TW390815B - Apparatus and method for vapor sterilization using inorganic hydrogen peroxide complexes - Google Patents
Apparatus and method for vapor sterilization using inorganic hydrogen peroxide complexes Download PDFInfo
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Α7 Β7 鐘濟部中央樣準工消费合作杜印轚 五、發明説明() 發明领域: 本發明係關於一以過氡化氫蒸氣來對物體如醫療器具進 行投菌之裝置及方法,更明確的來説,乃是以過氧化氫之無 機複合物來進行此一步擇。 相關技藝之説明: 傳統上醫療器具乃是以熱,如蒸氣,或化學物質,如甲 接或環氧乙坑之氣雅或蒸氣來進行滅菌。這些方法都有缺 點。許多醫療裝置,如光纖裝置,内視嬈,須插電的工具, 及其它,對熱,水分,或此兩者都很敏感。甲醛和環氧乙烷 均為有毒氣《因此訝醫療工作人貝的健康有潘在的危除。環 氡乙坑所造成的問題則更為嚴重,因其在使用時須經r-段長 時問才能將環氧乙烷氣髖由被殺酋物tt上完全移除。因此滅 菌所須時間變得非常長。此外,無譫是使用甲接或環氧乙 虼,系統内均須要有足羚多的水分β因此,在引入化學物質 前須先使欲投菌的物雅含有足夠的濃度,或者投菌時必須將 水蒸氣和化學物質同時引入。除了甲醛或環氧乙坑外,表1 «示在以各種化學物質之氣髖或蒸氣進行投茵時,水分也扮 演了一些角色。 (請先《讀背面之注*事項存填寫本霣) 訂 本纸張尺度遴用t國國家搮準(CNS > Α4规格(210X297公釐) A7 B7 五、發明説明() 表1 達最佳效果時所须之相讲港詹 環氡乙坑 25-50% 環氡丙坡 25-50% 臭氧 75-90%Α7 Β7 Zhong Ji ’s Central Prototype and Consumer Cooperation Du Yin 轚 5. Description of the invention () Field of the invention: The present invention is more specific about a device and method for injecting bacteria such as medical devices with hydrogen peroxide vapor. In other words, this step is based on the inorganic compound of hydrogen peroxide. Explanation of related skills: Traditionally, medical equipment is sterilized by heat, such as steam, or chemical substances, such as nail or epoxy epoxy. These methods all have shortcomings. Many medical devices, such as fiber optic devices, endoscopes, tools to be plugged in, and others are sensitive to heat, moisture, or both. Both formaldehyde and ethylene oxide are toxic. Therefore, the health of medical workers is at risk. The problem caused by Huanqiu Yikeng is even more serious, because it must be r-section long time before use in order to completely remove the ethylene oxide hips from the killed object tt. Therefore, the time required for sterilization becomes very long. In addition, the use of formazan or ethoxylate is not necessary, and there must be enough water in the system. There must be sufficient concentration of the substance to be injected before the introduction of chemicals, or Water vapor and chemicals are introduced simultaneously. In addition to formaldehyde or epoxy resin, Table 1 «shows that water also plays a role when inoculated with various chemicals such as hips or steam. (Please read the “Notes on the back side of the book” and fill in this card first.) The size of the paper used in the book is selected according to the national standard of the country (CNS > A4 size (210X297 mm) A7 B7 5. Description of the invention () Table 1 The best results when talking about the effect of Hong Kong Zhan Huanyi Yikeng 25-50% Huanqiang Po slope 25-50% Ozone 75-90%
甲接 >75% 1 戊二醛 80-90% 3 二氧化氩 60-80% 4 溴化甲坑 40-70% 1 卢丙内酯 >75% 1 過氡乙酸 40-80% 5 (請先W讀背面 ./1> 之注意事項再填寫本頁) 訂 Λ濟部中央樣舉曷負工消费含作社印裂 參考文獻: 1. Bruce, C. W. Gaseous Sterilization, Ann. Rev. Microbiology 15:245-262 (1961). 2. Janssen, D. W. and Schneider, P.M. Overview of Ethylene Oxide Alternative Sterilization Technologies, Zentralsterilisation 1:16-32 (1993). 3. Bovallius, A. and Anas, P. surface-Decontaminating Action of Glutaraldehyde in the Gas·Aerosol Phase. Applied and Enviromental Microbiology, 129-134 (Aug. 1977). 4. Knapp, J.E. et al. chotine Dioxide As a Gaseous Sterilant, Medical Device & Diagnostic Industry, 48-51 (Sept. 1986). 5. Portner, D.M. and Hoffman, R.K. Sporicidal Effect of Peracetic Acid Vapor, Applied Microbi〇i°Sy 1785 (1968). 3 _ 本紙張又度遑用中國國家揉準(CNS ) Α4规格(210X297公釐) 經濟部中夹橾率局貝工消费合作杜印製 Α7 Β7 五、發明説明() 相較於其它殺菌方法,己知以過氧化氫蒸氣來進行殺菌 有更多的優點(參見,如國美專利案第4,169,123號和第 4,169,124號),且如美專利案第4,643,876號中所揭露 的,合併使用過氧化氩舆雹漿(plasma)能提供一些额外的 優ft。在這痊已揭露範团中,過氡化氩蒸氣通常來自過氡化 氫水溶液,因此能保證系統中有足夠的水分存在。由這些己 揭露的範面,及表1中的結論可知欲使過氧化氳蒸氣產生效 用或使其展現出最大的滅菌能力,水分乃是必要的。然而, 在以過氡化氫水溶液來產生殺菌用的過氧化氫蒸氣時可能會 有一些問題。在高墨下,如大氣蜃下,系统中過量的水分會 造成凝結。因此,在?丨入過氧化氫水蒸氣前必須降低欲殺菌 物體Λ之相财溼度》 内含獷散效用無法抵達之面積的物《,如長型内室,對 想以遇氧化氫水溶液所產生的過氧化氫蒸氣來進行殺菌的方 法將會是一項極大的挑戮,因為: 1·水的蒸氣壓較遇氡化氩高,因此較遇氡化氩更容易由 水溶液中蒸發。 2.水的分子量較過氡化氩低,因此在蒸氣狀態下較過氡 化氫更容易擴散。 因此,當過氧化氫水溶液蒸發時,水會率先以較高的濃 度抵達欲進行滅酋的物《上。因此水蒸氣會限制過氣化氩蒸 氣在受限匾内的擴散情形,例如小洞《或長而窄的内腔。将 水自水溶液中移除並使用較高濃度的遇氣化氫蒸氣,由於溶 液本身的氡化力,可絕會對使用者造成傷害。 4 本纸張尺度逯用中國國家揲準(CNS ) A4規格(210X297公釐) I I - - ! !| — - ^^1 11 - - I - - m ―=二-I /mt (請先W讀背面之注意事項再填寫本頁) A7 B7 五、發明説明() 在美國專利案第4,642,165號和第4,744,951號中便 試圈解決這個問題。在前一專利案中每次均只將少量過氡化 氫溶液引至一受熱表面以確保在加入下一劑量的過氡化氫溶 液之前,前一劑量之遇氡化氩已完全被蒸發了。雖然此法可 幫助消弭過氡化氳和水之《蒸氣壓和揮發度的不同,但並未 去除在蒸氣狀態時,水較過氧化氫更易擴教的事實。 而在後一專利案中描述了一種由各類過氡化氫和水的稀 釋液中來濃缩過氧化氫的方法,並將濃縮後的過氧化氫蒸氣 引至一已減菌的内室隔問。此法牵涉到在將濃绾後的過氧化 氣蒸氣注入一已滅菌的内室隔間之前,先將溶液中大部分的 水蒸發並移除。濃缩後的遇氡化氫溶液重量比最好是在 50 %至80 %之間的範面。此法的缺點乃是溶液的操作渡度 乃落在對人tt有害的範面,亦即,遇氧化氫濃度《遘 65%,且並未將蒸氣狀態下的水分完全移除。由於水仍留 存在溶液中,因此會先被蒸發,更快被擴散,並會先到達欲 殺菌的物體。錡於具長而狹窄内室的物體,這種效應會更明 顯。 美國專利案第4,943,414號中揭露了一種方法,亦即 將内含少量探發的液想殺笛溶液的容器與欲殺菌内室相通, 在殺菌循環中當壓力下降時使殺菌溶液在揮發後直接流到物 «的内室中。此系统的優點是藉内室中的壓力差蓊水和遘氡 化氫蒸氣拉進内室,增加内室中的殺«速率,体其鈇贴《是 須--將容器接上欲殺笛的内室。此外,水也同樣會被先蒸 發並在過氧化氩蒸氣之前到達内室》 5 本紙張尺度適用中國國家揉丰(CNS ) Α4規格(210X297公釐) ί装-- (請先Μ讀背面之注意事項再填寫本頁) 訂 輕濟部中央檫率局貝工消费含作杜印«. A7 B7_ 五、發明説明() 美國專利案第5,008,106號中揭露了 一種聚N -丙烯雜 環化物(PVP)和過氧化氩形成之幾乎無水的複合物,用來 減低表面微生物的含量。此複合物,以極細的白色粉末存 在,被用作抗微生物之溶液,凝膠,软膏及其它。也可將其 用在紗布,棉花球,海棉及其它類似物。一旦舆含微生物之 表面的水接觸後,過氡化氩便會立刻被釋放出來。因此,此 法的殺菌效用須要水分的存在。 钂濟部中夹輮率Λ貝工消费合作社印簟 (請先W讀背面之注意事項再填寫本頁} 某些過氡化氫的無機複合物己被報導過,化合物包 括下列各類別中的一些範例:驗金屬和破酸氨璺,銓金屬草 酸鹽,銓金屬磷酸盪,酸金屬焦磷酸ft,氟化物和氫氡化 物。蘇聯專利案第SU 1 68 1 860 (Nikolskaya et a 1)中揭 露了一種不一定會到達無菌程度,以過氡化氫氟化氨 (NH4F . H2〇2)來對表面進行去污染的方法。但是,此過 氧化氩氟化氨無機複合物僅能在很窄的温度範面内70-86 ^提供表面去污染的作用。即使在此範面内,仍須相當長的 去污染時間,至少兩小時。此外,己知當溫度超過40 °C 時,氟化氨便會分解成氫氟酸。由於其毒性及反應性,在大 部分的殺菌系统中均不喜用氩氟酸。再者,Nikolskaya 等人也揭露了雖然在60 *C時,90 %的過氧化氩都會被釋 出,但在此溫度下NH4F . H2〇2並不具有能對表面進行 去污染的效用。因此,上述表面去污染的效用似乎是經由遇 氧化氩以外的其它因子之作用所達成的。 遘氡化氬觝與有機和無機化合物形成複合物。達些複合 物的結合乃歸功於複合化合物與過氡化氩中富含電子之官能 6 188?^^ ( CNS ) ( 210X2974i-i| ) ' A7 B7 五、發明説明() 基兩者閼所形成的氫鍵之故。商業及工業上均有此類複合物 的應用實例,如漂白劑,去感染劑,有機合成中的氡化劑, 及自由基引起之聚合反應中的催化劑。 一般來説,這類化合物的製備可藉將其由水溶液中結晶 出來而達成。例如,Lu及其同僚(J. dw. CAem. Soc. 63(1):1507-15 13(1941))藉將尿素溶液直接加到過氧化 氩溶液中並使其在適當條件下結晶來製備尿素過氧化氩複合 物。美國專利案第2,986,448號中述及在密閉循環系统, 溫度0-5 eC下以50-90 %之過氧化氫溶液來處理餸和的碳 酸鈉(Na2C03)溶液4至12小時,可製備瑗酸鈉遘氧化氩 複合物。最近,美國專利案第3,870,783中揭露了 一種讓 遇氡化氩水溶液與碳酸鈉在批式或連續式結易器t反摩以製 備碳酸鈉過氧化氫複合物的方法。以過濾或離心方式將結晶 分«,溶液並可用來產生更多的碳酸訥溶液。Titoval等 K{Zhurnal Neorg. Kkim .,3 0 : 2 2 2 2 · 2 2 2 7 )描述了瓖 酸鉀過氧化氫複合物(K2C03 . 3H2〇2)的合成方法,讓 碳酸鉀固體與過氧化氩溶液在低溫下一起反應之後再使複合 物由乙醇中結晶出來。這些方法對會由水溶液中產生安定、 無结晶流動的過氡化氩複合物產物而言非常有用。 美國專利案第3,376,110號和第3,480,557號中揭露 了 一種由水溶液中製備過氧化氫與聚N-丙烯離環化物 (PVP)组成之複合物的方法。所得複合物含不同量的遇氧 化氫及相當大量的水。美國專利橐第5,008,093號中述及 自由流動、安定、幾乎無水之遢氡化氫與聚N -丙烯馨環化 .Μ. I I I — I (請先閲讀背面之注$項再填寫本頁) 訂 Λ濟部中央揉车ΛΛ工消费合作杜印«. M濟部中夫標隼Λ貝工消费合作社印装 A7 B7 五、發明説明() 物(PVP)组成之複合物,可讓過氡化氫與聚N-丙烯雜環化 物(PVP)在無水有機溶劑似的乙酸乙酯中反應而得。最 近,美國專利案第5,077,047號中述及了一項製造聚N -丙 烯雜環化物(PVP)·過氡化氫產物的商業方法,將劃分得極 細之3 0 %至8 0 %的過氣化氫液滴加到一溫度維持在6 0 eC 的PVP流床上。得到一安定、幾乎無水、能自由流動且過 氡化氩濃度在1 5 · 2 4 %之產物。 美國專利案第5,030,380號中述及了一項製造與過氧 化氩形成固態聚合物似之電解複合物的方法,先在水溶液中 形成複合物之後在眞空下將反應物乾燥或以低溫將其吹乾以 避免產物的熱裂解。Formazan> 75% 1 glutaraldehyde 80-90% 3 Argon dioxide 60-80% 4 Methyl bromide 40-70% 1 Luprolactone > 75% 1 Peracetic acid 40-80% 5 ( Please read the notes on the back./1> before filling out this page) Order the Central Samples of the Ministry of Economic Affairs, Consumers and Consumers, including the printed reference of the agency: 1. Bruce, CW Gaseous Sterilization, Ann. Rev. Microbiology 15 : 245-262 (1961). 2. Janssen, DW and Schneider, PM Overview of Ethylene Oxide Alternative Sterilization Technologies, Zentralsterilisation 1: 16-32 (1993). 3. Bovallius, A. and Anas, P. surface-Decontaminating Action of Glutaraldehyde in the Gas · Aerosol Phase. Applied and Enviromental Microbiology, 129-134 (Aug. 1977). 4. Knapp, JE et al. chotine Dioxide As a Gaseous Sterilant, Medical Device & Diagnostic Industry, 48-51 (Sept 1986). 5. Portner, DM and Hoffman, RK Sporicidal Effect of Peracetic Acid Vapor, Applied Microbi0 °° Sy 1785 (1968). 3 _ This paper is again used in China National Standard (CNS) Α4 size (210X297 (Mm) Shellfish in the Ministry of Economic Affairs Fei He Du printed A7 B7 V. Description of the invention () Compared with other sterilization methods, it is known that sterilization with hydrogen peroxide vapor has more advantages (see, for example, GOME Patent Nos. 4,169,123 and 4,169,124) And, as disclosed in US Patent No. 4,643,876, the combined use of argon peroxide plasma can provide some additional advantages. In this case, the argon vapour is usually from a hydrogen peroxide solution, so it can ensure that sufficient water is present in the system. From these revealed aspects and the conclusions in Table 1, it can be seen that moisture is necessary to make the plutonium peroxide vapor effective or to exhibit the maximum sterilization ability. However, there may be some problems when generating hydrogen peroxide vapor for sterilization with an aqueous hydrogen peroxide solution. At high ink levels, such as atmospheric humidity, excessive moisture in the system can cause condensation. Thus, in?丨 Before entering the hydrogen peroxide water vapor, the relative humidity of the object to be sterilized must be reduced. "Contains an area that cannot be reached by the effect of tritium powder," such as a long inner chamber. The method of sterilizing with hydrogen vapor will be a great challenge, because: 1. The vapor pressure of water is higher than that with tritium argon, so it is easier to evaporate from aqueous solution than with tritium argon. 2. The molecular weight of water is lower than that of hydrogen peroxide, so it is easier to diffuse in the vapor state than hydrogen peroxide. Therefore, when the aqueous hydrogen peroxide solution evaporates, the water will first reach the object to be exterminated at a higher concentration. Water vapour will therefore limit the diffusion of over-gasified argon in confined plaques, such as small holes or long, narrow cavities. The removal of water from the aqueous solution and the use of a relatively high concentration of vaporized hydrogen vapor will definitely cause harm to the user due to the tritium force of the solution itself. 4 This paper uses China National Standard (CNS) A4 size (210X297 mm) II--!! | —-^^ 1 11--I--m ― = 二 -I / mt (Please first Read the notes on the reverse side and fill out this page) A7 B7 V. Description of the invention () In the US Patent Nos. 4,642,165 and 4,744,951, we tried to solve this problem. In the previous patent, only a small amount of hydrogen peroxide solution was introduced to a heated surface at each time to ensure that the previous dose of hydrogen peroxide had been completely evaporated before the next dose of hydrogen peroxide solution was added. . Although this method can help eliminate the difference in vapor pressure and volatility between water and hydrogen peroxide, it does not remove the fact that water is easier to expand than hydrogen peroxide in the vapor state. In the latter patent case, a method for concentrating hydrogen peroxide from various types of dilute hydrogen peroxide and water is described, and the concentrated hydrogen peroxide vapor is introduced into a sterilized inner chamber. Question every second. This method involves evaporating and removing most of the water in the solution before injecting the concentrated peroxide vapor into a sterilized inner compartment. The weight ratio of the concentrated hydrogenated hydrogenated solution is preferably in the range of 50% to 80%. The disadvantage of this method is that the operating temperature of the solution is in a range that is harmful to humans, that is, when the concentration of hydrogen oxide is <65%, and the moisture in the vapor state is not completely removed. Since water remains in the solution, it will evaporate first, diffuse faster, and reach the object to be sterilized first. This effect is more pronounced for objects trapped in long, narrow inner chambers. A method is disclosed in U.S. Patent No. 4,943,414, that is, a container containing a small amount of liquid to be killed is communicated with the inner chamber to be sterilized, and the sterilization solution flows directly after the volatilization when the pressure drops in the sterilization cycle. Into the inner room of the object «. The advantage of this system is that the pressure difference in the inner chamber is used to pull the water and hydrogen trioxide vapor into the inner chamber, which increases the killing rate in the inner chamber. Interior room. In addition, water will also evaporate first and reach the inner chamber before the argon peroxide vapor. 5 This paper size is applicable to China National Kung Fung (CNS) Α4 size (210X297 mm). Packing (Please read the first Note: Please fill in this page again.) Order the consumption of shellfish from the Central Ministry of Economy and Trade of the People's Republic of China, including Du Yin «. A7 B7_ 5. Description of the invention () US Patent No. 5,008,106 discloses a poly-N-propylene heterocyclic compound ( An almost anhydrous complex formed by PVP) and argon peroxide to reduce the content of surface microorganisms. This complex, which exists as an extremely fine white powder, is used as an antimicrobial solution, gel, ointment and others. It can also be used in gauze, cotton balls, sponges and the like. As soon as the water on the surface containing the microorganisms comes into contact, the tritium argon is released immediately. Therefore, the sterilization effect of this method requires the presence of water. In the Ministry of Health, the rate of ΛBeigong Consumer Cooperatives (please read the precautions on the back before filling out this page). Some hydrogenated inorganic compounds have been reported. The compounds include the following categories: Some examples: test metal and ammonium hydroxide, ammonium metal oxalate, ammonium metal phosphate, acid metal pyrophosphate ft, fluoride and hydrogen halide. US Patent SU 1 68 1 860 (Nikolskaya et a 1) A method of decontaminating the surface with ammonium hydrofluoride (NH4F.H2O2), which does not necessarily reach the degree of sterility, is disclosed in the article. However, this argon peroxide ammonium fluoride inorganic compound can only A very narrow temperature range of 70-86 ^ provides surface decontamination. Even within this range, a considerable decontamination time is required, at least two hours. In addition, it is known that when the temperature exceeds 40 ° C, Ammonium fluoride will decompose into hydrofluoric acid. Due to its toxicity and reactivity, argon fluoride is not preferred in most sterilization systems. Furthermore, Nikolskaya et al. Also revealed that although at 60 * C, 90 % Of argon peroxide will be released, but at this temperature NH4F. H2〇 2 does not have the effect of decontaminating the surface. Therefore, the above-mentioned effect of decontamination of the surface seems to be achieved by the action of factors other than argon oxide. Tritium argon forms a complex with organic and inorganic compounds. The combination of these complexes is attributed to the complex compounds and the electron-rich functionalities in perfluorinated argon 6 188? ^^ (CNS) (210X2974i-i |) 'A7 B7 V. Description of the invention () The formation of hydrogen bonds. Commercial and industrial examples of such complexes are used, such as bleaching agents, decontaminants, hydrating agents in organic synthesis, and catalysts in polymerization reactions caused by free radicals. General For example, the preparation of such compounds can be achieved by crystallizing them from aqueous solutions. For example, Lu and his colleagues (J. dw. CAem. Soc. 63 (1): 1507-15 13 (1941)) borrowed The urea solution is directly added to the argon peroxide solution and crystallized under appropriate conditions to prepare a urea argon peroxide complex. U.S. Patent No. 2,986,448 describes a closed circulation system at a temperature of 0-5 eC at 50- 90% hydrogen peroxide solution to treat plutonium And sodium carbonate (Na2C03) solution for 4 to 12 hours, can prepare sodium osmium sulfonium argon oxide complex. Recently, U.S. Patent No. 3,870,783 discloses a method for mixing a cyanide solution with sodium carbonate in batch or continuous A method of inverting friction to produce a sodium carbonate hydrogen peroxide complex. The crystals are separated by filtration or centrifugation, and the solution can be used to produce more carbonate solutions. Titoval et al. K {Zhurnal Neorg. Kkim., 3 0: 2 2 2 2 · 2 2 2 7) describes the synthesis method of potassium osmate hydrogen peroxide complex (K2C03. 3H2 02), which allows potassium carbonate solids to react with argon peroxide solution at low temperature. The complex was crystallized from ethanol. These methods are very useful for the production of stable, crystal-free perfluorinated argon complex products from aqueous solutions. U.S. Patent Nos. 3,376,110 and 3,480,557 disclose a method for preparing a complex consisting of hydrogen peroxide and polyN-propylene ionocycline (PVP) in an aqueous solution. The resulting composites contain different amounts of hydrogen peroxide and a considerable amount of water. U.S. Patent No. 5,008,093 describes free-flowing, stable, almost anhydrous hydrogen hydride and poly-N-acrylic acid cyclization. M. III — I (please read the note on the back before filling this page) Order Λ Central Ministry of Economic Cooperation, ΛΛIndustry and Consumer Cooperation Du Yin «. M Ministry of Economy and Trade Standards 隼 Λ Beigong Consumer Cooperative Cooperative Printing A7 B7 V. Description of the invention (PVP) The compound composed of PVP can make the transition Hydrogen is obtained by reacting poly (N-propylene heterocyclic compound) (PVP) in ethyl acetate like an anhydrous organic solvent. Recently, U.S. Patent No. 5,077,047 describes a commercial method for making poly-N-propylene heterocyclic compounds (PVP) · perhydrogenated products, which will be divided into extremely fine 30% to 80% overgassing. Hydrogen hydride droplets were added to a PVP fluid bed maintained at 60 eC. A stable, almost water-free, free-flowing product with a tritium argon concentration of 15 · 24% was obtained. U.S. Patent No. 5,030,380 describes a method for making an electrolytic composite similar to argon peroxide to form a solid polymer. The composite is first formed in an aqueous solution and then the reactant is dried in the air or blown at low temperature. Dry to avoid thermal cracking of the product.
