工具。 # 另一較佳具體實例包括在沒有標示出裝有可燃產品的 容器內貯存該組成物。術語”貯存”意欲包括短期貯存和長 期貯存。該貯存可能延長到等於或長於1分鐘之期間。其 可延長到等於或短於7天之期間。也可能爲長期貯存，例 如，將該混合物貯存到長於7天之期間。原則上，長期貯 存的上限不具關鍵性。實際上，該上限可能等於或短於數 . 年，例如，等於或短於1年。 根據另一較佳具體實例，本發明方法包括在沒有特別 # 針對燃燒危險予以防護的環境中打開裝有HFC-3 65mfc與 TDCE之容器。通常，在打開容器時，例如要檢查其內容 物，在將其一部份轉移到其他容器內或轉移到管線中以將 其遞送到另一場所之前將其轉接到連結器，或要將其施加 於要用其處理的物品（如用以在去脂或清潔）之時，容器 內的一部份氣體相，或，甚至於經由溢流出，裝在容器內 的一部份液體，都會與周圍大氣環境接觸。在打開裝有可 燃流體的容器之時，必須針對燃燒危險對環境加以防護。 例如，容器必須接地。此等皆爲在處理本發明組成物的至 -9 - 200835668 少一步驟中可以省略的預防措施之例子。 本發明另一較佳具體實例包括在沒有針對燃燒 別給予防護的環境中，將該組成物從第一容器轉移 容器或一表面。對於將可燃液體從一容器轉移到另 ，必須給予防護措施。例如，必須使用特別適用於 體的泵。有時候，要再塡充的容器要用惰性氣體予 。尤其是若一或兩個容器都是放在密閉空間內之時 間必須通風以從環境移除可燃液體，或必須放置有 。此等皆爲在應用本發明組成物時的至少一步驟中 略的例子。 將組成物轉移到一表面之步驟存在，例如，將 從容器轉移到從例如金屬，玻璃或塑膠所製品項的 用以將其去脂，或者給予清潔，將其乾燥或從其表 熱量之時實施者。在此情況中同樣地，轉移可燃流 驟要伴隨著採取上述針對燃燒危害的預防措施。此 地，在本發明方法中可以省略此等預防措施。 本發明又另一具體實例包括在沒有針對燃燒危 加上防護的環境中用該組成物接觸一表面。要接觸 可用不同的材料製成且可用於不同目的。 例如，用包含HFC-3 65mfc和TDCE的混合物 面的一較佳目的爲將其清潔或去脂。於此，一種較 爲任何金屬，且其品項較佳者爲例如，工具或構造 如高精密部件，在彼等的表面上包含油脂或其他塗 等部件時常具有複雜的表面且不是非常容易清潔， 危害特 到第二 一容器 可燃液 以沖滌 ，該空 滅火器 可以省 組成物 表面， 面移除 體的步 處同樣 害特別 的表面 接觸表 佳材料 部件， 料。此 尤其是 -10- 200835668 去脂。或者，該混合物可用來清潔因浸漬助熔劑及因來自 此助熔劑的殘渣而污染的印刷電路板。使用本發明方法接 觸表面之目的也意圖將其乾燥。例如來自電子工業、光學 工業或機械工業的物件，在高品質精密工作件的製造中， 該物件會與水或濕氣接觸，不論是有意者或無意者。水， 例如以濕膜形式，可能黏附到物件上。黏附水的存在對於 該物件的後續處理及/或對此等物件的可使用性與使用壽 命，時常係不合宜者。通常，在可燃組成物與要處理的此 等表面接觸之中，必須作防護措施以針對燃燒危險給予防 護。例如，包圍要處理的表面之氣體空間必須成爲惰性者 ，例如經由添加防火性氣體，如氮氣，作爲惰性化氣體。 或者，必須防止氧氣或空氣侵入要處理的表面之周圍內。 若應用本發明方法，則此等預防措施都可以省略。 根據一具體實例，係以液體形式應用包含 HFC-3 65mfc和TDCE的混合物。一較佳具體實例係關於使用蒸 氣形式或液體/蒸氣形式的組成物來實施之本發明方法。 因爲於蒸氣相時特別要顧慮到燃燒危險，所以本發明方法 在此較佳具體實例中特別有用。 一種非常較佳的具體實例係關於將物件去脂，尤其是 以蒸氣形式施用組成物之時。200835668 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method of operating a composition containing 1,1,1,3,3-pentafluorobutane, which is in particular in the form of a liquid or a vapor, for example , as a solvent, as a refrigerant, as a propellant/solvent for a sprayable composition, or as a cleaning and/or desiccant for a solid surface, such as a flux for removing electronic components or degreasing a metal, or for use in Fix toner in documents, printers, or copiers. [Prior Art] Fully halogenated chlorofluorocarbons (CFCs), especially 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-1 13 ), widely used in industry Used as a solvent for degreasing and cleaning of various surfaces, especially solid components that are difficult to clean with complex shapes. In addition to their use in electronic devices to clean solder fluxes to remove impregnating flux adhered to printed circuits, they are also routinely used to remove grease from metal components or to clean high quality and high precision machinery. Component. In these various applications, CFC-1 13 is most often used in combination with other organic solvents, preferably in the form of azeotropic or pseudoazeotropic compositions having substantially the same composition in both the gas phase and the liquid phase. They can be easily used under reflow. The composition based on CFC-1 13 is also conventionally used as a desiccant to remove water adsorbed on the surface of the solid component. However, CFC-1 13, and other fully halogenated chlorofluorocarbons, are suspected of being involved in the destruction of the stratospheric ozone layer, and for this reason, alternatives must be identified from -5 - 200835668. Often, these alternatives are based on HFCs. These compounds consisting of carbon, hydrogen and fluorine are all ozone friendly. Among these compounds, 1,1,1,3,3·pentafluorobutane (HFC-3 65mfc) has been identified as a particularly useful compound. It can be used, for example, as a solvent, a foaming agent for producing a foam, or a refrigerating agent. It can also be used, for example, to clean the surface 〇 EP patent application ΕΡ-Α-0 653484 discloses the inclusion of 1,1,153,3-pentafluorobutane, trans-1,2-dichloroethylene and optionally 1 to A composition of an alcohol of three carbon atoms. Trans-1,2-dichloroethylene and an alcohol having 1 to 3 carbon atoms are themselves flammable. U.S. Patent No. 5,7,144,298 discloses a toner fixative comprising HFC-3 65mfc and trans-1,2-dichloro-ethylene. Table II of the patent describes a mixture of 70% by weight of HFC-365mfc and 30% by weight of trans-1,2-dichloro-ethylene, which does not have a temperature in the range of -300 ° C to +40 ° C. The closed cup flashes. For this reason, the statement made in 1996 does not rule out the possibility that the flash point will exist at a higher temperature than the one tested in this case; especially if it is considered that the HFC-3 65mfc is not combustible Nowadays, it is considered to be flammable (see, for example, US 6080799), even though it can only ignite hard because it requires high ignition energy. ΕΡ-Α-0 6 1 8288 discloses a composition comprising HFC-365mfc and ethanol, which is suitable as a detergent or degreaser. It would be highly advantageous if 1,1,1,3,3-pentafluorobutane is used in at least one of its steps to operate without the conditions required to operate the combustible product. -6 - 200835668 SUMMARY OF THE INVENTION The present invention provides such methods. The method of the present invention using a nonflammable composition comprising 1,1,1,3,3-pentafluorobutane and trans-1,2-dichloroethylene (TDCE) comprises at least one of the compositions not operating the combustible composition The steps required to operate under conditions. The term "step" is preferably a unique step in the present invention after mixing HFC-3 65mfe and TDCE (optionally also with a stabilizer) and disposing of its TDCE composition. Of course, the process of the present invention can include two or more or even substantially all of the steps in which the composition does not operate under the conditions required to operate the combustible composition. According to one aspect of the invention, for example, after mixing, the composition is transferred to a container for transport or storage, possibly with a purification step (such as in the case of re-use), in which the composition is completely After partial transfer to other containers, the first step of opening the container to the point of use or when taking the test sample, the composition is applied to the item to be treated, or the composition is collected after use. The term "flammable" means according to any applicable standard, for example, according to the Pensky-Martens ASTM D 93-94, JIS Κ 2265-1 996, and preferably DIN/EN/ISO 1 3 73 6 Any flammability determined by the person defined in . Combustibility is the ability of a substance to form a mixture in air under conditions in which the material can undergo a self-propagating reaction. The term ''conditions'' includes measures intended to warn the public of the danger of burning. These measures inform the person of the use of the composition that the technical instructions are such that the composition is operated in a manner that prevents or at least reduces the risk of combustion and reduces the risk of explosion. 200835668, and to inform the public of the measures intended to warn the public about potential combustion hazards that are omitted in at least one step of operating the HFC-3 65mfc and TDCE compositions. These measures include, for example, in the step of transporting the composition. Or in the step of storing the composition, the container is marked with a flammable product. The term ''indicator') is intended to include a mark attached directly to the container, but also includes a shipping tool attached to the container, such as land. Tanker or rail freight train, marked above. The term "container" includes large containers, for example, those designed to have a capacity equal to or greater than 1 metric ton, especially ISO containers or land tankers for 20 metric tons of material. The term "container" also includes those having a medium capacity, for example, having a capacity equal to or greater than 1 〇 kg. For example, including a container having a capacity of 5 gallons, 60 kg, or 240 kg. The term "container" also includes For small capacity, for example, a container having a capacity of 10 kg or less. While large containers may be used in storage, shipping or large-scale industrial applications, retailers may use containers with smaller volumes for storage and/or distribution, such as for use in certain machines. For example, in a device for cleaning electronic components, used in a copying machine or a printing machine for toner fixing, or for cleaning and removing metal grease. The term "condition" required to operate a combustible product but omitted in at least one of the operational steps of the invention also includes active precautions against the risk of burning. Such measures that may be omitted in at least one of the operational steps of the invention are included in the operation. For example, in the storage, transport or application of the mixture, in the gas space above the HFC-3 6 5mfc composition, an inert gas such as nitrogen or argon is added; oxygen is excluded from the operation of the composition; or via application of a pressure strip - 8- 200835668 pieces to prevent oxygen or air from entering the gas space above the liquid mixture; or tools for preventing the formation of electric sparks, for example, via grounding. A preferred embodiment of the invention relates to the absence of a The composition is transported within a container of combustible product. This shipment includes transportation within short distances, such as in a room or factory, or in a longer distance, such as in a city, country, or even from one continent to another. Transportation, such as by hand, car, train, boat, airplane, or other tool suitable for transporting containers. This includes storing the composition in a container that is not labeled with a flammable product. The term "storage" is intended to include both short-term storage and long-term storage. The storage may be extended to a period equal to or longer than one minute. It may be extended to be equal to or shorter than During the 7-day period, it may also be long-term storage, for example, storing the mixture for a period of longer than 7 days. In principle, the upper limit of long-term storage is not critical. In fact, the upper limit may be equal to or shorter than the number. Is equal to or shorter than 1 year. According to another preferred embodiment, the method of the invention comprises opening a container containing HFC-3 65mfc and TDCE in an environment that is not protected against the risk of fire. Typically, when the container is opened , for example, to check its contents, transfer it to another container before transferring it to another container or transferring it to a pipeline to deliver it to another location, or to apply it to the other a portion of the gas phase in the container, such as when used for degreasing or cleaning, or even a portion of the liquid contained in the container through the overflow, It will be in contact with the surrounding atmosphere. When opening a container containing a flammable fluid, the environment must be protected against the risk of burning. For example, the container must be grounded. These are all less than -9 - 200835668 in the treatment of the composition of