Titoval 等人(Λι/ί·ί J. I nor g. C h e m .,40:384-387, 1 995)描述了將 Na4P2〇7 · 1 〇 H 2 〇 2 與 3 0 · 9 α% 之遇氡 化氩溶液混合後眞空乾燥來製造Na4P2〇7 · 3H2〇2複合 物的方法。己知曝露於不同溫度120 °C和140 eC下兩小 時,此複合物會呈現部分分解的現象。 所有上述用來製侑過氧化氫複合物的方法均使用過氧化 氩溶液。因此複合物不是在過氧化氫溶液中形成,就是將過 氡化氩溶液液滴嘖在含有反應物物質之流床上來形成。 蒸氣相或氣相均是眾所熟知的合成方法。例如,美國專 利案第2,812,244號中揭露了一種在困-氣態下去氫化,热 袋解,和去甲基化的方法。Fujimoto等人(J. Catalysis, 133:370·382 (1992))描述了 一種在氣態下對甲醇進行破 酸化的方法。Zellers 等人(Anal. Chem.,62:1222- 8 本纸張尺度適用中國國家揉準(CNS ) Α4規格(210X297公釐) ----------丨| (請先《讀背面之注意事項再填寫本頁) 訂 A7 一. ______B7 _ 五、發明説明() 1227 (1990))則討論了苯乙烯(styrene)蒸氣與平面四方 形的有機鉑複合物之間的反應。但是,這些先前技#中的蒸 氣相或氣相反應,並未被用來製造過氧化氫複合物。 發明目的輿概述: M濟部中央橾準货工消费合作社印* (請先閱讀背面之注意事項再填寫本頁) 本發明態樣之一乃係關於一以過氧化氫對物體進行殺菌 之裝置。此裝置包含一能固定欲殺菌物碰之容器,和一輿容 器相通且呈液氣平衡之過氡化氩蒸氣來源物。此氣髖來《物 包括一種不會分解產生由酸之過氧化氫無機複合物,且此蒸 氣來源物被設計成能舆物«接觸達到有效殺酋的目的。此裝 置也可選擇性的包含一可隔絕呼《I的設計。遘氡化氩蒸氣來 源物可位於容器内,或以錡入物形式位於容器中並以液態形 式與容器相接觸。如果所提供的是封入物形式,則彳在容器 與封入物《設置控制W。裝置内並可包含有加熱設施以加熱 過氡化氫無機複合物。當複合物位於容器内時,也可以一加 熱裝置來加熱容器。或者,當所提供的是一内含遢氧化氫複 合物之封入物時,也可以一加熱裝置來加热此封入物。因 此,一較佳實施例將钇含三個加热裝置,分別加熬容器,複 合物,和封入物。本裝置之另一個可有可無的元件是一能將 容器抽眞空的繁浦。如果所提供的是一封入物,繫浦可設計 成能将容器及封入物抽眞空,較好是艴個別獨力柚眞空。因 此,本裝X也可包含兩個幫浦,一個用來蓊寥器柚眞空,第 二個則用來將封入物抽眞空。也可選择性的含有一排氣闕用 於容器排氣。如果装置内含封入物,則可以第一個排氣閾來 9 本紙張尺度遴用中國國家梂準(CNS ) A4規格(210X297公釐) 鍾濟部中央揉隼爲長工消费合作杜印製 A7 B7 五、發明説明() 排除容器内氣體,第二個排氣閥則獨立於第一個排氣閥用來 排除封入物内之氣體。本裝置之另一個可有可無的元件是一 能產生電漿的機制。電漿可在容器内或容器外產生。許多種 複合物均可用。複合物較好是固髖。在一實施例中,複合物 是一磷酸鹽與冷凝磷酸®之過氡化氫複合物。在其它實施例 中,複合物是一萆酸盪,碳酸鹽,一硫酸霣或一矽酸霣之過 氧化氫複合物。 本發明之另一態樣乃係關於一以遇氧化氩蒸氣對物體進 行殺菌之方法。本方法包括讓物體接觸由過氡化氫無機複合 物中所釋出之過氡化氩蒸氣來逯行殺菌的步骤。所用之遇氡 化氫複合物不會分解釋出由酸。較好是,此複合物之含水量 低於10%且在25 eCtt下或更低之溫度下進行。某些複合物 在使用時》可加熱以促進複合物釋出蒸氣。财許多這類的複 合物而言,較好是將這要複合物加熱至86 ec*a上。較好是 以至少5 eC/min的速率來加熱,更好是以至少1〇 的速車來加熱,再更好是至少50 eC/min ,最好則是以 1000 T/min的速率來加熱。在一實施例中,加熱步驟乃 是藉著讓複合物與一己預熱之加熱裝置接觸而完成。本方法 可在大氣屡或低於大氣壓下進行。在某些實施例中,在將蒸 氣引入容器前先將容器抽眞空。如果容器被柚眞空,比較好 的是將其壓力降至50 torr以下,更好是低於2〇 torr以 下,而最好是低於10 to rr以下。可在封入物中置入遢氧 化氫複合物,在這種情沉下,容器與封入物之壓力可以相同 也可以不同。抽眞空的步驟最好是在讓物體舆容器接觸常進 本紙張尺度遑用t困國家標準(CNS ) A4规格(210X297公羡) (請先H讀背面之注意事項再填寫本頁)Titoval et. A method for producing a Na4P207 · 3H202 complex by mixing the tritium argon solution and air-drying. It has been known that this compound will partially decompose when exposed to different temperatures of 120 ° C and 140 eC for two hours. All of the methods described above for the preparation of tritium hydrogen peroxide complexes use an argon peroxide solution. Therefore, the complex is formed either in a hydrogen peroxide solution or by dropping a perylene argon solution droplet on a fluid bed containing a reactant substance. Both the vapor phase and the gas phase are well known synthetic methods. For example, U.S. Patent No. 2,812,244 discloses a method for hydrogenation in a trapped-gaseous state, thermal bag decomposition, and demethylation. Fujimoto et al. (J. Catalysis, 133: 370 · 382 (1992)) describe a method for deacidifying methanol in a gaseous state. Zellers et al. (Anal. Chem., 62: 1222- 8 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ---------- 丨 | (Please read " Note on the back, please fill out this page again) Order A7 I. ______B7 _ V. Description of the invention () 1227 (1990)) discusses the reaction between styrene vapor and the flat square organic platinum compound. However, the vapor phase or gas phase reactions in these prior arts have not been used to make hydrogen peroxide composites. Summary of the purpose of the invention: Printed by the Central Ministry of Economic Affairs and the Prospective Goods Consumer Cooperatives * (Please read the notes on the back before filling out this page) One aspect of the present invention is a device for sterilizing objects with hydrogen peroxide . The device includes a container capable of holding a substance to be sterilized, and a perforated argon vapor source which is in liquid-gas equilibrium and communicates with a container. The gas source includes an inorganic compound that does not decompose to generate hydrogen peroxide from acid, and the source of steam is designed to be able to contact the object to achieve effective killing. This device can also optionally include a design that can be isolated. The tritium argon vapor source may be located in the container, or it may be in the container in the form of a plutonium and contact the container in a liquid form. If provided in the form of an enclosure, set the control in the container and enclosure. The device may include heating means for heating the trihalide inorganic compound. When the compound is in the container, a heating device can also be used to heat the container. Alternatively, when an enclosure containing rhenium hydrogen oxide complex is provided, a heating device may be used to heat the enclosure. Therefore, a preferred embodiment contains three heating devices for yttrium, which respectively add a container, a compound, and an enclosure. Another optional component of the device is a pump that can empty the container. If a box is provided, the system can be designed to empty the container and the box, and it is better to empty the individual grapefruit. Therefore, this package X can also contain two pumps, one for emptying the grapefruit and the second for emptying the enclosure. Optionally, an exhaust plutonium can also be included for container venting. If the device contains an enclosure, the first exhaust threshold can be 9 paper sizes. China National Standards (CNS) A4 specifications (210X297 mm) are printed by the Central Committee of the Ministry of Economic Affairs. A7 B7 5. Description of the invention () Exhaust the gas in the container. The second exhaust valve is independent of the first exhaust valve to exhaust the gas in the enclosure. Another optional component of this device is a mechanism that generates plasma. Plasma can be generated inside or outside the container. Many complexes are available. The complex is preferably hip-fixed. In one embodiment, the complex is a perhydrogen complex of monophosphate and condensed phosphoric acid®. In other embodiments, the complex is a hydrogen peroxide complex of acid, carbonate, osmium monosulfate, or osmium silicate. Another aspect of the present invention relates to a method for sterilizing an object with argon oxide vapor. The method includes the step of subjecting an object to contact with the hydrogenated hydrogen argon vapor released from the hydrogenated hydrogen inorganic compound to perform sterilization. The hydrogen peroxide complexes used are not explained by acids. Preferably, the composite has a water content of less than 10% and is carried out at a temperature of 25 eCtt or lower. Certain compounds may be heated during use to promote the release of vapors from the compound. For many such compounds, it is preferred to heat the desired compound to 86 ec * a. It is preferably heated at a rate of at least 5 eC / min, more preferably at a speed of at least 10, still more preferably at least 50 eC / min, and most preferably at a rate of 1000 T / min. . In one embodiment, the heating step is performed by contacting the composite with a preheated heating device. This method can be performed in the atmosphere repeatedly or below atmospheric pressure. In some embodiments, the container is evacuated before the steam is introduced into the container. If the container is empty, it is better to reduce the pressure to less than 50 torr, more preferably less than 20 torr, and most preferably less than 10 to rr. The osmium hydroxide complex can be placed in the enclosure. In this case, the pressure of the container and the enclosure can be the same or different. The emptying step is best when the container is in constant contact with this object. This paper uses the national standard (CNS) A4 specification (210X297). (Please read the precautions on the back before filling this page)
I m ! - =1 - H - -- I - - - n I- - I I - - - I —1^- .1 I -訂---------------------- A7 ________B7 五、發明説明() 經濟部中*橾車局負工消费合作社印«. —.1 I ! - -- ϋ__— I- i I— I - I n I i^i am ^^1 /f\ <請先聞讀背面之注f項再填窝本頁) 行。一個可有可無的步驟乃是在將蒸氣引入容器後在物髏遇 圍產生電漿。電漿可在容器内生成或在容器外生成後再讓其 流入容器内環繞欲殺菌物髖。其它可有可無的步驟乃是在接 觸步驟時施以壓力脈衝式的蒸氣,或排氣使壓力降至低於或 等於大氣壓。許多種的無機複合物均可使用。在一較佳實施 例中,所用複合物乃是一磷酸a複合物或冷凝磷酸ft之複合 物,例如鉀鹽或餉鹽,鎂鹽或鈣鹽。在此實施例中,一種較 佳的複合物乃是與Na4P2〇7形成之過氡化氩複合物,較好 是一種舆二或多個遇氡化氫分子形成之複合物,更好的仍是 與Na4P2〇7 . 3H2〇2形成之複合物。其它較佳之複合物 乃是一锢過氡化氩分子與Na3P〇4 ,Na2HP〇4 , Na5P3〇 1 〇,Κ3Ρ04,Κ4Ρ2〇7(特別是具有二或多個遇 氣化氫分子),Κ2ΗΡ〇4,ΚΗ2Ρ〇4(特別是ΚΗ2Ρ〇4 · Η2〇2)和Ca2?2〇7 ,M g 2 P 2 〇 7。在另一實施例中,此 複合物是過氡化氩與草酸畫形成之複合物。一禮較佳之草酸 躉複合物乃是遇氡化氩輿K2C2〇4,特別是K2C2〇4 . H2〇2所形成之複合物。無機複合物也可以是過氡化氫和碳 酸Μ所形成之複合物,例如一釣鹽,鉀藥或釦竇。較佳之破 酸蜃複合物包括Na2C03(特別是Na2C03 · 1.5H2〇2) , K2CO3 , NaHC〇3 , KHCO3 和 Rb2C03。在另一實施树中,此複合物乃是過氧化氫舆一 硫酸竇形成之複合物,例如_釣*或_籯。在另一實施例 中,此複合物乃是遢軋化氩與一矽酸轚形成之複合物,例如 一納躉。較佳之矽酸躉複合物包括與Na2si03和 11 本紙浪尺度遑用中國國家揉率(CNS )八4洗格(2〖0’X297公釐) 經濟部中央標奉Λ貝工消费合作社印製 A7 ______B7 五、發明説明()I m!-= 1-H--I---n I--II---I —1 ^-.1 I -Order ----------------- ----- A7 ________B7 V. Description of the invention () Printed by the Ministry of Economic Affairs * Consumer Cooperative Consumers' Cooperatives «. —.1 I!--Ϋ __— I- i I— I-I n I i ^ i am ^^ 1 / f \ < Please read the note f on the back before filling in this page). An optional step is to generate plasma around the skull after introducing steam into the container. Plasma can be generated in the container or it can be generated outside the container and then allowed to flow into the container to surround the hips to be sterilized. Other optional steps are pressure pulsed steam applied during the contacting step, or venting to reduce the pressure below or equal to atmospheric pressure. Many kinds of inorganic compounds can be used. In a preferred embodiment, the complex used is a monophosphate a complex or a condensed phosphoric acid ft complex, such as a potassium or phosphonium salt, a magnesium salt, or a calcium salt. In this embodiment, a preferred compound is a tritiated argon compound formed with Na4P207, preferably a compound formed by two or more hydrogenated hydrogen molecules, and still more preferably Is a complex with Na4P20.7. 3H2O2. Other preferred composites are a trihalide molecule and Na3P04, Na2HP04, Na5P3104, K3P04, K4P207 (especially with two or more molecules of hydrogen gas in contact with gas), K2QP. 4, K 2 PO 4 (especially K 2 PO 4 · B 2 0 2) and Ca 2 2 0 7, M g 2 P 2 0 7. In another embodiment, the compound is a compound formed by tritium argon and oxalic acid painting. A better compound of arsenic oxalate is a compound formed by K2C2O4, especially K2C2O4.H2O2. The inorganic complex may also be a complex formed by hydrogen peroxide and carbonic acid M, such as a salt, potassium or button sinus. Preferred acid-decomposing complexes include Na2C03 (especially Na2C03.1.5H2O2), K2CO3, NaHC03, KHCO3 and Rb2C03. In another implementation tree, the complex is a complex formed by hydrogen peroxide and sinus sulfate, such as _ fishing * or _ 籯. In another embodiment, the compound is a compound formed by thorium rolled argon and thorium silicate, such as a nano-thorium. Preferred silicate complexes include Na2si03 and 11 paper paper scales, using the Chinese National Kneading Rate (CNS) of 8 and 4 grids (2 〖0'X297 mm). The central government of the Ministry of Economic Affairs has printed A7 printed by the Beigeong Consumer Cooperative. ______B7 V. Description of Invention ()
Na2Si3〇7形成之過氧化氩複合物。許多較佳之複合物, 和其它,在大氣壓及室溫下即可釋出過氧化氫。但是,對某 些複合物而言,須在低於大氣壓下才能使出過氧化氫。在另 一實施例中,接觸步驟包括由第二個來瘅物而來之遇氧化 氩。第二個來源物可以是第二種遇氡化氫複合物,包括一有 機過氣化氩複合物。在某些實施例中,以遇氧化氫複合物之 泥合物來提供過氧化氩蒸氣。此混合物可以是一物理性混合 物或一化學性混合物,這些專有名詞之定義於后。 本發明之更進一步鲶樣乃係鼷於一以過氧化氩蒸氣對物 «進行投«之另一種方法。此方法包括讓物ft接觸藉加熱 Na4P2〇7遇氧化氩複合物所釋出之過氧化氫蒸氣來對物II 進行殺菌的步驟。在一較佳實施例中,所用Na4P2〇 7過氡 化氩複合物乃是Na4P2〇7 · 3H2〇2。可在大氣麈下進行 接觸,或將容器抽眞空,因此當蒸氣進入容赛時,容器内之 氣壓將小於50 torr。也可將複合物加熱至約175 °C以有 效的釋出蒸氣。可在進行接觸步驟前先将物«置於容器内。 本發明之另一態樣乃係«於一以過軋化氫蒸氣對物《進 行殺菌之另一種方法。此方法包括將物饉置於容器内,再将 過氡化氳複合物舆一不會分解產生由酸蒸氣而舆物《接觸之 無機鹽一同放入容器中,讓容器在低於70 eC下靜E—段足 狗使遇氡化氩蒸氣由複合物中釋出並對物髖散有效投菌的時 «。容器可以是許多型式之容器中的任一種,包括袋子,室 或房《。在一較佳實施例中,所用無機鹽乃是磷酸鹽或冷凝 之磷酸鹽。在其它之實施例中,所用無機薑乃是一草酸薑, 12 本纸張尺度適用中困國家標準(CNS ) A4規格(210X297公釐) <請先聞讀背面之注f項再填寫本頁) '裝. 订 ..4 鋟濟部中夹樣準^貝工消费合作社印製 Α7 Β7 五、發明説明() 一硖酸躉,一硫酸鹽或一矽酸霣0在某些實施例中本發明之 此項態樣,讓容器在低於大氣壓下和或低於40 X:下靜置。 在某些實施例中,將複合物加熱至230 eC«上以促進蒸氣 的釋出。可將過軋化氩複合物製成許多型式,包括粉末和藥 鍵。在某些實施例中,遘氧化氩複合物乃位於封入物中。如 果所提供的是一封入物,則封入物可在容器内或容器外。可 選擇性的將封入物與容器間以閾隔開,且在某些贲施例中並 可輿容器分開。也可將封入物密封起來,較好是以氣體可通 透的材質來做。較佳之氣《可通透材質包括TYVEKTM, C S R包裝貘和纸。一個可有可無的步霹乃是將物ft曝露於 霓漿中,且當所提供的是可拆裝之封入物時,較好是在將封 入物由容器上拆下後再使欲殺苗物《與電槳接觸。 本發明之另一觀點乃係闕於一以遇氡化氩蒸氣對一具外 殼及狹窄内室之物體進行殺茵的方法。此方法包括連接含有 過氡化氫複合物之容器及此物II之内室,將物技置於容器 中,再將容器抽眞空,再使物«之狹長内室輿由過氡化氫複 合物中所釋出之過氧化氧蒸氣接觸。過氡化氫複合物乃是不 會分解並釋出氩由酸之祓合物。此類複合物之任一種均可使 用,例如磷酸和冷凝磷酸*,一草酸竇,一碳酸蠆,一硫酸 黴和一矽酸鹽。也可選擇性的讓物髏之外部與第二來源之殺 菌制接觸來進行殺菌,此第二來液之殺菌劑可以是許多適合 之殺菌劑中的任一種,例如置於容》内之遘氧化氩,置於容 器内之不同種類的過氡化氫,過氡化氩液tt或二氧化氣。另 一個可有可無的步驟乃是讓物Λ瀑露於電漿中。 13 本紙張尺度遒用中國國家標率(CNS ) Α4规格(210';<297公漦> H' ·ϋ_— i^n u· ·11 —ϋ Ufa I a-^^i 11 i^i>· 11 a—.— /f., (請先閱讀背面之注意事項再填窝本3f) «濟部中央揉率Λ貝工消费合作社印重 A7 ____________B7_ 五、發明説明() 圈示之簡蕈说明 第1圈乃是本發明蒸氣投菌裝置之簡單示意圈。 第2圈乃是本發明中内含電極之蒸氣殺菌裝置的簡單示意 圈,可選擇性的以此電極來產生電漿。 第3A圈乃是一可用來加熱過氡化氫複合物之裝置的簡單示 意圈。 第3B圈乃是依本發明用來裝殺菌用過氧化氩來源物之較佳 容器之的簡單示意圈。 第4圈乃是由一在眞空下不安定的葬水溶性甘油之無水過氡 化物複合物中釋出過氣化氩蒸氣之簡單示意圈。 第5圈乃是依據本發明,一種用來測定釋出之遇氡化氫或過 氧化氫無機複合物之分解特性的能董差择描器(DSC) 之麇力控制系統之簡單示意固。 第6圈《示以具有小孔的蓋子蓋住草酸_遇氡牝氫複合物 後,壓力對由草酸衅過氡化氩複合物中釋出過氣化 氫之影響。 第7A圈乃是依據本發明,在引入過氡化物蒸氣之前,用來 將過氡化氩蒸氣注入一内室之送風器的簡單示意 圈。 第7B围顦示第7圈之送風器在引入蒸氣時加熱盤與過氡化 物複合物接觸之示意圈。 第8圈乃是過氣化氫無機複合物之殺菌内室及加熱裝置的簡 單示意圈。 第9 K顯示一用於蒸氣殺箱時之過氡化氫複合物的擴散包装 14 本紙張又度適用中國8家橾準(CNS ) A4此格(210X297公釐) 1 -- I - I..... I - m . I 1 n» I - . In Hi m. In ^_f\ (請先w讀背面之注意事項再填寫本頁) Λ濟部中央橾率Λ貝工消费合作社印製 A7 ΒΊ___ 五、發明説明() 層。 第1 0圈颟示·以開放式鋁盎和有兩個孔之蓋子蓋住複合物, 在大氣壓下其對K2C2〇7 · H2〇2之DSC曲線的 影響。 第 1 1A 圈乃是 Na4P2〇7 . 2H2〇2 和 Na4P2〇7 . 3H2〇2 在 760 torr 下的 DSC 曲線。 第 1,1 B 圈乃是 Na4?2〇7 . 4 Η 2 0 2 在 7 6 0 t o rf 下的 DSC曲線。 第 1 2 圈乃是 N a 3 P 〇 4 · 5 Η 2 〇 2 在 7 6 〇 t 〇 r r,7 t 〇 r r 和 0.3 5 t o r r下的D S C曲線。 第 13 圈乃是 Na2HP〇4 · 1Η2〇2 和 Na2HP〇4 . 2 H 2 〇 2 在 7 6 0 t o r r 下的 D S C 曲線 〇 笫 14 圈乃是 Na5P3〇i〇 · H2〇2 在 760 torr 下的 DSC 曲線。 第 15 圈乃是 K3PO4 . 3.34H2〇2 在 760 torr,7 tofr 和torr下的DSC曲線。 第 16 圈乃是 K4P2O7 . 7H2〇2 在 760 to” 和 7 10”下 的DSC曲線。 第 17 圈乃是 K2HP〇4 · 3.15H202 在 760 torr 和 1 torr下的DSC命線。 第18圈乃是KH2P〇4 . H2〇2在760 to”下的DSC曲 線0 第 19 圈乃是 Na2C〇3 · 1·5Η2〇2 在 760 to"和 7 torr 下的DSC曲線。 15 ( CNS ) A4^*· ( 210X297/^ ) (請先Μ讀背面之注意事項存填寫本X) -訂 、發明説明() 第 2〇 圈乃是 Ca2P2〇7 · 3·4Η2〇2 在 760 托(Τ〇ΓΓ)下的 D S C曲線。 第 21 圖乃是 Mg2P2〇7 4·60Η2〇2 在 760 托(Torr)和 7托(Tor r)下的DSC曲線。 第 22 圖乃是 Na2S04.1.28H202 在 760 托(T〇rr)下的 D S C曲線。 第 23 囷乃是 K2S04 · 〇.62H2〇2 在 760 托(Torr)下的 DSC曲線》 第 24 圖乃是 Na2Si03 · 2.1 5H2〇2 在 760 托(T〇rr),1 托(Torr)和0.5托(Torr)下的DSC曲線。 第 25 圖乃是 Na2Si3〇7· 〇·68Η2〇2 在 760 托(Torr)下 的DSC曲線。 里1_對照說明 室10、30 欲殺菌物體12、56 門1 6 過氧化氫來源物1 8 溫度控制器22、46 真空幫浦26、36、122 出口 34 閥 38、43、44 過氧化氩封入物42 網路52 射頻供應器54 裝置 80、125、178 銘磐 90、1〇8、130、136、184 氣體可通透層92、106 架1 4 加熱裝置20、49 監測器2 4 開口 32 入口 4 0、4 1 電極5 0 加熱整· 9 4、1 8 6 鳇濟部中央揉率局貝工消费合作杜印氧 A7 ___________B7 五、發明説明() 派瑞氏盤(p y r e X p a 9 6、1 8 2 熱耦溫度計98 容器99 金屬盤1 00 溫度監視器101 鋁網 1 02、1 04 樣品室1 10 加熱盤1 12 壓力傳送子1 1 4 壓力表1 1 6 控制器1 1 8 壓力控制閥1 2 0 殺菌室1 3 1、1 70 過氧化物盤1 3 2 鋁製壓板1 3 4 箱1 3 8 鋁連接塊142 栓 1 44、146、 154 ' 156 座150 〇-形環 1 48、1 5 1 過氧化物釋出室 1 52 通道1 5 8 孔1 6 0 玻璃样1 72 不銹鋼刀片1 74 '176 派瑞氏碗(pyrex bawl)180 電線188 熱藕190 高溫黏性膠帶200 過氧化氫複合物粉末202 鋁箔層2 0 4 本發明之詳細說明 過去在使用過氧化氫殺菌劑時無可避免的均舍以過氧化 氩水溶液作為殺菌劑之來源。這些殺菌劑有因系統中水的存 在所造成的缺點。高壓下,例如大氣壓,系統中過量的水會 造成凝結。因此在引入過氧化氫蒸氣前,須花費额外的步驟 降低欲殺菌之封入物體内的相對濕度至一可接受的程度·這 些殺菌劑也有一些因水所造成的缺點,由於水具有較高的蒸 氣壓,因此在水溶液中較過氧化氩更容易揮發,且水,由於 本紙張尺度逋用中國國家揉準(CNS } A4规格(210 X 297公釐) ----------I------1T------^ ^/ν (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明() 分子量較低,也較過氧化氩擴散得快。當醫療器具或類似物 髏被封在殺菌器中時,與過氧化氫來源物之濃度相比,來自 過氧化氩來源物之最開始的殺菌劑濃度在到達裝置時已經被 稀釋了◦稀釋過的殺菌劑對較後來抵達之殺菌劑而言可能是 一種阻礙’特別是當欲殺菌的裝置乃是一物體時,例如具有 狹長内腔之内視鏡。試圖以濃縮的過氧化氫溶液來改善此缺 點,其結果已被證實並不能令人滿意,因溶液具有毒性。 本發明使用幾乎不含水分(亦即,幾乎無水)之過氧化氳 來源以釋出幾乎無水的過氧化氩蒸氣,因此能克服先前技藝 中所用過氧化氩殺菌劑的缺點β在一較佳實施例中,幾乎無 水的過氧化氫蒸氣乃直接由幾乎無水之過氧化氫複合物中產 生。但是,幾乎無水的過氧化氩蒸氣也可由複合物水溶液中 產生’只要在蒸發過程中將水分移去,如真空下,即可a因 此’當所用為過氧化氫複合物水溶液時,在執行本發明步觸 之過程中只要將複合物水溶液轉變成幾乎無水的過氧化氫複 合物即可。較好是’此幾乎無水的過氧化氫複合物含水量低 於2 0 % ’更好是含水量不高於i 〇 %,甚至不高於5 %,最 好則是含水量不高於2 %。 魍濟部中央揉率局貝工消费合作杜印裝 (請先閲讀背面之注意事項再填寫本頁) 訂 由上述本發明中幾乎無水的過氧化氩複合物之較佳含水 量可看出’最好的過氧化氫複合物及所生成之過氧化氩蒸氣 幾乎不含任何水分。但是,同樣的由附圖中可知,系統仍存 在有些許水分。這些水分有的可能來自過氧化氫分解時產生 的水及氧氣副產物,以及某些結合了氩氣的水再與複合物作 用而來。Ar2O3 complex formed by Na2Si3O7. Many of the preferred compounds, and others, release hydrogen peroxide at atmospheric pressure and room temperature. However, for some compounds, sub-atmospheric pressure is required to produce hydrogen peroxide. In another embodiment, the contacting step includes encountering argon oxide from a second source. The second source may be a second hydrogenated hydrogen compound, including an organic over-gasified argon compound. In some embodiments, the argon peroxide vapor is provided as a slurry of a hydrogen peroxide complex. The mixture may be a physical mixture or a chemical mixture, and these proper terms are defined later. A further aspect of the present invention is another method of «investing» an object with argon peroxide vapor. The method includes the step of sterilizing the substance II by exposing the substance ft to the hydrogen peroxide vapor released by heating the Na4P207 and argon oxide complex. In a preferred embodiment, the Na 4 P 2 0 7 perfluorinated argon complex is Na 4 P 2 07 3H 2 0 2. The contact can be carried out in the atmosphere, or the container can be emptied, so when the vapor enters the container, the air pressure in the container will be less than 50 torr. The compound can also be heated to about 175 ° C to effectively release steam. The contact «can be placed in a container before the contacting step. Another aspect of the present invention is «another method of sterilizing an object with rolled hydrogen vapor. This method includes placing the plutonium in a container, and then placing the plutonium compound into the container, which will not be decomposed to generate acid vapor and the "inorganic salt in contact with the material", and the container is kept below 70 eC. Static E—The time when the dog's argon vapor is released from the compound and the bacteria is effectively injected into the hip powder. The container can be any of many types of containers, including a bag, a chamber, or a house. In a preferred embodiment, the inorganic salt used is a phosphate or a condensed phosphate. In other embodiments, the inorganic ginger used is oxalate, 12 paper sizes are applicable to the National Standard for Medium and Difficulties (CNS) A4 (210X297 mm) < Please read the note f on the back before filling in this Page) 'Packing. Order .. 4 Samples of the Ministry of Economic Affairs ^ Printed by Bei Gong Consumer Cooperative Association A7 B7 V. Description of the invention () Monophosphonate, monosulfate or monosilicate in some embodiments In this aspect of the present invention, the container is allowed to stand at a pressure below atmospheric pressure and below 40 X :. In some embodiments, the composite is heated to 230 eC «to promote the release of vapor. Over-rolled argon composites can be made in many types, including powders and bonds. In some embodiments, the tritium argon oxide complex is located in an enclosure. If an enclosure is provided, the enclosure may be inside or outside the container. The enclosure can be selectively separated from the container by a threshold, and in some embodiments, the container can be separated. The enclosure can also be sealed, preferably made of a gas permeable material. Better gas "translucent materials include TYVEKTM, C S R packaging and paper. An optional step is to expose the object ft to the neon slurry, and when the removable enclosure is provided, it is better to remove the enclosure from the container before making the kill. Seedling "contact with electric paddle. Another aspect of the present invention resides in a method for sterilizing an object having a shell and a narrow inner chamber with argon vapor. This method includes connecting a container containing a hydrogen peroxide compound and an inner chamber of the object II, placing the material technology in the container, evacuating the container, and then recombining the long inner chamber of the object «by the hydrogen peroxide compound Oxygen peroxide vapor released from the contents comes into contact. Perhydrogen complexes are complexes that do not decompose and release argon from acids. Any of these complexes can be used, such as phosphoric acid and condensed phosphoric acid *, sinus oxalate, osmium carbonate, mold sulphate, and silicate. It is also possible to selectively contact the outside of the skull with a sterilization system from a second source. The sterilant of the second liquid can be any of a number of suitable sterilants, such as the one placed in the container. Argon oxide, different kinds of hydrogen peroxide, hydrogen peroxide solution tt or dioxide gas placed in the container. Another optional step is to expose the object Λ waterfall to the plasma. 13 This paper uses China National Standards (CNS) Α4 specifications (210 '; < 297 gong > H' · ϋ_ — i ^ nu · · 11 —ϋ Ufa I a-^^ i 11 i ^ i > · 11 a —.— / f., (Please read the notes on the back before filling in the book 3f) «The Central Ministry of Economic Affairs Λ Beigong Cooperative Co., Ltd. Printed A7 ____________B7_ 5. Explanation of the invention () The first circle of the mushroom description is a simple schematic circle of the steam sterilization device of the present invention. The second circle is a simple schematic circle of the steam sterilization device with an electrode in the present invention, and the electrode can be used to selectively generate a plasma. Circle 3A is a simple schematic circle of a device that can be used to heat a hydrogenated hydrogen compound. Circle 3B is a simple schematic circle of a preferred container for germicidal argon peroxide source according to the present invention. The fourth circle is a simple schematic circle that releases vaporized argon vapor from an anhydrous perfluorinated compound containing water-soluble glycerol that is unstable in the air. The fifth circle is based on the present invention. Decomposition of Decomposition Characteristics of Inorganic Complexes of Hydrogen Peroxide or Hydrogen Peroxide The simple illustration of the control system is solid. Circle 6 "shows the effect of pressure on the release of hydrogenated hydrogen from the argon argon complex caused by oxalic acid after the oxalic acid is met with a lid with a small hole. Circle 7A is a simple schematic circle according to the present invention, which is used to inject perfluorinated argon vapor into an inner chamber blower before introducing peroxide vapor. Round 7B shows the air blower in circle 7 at The schematic circle where the heating plate is in contact with the peroxide compound when the steam is introduced. The eighth circle is a simple schematic circle of the sterilization inner chamber and the heating device of the hydrogenated inorganic compound. The 9th K shows a steam kill box. Diffusion packaging of time-lapsed hydrogenated hydrogen compounds 14 This paper is again suitable for 8 Chinese standards (CNS) A4 this grid (210X297 mm) 1-I-I ..... I-m. I 1 n »I-. In Hi m. In ^ _f \ (Please read the precautions on the back before filling this page) Λ Central Ministry of Economic Affairs prints A7 ΒΊ ___ Cooperative Cooperative Fifth, 5. Description of the invention (). Lap 10: Instruction: Cover the composite with an open aluminum lid and a lid with two holes. At atmospheric pressure, it will affect K2C2 07 · H2 2 The effect of DSC curve. The 1A circle is the DSC curve of Na4P207. 2H2O2 and Na4P2 07. 3H2O2 at 760 torr. The 1st, 1B circle is Na4-20.7. 4 C 2 0 2 DSC curve at 7 6 0 to rf. The first 12 turns are Na 3 P 〇4 · 5 Η 2 〇2 at 7 6 〇t 〇rr, 7 t 〇rr and 0.3 5 torr DSC curve. The 13th circle is the DSC curve of Na2HP〇4 · 1Η2 02 and Na2HP〇4. 2 H 2 0 2 at 7 60 0 torr. The 14th circle is Na5P3 0i 2 · H2 0 2 at 760 torr. DSC curve. The 15th circle is the DSC curve of K3PO4. 3.34H2O2 at 760 torr, 7 tofr and torr. Round 16 is the DSC curve of K4P2O7. 7H2〇2 at 760 to ”and 7 10”. On the 17th lap is the DSC lifeline for K2HP〇4 · 3.15H202 at 760 torr and 1 torr. The 18th circle is the DSC curve of KH2P〇4. H2〇2 at 760 to 0. The 19th circle is the DSC curve of Na2C〇3 · 1 · 5〇2〇2 at 760 to " and 7 torr. 15 (CNS ) A4 ^ * · (210X297 / ^) (Please read the notes on the back and fill in this X first)-Order, invention description () The second circle is Ca2P2 07 · 3 · 4Η2 02 at 760 Torr ( DSC curve under Τ〇ΓΓ). Figure 21 is the DSC curve of Mg2P2 07 4 · 60Η2 02 at 760 Torr and 7 Torr. Figure 22 is Na2S04.1.28H202 at DSC curve at 760 Torr. 23rd is K2S04 · .62H2〇2 DSC curve at 760 Torr "Figure 24 is Na2Si03 · 2.1 5H2〇2 at 760 Torr ( DSC curve at 1 Torr and 0.5 Torr. Figure 25 shows the DSC curve of Na2Si30.7 · 68 · 2002 at 760 Torr. Lane 1_Control Explanation room 10, 30 Objects to be sterilized 12, 56 Doors 1 6 Hydrogen peroxide source 1 8 Temperature controller 22, 46 Vacuum pump 26, 36, 122 Outlet 34 Valve 38, 43, 44 Argon peroxide enclosure 42 Net Road 52 RF Supply 54 devices 80, 125, 178 Ming Pan 90, 108, 130, 136, 184 gas permeable layer 92, 106 1 heating device 20, 49 monitor 2 4 opening 32 inlet 4 0, 4 1 electrode 5 0 Heating rectification · 9 4, 1 8 6 Ministry of Economic Affairs, Central Rubbing Bureau, Shellfish Consumption Cooperation, Duyin Oxygen A7 ___________B7 V. Description of the invention () Pyrex plate (pyre X pa 9 6, 1 8 2 Thermocouple thermometer 98 Container 99 Metal plate 1 00 Temperature monitor 101 Aluminum mesh 1 02, 1 04 Sample chamber 1 10 Heating plate 1 12 Pressure transmitter 1 1 4 Pressure gauge 1 1 6 Controller 1 1 8 Pressure control valve 1 2 0 Sterilization chamber 1 3 1, 1 70 Peroxide disk 1 3 2 Aluminum pressure plate 1 3 4 Box 1 3 8 Aluminum connection block 142 Bolt 1 44, 146, 154 '156 Seat 150 0-ring 1 48, 1 5 1 Peroxide Release chamber 1 52 channel 1 5 8 hole 1 6 0 glass-like 1 72 stainless steel blade 1 74 '176 pyrex bawl 180 electric wire 188 hot 190 high temperature adhesive tape 200 hydrogen peroxide composite powder 202 aluminum foil Layer 2 0 4 Detailed description of the present invention In the past, when hydrogen peroxide fungicides were used, it was unavoidable to use an aqueous argon peroxide solution as a fungicide. Sources. These fungicides have disadvantages caused by the presence of water in the system. At high pressures, such as atmospheric pressure, excess water in the system can cause condensation. Therefore, before the introduction of hydrogen peroxide vapor, additional steps must be taken to reduce the relative humidity of the enclosed object to an acceptable level. These bactericides also have some disadvantages caused by water, because water has a higher vapor Pressure, so in the aqueous solution is more volatile than argon peroxide, and water, because the size of this paper uses the Chinese national standard (CNS} A4 (210 X 297 mm) ---------- I ------ 1T ------ ^ ^ / ν (Please read the notes on the back before filling in this page) A7 B7 V. Description of the invention () The molecular weight is lower and it diffuses faster than argon peroxide. When a medical device or the like is enclosed in a sterilizer, the initial concentration of the germicide from the argon peroxide source is diluted when it reaches the device compared to the concentration of the hydrogen peroxide source. Used fungicides can be a hindrance to later arrivals, especially when the device to be sterilized is an object, such as an endoscope with a narrow inner cavity. Attempts have been made to use concentrated hydrogen peroxide solutions. Improve this shortcoming, the result has been proven not Satisfactory, because the solution is toxic. The present invention uses a source of thorium peroxide that contains almost no water (ie, almost anhydrous) to release almost anhydrous argon peroxide vapor, thereby overcoming the argon peroxide sterilization used in the prior art Disadvantages of the agent β In a preferred embodiment, almost anhydrous hydrogen peroxide vapor is directly generated from the almost anhydrous hydrogen peroxide composite. However, almost anhydrous argon peroxide vapor can also be generated from the aqueous composite solution ' As long as the water is removed during the evaporation process, such as under vacuum, a. Therefore, when the aqueous hydrogen peroxide composite solution is used, in the process of performing the steps of the present invention, as long as the composite aqueous solution is converted into an almost anhydrous The hydrogen oxide compound is sufficient. It is preferably 'the water content of this almost anhydrous hydrogen peroxide compound is less than 20%', more preferably the water content is not higher than i 0%, or even not higher than 5%, and the best is The moisture content is not higher than 2%. The Central Ministry of Economic Affairs, Central Rubbings Bureau, Shellfish Consumer Cooperative Du Printing Pack (please read the precautions on the back before filling this page). The preferred water content of the argon oxide composite can be seen in the 'best hydrogen peroxide composite and the generated argon peroxide vapor contains almost no moisture. However, as can be seen from the drawings, the system still has some Moisture. Some of this water may come from water and oxygen by-products generated during the decomposition of hydrogen peroxide, and some water combined with argon will react with the complex.