the present invention. An example of a precaution that can be omitted in one step. Another preferred embodiment of the invention includes transferring the composition from the first container to a surface or a surface in an environment where no protection is provided for combustion. If a container is transferred to another, protective measures must be given. For example, a pump that is particularly suitable for use in the body must be used. Sometimes, the container to be refilled should be filled with inert gas, especially if one or both containers are placed in a closed atmosphere. The time within the space must be vented to remove flammable liquids from the environment, or must be placed. These are all examples of at least one step in the application of the compositions of the present invention. The step of transferring the composition to a surface exists, for example, from a container to a product such as a metal, glass or plastic to degrease it, or to clean it, dry it or heat it from its surface. Implementer. In this case as well, the transfer of the flammable stream is accompanied by the adoption of the above-mentioned precautions against the hazard of combustion. Here, such precautions can be omitted in the method of the invention. Yet another embodiment of the invention includes contacting a surface with the composition in an environment that is not protected against combustion hazards. The contact can be made of different materials and can be used for different purposes. For example, a preferred purpose of using a mixture comprising HFC-3 65mfc and TDCE is to clean or degrease it. Herein, a relatively any metal, and the item of which is preferably, for example, a tool or a structure such as a high-precision component, often has a complicated surface on the surface of the surface containing grease or other coatings and is not very easy to clean. The hazard is special to the second container of combustible liquid to wash away. The empty fire extinguisher can save the surface of the composition, and the step of removing the body is also harmful to the surface of the material. This is especially -10- 200835668 to remove fat. Alternatively, the mixture can be used to clean printed circuit boards that are contaminated by the impregnating flux and the residue from the flux. The purpose of contacting the surface using the method of the invention is also intended to be dry. For example, articles from the electronics, optical, or mechanical industries, in the manufacture of high-quality precision work pieces, which are in contact with water or moisture, whether intentional or unintentional. Water, for example in the form of a wet film, may adhere to the object. The presence of adherent water is often unsuitable for subsequent handling of the article and/or its usefulness and usefulness for such articles. Often, in the event of contact of the flammable composition with such surfaces to be treated, protective measures must be taken to protect against the risk of burning. For example, the gas space surrounding the surface to be treated must be inert, for example by adding a fire-retardant gas such as nitrogen as the inerting gas. Alternatively, it is necessary to prevent oxygen or air from entering the periphery of the surface to be treated. These precautions can be omitted if the method of the invention is applied. According to a specific example, a mixture comprising HFC-3 65mfc and TDCE is applied in liquid form. A preferred embodiment relates to the process of the invention carried out using a composition in the form of a vapor or a liquid/vapor. The process of the invention is particularly useful in this preferred embodiment because of the particular risk of burning during the vapor phase. A very preferred embodiment relates to the degreasing of articles, especially when the composition is applied in vapor form.
原則上，本發明方法可用包含HFC-3 65mfc和TDCE 的任何不燃組成物來實施。 在本發明組成物中的1，1，1，3,3-五氟丁烷和反-1，2-二 氯乙烯之含量可依所擬用途而在廣限制値之內變異。 -11 - 200835668 在本發明方法中施用的組成物含有使其不可燃的量之 HFC-3 65mfc和TDCE，無論液相與蒸氣相均是如此。一組 成物是否不可燃可由可用到的標準方法予以核驗。一種較 佳的標準方法爲上面所提的根據DIN/EN/ISO 1 3 73 6之方 法。此標準方法在實施例中有詳細說明。別的標準，例如 ，JIS K2265 - 1 996，係諳於此技的專家所知者。 業經發現含HFC-3 65mfc、95重量％反-1，2-二氯乙烯 • 和近於〇·5重量％異丙醇的組成物不具閃點。同樣地，業 經發現只含5重量％反-1，2-二氯乙烯的組成物亦不具閃點 。此證實本發明方法可用包含廣範圍的HFC-3 65mfc和反-1，2 -二氯乙烯的組成物來實施。據此，本發明方法可用包 含等於或多於2重量％，較佳者等於多於4·5重量％的 H F C - 3 6 5 m fc的組成物來應用。同樣地，本發明方法可用 包含等於或多於2重量％，較佳者等於或多於45重量 %TDCE之組成物來實施。 • 本發明方法可用包含等於或少於9 8重量％，較佳者 95.5重量％的組成物來實施。其可用包含等於或少於98 重量％ ’較佳者95 ·5重量％TDCE的組成物來實施。 本發明方法也可用包含安定劑的組成物來實施。於此 情況中，該方法較佳者係用含佔HFC-3 65mfc或TDCE各 別重里之多於0重重°/g，較佳者多於〇 · 〇 5重量％的及安定 劑之組成物來實施。較佳地，其中包含等於或少於〇 . 5重 量％的安定劑。若組成物中包含安定劑，一個別量的HFC_ 3 65mfc或TDCE係以安定劑予以取代。 -12- 200835668 如後面要詳細解釋者，該組成物也可包含添加劑。 時常地，該等組成物含有等於或多於4 5重量％的 1，1，1，3,3-五氟丁烷。彼等有利地係含有等於或多於50重 量％的1，1，1，3,3-五氟丁烷。於一特別較佳方式中，彼等含 有等於或多於60%的1，1，1，3,3-五氟丁烷。彼等常含有等 於或多於95重量％的1，1，1，3,3-五氟丁烷。最常者，彼等 含有等於或低於85重量％的1，1，1，3,3-五氟丁烷。 # 本發明組成物時常含有等於或多於5重量％的反-1，2-二氯乙烯。彼等較佳地含有等於或於15重量％的反-1，2-二氯乙烯。時常地，彼等組成物包含等於或少於5 5重量％ 的 TDCE。較佳地，彼等含有等於或少於50重量％的 TDCE。於一特佳方式中，彼等含有等於或少於40重量％ 的 TDCE。 各種添加劑可隨意地包含在本發明組成物中。本發明 組成物可因而含有界面活性劑或可用來改良本發明組成物 • 在使用中的行爲之任何其他添加劑。此等添加劑的本質和 用量係決定於所擬用途且皆爲諳於此技藝者所容易界定者 。一般而言，本發明組成物中所含添加劑的量不超過組成 物的約20重量％，最常者不多於1 〇%。較佳者，包含少於 5%的添加劑。 較佳地，該組成物不包含氯氟碳化合物。 於一具體實例中，本發明方法係用由HFC-3 65mfc和 TDCE所組成的組成物來實施。此具體實例較佳地係用其 中所含HFC-3 65mfc和TDCE的比例爲使彼等形成共沸物 -13- 200835668 或假共沸物之組成物來實施。 於另一較佳具體實例中，含1，1，1，3,3-五氟丁烷及/或 TDCE的組成物係包含安定劑。例如，可將HFC_3 65mfc 安定化以對抗脫氫鹵化（dehydrohalogenation)，或將 TDCE安定化以對抗聚合。含HFC-3 65mfc、TDCE及一或 多種安定劑的不可燃組成物可以有利地用於本發明方法中 〇 # 於本發明方法中，較佳地，在該組成物中包含烷醇作 爲安定劑。一種特佳烷醇爲異丙醇。異丙醇可同時安定化 該兩化合物以分別對抗降解及聚合。其在含HFC-3 6 5mfc 和TDCE的混合物中之量時常爲等於或高於0.05重量％。 