< m 、發明説明( ^我們在一系列的測試中,以維持在各種相對濕度的殺菌 至來測試水的影蜜·測試條件如以下範例1中所述,將含有 孢子 < 不銹鋼(SS)刀片置於3mm X 50cm之狹長不銹鋼内 室中 〇 如类 〇 衣2所示’在測試情況下,5 %的相對溼度對殺菌 效果沒有影響’但! 〇 %的相對渔度則會降低殺菌速率^這 一範例顯tf由幾乎無水之過氧化氫複合物中產生過氧化氫蒸 氣之系統中可以容許有少量水分存在,且可藉增加殺菌時間 來克服系統中存在水分的影響。 表2 /V 请先閲讀背面乏注意事項再填寫本頁 相對漫度對位於3mm X 50cm之狹長不銹鋼内室中 之不銹鋼(SS)刀片殺菌效率的影蜜 擴散時叫 殺菌途率 (正反應/樣品嫌教、 1 % R Η 5 % R Η 10% 1 5 0/3 0/3 3/3 10 0/3 0/3 2/3 15 0/3 0/3 0/3 30 0/3 0/3 0/3 過氧化氫來源組成的一項主要條件乃是,其安定度與過 氧化氩蒸發速率間的關係為溫度和壓力的函數《過氧化氣之 蒸發速率可高可低,過氧化物來源可以被加熱也可以不被加 熱,端視殺菌過程中的參數而定,亦即,壓力,溫度,及其 它。某些過氧化物複合物有足夠高的蒸氣壓,因此毋須加熱< m, description of the invention (^ We in a series of tests, to maintain the sterilization of water at various relative humidity to test the impact of honey. Test conditions are as described in Example 1 below, will contain spores < stainless steel (SS ) The blade is placed in a narrow stainless steel inner chamber of 3mm X 50cm. 0 As shown in class 0, 'In the test case, the relative humidity of 5% has no effect on the sterilization effect', but 〇% relative fishery will reduce the sterilization. Rate ^ This example shows that a small amount of water can be tolerated in a system where tf is generated from hydrogen peroxide vapor in an almost anhydrous hydrogen peroxide complex, and the effect of moisture in the system can be overcome by increasing the sterilization time. Table 2 / V Please read the lack of attention on the back before filling in this page. The diffuseness of the sterilization efficiency of the stainless steel (SS) blades located in the narrow stainless steel inner chamber of 3mm X 50cm is called the sterilization rate (positive reaction / sample suspect). , 1% R Η 5% R Η 10% 1 5 0/3 0/3 3/3 10 0/3 0/3 2/3 15 0/3 0/3 0/3 30 0/3 0/3 0 / 3 A major condition for the composition of the source of hydrogen peroxide is that its stability and argon peroxide vaporization The relationship between hair growth rate is a function of temperature and pressure. The evaporation rate of peroxide gas can be high or low. The source of peroxide can be heated or not. It depends on the parameters in the sterilization process, that is, the pressure. , Temperature, and others. Some peroxide compounds have a sufficiently high vapor pressure, so no heating is required.
,1T 泉,· 經濟部中央揉準局貞工消费合作社印簟 本紙張尺度逋用中國國家揉準(CNS > A4洗格(210X297公釐) A7 B7 五、發明説明() 即可釋出非常顯著量的過氧化氣蒸氣。一般而言,加熱複合 物可增加過氧化氩之蒸氣壓並加速由複合物中釋出過氧化 物。 欲提供所須之高蒸發速率,過氧化氩來源物之表面積最 好比較大。因此,過氧化氩來源物可以是極細的粉末或被鍍 在一表面積極大的物質上。當然,物質之安全性、是否容易 取得及價格也是極重要的因素。分別評估由過氧化氩與尿 素,聚丙稀"I»比哈酮(p〇lyvinylpyrr〇Hd〇ne),尼龍_ 6(nylon-6)和無水甘氨酸,和ι,3 -二曱基尿素(1,3· dimethyl urea)所形成之複合物中釋出過氧化氩的情形。 此1,3 - 一甲基尿素過氧化物複合物乃是一種液艘。相較於 其它複合物,無水甘氨酸過氧化氩複合物在減壓環境下比較 不安定’而在真空下,大部分的複合物均可在不加熱的情況 下釋出過氧化氫》 藥錠形式之尿素過氧化氩複合物可由福卡化學公司 (Fluka Chemical Corp·,Ronkonkoma,NY)購得,而 粉末式之複合物則可由阿里其化學公司(Aldrich chemical Co.,Milwaukee, WI)購得。此複合物亦被 稱為過氧化解(urea peroxide),過氧化氳尿素複合物 (hydrogene peroxide urea complex),尿素過氧化物 (.peroxide urea),尿素過氧化物加成物(peroxide urea adduct),過氧化脾加成物(urea peroxide adduct),過 氧化脾(percarbamide,percarbamide perhydrate » carbamate peroxide)。在此所用“過氧化脚”一詞,包 20 _ 本纸張尺变適用中Ha家搮準(CNS ) A4規格(210X297公嫠) ----------:裝-- (請先閲讀背面之注$項再填寫本頁) -訂 經濟部中央櫟率扃頁工消费合作社印装 A7 B7 經濟部中央標準局負工消费合作社印装 五、發明説明( 含所有前述名詞。 聚丙烯也略酮-過氧化氩複合物(poly_ vmylpyrrolidone-hydrogen peroxide complex, PVP-H2〇2),可以國際專利案號w〇 92/17158中所述 之方法加以製備。或者’也可以以下所揭露之詳細步驟製備 與聚丙晞毗咯酮(p〇lyVinylpyrr〇Hd〇ne),尼龍- 6(nyl〇n-6)和無水甘氨酸,.以及其它有機和無機化合物所 形成之複合物。 可藉提高溫度和或減壓來促進由來源物中釋出無水過氧 化物蒸氣並達成適當之蒸發速率。因此,用於過氧化物來源 物之加熱裝置和或將殺菌室抽真空之真空幫浦最好都屬於殺 菌器的一部分。較好是,以一層氣體可通透的物質,如 TYVEKTM之聚乙缔不織織維,如SPUNGUARDTM之聚 丙烯不織纖維’或類似的材質,來覆蓋來源物,能使過氧化 物蒸氣逸出但不會使過氧化氫複合物逸出。也可用孔狀的鋁 或其它適宜的孔狀物來作為覆蓋的材質。 第3A圖顯示一用來測量各種溫度範圍下由過氧化氫複 合物中釋出過氧化氫之裝置80。在此裝置中,一鋁盤90以 一氣體可通透層92覆蓋’例如一層醫療級的TYVEKTM。 該盤90乃置於一加熱墊94之上,而加熱墊94又位於派瑞 氏盤(pyrex pan)96之中。在銘盤90之外側由底部算起1 公分的位置放了一個熱耦溫度計98。在一較佳實施例中, 鋁盤90乃是與大氣相通的,如此可容許草酸奸過氧化氫複 合物在大氣整下有較多的釋出。 21 本纸張尺度逋用中國國家揉準(CNS ) A4规格(210X297公釐) ----------t,------、訂------^ . (锖先《讀背兩之注f項再填寫本頁) 經濟部中夬揲準局工消费合作社印It 22 Α7 Β7 玉、發明説明() 第3B圈顯示一可用來裝過氧化物來源物之較佳的容器 99々容器99包括一金屬盤1〇〇,亦即一鋁盤,可選擇性的 裝有一用來加熱過氧化物固體之加熱裝置β可在盤100中 裝上一個溫度監視器1 〇 1 ’例如溫度計,來監測溫度。可將 過氧化物複合物直接置於盤1〇〇上。或者,為使所有的過 氧化物複合物受熱均勻’可將過氧化物複合物放在盤1〇0 上方之一或多層的鋁網1〇2、1〇4之間》鋁網102、104 可提供較大的表面積並且當大量過氧化物被使用時可提供均 勻的加熱。之後以一層氣體可通透層1〇6,如tYVEKtm 或SPUNGUARDTM來復蓋過氧化物複合物或該網1〇2, 104 ’使複合物中所釋出之過氧化氩在擴散進殺菌室前能先 透過覆蓋物106 。可選擇性的在tYVEKtm或 SPUNGUARDTM層1〇6上加上一孔狀鋁盤1()8,以提供 壓力並保持複合物能與加熱盤1〇〇相接觸,以確保複合物 的均勻受熱。 上述裝置能提供複合物均勻的受熱,因此也能增加由過 氧化物複合物中所釋出之過氧化氫蒸氣的量。 第1圖乃是本發明中過氧化氫蒸氣殺菌裝置之簡單示意 圈。室10中裝了欲進行殺菌的物體12,為方便之故,將其 置於架14上。由門16可進入室〗〇β在可有可無的加熱裝 置20中有一非水溶液式的過氧化氩來源物18,由溫度控制 器22加以控制。由可有可無的監測器24中監視過氧化物 漢度。必要時,可以幫浦26將室1〇抽真空;但是,也可 在大氣壓下完成殺菌過程。 本纸張ΛΑϋ财8Β家制M cns ) ( 21〇χ丨 ----------It------訂------線 (請先閲讀背面之注意事項再填頁) 經濟部中央橾準局貝工消费合作社印篥 A7 B7 五、發明説明() 用來裝欲殺菌物體之容器可以是已被抽真空的傳統的殺 菌室’或大氣壓下的一個容器(或房間)· 殺菌時間視欲殺菌物體之性質’數目和物體的包裝方式 及在容器中的置放方式而定。或者,也可對殺菌室本身(整 個房間)作殺菌。無論是那一種情況,最佳的殺菌時間須由 實驗來決定。在非水溶液式的過氧化氫操作中,也可以大家 熟知的壓力脈衝來提高殺菌劑的滲透及抗微生物性質。此種 壓力脈衝的範例,可和在此所述之方法及裝置一起使用,如 美國專利案號第5, 527,508號中所述。如以下更詳盡的描 述’也可用電漿來進一步提高活性和或去除殘餘物。 在殺菌過程結束時,可藉與空氣交換來將過量的過氧化 氩由對過氧化物具親和性之裝置中加以移除。此可藉著讓熱 空氣流入裝置中一段長時間或抽真空來達成。 可將已經過氧化氩蒸氣殺菌之物體曝露於電漿中以除去 物趙上可能殘存的過氡化氫。由於在電漿處理過程中,過氧 化氩會分解成不具毒性的產物,因此被殺菌物體可以不必再 經其它額外步驟的處理即可使用。 在過氧化氩蒸氣釋出後可能須要將過氧化氫來源物與殺 菌器分開’以避免蒸氣之再吸附,或者是在使用電漿時,避 免過氧化氩來源物曝露於電聚中。當所用複合物在真空下不 安定時’將過氧化氫來源物與殺菌器分開也有好處。可使用 閥或其它熟知的分離裝置來達成分離的目的。 第2囷乃是本發明之過氧化氫電漿殺菌系統之簡圖。可 在有或無電漿存在下完成殺菌。可以電聚來提高過氧化氩蒸 ^ ^--- 23 本紙張朗t國國家揉準(CNS ) A4«L4M 210X297公釐) -- ----------艮------訂------線.- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉率局貝工消费合作社印製 A7 B7___ 五、發明説明() 氣殺孢子的活性’和或除去欲殺菌物體上任何殘存之過氧化 氫。 殺菌乃在室30中進行,此室包含一個可置入欲般菌物 體之門或開口 32。室30包括一個通至真空幫浦36之出口 34,經此幫浦由可將室抽真空《出口 34包含一能將室與真 空幫浦36隔開的閥38。室30尚包括一個接在内含過氧化 氩複合物之封入物42上的入口 40。入口 40包括一個能將 室與封入物42隔開的閥44。殺菌系統尚包括一個連接之封 入物42及内含閥43之真空幫浦36的入口 41 »系統能同 時將封入物42及室30抽真空,或單獨對封入物42或室 30抽真空。藉由閥38, 44,和43的開關來控制真空的程 度。本領域中習知技藝的人士應不難了解,本系統也可使用 兩個幫浦,每一室各一個。 封入物42也可選擇性的接上裝有溫度控制器46來控制 過氧化氫複合物溫度之加熱裝置49。過氧化氫複合物之蒸 氣濃渡可以可有可無的過氧化物監視器來監測.室内部含一 接在合適網路52和射頻(RF)供應器54之射頻(RF)電極 50。一種方便的電極形式乃是環繞著樣品且兩端開口之孔 狀圓柱體。本方法一般的施行步驟如下: 1. 在室30中置入欲殺菌物體56。 2. 室30可以在大氣壓下’或者,可抽真空以促進過氧 化氫的穿透。藉打開閥38和真空繫浦36來完成抽真空的 步用:。或者,也可同時打開閥38, 44,和/或43對室30 和封入物42抽真空。 _ 24 本纸張尺度逋用t國國家揉準(CNS )A4規格(210X297公着) --- I n n I n n I— n n n n 1^1 1 n n n I ^ (請先閎讀背面之注^^項再填寫本頁) 經濟部中央揉準局貝工消费合作社印*. A7 B7 五、發明説明() 3. 將閥38和43關閉以使真空幫浦36和室30及封入 物42隔離,並打開閥44。將由過氧化氫來源物釋出之過氧 化氩蒸氣送至室30中’並可藉加熱來提高過氧化氫蒸氣的 釋出。也可選擇性的加入空氣或惰性氣體。 4. 在殺菌時才以過氧化氫蒸氣來處理欲殺菌物體56或 者在以足夠大馬力進行電漿處理前先在室30中以過氧化氣 蒸氣對欲殺菌物體56作前處理•必要時,可在此時將室30 抽真空以促進電漿的穿透。以電槳作前處理的時間視所用包 裝的形式,欲殺菌物禮之數目及性質,和在室中的置放情形 而定。可由實驗定出其最佳反應條件。 5·讓欲殺菌物體56曝露於由射頻(RF)供應器54供電 至射頻(RF)電極50所產生的電漿下。用以產生電漿之無線 電能量可以是脈衝式的或連續式的》讓欲殺菌物體56留在 電漿中一段足以有效完成殺菌和/或去除過氧化氩殘留物的 時間。在某些較佳實施例中’所用電漿時間是5至30分 鐘。但是,最佳反應時間應由實驗決定。 在本發明之詳細說明及申請專利範園中所提到之“電 漿’’一詞’乃是包括以電場,含任何可能產生之輻射,來產 生含有電子,離子’自由基,解離和或激發態之原子或分子 之氣髏或蒸氣之任一部分。所用電場涵蓋一寬廣的頻率範 圍;但是,通常都是用無線電波或微波》 本發明中所揭露之非水溶液式的過氧化氩運送系統也可 和以美國專利案第4,643,876號中所述方法產生的電漿一 同使用。或者,也可和以美國專利案第5, η5,166號或第 _____25 本紙張ΛΑ逋用中BIH家揉丰(CNS ) A4^ ( 21()χ297公羞) - - (請先聞讀背面之注f項再填寫本筲), 1T Quan, · Printed paper size of Zhengong Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China (CNS > A4 Washer (210X297mm) A7 B7 5. The invention description () will be released A very significant amount of peroxide vapor. In general, heating the compound increases the vapor pressure of argon peroxide and accelerates the release of peroxide from the compound. To provide the required high evaporation rate, the argon peroxide source The surface area is preferably relatively large. Therefore, the source of argon peroxide can be an extremely fine powder or plated on a material with a large surface area. Of course, the safety of the material, whether it is easily available, and the price are also very important factors. Assessed by argon peroxide and urea, polypropylene " I »bihalone (polyolylpyrrohydrone), nylon-6 (nylon-6) and anhydrous glycine, and ι, 3-dihydrazyl urea (1 In the case of argon peroxide released from the complex formed by 3, dimethyl urea), this 1,3-monomethyl urea peroxide complex is a liquid vessel. Compared with other complexes, anhydrous glycine Argon oxide complex in decompression ring The environment is relatively unstable, and under vacuum, most of the compounds can release hydrogen peroxide without heating. "Urea-argon peroxide compounds in the form of tablets can be obtained from Fluka Chemical Corp. (Ronkonkoma, NY), and powdered complexes are available from Aldrich Chemical Co. (Milwaukee, WI). This complex is also known as urea peroxide, peroxidation Hydrohydrogen peroxide urea complex, urea peroxide (.peroxide urea), urea peroxide adduct, peroxide peroxide adduct, spleen peroxide ( percarbamide, percarbamide perhydrate »carbamate peroxide). As used herein, the term" peroxidized feet ", including 20 _ This paper ruler has been adapted to the Ha Jiazheng Standard (CNS) A4 specification (210X297 cm) ------ ----: Installation-(Please read the note on the back of the page before filling in this page)-Order printed by the Central Quotation Leader of the Ministry of Economic Affairs of the Consumers Cooperative A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives , Invention description ( All the term polypropylene is also slightly keto - argon peroxide complex (poly_ vmylpyrrolidone-hydrogen peroxide complex, PVP-H2〇2), International Patent Nos w〇 can be prepared of the method 92/17158. Or 'can also be prepared with the detailed steps disclosed below with polypropylene (PollyVinylpyrrohydrone), nylon-6 (nylon-6) and anhydrous glycine, and other organic and inorganic compounds Of the complex. Elevated temperature and / or reduced pressure can be used to promote the release of anhydrous peroxide vapor from the source and achieve an appropriate evaporation rate. Therefore, heating devices for peroxide sources and / or vacuum pumps that evacuate the sterilization chamber are preferably part of the sterilizer. Preferably, a layer of gas permeable material, such as TYVEKTM's polyethylene non-woven fabric, such as SPUNGUARDTM's polypropylene non-woven fiber 'or similar material, is used to cover the source material, allowing peroxide vapor to escape. Out without causing the hydrogen peroxide complex to escape. Hole-shaped aluminum or other suitable holes can also be used as the covering material. Figure 3A shows a device 80 for measuring the release of hydrogen peroxide from a hydrogen peroxide compound at various temperature ranges. In this device, an aluminum pan 90 is covered with a gas permeable layer 92 ', such as a medical grade TYVEKTM. The pan 90 is placed on a heating pad 94 which is located in a pyrex pan 96. A thermocouple thermometer 98 is placed 1 cm from the bottom of the name plate 90 on the outside. In a preferred embodiment, the aluminum pan 90 is open to the atmosphere, which allows the hydrogen oxalate compound to be released more in the atmosphere. 21 This paper size is in accordance with China National Standard (CNS) A4 (210X297 mm) ---------- t, ------, order ------ ^. ( (First read "Note f of the back two" and then fill out this page) Printed in the Ministry of Economic Affairs of the Provincial Bureau of Industrial and Commercial Consumer Cooperatives It 22 Α7 Β7 Jade and Invention Description (3) Circle 3B shows that it can be used to hold peroxide sources. The preferred container 99. The container 99 includes a metal plate 100, that is, an aluminum plate, optionally equipped with a heating device for heating the peroxide solids. A temperature monitor may be installed in the plate 100. 1 〇 'such as a thermometer to monitor the temperature. The peroxide complex can be placed directly on the tray 100. Alternatively, in order to uniformly heat all the peroxide composites, 'the peroxide composites may be placed on one or more layers of aluminum meshes 100, 104 between the trays 100> aluminum meshes 102, 104 Provides a large surface area and provides uniform heating when a large amount of peroxide is used. A gas permeable layer 10, such as tYVEKtm or SPUNGUARDTM, is then used to cover the peroxide compound or the net 10, 104 'so that the argon peroxide released from the compound is diffused into the sterilization chamber. Can pass through the cover 106 first. Optionally, a hole-shaped aluminum pan 1 () 8 can be added to the tYVEKtm or SPUNGUARDTM layer 106 to provide pressure and keep the composite in contact with the heating pan 100 to ensure uniform heating of the composite. The above device can provide uniform heating of the composite, and therefore can increase the amount of hydrogen peroxide vapor released from the peroxide composite. Fig. 1 is a simple schematic circle of a hydrogen peroxide vapor sterilization device in the present invention. The chamber 10 contains an object 12 to be sterilized, and is placed on a rack 14 for convenience. The chamber can be accessed through the door 16 and the optional heating device 20 has a non-aqueous argon peroxide source 18, which is controlled by a temperature controller 22. The peroxide degree is monitored by the optional monitor 24. If necessary, the chamber 10 can be evacuated by pump 26; however, the sterilization process can also be performed at atmospheric pressure. This paper ΛΑϋ 财 8Β home-made M cns) (21〇χ 丨 ------------------ Order ------ line (Please read the precautions on the back before (Fill in pages) Seal A7 B7, Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention () The container used to hold the object to be sterilized can be a traditional sterilization chamber that has been evacuated, or a container at atmospheric pressure ( Or room) · The sterilization time depends on the nature of the object to be sterilized, the number of objects, the packaging method of the object, and the storage method in the container. Alternatively, the sterilization room itself (the entire room) can be sterilized. In either case The optimal sterilization time must be determined by experiments. In non-aqueous hydrogen peroxide operation, well-known pressure pulses can also be used to improve the penetration of antiseptic and antimicrobial properties. Examples of such pressure pulses can be combined with The methods and devices described herein are used together, as described in U.S. Patent No. 5,527,508. As described in more detail below, 'plasma can also be used to further increase activity and / or remove residues. At the end of the sterilization process Can be replaced by air exchange Excessive argon peroxide is removed from the device that has affinity for peroxide. This can be achieved by letting hot air flow into the device for a long time or evacuating. Objects that have been sterilized by argon peroxide vapor can be exposed. In the plasma to remove the residual hydrogen peroxide that may remain on Zhao. Since argon peroxide is decomposed into non-toxic products during the plasma treatment, the sterilized object can be treated without additional steps. Can be used. After the release of argon peroxide vapor, it may be necessary to separate the hydrogen peroxide source from the sterilizer to avoid resorption of the vapor, or to avoid exposure of the argon peroxide source to electropolymerization when using plasma. It is also beneficial to separate the source of hydrogen peroxide from the sterilizer when the compound used is disturbed under vacuum. The valve can be used to achieve the purpose of separation. The second one is the hydrogen peroxide of the present invention. Schematic diagram of the plasma sterilization system. It can be sterilized in the presence or absence of plasma. It can be electropolymerized to improve the argon peroxide steaming ^ ^ --- 23 S) A4 «L4M 210X297mm)----------- Gen ------ Order ------ Line.- (Please read the notes on the back before filling this page ) Printed by A7 B7___, Shellfish Consumer Cooperative of the Central Rubbing Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Aerospore activity and removal of any remaining hydrogen peroxide on the object to be sterilized. Sterilization is carried out in a chamber 30, which contains a door or opening 32 into which a desired germ body can be placed. The chamber 30 includes an outlet 34 to a vacuum pump 36 through which the chamber can be evacuated. The outlet 34 includes a valve 38 that can separate the chamber from the vacuum pump 36. The chamber 30 also includes an inlet 40 connected to the enclosure 42 containing the argon peroxide compound. The inlet 40 includes a valve 44 that separates the chamber from the enclosure 42. The sterilization system also includes an inlet 42 for the enclosed enclosure 42 and a vacuum pump 36 containing a valve 43. The system can simultaneously evacuate the enclosure 42 and the chamber 30, or the enclosure 42 or the chamber 30 can be evacuated separately. The degree of vacuum is controlled by the switching of valves 38, 44, and 43. Those skilled in the art should understand that this system can also use two pumps, one for each room. The enclosure 42 may optionally be connected to a heating device 49 provided with a temperature controller 46 to control the temperature of the hydrogen peroxide compound. The vapor concentration of the hydrogen peroxide complex can be monitored by the optional peroxide monitor. The interior of the room contains a radio frequency (RF) electrode 50 connected to a suitable network 52 and a radio frequency (RF) supply 54. A convenient form of electrode is a hole-shaped cylinder that surrounds the sample and has open ends. The general implementation steps of this method are as follows: 1. An object to be sterilized 56 is placed in the chamber 30. 2. The chamber 30 may be at atmospheric pressure 'or may be evacuated to promote the penetration of hydrogen peroxide. By opening the valve 38 and the vacuum pump 36 to complete the evacuation step:. Alternatively, valves 38, 44, and / or 43 can be opened simultaneously to evacuate chamber 30 and enclosure 42. _ 24 The size of this paper is in accordance with the national standard (CNS) A4 (210X297) --- I nn I nn I— nnnn 1 ^ 1 1 nnn I ^ (Please read the note on the back ^^ (Please fill in this page again.) Printed by the Central Bureau of the Ministry of Economic Affairs, Pui Gong Consumer Cooperatives *. A7 B7 V. Description of the invention () 3. Close the valves 38 and 43 to isolate the vacuum pump 36 and the chamber 30 and the enclosure 42, and The valve 44 is opened. The argon peroxide vapor released from the hydrogen peroxide source is sent to the chamber 30 'and the release of the hydrogen peroxide vapor can be enhanced by heating. Optionally, air or inert gas can also be added. 4. Treat the object 56 to be sterilized with hydrogen peroxide vapor only during sterilization or pre-treat the object 56 to be sterilized with peroxide vapor in the chamber 30 before performing plasma treatment with sufficient horsepower. • If necessary, The chamber 30 may be evacuated at this time to promote penetration of the plasma. The time for pretreatment with electric paddles depends on the type of packaging used, the number and nature of the items to be sterilized, and the placement in the room. The best reaction conditions can be determined experimentally. 5. Expose the object 56 to be sterilized to the plasma generated by the radio frequency (RF) power supply 54 to the radio frequency (RF) electrode 50. The wireless electrical energy used to generate the plasma may be pulsed or continuous. "The object 56 to be sterilized is left in the plasma for a time sufficient to effectively sterilize and / or remove argon peroxide residue. In some preferred embodiments, the plasma time used is 5 to 30 minutes. However, the optimal reaction time should be determined experimentally. The term "plasma" mentioned in the detailed description of the present invention and the patent application patent garden includes the use of an electric field, including any possible radiation, to generate electrons, ions, free radicals, dissociation and or Any part of an atomic or molecular gas skeleton or vapor in an excited state. The electric field used covers a wide range of frequencies; however, it is usually radio waves or microwaves. The non-aqueous argon peroxide transport system disclosed in the present invention It can also be used with the plasma generated by the method described in U.S. Patent No. 4,643,876. Alternatively, it can also be used with U.S. Patent No. 5, η5,166 or ____25. Feng (CNS) A4 ^ (21 () χ297 public shame)--(Please read the note f on the back before filling in this card)
.IT A7 _B7 __ 五、發明説明() 5,087,418號中所述方法產生的電聚一同使用,欲殺菌物 體則是位於與產生電漿之來源物隔離的殺菌室中。 上述裝置對真空下不安定之過氧化氫複合物之使用特別 有利。至少有兩種方法可用來減低真空過程中過氧化氫的損 失。第一,單獨對小殺菌室抽真空。第二,如果所用的殺菌 室夠小,則根本毋須對此小殺菌室抽真空。 甘氨酸無水過氧化物即屬於這種不安定之非水溶液式過 氧化氫複合物。在真空下,此化合物會釋放出過氧化氩蒸 氣。第4圖顯示真空下由甘氨酸無水過氧化物中釋出過氧化 氫蒸氣的情形。所用由甘氨酸無水過氧化物中釋出過氧化氫 蒸氣的步驟如下:(1)在室30抽真空時將閥43和44關 閉。(2)含過氧化氫複合物42之室抽真空時將閥38和44 關閉並打開閥43。(3)將閥43關上並打開閥44以使過氧 化氫蒸氣能擴散進入室3 0。 如圖所示,在減壓的情況下’即使沒有额外的加熱步 驃,過氧化氫蒸氣也會由複合物中釋出》如第4圖所示,將 複合物加熱至一高溫可顯著的增加所釋出之過氧化物蒸氣。 因此’即使是不安定之過氧化氫複合物在本發明的殺菌方法 中也很有用。 本發明較先前提出之過氧化氩殺菌法至少可額外提供四 項優點: 1. 克服使用濃縮過氧化氩溶液可能有毒之缺點。 2. 克服須事先降低欲殺菌表面相對溼度以避免產生凝結 之缺點。.IT A7 _B7 __ V. Invention description () No. 5,087,418 is used together with the electropolymer produced by the method described above. The above device is particularly advantageous for the use of unstable hydrogen peroxide compounds under vacuum. There are at least two methods that can be used to reduce the loss of hydrogen peroxide during vacuum. First, evacuate the small sterilization chamber separately. Second, if the sterilization chamber used is small enough, there is no need to evacuate the small sterilization chamber at all. Glycine anhydrous peroxide belongs to this unstable non-aqueous hydrogen peroxide complex. Under vacuum, this compound releases argon peroxide vapor. Figure 4 shows the release of hydrogen peroxide vapor from glycine anhydrous peroxide under vacuum. The procedure used to release hydrogen peroxide vapor from glycine anhydrous peroxide is as follows: (1) Valves 43 and 44 are closed while the chamber 30 is evacuated. (2) When the chamber containing the hydrogen peroxide compound 42 is evacuated, the valves 38 and 44 are closed and the valve 43 is opened. (3) Close the valve 43 and open the valve 44 so that the hydrogen peroxide vapor can diffuse into the chamber 30. As shown in the figure, under reduced pressure, 'even without an additional heating step, hydrogen peroxide vapor will be released from the composite.' Increase the release of peroxide vapor. Therefore, even an unstable hydrogen peroxide complex is useful in the sterilization method of the present invention. Compared with the previously proposed argon peroxide sterilization method, the present invention can provide at least four additional advantages: 1. Overcoming the disadvantages of using a concentrated argon peroxide solution which may be toxic. 2. To overcome the disadvantage that the relative humidity of the surface to be sterilized must be reduced in advance to avoid condensation.
經濟部中央揉準局貝工消费合作社印簟 A7 ____________B7_ 五、發明説明() 3. 系統中不再須要水分的存在,因此在擴散進入狹長内 室時’水和過氧化氫蒸氣也毋須再競爭。 4. 毋須加裝特殊容器才能將殺菌蒸氣送入狹長内室中。 在幾乎無水的情況下以過氧化氫蒸氣來達成有效的殺菌 乃是本發明最驚人的發現。先前技藝顯示在以化學物氣體或 蒸氣殺菌的過程中,想要達到殺菌的目的必須要有水分的存 在。本發明的優點是,幾乎將水分完全排除於系統外,且得 到一更迅速,有效的殺菌。 所測定各種非水溶液式過氧化氫複合物之殺菌效率詳述 於以下範例1至4。 籯例1 殺菌效率數據乃是以由幾乎無水的過氧化脲複合物中所 釋出之遇氧化氫蒸氣對金屬及鐵氟龍(TEFLONTM)塑膠内 室中的枯草桿菌芽胞(5<aci//wj να/·· fnfgerj) 進行殺菌而獲得。 A .測栻步騾 1·儀器 如第3A圖所示’將4克過氧化氣尿素加成物藥錠 (Fluka Chemical C o r ρ .,R ο n k ο n k o m a,N Y)悉碎置於 鋁盤90上。在盤90上覆蓋一層醫用級TYVEKTM (可容 許呼吸之拉長的聚乙烯纖維)使複合物釋出之過氧化氫蒸氣 * 在擴散進入殺菌室前須先通過此層覆蓋物。將鋁盤9〇置於 鋁製殺菌室(參見第1 _)底部派瑞氏盤(pyrex dish)96 ./—Λ, 請先閲讀背面之注$項再填寫本頁) 訂Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative Seal A7 ____________B7_ V. Description of the Invention () 3. The system no longer needs the existence of water, so when water diffuses into the narrow inner chamber, 'water and hydrogen peroxide vapor no longer need to compete. . 4. No special container is needed to send sterilizing vapor into the narrow inner chamber. The achievement of effective sterilization with hydrogen peroxide vapor in almost anhydrous conditions is the most surprising discovery of the present invention. Previous techniques have shown that in the process of sterilizing with chemical gas or steam, the existence of moisture is required to achieve the purpose of sterilization. The advantage of the present invention is that the water is almost completely excluded from the system, and a more rapid and effective sterilization is obtained. The measured sterilization efficiency of various non-aqueous hydrogen peroxide compounds is described in Examples 1 to 4 below.籯 Example 1 The bactericidal efficiency data are based on the hydrogen peroxide vapor released from the almost anhydrous urea peroxide compound against the Bacillus subtilis spores (5 < aci // in the plastic inner chamber of metal and TeflonTM) released from the almost anhydrous urea peroxide compound. wj να / ... fnfgerj) is obtained by sterilization. A. Measurement step 1. The instrument is shown in Figure 3A. 'Fluka Chemical C or ρ. (R ο nk ο nkoma, NY) 4 grams of peroxide peroxide urea tablets are crushed and placed on an aluminum plate. 90 on. The disc 90 is covered with a layer of medical-grade TYVEKTM (elongated polyethylene fiber that allows breathing) to release hydrogen peroxide vapor from the composite. * This layer must be passed through before spreading into the sterilization chamber. Place the aluminum pan 90 in the aluminum sterilization chamber (see section 1 _) at the bottom of a pyrex dish 96 ./—Λ, please read the note on the back before filling this page) Order
經濟部中央棣準局員工消费合作杜印轚 A7 _______B7_ 五、發明説明() 内之加熱墊94上。該殺菌室,其體積約134升,内含: .一能測定蒸氣相中過氧化氩濃度之過氧化氫監測器。 .一能控制加熱墊溫度之溫度控制器。 •一能將過氧化氩液體注入殺菌室之注射口。 •一能容納測試用’具内室裝置之塑膠盤的金屬架。 •在效率測試時位於殺菌室外壁能維持殺菌溫度在45 t之 電阻加熱器。 2.生物測試及挑職 為評估非水溶液式過氧化物傳送系統的效率,將含 1.04 X 1〇6 枯草桿菌芽胞 之不銹鋼刀片以相同距離間隔分別由3mm内徑χ 40cm 長 ’ 3mm 内徑 X 50cm 長,和 1mm 内徑 X 5〇cm 長之不銹鋼内室兩端底部開始排列•這些内徑和長度均為醫 療器具之内室中經常用到的。每一内室中生物測試樣品所在 隔間的大小為13mm内徑X 7.6cm長》以金屬内室所作的 生物測試,每一測試中總共評估了 9個内室。包括3種不同 内徑和長度的組合,每一種組合中有3個内室。 以含4.1 X 1〇6枯草桿菌芽胞(5acH/U)S v ar be r))之長紙片(6mm x 4mm Whatman 1 號色 層分析遽紙)置於1mm内徑x lm長,1mm内徑x 2m 長’ 1mm内徑χ 3m長,和1mm内徑x 4m長之鐵氟龍 (TEFLONTM)内室底部來進行類似的實驗。這些内室中央 生物測試樣品所在隔間的大小為15mm内徑χ 7.6cm長。 以鐵氟龍(TEFLONTM)内室所作的生物測試,每一測試中 ---- _28__ 本纸張適用中國國家檁準(CNS ) A4«UM 210X297公釐)一一 (請先閲讀背面之注意事項再填寫本頁} · -*?τ 經濟部中央揉率局貝工消费合作杜印裝 A7 -----------— _B7 五、發明説明() 總共評估了 12個内室。包括3種不同内徑和長度的组合, 每一種组合中有4個内室。 將含生物測試樣品之内室置於一塑膠盤上,再將整個塑 膠盤放在殺菌室的架上。關上殺菌室的門並以真空幫浦將殺 菌至抽真空至壓力為〇2托(T〇rr)。將含過氧化氩尿素加 成物之鋁盤加熱至80_8lt 5分鐘,以距盤底約lcm之鋁 盤側面壁上的熱耦溫度計來測量溫度。在此期間由過氧化 物監測器中可知殺菌室内過氧化氫的濃度已增加至 6mg/L。 讓生物測試樣品分別曝露於過氧化氫蒸氣下5,1〇, 15 ’20’和25分鐘》之後將生物測試樣品移至内含277 單位催化每之15ml的胰蛋白酵素黃豆培養基(trypticase s〇y broth)中’以中和測試樣品上任何殘存的過氧化氫蒸 氣。將所有的樣品在32。(:下培養7天並觀察細菌生長的情 形。 為對照起見’也在殺菌室中注入50 %過氧化氫水溶液並 使其由已加熱的注射器表面揮發(一加熱的金屬表)。注入 過氧化氫溶液之醴積所產生之氣相中過氧化氫濃度為 6 m g / L。在這些測試及生物測試樣品中所用的測試内室與 非水溶液式過氧化氩複合物測試中所用的相同。而在將其曝 露於過氧化氩的步驟後’處理生物測試樣品的方式也都相 同。 測弒結旲 ___29 表紙張尺度適用中國國家揉準(CNS > Ai规格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) _、裝· 訂 味 經濟部中央揉準局貞工消费合作社印装 A7 _____B7 五、發明説明() - 以不銹鋼及鐵氟龍(TEFLONTM)内室所進行之測試結 果,分別顯示於表3及表4,可看出非水溶液式過氣化氩傳 送系統在兩種金屬及非金屬内室上的效果。在所評估具最小 内徑及最長内室之非水溶液式過氧化氫傳送系統可在5分鐘 内達到細菌芽胞完全被殺死的效果。同時,在以5〇 %過氧 化氩水溶液進行擴散的系統中’即使在25分鐘後仍無法達 到完全殺死細菌芽胞》 裊3 水溶液/非水溶液式殺菌效率的比較 不銹鋼刀片在不銹鋼内室 殺菌力結果 _(正反應/樣品數) 過氧化物 擴散時間 3mm X 3mm χ 1mm x 來源 (分) 4 0cm 5 0 c m 5 0cm 5 3/3 3/3 3/3 10 0/3 2/3 3/3 5 0%溶液 15 1/3 1/3 1/3 20 0/3 0/3 1/3 25 0/3 0/3 1/3 5 0/3 0/3 0/3 10 0/3 0/3 0/3 過氧化將 15 0/3 0/3 0/3 20 0/3 0/3 0/3 25 0/3 0/3 0/3 ------ 30 本紙張尺度逍用中國國家揉準(CNS)A45^.(21〇x297^a) (請先閲讀背面之注f項再填寫本頁) 、?τ A7 B7 五、發明説明() *4 水溶液/非水溶液式殺菌效率的比較 6mm X 4mm紙片在鐵氟龍(TEFLONTM)内室 殺菌力結果 (正反應/樣品數) 過氧化物 擴散時間 1 mm X 1 mm x 1mm 來源 (分) lm 2 m 3 m 5 3/3 3/3 3/3 10 3/3 3/3 3/3 5 0 %溶液 15 0/3 1/3 1/3 20 0/3 0/3 0/3 25 0/3 0/3 0/3 5 0/3 0/3 0/3 10 0/3 0/3 0/3 過氧化脲 15 0/3 0/3 0/3 20 0/3 0/3 0/3 25 0/3 0/3 0/3 mm 4m 3/3 3/3 2/3 1/3 U3 0/3 0/3 0/3 0/3 0/3Du Yin 轚 A7 _______B7_ of the Ministry of Economic Affairs, Consumer Consumption Cooperation of Employees V. The heating pad 94 in the description of the invention (). The sterilization chamber, with a volume of about 134 liters, contains: a hydrogen peroxide monitor capable of measuring the concentration of argon peroxide in the vapor phase. A temperature controller that can control the temperature of the heating pad. • An injection port capable of injecting argon peroxide liquid into the sterilization chamber. • A metal rack that can hold the plastic disc with the inner chamber device for testing. • A resistance heater located at the exterior wall of the sterilization chamber to maintain a sterilization temperature of 45 t during the efficiency test. 2. Biological test and challenge In order to evaluate the efficiency of the non-aqueous solution peroxide delivery system, stainless steel blades containing 1.04 X 106 bacillus subtilis spores were made from 3mm inner diameter x 40cm long and 3mm inner diameter X at the same distance. 