較佳者，其係等於或高於0.1重量％。其量時常爲低於0.5 重量％。較佳地，其爲等於或低於〇 · 4重量％。非常較佳地 ，其爲等於或低於0.25重量％。 業經發現者，含HFC-3 65mfc、TDCE和異丙醇的混合 ® 物也表現出像共沸物一般。所以，異丙醇會與HFC_ 3 6 5mfc和TDCE —起進入蒸氣相且繼續其安定化作用。所 以，上面所給對H F C - 3 6 5 m f c、T D C E及，若含有，且較佳 者爲含有，異丙醇之比例，預期也描述該組成物在液相中 及在氣相中的含量。 必須視爲係特別令人訝異者，包含HFC-365mfc、 TDCE和，例如，異丙醇的混合物係不可燃者且完全可應 用在本發明方法中。 根本上，流體的熱力學狀態係由四項獨立的變數所界 -14- 200835668 定：壓力（P)，溫度（T)，液相組成（X)和氣相組成 (γ)。共沸物係包含至少二種成分的特定系統，其中於 一給定溫度和給定壓力下，X係確切地等於γ。假共沸物 係一包含至少二種成分的系統其中，於一給定溫度和給定 壓力下，X係實質地等於Y。實際上，此意指此等共沸物 或假共沸物系統的組份不會容易地經由蒸餾所分離，且因 此於溶劑清潔操作中，以及於用蒸餾回收廢餘溶劑的操作 中，彼等的組成實質地保持固定。 對於本發明的目的而言，對於形成共沸物的混合物， 術語π假共沸物”係經理解爲意指包含二種或多種組分的混 合物，其（於一給定壓力下）的沸點係與共沸物的沸點相 差最多0.2 °c。 當1，1,1，3,3-五氟丁烷和反-1，2-二氯乙烯在彼等的混 合物中基本上由56重量％至82重量％的1，1，1，3,3-五氟丁 烷，和44至18重量％的反-1，2-二氯乙烯所組成之時，形 成一種二元共沸物或假共沸物。一形成共沸物或假共沸物 的較佳組成物爲由60至78重量％的1，1，1，3,3-五氟丁烷和 40至22重量％的反-1，2-二氯乙烯所組成者。於1 022毫巴 (mbar)的壓力下，基本上係由約70重量％的1，1，1，3,3-五氟丁烷和約30重量％的反-1，2-二氯乙烯所組成的二元 組成物構成其沸點爲36.3°C的共沸物。此組成物係非常有 利者。 對於包含異丙醇的三元組成物而言，業經發現到氣相 的組成基本上對應於液相組成。因此，含1，1，1，3,3-五氟 -15- 200835668 丁院、反-1，2 -二氯乙烯和異丙醇的不可燃組成物在彼等的 混合物基本上由55·5重量％至81·5重量％的丨^^^五 氟丁院，4 4至1 8重量％的反-1，2 -二氯乙嫌和介於〉0與等 於或較佳者小於〇 · 5重量％的異丙醇所組成之時’形成一 種三元假共沸物。含HFC_3 65mfc、TDCE和異丙醇的三元 組成物形成之共沸物尙未經鑑定過。對於不形成共沸物的 組成物而言，在本發明框架中的’’假共沸物’’ 一詞，表一種 下述組成物，此組成物在定溫下蒸發掉50%的初始液體質 量之後，於初始混合物的蒸氣壓與最終混合物的蒸氣壓之 間的百分比變異係低於約10%。參見D.A· Didion和D.B. Bivens 於 Int. J. of Refrigeration 13 ( 1990) ，163 至 1 7 5頁中的論文內容。 形成假共沸物的較佳組成物包含59.5至77.5重量％ 的1，1，1，3,3-五氟丁烷，40至22重量％的反-1，2-二氯乙烯 和介於>〇且等於或較佳者小於0.5重量％的異丙醇。非常 較佳的組成物基本上包含59.6至77.5重量％的1，1，1，3,3-五氟丁烷，40至22· 1重量％的TDCE和>0至0.4重量％的 異丙醇。 使用上述不可燃組成物的本發明方法原則上可應用於 至此之前已經使用包含HFC-3 65mfc和TDCE，較佳者與 安定劑，尤其是異丙醇一起的混合物之方法。特別者，本 發明方法可應用於在該組成物係用於或預期用爲清潔劑， 或作爲表面清潔劑之時，例如用於清潔部件，例如，精密 部件’由塑膠或無機材料製成者，例如從金屬，玻璃，或 -16- 200835668 陶瓷製成者。該清潔方法可在超聲波槽內應用。術語”清 潔”包括’例如，清潔紡織品，一般性除脂，例如動物毛 皮除脂，表面清潔，例如清潔，特別是金屬，玻璃，或陶 瓷部件的除脂；光學透鏡的清潔，電子裝置的清潔，例如 被浸漬助熔劑所污染及來自此助熔劑的殘留物所污染的印 刷電路板，經由沖滌彼等以清潔氣候適應裝置的管件或其 他部件，或清潔不溶於組成物中的固體化學品。例如，碳 Φ 或無機化合物等的具有小於1 〇·3公尺的尺寸之小粒子、具 有小於1〇_6公尺的尺寸之微粒子、和具有小於l(T9公尺的 尺寸之奈米粒子，都可處理。固體物件可經乾燥來移除吸 附在固體物件表面的水。本發明方法可應用於該組成物要 用爲或預期用爲溶劑之時，例如，用爲化學反應的溶劑或 用於運送溶解化合物的載體液體，包括彼等作爲用於層析 分析目的載體之用途，或用於備用的化學品所用之溶劑， 例如，清漆或塗料等。 • 本發明另一具體實例爲容器或其他容限物（ containments )，彼等都沒有標示著有關燃燒危險之警告 _ 標誌，且彼等裝著含HFC-3 65mfc和TDCE，及，較佳者 ，安定劑，尤其是異丙醇之不可燃組成物。 包含廣範圍的HFC-3 65mfc和反-1，2-二氯乙烯，及隨 意地含安定劑，尤其是異丙醇之組成物爲不可燃者之發現 ，使此等混合物特別可用於本發明方法中。其可用於’例 如，其中HFC-3 65mfc和1，2-反-二氯乙烯的起始含量，分 別從起始濃度轉變爲在2與98重量％之間的任何濃度之應 -17- 200835668 用中。 本發明係利用下述驚人發現：包含 TDCE (兩者皆爲可燃性化合物）的混合 包含可燃性化合物異丙醇作爲安定劑時， 其結果爲至少在一步驟中，其操作係經簡 。例如，在操作該組成物之時，不需採取 預防措施，如不需在惰性氣體下作業；不 空氣進入應用或操作該組成物所處的隔間 及的裝置或容器接地；不需要採用針對該 不需要在容器或運送工具上加上指示燃燒 後來可能將彼等移除）；陸路油罐車或火 況中會限制的區域。於漏電的情況中，不 。不標示的另一優點爲人們不必受到針對 警告而驚慌。 【實施方式】 下列實施例，無意限制之下，係以更 發明。 實施例 實施例1:包含1，1，1，3,3-五氟丁烷 ，反-1，2·二氯乙烯（TDCE)及作爲安定 #物的製備 將包含約 0 · 5重量％異丙醇的反- HFC-365mfc 和I 物及特別是彼等 具有不可燃性； 化且較低成本者 針對燃燒危險的 需要防止氧氣或 內；不需要將涉 危險的警告，如 危險的標示（及 車可通過別的情 必驚動安全人員 火災危害的錯誤 詳細方式闡明本 (HFC-3 6 5mfc ) 劑的異丙醇之混 1，2-二氯乙烯與 -18- 200835668 1，1，1，3,3-五氟丁烷以3 0:70的重量比例混合。所得混合物 包含 68.99 重量％的HFC-365mfc，30·86重量％的TDCE和 0.16重量％的異丙醇（100重量％總和的〇·01重量°/。差異 係四捨五入的結果）。 燃燒性檢驗： 燃燒性檢驗係根據DIN/EN/ISO 1 3 73 6實施。該測定 係於一內體積75毫升的密閉杯內實施。該杯也包含一攪 拌器和一探針來測定受檢驗的液體之溫度。該杯也包括一 用於升高溫度之工具。於杯子的蓋子中，包含一裝置，其 可導引檢驗火焰到要接受測定其可燃性的液體之表面。使 用的裝置具有一熱偵測器，其可對應所測量的溫度之快速 上升（指示出火焰的發生）。 將攪拌器緩慢地旋轉（約3 0 rpm )。杯中的液體經緩 慢地升溫。每當溫度升高〇.5°C，即點燃檢驗火焰並確認 熱感應器有否回應。若有，則表在液體上方的氣相中有發 生燃燒程序。 實施例1 . 1 :實施例1的混合物 對於實施例1的組成物，根據DIN/EN/SIO 1 3 736沒 有觀測到閃點。 藉由將HFC-3 65mfc與包含約〇·5重量％作爲安定劑的 異丙醇之1，2-反-二氯乙烯混合，製備其他組成物且予以 檢驗。H F C - 3 6 5 m f c和經異丙醇安定化的1，2 -反-二氯乙燒 -19- 200835668 (TD CE )的混合比例和檢驗結果經整理於下表中（量係 以重量份數給出）： 實施例 HFC-3 65mfc 異丙醇安定化的TDCE 結果 1.2 95 5 無閃點 1.2a 95 5 無閃點 1 .3 80 20 無閃點 1.3a 80 20 無閃點 1.4 72 28 無閃點 1.4a 72 28 無閃點 1 .5 60 40 無閃點 1.5a 60 40 無閃點 1.6 68 32 無閃點 由” a”註記的實施例爲以相同混合比例重複前面實驗以確 i忍各自的結果之實驗。 熱力學性質的測定： 對實S&例1的組成物使用V i g r e u X塔在大氣壓下施以 蒸餾。沸騰溫度固定地保持在等於35 ·7 t;。在已蒸掉 50重量％的組成物之後，以氣相層析術分析蒸餾物和在蒸 餾容器中的殘餘組成物之組成。所得結果整理於表丨中。In principle, the process of the invention can be carried out with any non-combustible composition comprising HFC-3 65mfc and TDCE. The content of 1,1,1,3,3-pentafluorobutane and trans-1,2-dichloroethylene in the composition of the present invention may vary within a wide range of limits depending on the intended use. -11 - 200835668 The composition applied in the process of the invention contains HFC-3 65mfc and TDCE in an amount which renders it non-flammable, both liquid phase and vapor phase. Whether a group of products is non-flammable can be verified by standard methods available. A preferred standard method is the method according to DIN/EN/ISO 1 3 73 6 mentioned above. This standard method is described in detail in the examples. Other standards, for example, JIS K2265 - 1 996, are known to experts skilled in the art. Compositions containing HFC-3 65mfc, 95% by weight of trans-1,2-dichloroethylene • and nearly 5% by weight of isopropanol were found to have no flash point. Similarly, it has been found that a composition containing only 5% by weight of trans-1,2-dichloroethylene does not have a flash point. This demonstrates that the process of the present invention can be carried out with a composition comprising a wide range of HFC-3 65mfc and trans-1,2-dichloroethylene. Accordingly, the process of the present invention can be applied by a composition comprising equal to or more than 2% by weight, preferably equal to more than 4.6 % by weight of H F C - 3 6 5 m fc. Likewise, the process of the invention can be practiced with a composition comprising equal to or more than 2% by weight, preferably equal to or more than 45% by weight of TDCE. • The process of the invention can be carried out with a composition comprising equal to or less than 98% by weight, preferably 95.5% by weight. It can be carried out with a composition comprising 98% by weight or less, preferably 95.5% by weight of TDCE. The method of the invention can also be practiced with a composition comprising a stabilizer. In this case, the method preferably comprises a composition containing more than 0% by weight of HFC-3 65mfc or TDCE, preferably more than 5% by weight of 〇·〇, and a stabilizer composition. To implement. Preferably, it contains a stabilizer of equal to or less than 0.5% by weight. If the composition contains a stabilizer, an additional amount of HFC_3 65mfc or TDCE is replaced with a stabilizer. -12- 200835668 The composition may also contain additives as will be explained in detail later. Frequently, the compositions contain equal to or more than 45 wt% of 1,1,1,3,3-pentafluorobutane. They advantageously contain 1,1,1,3,3-pentafluorobutane equal to or more than 50% by weight. In a particularly preferred mode, they contain equal to or more than 60% of 1,1,1,3,3-pentafluorobutane. They often contain equal to or more than 95% by weight of 1,1,1,3,3-pentafluorobutane. Most often, they contain 1,1,1,3,3-pentafluorobutane equal to or lower than 85% by weight. # The composition of the invention often contains equal to or more than 5% by weight of trans-1,2-dichloroethylene. They preferably contain equal to or 15% by weight of trans-1,2-dichloroethylene. Often, these compositions contain TDCE equal to or less than 55 wt%. Preferably, they contain TDCE equal to or less than 50% by weight. In a particularly preferred manner, they contain TDCE equal to or less than 40% by weight. Various additives may optionally be included in the composition of the present invention. The compositions of the present invention may thus contain a surfactant or any other additive that may be used to modify the composition of the present invention. The nature and amount of such additives are determined by the intended use and are readily defined by those skilled in the art. In general, the amount of the additive contained in the composition of the present invention is not more than about 20% by weight of the composition, and most usually not more than 1% by weight. Preferably, less than 5% of the additive is included. Preferably, the composition does not comprise a chlorofluorocarbon. In one embodiment, the process of the invention is practiced with a composition consisting of HFC-3 65mfc and TDCE. This specific example is preferably carried out by using a ratio of HFC-3 65mfc and TDCE contained therein to form a composition of an azeotrope -13-200835668 or a pseudo azeotrope. In another preferred embodiment, the composition comprising 1,1,1,3,3-pentafluorobutane and/or TDCE comprises a stabilizer. For example, HFC_3 65mfc can be stabilized to combat dehydrohalogenation, or TDCE can be stabilized to combat polymerization. A non-flammable composition comprising HFC-3 65mfc, TDCE and one or more stabilizers can be advantageously used in the process of the invention. In the process of the invention, preferably, the composition comprises an alkanol as a stabilizer. . One particularly preferred alkanol is isopropanol. Isopropanol can simultaneously stabilize the two compounds to combat degradation and polymerization, respectively. It is often equal to or higher than 0.05% by weight in the amount of the mixture containing HFC-3 6 5mfc and TDCE. Preferably, it is equal to or higher than 0.1% by weight. The amount is often less than 0.5% by weight. Preferably, it is equal to or lower than 〇·4% by weight. Very preferably, it is equal to or lower than 0.25 wt%. It has been found that a blend of HFC-3 65mfc, TDCE and isopropanol also exhibits an azeotrope. Therefore, isopropanol will enter the vapor phase with HFC_ 3 6 5mfc and TDCE and continue its stabilization. Therefore, the above given amounts of H F C - 3 6 5 m f c, T D C E and, if present, and preferably, the ratio of isopropanol, are also expected to describe the content of the composition in the liquid phase and in the gas phase. It must be considered to be particularly surprising that mixtures comprising HFC-365mfc, TDCE and, for example, isopropanol are non-flammable and are fully applicable in the process of the invention. Fundamentally, the thermodynamic state of the fluid is defined by four independent variables -14-200835668: pressure (P), temperature (T), liquid phase composition (X) and gas phase composition (γ). Azeotrope is a specific system comprising at least two components, wherein at a given temperature and a given pressure, the X system is exactly equal to gamma. A pseudo azeotrope is a system comprising at least two components wherein the X system is substantially equal to Y at a given temperature and a given pressure. In practice, this means that the components of such azeotrope or pseudo-azeotrope systems are not readily separated by distillation, and therefore in the solvent cleaning operation, as well as in the operation of recovering waste solvent by distillation, The composition of the etc. remains substantially fixed. For the purposes of the present invention, the term "π pseudo azeotrope" is understood to mean a mixture comprising two or more components, the boiling point (at a given pressure), for a mixture forming an azeotrope. The difference from the boiling point of the azeotrope is at most 0.2 ° C. When 1,1,1,3,3-pentafluorobutane and trans-1,2-dichloroethylene are substantially 56% by weight in their mixture Forming a binary azeotrope or a dummy when composed of 82% by weight of 1,1,1,3,3-pentafluorobutane and 44 to 18% by weight of trans-1,2-dichloroethylene