50cm long and 1mm inner diameter X 50cm long stainless steel inner chambers are arranged at both ends and bottoms. These inner diameters and lengths are often used in the inner chambers of medical appliances. The size of the compartment where the biological test sample is located in each inner chamber is 13mm inner diameter X 7.6cm long. The biological test was performed with a metal inner chamber. A total of 9 inner chambers were evaluated in each test. Includes 3 different inner diameter and length combinations, each with 3 inner chambers. A long piece of paper (6mm x 4mm Whatman No. 1 color analysis analysis paper) containing 4.1 X 106 bacillus subtilis spores (5acH / U) S v ar be r)) was placed on an inner diameter of 1 mm x a length of 1 mm and an inner diameter of 1 mm x 2m long '1mm inner diameter x 3m long, and 1mm inner diameter x 4m long Teflon (TM) inner chamber bottom for similar experiments. The size of the compartment in which the biological test samples are located in the center of the inner chamber is 15 mm in inner diameter x 7.6 cm long. Teflon (TEFLONTM) internal test biological test, each test ---- _28__ This paper is applicable to China National Standard (CNS) A4 «UM 210X297 mm) one by one (please read the notes on the back first) Please fill in this page again for the matters} ·-*? Τ Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperation Du printed A7 ------------- _B7 V. Description of the invention () A total of 12 The chamber includes three different inner diameter and length combinations, each of which has four inner chambers. The inner chamber containing the biological test sample is placed on a plastic tray, and the entire plastic tray is placed on the rack of the sterilization chamber. .Close the door of the sterilization chamber and vacuum sterilize to a pressure of 0 2 Torr (Torr) with a vacuum pump. Heat the aluminum pan containing the argon peroxide urea adduct to 80_8lt for 5 minutes to the bottom of the pan. A thermocouple thermometer on the side wall of an aluminum plate of about 1 cm measures the temperature. During this period, it can be known from the peroxide monitor that the hydrogen peroxide concentration in the sterilization chamber has increased to 6 mg / L. Expose the biological test samples to peroxide respectively. After 5, 10, 15 '20' and 25 minutes under hydrogen vapor, the biological test sample was moved to the containing 277 The unit catalyzes every 15 ml of trypticase soy broth to 'neutralize any residual hydrogen peroxide vapor on the test sample. All samples were incubated at 32. (: 7 days and observed bacteria The growth situation. For comparison, '50% hydrogen peroxide solution was also injected into the sterilization chamber and allowed to evaporate from the surface of the heated syringe (a heated metal table). The concentration of hydrogen peroxide in the gas phase is 6 mg / L. The test chamber used in these test and biological test samples is the same as that used in the non-aqueous argon peroxide complex test. It was exposed to argon peroxide After the steps, the method of processing biological test samples is also the same. 测 弑 结 旲 29 The paper size of the table applies to the Chinese national standard (CNS > Ai size (210X297 mm)) (Please read the precautions on the back before filling in this Page) _, loading, ordering, printing, printing, A7, Zhengong Consumer Cooperative, Central Bureau of the Ministry of Economic Affairs _____B7 V. Description of the invention ()-Testing performed in the stainless steel and TeflonTM inner chamber The results are shown in Tables 3 and 4, respectively, and the effect of the non-aqueous over-gasification argon delivery system on the two metal and non-metal inner chambers can be seen. In the non-aqueous solution with the smallest inner diameter and the longest inner chamber evaluated The complete hydrogen peroxide delivery system can achieve the effect of completely killing the bacterial spores within 5 minutes. At the same time, in a system that diffuses with a 50% argon peroxide aqueous solution ', the complete killing of bacteria cannot be achieved even after 25 minutes "Spores" 袅 3 Comparison of sterilization efficiency of aqueous / non-aqueous solution. The sterilization result of stainless steel blade in stainless steel inner chamber_ (positive reaction / number of samples) peroxide diffusion time 3mm X 3mm χ 1mm x source (minutes) 4 0cm 5 0 cm 5 0cm 5 3/3 3/3 3/3 10 0/3 2/3 3/3 5 0% solution 15 1/3 1/3 1/3 20 0/3 0/3 1/3 25 0/3 0/3 1/3 5 0/3 0/3 0/3 10 0/3 0/3 0/3 Peroxide will be 15 0/3 0/3 0/3 20 0/3 0/3 0/3 25 0/3 0/3 0/3 ------ 30 This paper uses Chinese National Standards (CNS) A45 ^. (21〇x297 ^ a) (Please read note f on the back before filling in this Page),? Τ A7 B7 V. Description of the invention () * 4 Aqueous / non-aqueous Comparison of sterilization efficiency 6mm X 4mm paper sheet sterilization force results in TeflonTM (positive reaction / number of samples) peroxide diffusion time 1 mm X 1 mm x 1mm source (min) lm 2 m 3 m 5 3 / 3 3/3 3/3 10 3/3 3/3 3/3 50% solution 15 0/3 1/3 1/3 20 0/3 0/3 0/3 25 0/3 0/3 0 / 3 5 0/3 0/3 0/3 10 0/3 0/3 0/3 Urea peroxide 15 0/3 0/3 0/3 20 0/3 0/3 0/3 25 0/3 0 / 3 0/3 mm 4m 3/3 3/3 2/3 1/3 U3 0/3 0/3 0/3 0/3 0/3
X /1· (請先閱讀背面之注f項再填寫本貫) 订 鐘濟部中失橾準局貝工消费合作社印拏 進行 31 通常在以各種除了過氧化氫外的殺菌劑之化學氣體/蒸氣 相作殺菌的過程中都會有水分的存在,因此在幾乎無水的情 況下可違到快速殺菌的事實相當出人意料之外。由於在過氧 化氩蒸氣相殺菌系統中所用的是過氧化氩水溶液,因此在那 些系統中也有水分的存在》 為測試各種其它過氧化物複合物的殺菌效率, 本纸張尺度逋用中國國家樣车(CNS ) A4規格(21〇X297公釐) A7 _____B7 __ 五、發明説明() 下的實驗》 釐例2J和4 以範例1的儀器裝置來測試聚丙晞也咯酮·過氧化氩複 合物(範例2 )’尼龍6 -過氧化氩複合物(範例3 )和1,3 -二甲基尿素過氧化氫複合物(範例4)之殺菌效率。依后列範 例12和13中之方法來合成這些化合物。測試參數如下: 範例2 範例3 MlM 4 殺菌室溫度 4 5°〇 4 5〇C 4 5t 初壓 〇·2托 1.0托 1.0托 過氧化物重量 17% 10.5 % 2 6.6 % 百分比 過氧化物濃度 6mg/L 6mg/L 6mg/L 每一循環所用過 8 g 18g 6g 氧化物重量 釋出過氧化物 1 1 oec no°c 8〇°C 之溫度 經濟部中央橾準局負工濟费合作社印裂 mm (請先閲讀背面之注意事項再填寫本頁) 在每一情況’細菌芽孢乃位於塑膠内室中6mm x 4 紙片和不銹铜内室中之不銹鋼刀片上β殺菌效率的結果如下 表5。 本纸張財ΗΒ家揉準(CNS ) Α4%#· < 210X2!^# 五、發明説明( A7 B7 聚丙埽毗咯酮,尼龍6,和〗,3_二甲基尿素 與過氧化氫所形成複合物之殺菌效率 殺菌力結果(正反應/樣品數) _ψ露5分鐘 内室型式 内室大小 範例2 範例3 範例4 1mm X 1 m 0/3 0/3 0/3 - 1mm X 2m 0/3 0/3 0/3 鐵氟龍TM 1mm X 3m 0/3 0/3 0/3 1mm X 4 m 0/3 0/3 0/3 3mm X 4 0cm 0/3 0/3 0/3 不銹鋼 3mm X 5 0cm 0/3 0/3 0/3 1mm X 5 0cm 0/3 0/3 0/3 經濟部中央輮率局貞工消费合作社印«. 表5之結果顯示只須5分钹的曝露時間,每一測試之過 氧化氫複合物所產生的過氧化物蒸氣已足夠提供有效的殺 菌。 上列使過氧化氫蒸氣由過氧化物固體中釋出所須之溫 度,乃是以招盤外側由底部算起lcm位置之熱竊溫度計所 測得。如下列範例5所述,以位於内部盤底之溫度計,例如 氟溫度計,來作進一步的測量’得知盤底部溫度約高出3〇_ 35°C。因此,在前一範例中,當熱藕溫度計所測得溫度為 80 °C時,盤底溫度應约為110-115 °C,且當熱藕溫度計所 測得溫度為1 1 0 eC時,盤底溫度應約為1 4 0 - 1 4 5。(:》 aa. 表纸張尺度適用中國國家標準(CNS ) Λ4规格(21 OX297公羞) ----------裝------^------ (錆先閲讀背面之泣意事項鼻^^本 經濟部中央揉準f Η消费合作杜印装 A7 __________ 五、發明説明() 篪例5 將一氟溫度計貼在鋁盤底部’來測定襞有過氧化物複合 物固體之鋁盤底部的溫度。將一奥米茄溫度計 (OmegaTM)放在鋁盤外側由底部算起lcm位置。記錄 兩溫度計之差值。每次當鋁盤被加熱至盤側溫度計所顯示之 溫度時,讓其冷卻後’再重新加熱至所須溫度。所記錄下之 溫度如下所示: 側之谋_ 盤底部之溫度C 、 第一次 第二次 第三汝 平均 8 0 eC 110.9 110.6 110.6 110. 100°C 13 1.5 132.6 132.0 132. 結果類示盤底溫度較盤外側熱藕溫度計所顯示之溫度高出約 3〇-35〇C。 進行進一步測試來比較開放(無内室)系統中由水溶液 式和非水溶液式之過氧化物來源所得殺菌效率之數據。實驗 步驟詳列於下。 酱例6 以範例1之儀器裝置來對封在TYVEKTM/mYLARTM 信封中,6mm X 4mm含有6.8 X 105枯草桿菌芽胞 var. 之 Whatman #1 號 遽紙。(TYVEKTM是一種由聚乙稀·製成的可透氣的纖 Ϊ紙張ΛΑϋ用 tBI8 家揉準(CNS ) 44祕(21Gx29371公釐)~~ ----------------ίτ------^ (請先閲讀背面之注意事項再填寫本頁) 五、發明説明() A7 B7 經濟部中央揉準局貝工洧费合作社印簟 $eMYLARTM則是一種聚酯類不透氣物質)。將欲進行 生物測試的紙片分別置於含有一可調整型光纖鏡的聚亞苯氧 盤之前端’中間和後面。將盤放在一聚亞苯氧容器内,容器 的上方有—排氣口,底部則有兩個,以方便擴散《在直徑四 英叫的氣口上覆蓋一可透氣的聚丙烯封裝物 (SPUNGUARDTM 重滅菌包膜,Kimberly-Clark, Dallas,TX)以維持容器内含物在殺菌過程後仍能保持無 菌。將容器放入範例1之儀器裝置並將殺菌室壓力降至〇.2 托。將含2g過氧化氫尿素加成物(Fluka Chemical c〇rp.)之鋁盤加熱80-81 eC 5分鐘以提供殺菌室内 3mg/L之過氧化氫蒸氣,以距盤底約lcin之鋁盤側面壁上 的熱耦溫度計來測量溫度。讓生物測試樣品曝露於過氧化氳 蒸氣5和1〇分鐘。在蒸氣曝露後,所有的生物測試樣品均 以範例1之步驟方法來處理。 為對照起見,也在殺菌室中注入5 0 %過氧化氫水溶液並 使其由已加熱的注射器上揮發。注入過氧化氩溶液之體積所 產生之氣相中過氧化氩濃度為3 m g / L。測試的組態,及生 物測試樣品之組成,和將生物測試樣品曝露於過氧化氩後之 處理方式,與用於非水溶液式過氧化氮測試之處理步驟完全 相同。測試結果顯示於表6中。 (請先閲讀背面之注意事項再填寫本頁) € 本纸張尺度逋用中國國家標準(CNS > A4規格(210X297公釐) 經濟部中央橾準扃負工消费合作社印装 A7 __ __B7 五、發明説明() 袅6 開放系統中水签非水浓该< > 殺茴故率無内室測詨、 過氧化物來源 擴散時間 (分鐘) 殺菌結果 (正反應/樣品總數) 5 0 %溶液 5 3/3 10 3/3 過氧化每 5 1/3 10 0/3 測試結果顯示在開放系統中’亦即生物測試樣品並非被 置於一内室,相較於水溶液式過氧化氩複合物,非水溶液式 具有更大的殺菌效率。再一次,出乎意料外的發現,即使在 毋須讓過氧化氩蒸氣擴散進入一狹長内室的情況下,非水溶 液式系統仍能提供較佳的殺菌效率。此暗示在有水或無水的 系統中’過氧化氫的作用模式並不相同。 為測定非水溶液式過氧化物蒸氣在正常,非減壓情況不 之殺菌效率’進行了以下的試驗。測試情況詳述於下β 篕例7 以大氣壓下由過氧化每複合物中所釋出之過氧化氩蒸氣 於開放系統中進行殺菌效率的測試。在此測試中,將含 1.04 X ΐ〇ό枯草桿菌芽胞川^ 「《z’ger))之不餘鋼刀片封在一 TYVEKTM/MYLARTM信 本纸張逍用中國國家捃準从胁(21〇χ J76公釐) - --- ----------------訂 Z8I.· {請先聞讀背面之注意事項再填寫本頁} Α7 Β7 五、發明説明() 封中。將進行生物測試之刀片置於聚亞苯氧盤之前端,中間 和後面。將盤置於範W1之裝置中並關閉殺菌室門。在測試 期間將含4g過氧化氣尿素加成物(Fiuka chemical C〇rP )之鋁盤加熱至8〇-8lt:,以距盤底約lcm之鋁盤 側面壁上的熱耦溫度計來測量溫度。讓生物測試樣品曝露於 過氧化氫蒸氣5,1〇,2〇,和3〇分鐘。在蒸氣曝露後,所 有的生物測試樣品均以如同範例丨之步驟加以處理β表7顯 示這些測試結果及非水溶液式過氧化物於大氣下開放系統内 的殺菌效率。 表7 非水溶液式過氧化物 在大氣壓下之開放系統中的殺菌效率 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部_央揉隼局負工消费合作社印«. 過氧化物 擴散時間 殺菌結果 來源 (分鐘) (正反應/樣品總數) 過氧化每 5 3/3 10 1/3 20 0/3 3 0 0/3 為測定在各種溫度下由過氧化氩尿素複合物中釋出之過 氧化物量, 進行了以下進一步的試驗。 測試情況詳述於範例 8中。 本纸張尺度逍用中國國家棣準(CNS ) Α4规格(210X297公釐) A7 -—_____ B7 五、發明説明() 簏例8 將市售藥较(Fluka chemical Corp.)壓碎以得過氧 化每粉末’並置於第3B囷裝置中兩個12.7cm X 12.7cm之銘網間。之後將鋁盤加熱並以位於鋁盤一角之溫 度計來監測溫度。表8列出在各種溫度下加熱5分鐘後釋出 之過氧化物的约略百分比。數據顯示140 °C可100 %將過氧 化物由複合物中釋出。較低溫度所釋出之過氧化物百分比較 低。 夹8 非水溶液式過氧化物 在各種溫度下的釋出情形 (請先閲讀背面之注意事項再填寫本頁) 釋出之過氣化物百合比 8 0°C 〜2 5 % loot 〜6 5 0/〇 1 20°c ~ 8 0 % 13 0°C -90% 140°C 〜1 0 0 〇/〇 -泉' 經濟部中央橾準Λ貝工消费合作社印装 過氧化物複合物能在室溫及大氣壓下釋出過氧化氫蒸 氣,例如過氧化每複合物,因此能有效的被用在各種殺菌 應用中。本發明之化合物不僅可用於上述本發明之殺菌裝 置,也可被當做自助式殺菌包裝物質的一部分被使用,或塗 在支持物如紗布,海綿,綿花及其它類似物上。此化合物能 在室溫或高溫下用來殺菌已封裝起來的物質,對已封裝的醫 __ _____22___ ^纸張尺度適用中國國家揉準(CNS ) Α4规格(210X297公釐) A7 -__B7__ 五、發明説明() 療或手術產品的殺菌特別有用。 本發明化合物的一些特定用處詳述於下列範例中β下列 範例中所用的過氧化物複合物為藥錠型式的過氧化每 (Fluka chemical Corp.)或由藥鍵麼碎而得的粉末。 簏例9 將一自助式殺菌袋以下列方式來組裝:將表面含3 8 X 1〇5 枯草桿菌芽胞να,· •容e/^)之 不銹鋼刀片放在一殺菌的培養皿上。將培養血與lg藥鍵型 式或粉末型式的過氧化每複合物一起放進一更大的培養皿 中》之後將較大的培養皿放進由TYVEKTM/mylarTM (可透氣,表9) ,M YLARTM/m YLARTM (不透氣,表 10)或紙/ MYLARTM (透氣’表1〇)製成的殺菌袋中β 之後將殺菌袋封起來》 將每一個殺菌袋在各溫度下曝露不同的時間,如下表9 和10中所示。以範例1的方法來評估對生物測試樣品的殺 菌效果。結果示於表9和10中,“ + ”號表示有細菌的生 長0 , (請先閲讀背面之注意事項再填寫本頁) 訂 气, 鯉濟部中央樣率局貝工消费合作社印装 率 揉 家 國 國 中 用ΙΑ 22 ¥ 公 7 29 A7 B7 五、發明説明() 裊9 盗阻礙物(TYVEKTM/MYLARTM ) 之 自助式殺 结袋 溫度 過氧化物型式 1小時 2小時 3小時 4小時 2 3 °C 粉末 十 - - - 藥錠 + + - - 4 0°C 粉末 - - - 藥錠 - - - - 6 0°C 粉末 - - - 藥錠 - (請先聞讀背面之注$項再填寫本頁) 裝 * 訂 表10列出有(紙/MYLARTM)和無(MYLARTM/ MYLARtm)可透氣阻礙物之自助式殺菌袋殺菌效率的結 果。殺菌袋乃是以上述方法組裝,但僅使用粉末式的過氧化 每作為過氧化物蒸氣的來源。 裊10 經濟部中央橾率局貝工消费合作社印氧 有或無含可透氣阻礙物之自助式殺菌4 k 溫度 封裝型式 2小時 4小時 2 3 t M YLAR/MYLAR - • 紙/MYLAR + 4 0°C M YLAR/MYLAR • 紙/MYLAR • 6 0eC M YLAR/MYLAR • 紙/MYLAR - ^逋用中困國家標準(CNS ) A4规格(210X297公釐) 經濟部中央揉準局負工消费合作社印裝 A7 _____ _ B7 五、發明说明() — 測試節果顯示包含在有和無可透氣阻礙物之自助式殺菌 袋内(本發明過氧化每複合物,能在短短的2至3小時 内,沒有水分,室溫及大氣壓下對殺菌袋内之物體提供有效 的殺菌。 為測定本發明殺菌系統在一密閉容器内之殺菌效率,進 行了以下的實驗。 範例10 將一自助式殺菌容器以下列方式來組裝:將表面含3 8 X 1〇5 (表11)或9.2 X 1〇5 (表12)枯草桿菌芽胞 (5aci//i/j ίΜδίίΠί ναΓ,(nig"))之不銹鋼刀片,放在 一表面上有20個洞(大小為3/16英吋)之小型聚乙烯 (PE)管子的内部。再將此管子放進一更大的聚乙烯(pE)管 子中’以不透氣的蓋予’或一層可透氣的SPUNGUARD® (CSR包膜)加以覆蓋。在此較大的聚乙締(pE)管子中,尚 有第二根聚乙烯(P E)管子’同樣其表面也有2 〇個洞(大小 為3/16英吋)。此管内含lg之過氧化每粉末或藥錠,並 封於 SPUNGUARD ®(CSR 包膜)或 TYVEKTM 袋中, 將每一個容器在各溫度下曝露不同的時間,如下表 和1 2中所示。以範例1的方法來評估對生物測試樣品的殺 菌效果。結果示於表11和12中,“ + ”號表示有細菌的生 長。 __ 11_ 本纸張尺度適用中國躅家搮準(CNS ) Α4^格(2丨0X297公釐) (請先閲讀背面之注$項再填寫本頁) 、1ΤX / 1 · (please read the note f on the back before filling in the original text) Ordering by the Ministry of Economic Affairs of the Ministry of Justice, Shellfish Consumer Cooperatives, India, 31. Usually used in a variety of chemical gases other than hydrogen peroxide fungicides In the process of sterilization / steam, water is always present, so the fact that rapid sterilization can be violated in almost anhydrous conditions is quite unexpected. Because the argon peroxide vapor phase sterilization system uses an argon peroxide aqueous solution, there is also the presence of water in those systems. To test the sterilization efficiency of various other peroxide compounds, this paper uses the national sample of China. Vehicle (CNS) A4 specification (21 × 297 mm) A7 _____B7 __ V. Experiments under the description of the invention () Example 2J and 4 The equipment of Example 1 was used to test the polyproporoxolone · argon peroxide compound (Example 2) Sterilization efficiency of 'nylon 6-argon peroxide complex (Example 3) and 1,3-dimethyl urea hydrogen peroxide complex (Example 4). These compounds were synthesized as described in Examples 12 and 13 below. The test parameters are as follows: Example 2 Example 3 MlM 4 Temperature of the sterilization chamber 4 5 ° 〇4 5〇C 4 5t Initial pressure 0.2 Torr 1.0 Torr 1.0 Torr Peroxide weight 17% 10.5% 2 6.6% Percent peroxide concentration 6mg / L 6mg / L 6mg / L 8g 18g 6g oxide weight used per cycle releases peroxide 1 1 oec no ° c 80 ° C temperature cracked by the Ministry of Economic Affairs Central Central Standards Bureau negative labor cost cooperative mm (Please read the precautions on the back before filling this page) In each case, the bacterial spores are located in a plastic inner chamber of 6mm x 4 pieces of paper and a stainless steel blade in a stainless copper inner chamber. The results of β sterilization efficiency are shown in Table 5 below. . The property of this paper is BCN (A4% #) < 210X2! ^ # 5. Description of the invention (A7 B7 Polypropyrrolidinone, Nylon 6, and〗 3_ Dimethyl urea and hydrogen peroxide Result of sterilization efficiency and sterilization power of the formed compound (positive reaction / number of samples) _ψexposure within 5 minutes chamber type inner chamber size example 2 example 3 example 4 1mm X 1 m 0/3 0/3 0/3-1mm X 2m 0/3 0/3 0/3 TeflonTM 1mm X 3m 0/3 0/3 0/3 1mm X 4 m 0/3 0/3 0/3 3mm X 4 0cm 0/3 0/3 0 / 3 Stainless steel 3mm X 5 0cm 0/3 0/3 0/3 1mm X 5 0cm 0/3 0/3 0/3 Printed by Zhengong Consumer Cooperative, Central Bureau of Economic Affairs, Ministry of Economic Affairs «. Table 5 shows that only 5 points are required The exposure time of radon, the peroxide vapor generated by each of the hydrogen peroxide compounds tested is sufficient to provide effective sterilization. The temperatures listed above for the release of hydrogen peroxide vapor from peroxide solids are based on The outside of the tray is measured by a thief thermometer located 1 cm from the bottom. As described in Example 5 below, further measurements are made with a thermometer located at the bottom of the inner tray, such as a fluorine thermometer, 'the temperature at the bottom of the tray is about higher 3〇_ 35 ° C. Therefore, in the previous example, when the temperature measured by the thermal radon thermometer is 80 ° C, the temperature at the bottom of the pan should be about 110-115 ° C, and when the temperature measured by the thermal radon thermometer is 1 1 0 eC, The temperature at the bottom of the pan should be about 1 40-1 4 5. (: aa.) The paper size of the table applies to the Chinese National Standard (CNS) Λ4 specification (21 OX297). ----- ^ ------ (锖 Read the sobbing items on the back of the nose first ^^ The central government of the Ministry of Economic Affairs f 准 ΗConsumer cooperation Du printed A7 __________ 5. Description of the invention () 篪 Example 5 will be a A fluorine thermometer is attached to the bottom of the aluminum pan to measure the temperature of the bottom of the aluminum pan containing the solids of the peroxide compound. An OmegaTM thermometer (OmegaTM) is placed on the outside of the aluminum pan from the bottom 1cm from the bottom. Record the two thermometers. Difference. Each time the aluminum pan is heated to the temperature indicated by the pan-side thermometer, let it cool down and then re-heat to the required temperature. The recorded temperature is as follows: C, the first time, the second time and the third time, the average is 8 0 eC 110.9 110.6 110.6 110. 