Azeotrope. A preferred composition for forming an azeotrope or pseudoazeotrope is from 60 to 78% by weight of 1,1,1,3,3-pentafluorobutane and 40 to 22% by weight of anti- Composition of 1,2-dichloroethylene. Basically from about 70% by weight of 1,1,1,3,3-pentafluorobutane and about 30 weights at a pressure of 1 022 mbar. The binary composition of % trans-1,2-dichloroethylene constitutes an azeotrope having a boiling point of 36.3 ° C. This composition is very advantageous. For a ternary composition comprising isopropanol It has been found that the composition of the gas phase is basically It should be composed in the liquid phase. Therefore, the incombustible composition containing 1,1,1,3,3-pentafluoro-15-200835668 Dingyuan, trans-1,2-dichloroethylene and isopropanol is in their The mixture consists essentially of 55.5% by weight to 81.5% by weight of 五^^^pentafluoride, 4 4 to 18% by weight of trans-1,2-dichloroethylene and between >0 and equal Or preferably less than 〇·5 wt% of isopropanol formed to form a ternary pseudo-azeotrope. The azeotrope formed by the ternary composition containing HFC_3 65mfc, TDCE and isopropanol has not been formed. For the composition that does not form an azeotrope, the term ''pseudo-azeotrope'' in the framework of the present invention is a composition of the following composition, which evaporates 50% at a constant temperature. After the initial liquid mass, the percent variation between the vapor pressure of the initial mixture and the vapor pressure of the final mixture is less than about 10%. See DA· Didion and DB Bivens in Int. J. of Refrigeration 13 (1990), 163 To the content of the paper on page 175. The preferred composition for forming the pseudo azeotrope comprises 59.5 to 77.5 wt% of 1,1,1,3,3-pentafluorobutane, 40 22% by weight of trans-1,2-dichloroethylene and isopropanol at > 〇 and equal to or preferably less than 0.5% by weight. A very preferred composition consists essentially of 59.6 to 77.5 wt% of 1 1,1,3,3-pentafluorobutane, 40 to 22.1% by weight of TDCE and > 0 to 0.4% by weight of isopropanol. The method of the invention using the above nonflammable composition is applicable in principle A method comprising a mixture of HFC-3 65mfc and TDCE, preferably with a stabilizer, especially isopropanol, has heretofore been used. In particular, the method of the invention can be applied when the composition is used or intended to be used as a cleaning agent, or as a surface cleaning agent, for example for cleaning parts, for example, precision parts 'made of plastic or inorganic materials For example, made from metal, glass, or -16- 200835668 ceramics. This cleaning method can be applied in an ultrasonic bath. The term "cleaning" includes, for example, cleaning textiles, general degreasing, such as animal fur degreasing, surface cleaning, such as cleaning, especially degreasing of metal, glass, or ceramic parts; cleaning of optical lenses, cleaning of electronic devices , for example, printed circuit boards contaminated with impregnated flux and from residues of this flux, which are cleaned to clean the fittings or other parts of the climate-compliant device, or to clean solid chemicals that are insoluble in the composition. . For example, small particles having a size of less than 1 〇·3 meters, such as carbon Φ or an inorganic compound, fine particles having a size of less than 1〇-6 meters, and nano particles having a size smaller than 1 (T9 meters) Can be treated. The solid object can be dried to remove water adsorbed on the surface of the solid object. The method of the present invention can be applied when the composition is used or expected to be used as a solvent, for example, as a solvent for chemical reaction or Carrier liquids for transporting dissolved compounds, including their use as carriers for chromatographic purposes, or solvents for use in spare chemicals, such as varnishes or coatings, etc. • Another embodiment of the invention is a container Or other containment, none of which is marked with a warning mark on the hazard of ignition, and they contain HFC-3 65mfc and TDCE, and, preferably, stabilizers, especially isopropanol a non-combustible composition. The discovery that a wide range of HFC-3 65mfc and trans-1,2-dichloroethylene, and optionally a stabilizer, especially isopropyl alcohol, are non-flammable, makes this Mixture It can be used in the process of the invention. It can be used, for example, in which the initial content of HFC-3 65mfc and 1,2-trans-dichloroethylene is changed from a starting concentration to any between 2 and 98% by weight, respectively. The concentration is -17-200835668. The present invention utilizes the surprising discovery that when a mixture comprising TDCE (both are flammable compounds) comprises a flammable compound isopropanol as a stabilizer, the result is at least in one In the step, the operation is simplified. For example, when the composition is operated, no precautions need to be taken, such as no need to operate under an inert gas; no air enters the application or operates the compartment in which the composition is located and The device or container is grounded; there is no need to use an area that is limited in the case of a land tanker or fire, as it is not necessary to add an indication to the container or shipping tool. In the case of leakage, no. Another advantage of not being labeled is that people do not have to be panicked about warnings. [Embodiment] The following examples, which are not intended to be limiting, are further invented. EXAMPLES Example 1: Preparation of 1,1,1,3,3-pentafluorobutane, trans-1,2·dichloroethylene (TDCE) and as a stabilizer # will contain about 0.5 wt% The anti-HFC-365mfc and I substances of propanol and especially their non-flammability; and the lower cost ones need to prevent oxygen or the need for combustion hazards; there is no need to warn of dangers such as hazard indications ( The vehicle can be used to illuminate the isopropyl alcohol blend of 1, HFC-3 6 5mfc and -18- 200835668 1,1,1 by other details. 