100 ° C 13 1.5 132.6 132.0 132. The outside temperature display thermometer higher thermal coupling about 3〇-35〇C. Further tests are more open (no internal chamber) system data from the obtained aqueous and non-aqueous source of peroxide type of sterilization efficiency. The experimental steps are detailed below. Example 6 Use the device of Example 1 to seal in a TYVEKTM / mYLARTM envelope, 6mm X 4mm containing 6.8 X 105 Bacillus subtilis var. Of Whatman # 1 paper. (TYVEKTM is a kind of breathable cellulose paper ΛΑϋ made of polyethylene. It is tBI8 (CNS) 44 secret (21Gx29371 mm) ~~ -------------- --ίτ ------ ^ (Please read the notes on the back before filling out this page) V. Description of the invention () A7 B7 Printed by the Central Government Bureau of the Ministry of Economy Ester impermeable substances). The pieces of paper to be subjected to the biological test were respectively placed in the middle and back of the front end 'of a polyphenylene oxide disk containing an adjustable fiberscope. Place the tray in a polyphenylene oxide container with an air vent above the container and two at the bottom to facilitate diffusion. A four-diameter port is covered with a breathable polypropylene package (SPUNGUARDTM Resterilize the envelope (Kimberly-Clark, Dallas, TX) to keep the contents of the container sterile after the sterilization process. Place the container in the apparatus of Example 1 and reduce the pressure in the sterilization chamber to 0.2 Torr. An aluminum pan containing 2 g of hydrogen peroxide urea adduct (Fluka Chemical corp.) Was heated at 80-81 eC for 5 minutes to provide 3 mg / L of hydrogen peroxide vapor in a sterilization chamber, and an aluminum pan about lcin from the bottom of the pan Thermocouple thermometer on the side wall to measure temperature. The biological test sample was exposed to rhenium peroxide vapor for 5 and 10 minutes. After the vapor exposure, all biological test samples were processed using the procedure of Example 1. For comparison, a 50% aqueous hydrogen peroxide solution was also injected into the sterilization chamber and allowed to evaporate from the heated syringe. The concentration of argon peroxide in the gas phase produced by the injection of the volume of the argon peroxide solution was 3 mg / L. The configuration of the test, the composition of the biological test sample, and the treatment method after the biological test sample is exposed to argon peroxide are the same as those used for the non-aqueous nitrogen peroxide test. The test results are shown in Table 6. (Please read the notes on the back before filling in this page) € This paper size is in accordance with Chinese National Standards (CNS > A4 size (210X297 mm)) Printed by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs and Consumer Cooperatives A_ __ __B7 5 、 Explanation of the invention () 袅 6 Water-labeled non-water-concentrated in the open system The < > Anthracitic rate without internal chamber measurement, peroxide source diffusion time (minutes), sterilization result (positive reaction / total number of samples) 5 0 % Solution 5 3/3 10 3/3 per 5 1/3 10 0/3 The test results show that in the open system, that is, the biological test sample is not placed in an internal chamber, compared with the aqueous solution type argon peroxide. The compound, non-aqueous solution type has greater sterilization efficiency. Once again, it was unexpectedly discovered that even without the need to allow argon peroxide vapor to diffuse into a narrow inner chamber, the non-aqueous type system can still provide better This implies that the mode of action of hydrogen peroxide is not the same in systems with or without water. To determine the sterilization efficiency of non-aqueous peroxide vapor under normal and non-decompression conditions, the following was performed test The test conditions are detailed in the following β. Example 7 The sterilization efficiency test was performed in an open system by argon peroxide vapor released from each compound at atmospheric pressure under atmospheric pressure. In this test, it will contain 1.04 X ΐ〇 ό Bacillus subtilis spore ^ "z" ger)) The remaining steel blade is sealed in a TYVEKTM / MYLARTM letter paper used in China (21〇χ J76mm)----- -------------- Order Z8I. · {Please read the notes on the back before filling in this page} Α7 Β7 V. Description of the invention () Sealed. The blade for biological test will be set At the front, middle, and back of the polyphenylene oxide disk. Place the disk in the device of Fan W1 and close the door of the sterilization chamber. During the test, aluminum containing 4 g of the peroxide gas urea adduct (Fiuka chemical Coorp) was used. Pan heated to 80-8lt: Measure the temperature with a thermocouple thermometer on the side wall of the aluminum pan about 1 cm from the bottom of the pan. Expose the biological test sample to hydrogen peroxide vapor 5, 10, 20, and 30. Min. After the vapor exposure, all biological test samples were processed in the same way as in Example 丨 Table 7 shows these test results and Sterilization efficiency of solution type peroxide in open system under the atmosphere. Table 7 Sterilization efficiency of non-aqueous type peroxide in open system under atmospheric pressure (Please read the precautions on the back before filling this page) Order Ministry of Economic Affairs_ Printed by the Central Government Bureau of Labor and Consumer Cooperatives «. Peroxide diffusion time Source of sterilization results (minutes) (Positive reaction / total number of samples) Peroxide per 5 3/3 10 1/3 20 0/3 3 0 0/3 is The amount of peroxide released from the argon peroxide urea complex at various temperatures was measured, and the following further tests were performed. The test conditions are detailed in Example 8. The size of this paper is in accordance with China National Standards (CNS) A4 specification (210X297 mm) A7 --- _____ B7 V. Description of the invention () 簏 Example 8 The commercial medicine is crushed to get over (Fluka chemical Corp.) Each powder was oxidized and placed between two 12.7 cm x 12.7 cm inscribed meshes in the 3B 囷 device. The aluminum pan was then heated and the temperature was monitored with a thermometer located at a corner of the aluminum pan. Table 8 shows the approximate percentages of peroxide released after 5 minutes of heating at various temperatures. Data show that 100 ° C releases peroxide from the compound at 140 ° C. The lower percentage of peroxide released at lower temperatures. Clip 8 Release of non-aqueous peroxide at various temperatures (please read the precautions on the back before filling out this page) The released gaseous lily ratio 8 0 ° C ~ 2 5% loot ~ 6 5 0 / 〇1 20 ° c ~ 80% 13 0 ° C -90% 140 ° C ~ 100% 〇 / 〇- 泉 'Central Ministry of Economic Affairs Zhun ΛPei Gong Consumer Cooperative Co., Ltd. printed peroxide compound can be in the room The release of hydrogen peroxide vapor at mild atmospheric pressure, such as per-peroxide complex, can be effectively used in a variety of sterilization applications. The compound of the present invention can be used not only in the above-mentioned sterilizing device of the present invention, but also as a part of a self-service sterilizing packaging material, or coated on a support such as gauze, sponge, cotton, and the like. This compound can be used to sterilize packaged substances at room temperature or high temperature. For packaged medical __ _____22___ ^ Paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) A7 -__ B7__ V. Description of the invention () Sterilization of therapeutic or surgical products is particularly useful. Some specific uses of the compounds of the present invention are detailed in the following examples. The peroxide complexes used in the following examples are tablets of peroxide type (Fluka chemical Corp.) or powders obtained by crushing the bond. Example 9 A self-service sterilization bag was assembled in the following manner: A stainless steel blade containing 3 8 X 105 bacillus subtilis spores να, · • e / ^) on a surface was placed on a sterilized petri dish. Put the cultured blood together with the lg drug bond type or the powder type peroxidation compound into a larger petri dish. After that, put the larger petri dish into the TYVEKTM / mylarTM (breathable, Table 9), M YLARTM / m YLARTM (air-tight, table 10) or paper / MYLARTM (air-permeable 'table 10) in a sterilization bag β and then sealing the sterilization bag》 Expose each sterilization bag at different temperatures for different times, as follows Shown in Tables 9 and 10. The method of Example 1 was used to evaluate the bactericidal effect on biological test samples. The results are shown in Tables 9 and 10. The "+" sign indicates the growth of bacteria 0. (Please read the precautions on the back before filling in this page.) Gas booking, the print rate of the Central Laboratories Bureau of the Ministry of Carp, Printing and Cooperative For domestic use, IA 22 ¥ Public 7 29 A7 B7 V. Description of the invention () 袅 9 Self-killing anti-theft bag temperature theft type (TYVEKTM / MYLARTM) Peroxide type 1 hour 2 hours 3 hours 4 hours 2 3 ° C Powder Ten---Tablets + +--4 0 ° C Powder---Tablets----60 ° C Powder---Tablets-(Please read the note on the back side before filling in This page) Binding * Order Table 10 lists the results of the sterilization efficiency of self-service sterilization bags with (paper / MYLARTM) and without (MYLARTM / MYLARtm) breathable barriers. The sterilization bag is assembled by the above method, but only powdered peroxide is used as a source of peroxide vapor.袅 10 Self-help sterilization with or without breathable obstruction 4K temperature encapsulation type 2 hours 4 hours 2 3 t M YLAR / MYLAR-• Paper / MYLAR + 4 0 ° CM YLAR / MYLAR • Paper / MYLAR • 6 0eC M YLAR / MYLAR • Paper / MYLAR-^ Using the National Standard for Difficulties (CNS) A4 (210X297 mm) Printed by the Central Government Bureau of the Ministry of Economic Affairs A7 _____ _ B7 V. Description of the invention ()-The test results show that it is contained in self-service sterilization bags with and without breathable obstructions (per compound of the present invention can be peroxidized in just 2 to 3 hours, No moisture, effective sterilization of the objects in the sterilization bag at room temperature and atmospheric pressure. To determine the sterilization efficiency of the sterilization system of the present invention in a closed container, the following experiments were performed. Example 10 The following is a self-service sterilization container. Way to assemble: a stainless steel blade containing 3 8 X 105 (Table 11) or 9.2 X 105 (Table 12) Bacillus subtilis spores (5aci // i / j ίΜδίίΠί (ναΓ)) on the surface, put 20 holes (size 3/16 inch) inside a small polyethylene (PE) tube. This tube is then placed in a larger polyethylene (pE) tube 'with an airtight cover' or a layer of breathable SPUNGUARD® ( CSR film) to cover. In this larger polyethylene (pE) tube, there is a second polyethylene (PE) tube. It also has 20 holes on its surface (3/16 inch) This tube contains lg of peroxidized powder or tablets, and is sealed in SPUNGUARD ® (CSR film) or TYVEKTM bag. Each container is exposed to different temperatures at different times, as shown in the following table and 12 The method of Example 1 was used to evaluate the germicidal effect on the biological test samples. The results are shown in Tables 11 and 12. The "+" sign indicates the growth of bacteria. __ 11_ This paper standard is applicable to China National Standards (CNS) Α4 ^ Grid (2 丨 0X297mm) (Please read the note on the back before filling this page), 1Τ
>·^I 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明()> · ^ I Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention ()
表UL 沒有可透氣視窗之自助式殺菌容器 溫度 封裝型式 2小時 6小時 2 3 °C 未包裝藥錠 + - C/C*包裝藥錠 + - C/C*包裝粉末 + - 4 0°C 未包裝藥錠 - - C/C包裝藥錠 C/C包裝粉末 - - 6 0°C 未包裝藥錠 • - C/C包裝藥錠 - - c / C包裝粉末 睡 - * -由CSR包膜製成之袋子 (請先閲讀背面之注_項再填寫本頁)Table UL Self-service sterilization container without breathable window Temperature sealed type 2 hours 6 hours 2 3 ° C Unpacked tablets +-C / C * Packed tablets +-C / C * Packed powder +-4 0 ° C Not Packaged tablets--C / C packaged tablets C / C packaged powder--60 ° C Unpackaged tablets--C / C packaged tablets--c / C packaged powder sleep-*-made by CSR film Chengzhi bag (please read the note on the back before filling this page)
、1T ".'! 42 本紙張尺度適用中國國家標準(CNS ) Α4说格(210Χ297公釐) 經濟部中央樣準局貝工消费合作社印装 A7 B7 五、發明説明()、 1T ". '! 42 This paper size applies to Chinese National Standards (CNS) Α4 grid (210 × 297 mm) Printed by the Shell Consumer Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs A7 B7 5. Description of Invention
Ml 12 沒有可透氣CSR視窗之自助式殺菌容器 溫度 封裝型式 0.5 小時 1.0 小時 1 . 5 小時 2 . 0 小時 3 . 0 小時 4.0 小時 2 3 °C 未包裝藥錠 + + + - . 未包裝粉末 + + + . T/T *包裝藥錠 + + + + T/T包裝粉末 + + + - - C/C * *包裝藥錠 + + + - - C/C包裝粉末 + + + . . 4 0 °C 未包裝藥錠 . 未包裝粉末 • . . T/T*包裝藥錠 + - . T/T包裝粉末 • - • . C / C包裝藥錠 - - - - C/C包裝粉末 - - _ - 6 0 °C 未包裝藥錠 - - ㈣ - 未包裝粉末 - - - - T/T包裝藥錠 . . -· - T/T包裝粉末 • • . . C/C包裝藥錠 . . . . C/C包裝粉末 - - - - * -由T Y VEKTM製成之袋子 * * -由C S R包膜製成之袋子 ^1. - - - - - - - - - - - I- - ——\.^I……------ T*,vs /—λ (請先閱讀背面之注意事項再填寫本頁) 43 本紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐) A7 B7 經濟部中央揉準局貝工消费合作社印製 五、發明説明( 這些測試結果顯示裝在有或無可透氣阻礙物之容器内的 非水溶液式過氧化每複合物,在室溫下3 - 4小時内即能提 供有效的殺菌。在較高溫度下,僅須半小時即能提供有效的 殺菌。 已知由#水溶液式過氧化物複合物中所釋出之過氧化物 蒸氣對室溫下的殺菌工作非常有效,若在高溫下,則效果更 好。可將這類複合物置於殺菌袋’容器,殺菌室,房間或任 何能加以密封的地區中,使釋出之過氧化物蒸氣能對物體作 有效的殺菌。可將複合物加熱以促進蒸氣的釋放,並使其能 在室溫下以較短的時間完成殺菌。因此本發明化合物對許多 須要殺菌的應用非常有用。只要將複合物置於一含有欲殺菌 物體的密閉區域,即可完成殺菌步驟^與先前技藝所用方法 不同的是,毋須水分的接觸來提供活化的過氧化氫。 為確定能有效的以非水溶液式過氧化物複合物在短時間 低壓下達到殺菌的目的,進行了以下的實驗。 簏》】11 將一自助式殺菌容器以下列方式來組裝:將表面含9 2 X 1〇5枯草桿菌芽胞(5aciiiui 之不錄鋼支持物’放在一表面上有20個洞(大小為3/16 英吋)之小型聚乙缔(PE)管子的内部。再將此管子放進一 更大的聚乙烯(PE)管子中,以可透氣的蓋子,或一廣CSR 包膜(SPUNGUARDTM)加以覆蓋。在此較大的聚乙埽 (PE)管子中,尚有第二根聚乙缔(PE)管子,同樣其表面也 44 本紙張尺度通用中國國家標準(CNS > A4規格(210X297公釐) I ^1 丨— I^I — — I — 線— i f 、 (請先閲讀背面之注$項再填寫本頁) A7 _B7____ 五、發明説明() 有20個洞(大小為3/16英吋)。此管内含lg之過氧化 每粉末或藥錠,並封於CSR包膜或TYVEKTM袋中。 將大管放在一體積4.5L或173L的殺菌室中。讓每一 個容器在壓力1〇〇托及23 eC下曝露2小時,如下表13所 示。以範例1的方法來評估對生物測試樣品的殺菌效果。結 果示於表1 3中。 裊13 減壓下有可透氣視窗之自助式殺苗宏器 (請先閲讀背面之注意事項再填寫本頁) 溫度 封裝型式 4.5L之殺菌室 1 73 L之殺菌室 2 3 °C 未包裝粉末 - T/T包裝粉末 - C/C包裝藥錠 • 訂 經濟部中央標準局貞工消費合作社印裝 結果顯示有可透氣阻礙物之自助式殺菌容器在100托 室溫下2小時内即可提供有效的殺菌。當與表1 2的結果相 比下,這些結果顯示相較於大氣壓下殺菌所須的時間,本發 明之過氧化物複合物化合物能在減壓下以較短時間達到殺菌 的目的。 因此,發明之過氧化氩複合物化合物能在較短時間内提 供顯著的殺菌效果。此外’如以上所討論,可以電裝來提高 過氧化氫蒸氣之殺菌活性。在曝露於過氧化氩蒸氣後,再將 欲殺菌物與電漿接觸_段足以完成殺菌的時間。 45 本紙張尺度適用中國囷家標準(CNS ) A4規格(210X297公釐) ' 五、發明説明() 可將已經過氧化氫蒸氣殺菌之物體再曝露於電漿中以去 除物體上殘留的過氧化氫。因殘餘的過氧化氫在以電漿處理 時會分解成無毒性之產物,因此殺菌物在處理後毋須再經任 何额外的步驟即可被使用。 非水溶液式過氧化物複合物對許多須要殺菌應用非常有 用,包括自助式殺菌包裝的一部分。此外,複合物也可被用 在許多以蒸氣對物體進行殺菌的方法中,例如,美國專利案 第4,943,4 14號中所描述的方法^本專利案揭露了 —種方 法,該法包括一容器其内室含少量可揮發之殺菌溶液液體, 在殺菌循環中當壓力下降時,此殺菌液揮發後會直接流向内 室中欲殺菌之物體。可將本專利案所揭露之方法加以修改以 便使用非水溶液式過氧化物。此化合物被置於容器内並連接 至含有欲殺菌物體的内室中,之後再將物體置入容器内並抽 真空。物體之内部及外部可接觸到由非水溶液式複合物中所 釋出之過氧化物蒸氣。可選擇性的生成電漿並以其來提高殺 菌和/或去除物體上殘留之過氧化氫。