3,3-pentafluorobutane is mixed in a weight ratio of 30:70. The resulting mixture contains 68.99 wt% of HFC-365mfc, 30.86 wt% of TDCE and 0.16 wt% of isopropanol (100 wt% sum 〇·01 weight ° /. The difference is the result of rounding.) Flammability test: The flammability test is carried out according to DIN/EN/ISO 1 3 73 6. The test is carried out in a closed cup of 75 ml internal volume. The cup also includes a stirrer and a probe to determine the temperature of the liquid being inspected. The cup also includes a A tool for raising the temperature. The lid of the cup contains a device that guides the test flame to the surface of the liquid to be tested for its flammability. The device used has a thermal detector that corresponds to the measured A rapid rise in temperature (indicating the occurrence of a flame). Slowly rotate the stirrer (about 30 rpm). The liquid in the cup slowly heats up. When the temperature rises by 55 °C, the test flame is ignited. It is confirmed whether the thermal sensor responds. If there is, the combustion process occurs in the gas phase above the liquid. Example 1. 1 : The mixture of Example 1 For the composition of Example 1, according to DIN/EN/SIO No flash point was observed in 1 3 736. Other compositions were prepared and tested by mixing HFC-3 65mfc with 1,2-trans-dichloroethylene containing about 5% by weight of isopropanol as a stabilizer. The mixing ratio and test results of HFC-3 3 5 mfc and isopropanol stabilized 1,2 -trans-dichloroethane -19-200835668 (TD CE) are compiled in the following table (quantity by weight) Parts are given): Example HFC-3 65mfc Isopropanol stabilized TDCE Result 1.2 95 5 No flash point 1.2a 95 5 No flash point 1. 3 80 20 No flash point 1.3a 80 20 No flash point 1.4 72 28 No flash point 1.4a 72 28 No flash point 1. 5 60 40 No flash point 1.5a 60 40 No flash point 1.6 68 32 Example without flash point Annotated by "a" is an experiment in which the previous experiment was repeated at the same mixing ratio to confirm the respective results. Determination of thermodynamic properties: The composition of the real S & Example 1 was subjected to distillation at atmospheric pressure using a V i g r e u X column. The boiling temperature is fixedly maintained at equal to 35 · 7 t; After 50% by weight of the composition had been distilled off, the composition of the distillate and the residual composition in the distillation vessel was analyzed by gas chromatography. The results obtained are compiled in the form.
表I 蒸餾物 的餾份 H F C - 3 6 5 m f c (重量％ ) TDCE (重量％ ) 異丙醇 __(重量％ ) 蒸餾物 68.59 3 1.29 Π 1 ? 殘餘物 70.99 28.82 一 \} φ X ^ _ 0.19 所得蒸餾物和容器中的殘餘物之組成顯示由 -20- 200835668 1，1，1，3，3 -五氟丁焼，反-1，2 -二氯乙儀和異丙醇組成的組 成物之假共沸物行爲的存在。蒸餾物和殘留物的組成物之 測定也顯示出氣相包含所有三種本身爲可燃的化合物，但 成爲組成物卻爲不可燃者。其也顯不出對組成物的氣相也 預期有異丙醇的安定化效應。 實施例2 :本發明方法之實施 2.1.紡織品清潔 將紡織物件裝到使用實施例1組成物操作的洗滌機器 內。下列步驟中至少一個不在操作可燃組成物所需條件下 :將紡織物件裝到該機器內之步驟，洗滌該紡織品之步驟 ，打開該機器的步驟和將該紡織品乾燥以從該紡織品移除 殘留組成物之步驟。例如，一或多個此等步驟係在沒有採 取燃燒危害的預防措施下實施，包括防止該組成物和紡織 品與空氣接觸的預防措施。此外，洗滌機器也沒有上燃燒 危險的標示。 2.2·重複實施例2.1，使用地毯作爲要清潔的品項 2.3.複雜金屬部件之清潔（蒸氣去脂） 金屬組件可經在表面上施用油脂以保護其抵抗腐鈾。 黏附油脂也可經由在金屬組件的成型中施加潤拉（ drawing )鱲，潤拉脂或潤拉油所造成。高精密金屬部件 的清潔步驟係在蒸氣去脂器內實施。 可應用具有兩個溶劑塡充儲器的蒸氣浸沒單元。一煮 沸清潔槽包含溶劑混合物，此溶劑混合物除了包含較高沸 -21 - 200835668 點溶劑成分之外，另外包含上述不可燃組成物。一沖洗槽 僅包含上述不可燃組成物。 金屬組件經集合於一籃子中並浸到沸騰清潔槽內以溶 解黏著油脂。彼等接著被取出並浸到沖洗槽內，於其中沖 洗掉來自沸騰清潔槽的黏著溶劑混合物。隨後將組件以沖 洗槽的較低沸點組成物予以覆蓋。隨後從沖洗槽中取出籃 子並存放於槽上的氣體空間中。黏著在金屬部件表面上的 溶劑變化到氣相中。在接近蒸氣除脂氣的頂部有三組冷卻 線圈，於此處蒸氣在其從單元逸出之前凝結。凝結的蒸氣 流回乾淨的凝結液槽中且可再使用。一部分的蒸氣係經送 到乾燥單元以從其移除水分。經除脂的乾燥金屬部件即可 從蒸氣除脂器取出。 至少一個下列步驟，且隨意地二或更多個且甚至所有 下列步驟，不在操作可燃產品所需的條件下實施（如，防 止與空氣接觸、接地）：打開裝有實施例1組成物的容器 :將管線連接到彼；利用泵將組成物轉移到冷儲槽與進入 熱儲槽內；拆離管線；封閉貯存容器；打開蒸氣除脂器以 放置有上脂的金屬部件到多孔金屬上；從多孔金屬上取出 經去脂的金屬部件；再塡充該蒸氣除脂器。在貯存槽、管 線、蒸氣除脂器、及放置貯存槽和蒸氣除脂器之房間（該 房間中沒有其他可燃材料）都沒有加上針對燃燒危險的警 告標示。此實施例證明本發明方法可用時在液相和蒸氣相 中應用該組成物。 2.4.將經由焊接電部件於個別板上所製成的印刷電路 -22- 200835668 浸沒在部份裝塡著實施例1組成物的容器內以移除黏附的 焊劑。於浸漬及移除焊劑之後，將印刷電路從組成物提出 且乾燥。至少一個下列步驟，且隨意地二或更多個或甚至 所有步驟，不在操作可燃產品所需條件下貫施：用實施例 1組成物部份塡充容器；將印刷電路放置在組成物上方； 將其浸沒在其內；將其取出；將其乾燥；從容器取出廢餘 組成物及將其轉移到蒸餾裝置以回收其供再使用所用。 φ 2·5·運送組成物：要利用陸路油罐車將20公噸的實施 例1組成物運送到使用場所。所以，在製造場所上的容器 與該陸路油罐車所載容器之間要連接一管線。利用泵轉移 實施例1組成物。其後，拆掉管線且該陸路油罐.車開往其 目的地，於該處將該組成物轉移到貯存容器。至少一個下 列步驟，且隨意地二或更多個且甚至所有下述諸步驟，不 在操作可燃產品所需條件下實施：連接該等容器；從一容 器將組成物轉移到製造場所的另一容器；脫離該等容器； # 利用陸路油罐車將組成物運送到使用場所（包括通過禁止 運送可燃產品的陸路油罐車通過的隧道）；將組成物轉移 到在使用場所的貯存容器；連接與脫離該目的所用的容器 。此外，該貯存容器以及該陸路油罐車都不必標示針對可 燃產品的危險之警告。 2.6.資料表與貨物文件都不必包含針對火災危險的警 告。 實施例3 :(比較實施例） -23- 200835668 將甲醇添加至實施例1的組成物中，使得所得混合物 包含3.6重量％的甲醇。觀測到於-21.5 °c的閃點。Table I Distillate fraction HFC - 3 6 5 mfc (% by weight) TDCE (% by weight) Isopropyl alcohol __ (% by weight) Distillate 68.59 3 1.29 Π 1 ? Residue 70.99 28.82 a \} φ X ^ _ 0.19 The composition of the distillate and the residue in the vessel is composed of -20-200835668 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethane and isopropanol. The existence of false azeotropy behavior. The determination of the composition of the distillate and the residue also showed that the gas phase contained all three compounds which were themselves flammable, but the composition was not flammable. It also shows that the gas phase of the composition is also expected to have an effect of stabilizing isopropanol. Example 2: Implementation of the method of the invention 2.1. Textile cleaning The textile article was loaded into a washing machine operated using the composition of Example 1. At least one of the following steps is not under the conditions required to operate the flammable composition: the step of loading the textile article into the machine, the step of washing the textile, the step of opening the machine, and drying the textile to remove residual constituents from the textile The steps of things. For example, one or more of these steps are carried out without precautions to take the hazard of combustion, including precautions to prevent contact of the composition and textile with air. In addition, the washing machine is not marked with a burning hazard. 2.2. Repeat Example 2.1, using carpet as the item to be cleaned 2.3. Cleaning of complex metal parts (vapor degreasing) Metal parts can be protected against uranium by applying grease on the surface. Adhesive grease can also be caused by applying a drawing, a lubricant or a lubricating oil in the molding of the metal component. The cleaning steps for high precision metal parts are carried out in a vapor degreaser. A vapor immersion unit having two solvent reservoirs can be used. A boil cleaning tank comprises a solvent mixture which, in addition to the higher boiling point - 21 - 200835668 point solvent component, additionally comprises the above non-combustible composition. A rinse tank contains only the above non-flammable composition. The metal components are collected in a basket and immersed in a boiling cleaning tank to dissolve the grease. They are then removed and immersed in a rinse tank where the adhesive solvent mixture from the boiling cleaning bath is rinsed. The assembly is then covered with the lower boiling composition of the wash tank. The basket is then removed from the rinse tank and stored in the gas space on the tank. The solvent adhering to the surface of the metal member changes into the gas phase. There are three sets of cooling coils on top of the vapor degreasing gas where the vapor condenses before it escapes from the unit. The condensed vapor flows back into the clean condensate tank and can be reused. A portion of the vapor is sent to the drying unit to remove moisture therefrom. The degreased dry metal parts can be removed from the vapor degreaser. At least one of the following steps, and optionally two or more and even all of the following steps, are not carried out under the conditions required to operate the combustible product (eg, preventing contact with air, grounding): opening the container containing the composition of Example 1. : connecting the pipeline to the other; transferring the composition to the cold storage tank and entering the thermal storage tank by using a pump; detaching the pipeline; closing the storage container; opening the vapor degreaser to place the greased metal component onto the porous metal; The degreased metal part is removed from the porous metal; the vapor degreaser is then charged. Warning signs for fire hazards are not added to storage tanks, pipelines, vapor degreasers, and rooms where storage tanks and vapor degreasers are placed (no other combustible materials in the room). This example demonstrates that the process of the present invention can be used in liquid and vapor phases when available. 2.4. Printed circuit -22-200835668 made on individual boards via soldered electrical components was immersed in a container partially encased in the composition of Example 1 to remove the adhered flux. After impregnation and removal of the flux, the printed circuit is lifted from the composition and dried. At least one of the following steps, and optionally two or more or even all of the steps, are not performed under the conditions required to operate the combustible product: filling the container with the portion of the composition of Example 1; placing the printed circuit over the composition; Immerse it therein; take it out; dry it; take the waste composition from the container and transfer it to a distillation unit to recover it for reuse. φ 2·5·Conveying composition: 20 metric tons of the composition of Example 1 was transported to a place of use by a land tanker. Therefore, a line is required between the container on the manufacturing site and the container carried by the land tanker. The composition of Example 1 was transferred using a pump. Thereafter, the pipeline is removed and the land tanker is driven to its destination where it is transferred to a storage vessel. At least one of the following steps, and optionally two or more and even all of the following steps, are not carried out under the conditions required to operate the combustible product: joining the containers; transferring the composition from one container to another container at the manufacturing site Off the containers; #Use the land tanker to transport the composition to the place of use (including the tunnel through which the land tanker is prohibited from transporting the combustible product); transfer the composition to the storage container at the place of use; The container used for this purpose. In addition, the storage container and the land tanker do not have to indicate a warning of the hazard to the flammable product. 2.6. The data sheet and cargo documents do not have to contain warnings for fire hazards. Example 3: (Comparative Example) -23- 200835668 Methanol was added to the composition of Example 1 such that the resulting mixture contained 3.6% by weight of methanol. A flash point of -21.5 °c was observed.
-24--twenty four-