在系統中使用上述非 水溶液式過氧化物複合物可克服水溶液中水分揮發較快並搶 在過氧化氫蒸氣之前抵達内室的缺點β因此,可在較短的時 間内達到較有效的殺菌。過氧化氫複合物,例如無水甘氨 酸,特別具優勢,因其能在毋須加熱複合物之減壓情況下釋 出顯著量的過氧化氫蒸氣來進行殺菌。 IL丞溶液式過氣化箱碑合物之厶成 本發明更進一步提供一非水溶液式過氧化氫複合物的 經濟部中央標準局貝工消費合作社印«. A 7 _____B7 五、發明説明() 備方法’該非水溶液式過氧化氫複合物可作為上述過氧化氫 蒸氣殺菌劑來源,或自助式殺菌包裝組成的一部分。當然, 也可將過氧化氫複合物用在其它應用上,例如漂白劑,隱形 眼鏡溶液,催化劑,和此領域中熟習技藝人士所熟知的其它 應用上。 本發明之非水溶液式過氧化氫複合物的一般製備方法如 下: (η蔣反應物置於殺苗玄内 與過氧化氫反應的物質可以是以各種形式存在的固體 (例如,粉末,結晶,薄膜及其它,較好是具有很高的表面 積以增進反應速率)。在殺菌室減壓後,如果有足夠的時間 使溶劑揮發’則反應物物質也可以是溶於水或其它溶質之溶 液。物質也可以是沸點較過氧化氫高(150 °c)的液體。由 於高溫下反應速率較快,因此殺菌室較好是在引入反應物之 前或之後開始加熱。然而,不可使溫度過高以致反應物被沸 騰或揮發。 可將反應物置入任何能接觸到過氧化物蒸氣的容器中。 如果是粉末或其它形式,當殺菌室抽真空時,可能會被吹 走,則可將反應物置於可透氣的容器内,使過氧化氫蒸氣能 擴散進入容器中。 f 2 1殺菌室抽真空 在某些實施例中,殺菌室被抽真空至低於大氣壓的情 況,例如,低於過氧化氩蒸氣壓下(視其濃度及溫度而 定),以確保所有的過氧化物均處於蒸氣狀態。蒸氣壓隨著 47 本紙張尺度適用中國國家標率(CNS > Α4規格(210X297公釐) (請先閲讀背面之注$項再填寫本頁) 訂 B7 五、發明説明() 溫度的上升而增加,隨著過氧化物濃度的增加而下降。對大 部分的實驗而言’將殺菌室抽真空至0.2托,溫度則維持 在室溫或室溫以上。 (3 )產生過氳化氤基氳 過氧化氫蒸氣可以由過氧化氫溶液或一幾乎無水的過氧 化氳複合物來生成。後者會產生乾燥的過氧化氫蒸氣,此對 將與蒸氣進行反應的物質或所形成易吸濕複合物而言可能是 一項優點》由一幾乎無水的過氧化氫複合物來生成過氧化氣 蒸氣的另一項優點乃是複合物較過氧化氫水溶液能產生較高 百分比之過氧化氫蒸氣。此可能是由於在以過氧化氫水溶液 能產生蒸氣時,水分子與過氧化氫蒸氣分子彼此競爭複合物 上的結合位置所致。 也可讓過氧化氩蒸氣在裝有欲殺菌物體之殺菌室内或另 一以真空閥與殺菌室分開來的内室中生成。 (4) 反應物質輿過氣化氪反應 反應時間視反應物質與過氧化氫之間的反應速率而定。 經濟部中央標準局貝工消费合作社印製 可藉監測壓力由實驗中得知,反應壓力會隨反應物質與過氧 化氩結合而降低。一搬而言,反應時間約為5-30分鐘。揮 發的過氧化氫濃度與起始物之重量決定反應終產物中過氧化 物的重量百分比。當反應物與過氧化氫之比值增加時,複合 物中過氧化氫的重量百分比會跟著降低。可重覆進行反應以 增加複合物中過氧化氫的濃度。 (5) 將殺菌室再;j:柚直中 反應終止後,將殺菌室再次抽真空至壓力約為2托以除 ____48______ 未紙張尺度逋用中國國家梯準(CNS ) A4规格(210X297公釐) 經濟部中央梯準局貝工消費合作社印製 A7 B7 五、發明説明() 去任何未反應的過氧化氫。 (6 )將菌室抽氣並取出過氧化氤葙合妝 過氧化氫如何與反應物形成複合物的機制仍不完全清 楚。一般相彳s複合物的形成中牵涉到過氧化氫與反應物中含 氧和或氮原子官能基上的電子產生氩鍵所致。是否此即為唯 一的鍵結模式,目前並不清楚;但是,目前也已知具有多樣 性官能基的物質也能和過氧化氳形成複合物。 氣相反應較其它先前提出製造過氧化氩複合物的方法有 以下的優點包括: 1.藉著改變蒸氣相中過氧化氫含量或曝露於蒸氣中之反應物 含量可精確的控制過氧化氫與反應物之比值。 2 .不再須要由反應產物中將溶劑移除。 3 .可形成過氧化物複合物液體或固體,例如粉末,結晶,薄 膜,及其它。 4 ·可製備易溼性物質之過氧化物複合物。 以下範例進一步描飧了本發明非水溶液式過氧化物複合 物的合成方法。本領域中熟習技藝的人士應能很輕易的明 瞭,許多這類化合物除了在此所述之用途外,也可當作催化 劑使用。範例代表本發明組成及製備方法之實施例,但本發 明之範疇並不因此受到限制。 範例12 無水甘氨酸與過氧化氳所形成之複合物的製備方法如 下:將^無水甘氨酸(阿里其化學公司(Aldrich _______ 49 (請先閲讀背面之注f項再填寫本耳) 訂 - 5 / 3 - "· - - V 'f 9 公 7 9 2 ehemical c〇,),Milwaukee,WI)置於一溫度 45°C 禮 積173L的殺菌室中的鋁盤上。鋁盤上方以tyvekTM不 織性纖維加以覆蓋,以防止殺菌室減壓但仍可呼吸時無水甘 氣酸选出盤外,且不會吸附過氧化氫。關閉殺菌室門並以真 2繁浦抽氣將殺菌室之壓力降低至〇.2托。藉著讓適當禮 積之7 〇 %過氧化氫溶液揮發進入殺菌室,以使過氧化氩滚 度達到 10mg/L (FMC Corp., Philadelphia,PA)。 保持過氧化氫蒸氣與無水甘氨酸接觸20分鐘。反應終止 時’先將殺菌室壓力降至0.2托後再使其重新回到大氣 壓。將產物移出並以下列碘滴定反應來決定產物中過氧化氫 的重量百分比。Ml 12 Self-service sterilization container without air-permeable CSR window. Temperature packaging type 0.5 hours 1.0 hours 1.5 hours 2.0 hours 3.0 hours 4.0 hours 2 3 ° C Unpackaged tablets + + +-. Unpackaged powder + + +. T / T * packaged tablets + + + + T / T packaged powder + +---C / C * * packaged tablets + +---C / C packaged powder + +.. 4 0 ° C Unpacked tablets. Unpacked powders... T / T * packaged tablets +-. T / T packaged tablets •-•. C / C packaged tablets----C / C packaged powders--_- 6 0 ° C Unpackaged tablets--㈣-Unpackaged powders----T / T packaged tablets..---T / T packaged powders • •.. C / C packaged tablets... C / C Packaging powder----*-Bag made of TY VEKTM * *-Bag made of CSR film ^ 1.-----------I--—— \. ^ I …… ------ T *, vs / —λ (Please read the notes on the back before filling in this page) 43 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by Shelley Consumer Cooperative of Central Bureau of the Ministry of Economic Affairs V. Description of the invention (These test results show that the non-aqueous peroxide-containing compound in a container with or without a breathable obstruction can provide effective sterilization within 3 to 4 hours at room temperature. It can provide effective sterilization in only half an hour at temperature. It is known that the peroxide vapor released from the #water solution type peroxide compound is very effective for sterilization at room temperature. If it is at high temperature, The effect is better. This kind of compound can be placed in a sterilization bag 'container, sterilization room, room or any area that can be sealed, so that the released peroxide vapor can effectively sterilize the object. The compound can be heated In order to promote the release of steam and enable it to complete sterilization in a short time at room temperature. Therefore, the compound of the present invention is very useful for many applications requiring sterilization. As long as the compound is placed in a closed area containing an object to be sterilized, that is, The sterilization step can be completed ^ Different from the method used in the prior art, no contact with water is required to provide activated hydrogen peroxide. To determine that non-aqueous peroxygen can be effectively used The compound complex achieves the purpose of sterilization under low pressure for a short time, and the following experiments have been performed. 簏》] 11 A self-service sterilization container was assembled in the following manner: The surface contained 9 2 X 105 bacillus subtilis spores (5aciiiui The non-recorded steel support is placed inside a small polyethylene (PE) tube with 20 holes (3/16 inches in size) on one surface. This tube is then placed in a larger polyethylene (PE) tube, covered with a breathable lid, or a wide CSR envelope (SPUNGUARDTM). Among the larger polyethylene pipes, there is also a second polyethylene pipe, and its surface is also 44 paper sizes common to Chinese national standards (CNS > A4 size (210X297 mm) I ^ 1 丨 — I ^ I — — I — line — if, (please read the note on the back before filling in this page) A7 _B7____ 5. Description of the invention () There are 20 holes (the size is 3/16 inches) ). This tube contains lg of peroxide per powder or tablet and is sealed in a CSR envelope or TYVEKTM bag. Place the large tube in a sterilization chamber with a volume of 4.5L or 173L. Let each container under pressure 1〇 〇 Torr and 23 eC exposure for 2 hours, as shown in Table 13 below. The method of Example 1 was used to evaluate the sterilization effect on biological test samples. The results are shown in Table 13. 袅 13 Self-help with a breathable window under reduced pressure Macro Seed Killer (Please read the precautions on the back before filling out this page) Temperature-sealed 4.5L sterilization chamber 1 73 L sterilization chamber 2 3 ° C Unpackaged powder-T / T packaging powder-C / C packaging Medicinal tablets • Ordered by the Central Standards Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative, printed results showing self-help with breathable obstructions The sterilization container can provide effective sterilization within 2 hours at room temperature of 100 Torr. When compared with the results in Table 12, these results show that the peroxide compound of the present invention is compared with the time required for sterilization at atmospheric pressure. The compound can achieve sterilization in a short time under reduced pressure. Therefore, the invented argon peroxide complex compound can provide a significant sterilization effect in a short time. In addition, 'as discussed above, it can be improved by electric equipment. The germicidal activity of hydrogen peroxide vapor. After exposure to argon peroxide vapor, contact the material to be sterilized with the plasma for a period of time that is sufficient to complete sterilization. 45 This paper size applies to the Chinese family standard (CNS) A4 specification (210X297) (Mm) 5. Description of the invention () The object that has been sterilized with hydrogen peroxide vapor can be exposed to the plasma again to remove the residual hydrogen peroxide on the object. The residual hydrogen peroxide will decompose when treated with the plasma. It is a non-toxic product, so the germicidal substance can be used without any additional steps after processing. Non-aqueous peroxide compound is used for many sterilizing applications. Often useful, including part of a self-service sterilization package. In addition, the compound can also be used in many methods to sterilize objects with steam, for example, the method described in U.S. Patent No. 4,943,4 ^ this patent The case discloses a method that includes a container whose inner chamber contains a small amount of a volatile sterilization solution liquid. When the pressure decreases during the sterilization cycle, the sterilization liquid will flow directly to the object in the inner chamber to be sterilized. The method disclosed in this patent is modified to use a non-aqueous peroxide. The compound is placed in a container and connected to the inner chamber containing the object to be sterilized, and the object is then placed in the container and evacuated. The inside and outside of the object can come into contact with the peroxide vapor released from the non-aqueous compound. The plasma can be selectively generated and used to enhance sterilization and / or remove residual hydrogen peroxide from objects. The use of the above-mentioned non-aqueous type peroxide compound in the system can overcome the shortcomings of rapid evaporation of water in the aqueous solution and grab the inner chamber before the hydrogen peroxide vapor β. Therefore, more effective sterilization can be achieved in a shorter time. Hydrogen peroxide compounds, such as anhydrous glycine, are particularly advantageous because they can release a significant amount of hydrogen peroxide vapor for sterilization without the need to heat the compound under reduced pressure. The cost of the IL 丞 solution type supergasification box tablet compound was further invented to provide a non-aqueous solution type hydrogen peroxide complex printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs «. A 7 _____B7 V. Description of the invention () Method 'The non-aqueous hydrogen peroxide complex can be used as a source of the above-mentioned hydrogen peroxide vapor germicide or as part of a self-service sterilization package. Of course, the hydrogen peroxide complex can also be used in other applications, such as bleach, contact lens solutions, catalysts, and other applications well known to those skilled in the art. The general preparation method of the non-aqueous-type hydrogen peroxide complex of the present invention is as follows: (η Chiang reactant is placed in the killing mysterious substance and reacts with hydrogen peroxide may be a solid in various forms (for example, powder, crystal, film Among other things, it is preferable to have a high surface area to improve the reaction rate.) After the decompression of the sterilization chamber, if there is sufficient time for the solvent to evaporate, the reactant substance may also be a solution dissolved in water or other solutes. Substance It can also be a liquid with a higher boiling point (150 ° c) than hydrogen peroxide. Because the reaction rate is faster at high temperatures, it is better to start the sterilization chamber before or after introducing the reactants. However, the temperature must not be too high for the reaction The product is boiled or volatilized. The reactant can be placed in any container that can contact the peroxide vapor. If it is in powder or other form, when the sterilization chamber is evacuated, it may be blown away. In a vented container, the hydrogen peroxide vapor can diffuse into the container. F 2 1 Evacuation of the sterilization chamber In some embodiments, the sterilization chamber is evacuated to less than Air pressure conditions, for example, lower than the argon peroxide vapor pressure (depending on its concentration and temperature) to ensure that all peroxides are in a vapor state. The vapor pressure is subject to the Chinese national standard with 47 paper standards ( CNS > Α4 specification (210X297 mm) (Please read the note on the back before filling this page) Order B7 V. Description of the invention () The temperature increases and rises with the increase of peroxide concentration. In most experiments, the sterilization chamber is evacuated to 0.2 Torr, and the temperature is maintained at or above room temperature. (3) Hydrogen peroxide vapor can be generated from a hydrogen peroxide solution or an almost Anhydrous perylene complex is produced. The latter produces dry hydrogen peroxide vapor, which may be an advantage for the substance that will react with the vapor or the hygroscopic compound formed. Another advantage of the hydrogen peroxide compound to generate peroxide vapor is that the compound can generate a higher percentage of hydrogen peroxide vapor than aqueous hydrogen peroxide solution. This may be due to the use of hydrogen peroxide water When the liquid can generate vapor, water molecules and hydrogen peroxide vapor molecules compete with each other for the binding position on the complex. Argon peroxide vapor can also be placed in a sterilization room containing an object to be sterilized or another vacuum valve and sterilization room It is generated in the separated inner chamber. (4) The reaction time of the reaction substance and the over-gasification reaction depends on the reaction rate between the reaction substance and hydrogen peroxide. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs can be monitored. The pressure is known from the experiment. The reaction pressure will decrease with the combination of the reaction substance and argon peroxide. The reaction time is about 5-30 minutes. The concentration of volatile hydrogen peroxide and the weight of the starting material determine the end of the reaction. The weight percentage of peroxide in the product. When the ratio of reactants to hydrogen peroxide increases, the weight percentage of hydrogen peroxide in the composite will decrease. The reaction can be repeated to increase the concentration of hydrogen peroxide in the composite. (5) Re-sterilize the chamber again; j: After the reaction of Citrus Straight is terminated, evacuate the sterilization chamber again to a pressure of about 2 Torr divided by ____48______. For paperless scales, use China National Standard (CNS) A4 (210X297). (%) A7 B7 printed by the Shellfish Consumer Cooperative of the Central Government of the Ministry of Economic Affairs. 5. Description of the invention () Remove any unreacted hydrogen peroxide. (6) The bacteria chamber is evacuated and the peroxide peroxide is removed. The mechanism of how hydrogen peroxide forms a complex with the reactants is still not completely clear. In general, the formation of the 彳 s complex involves hydrogen peroxide and argon bonding between the oxygen- and nitrogen-containing functional groups in the reactant. It is not clear whether this is the only bonding mode; however, it is also known that substances with diverse functional groups can also form complexes with europium peroxide. The gas phase reaction has the following advantages over other previously proposed methods for the production of argon peroxide composites: 1. The hydrogen peroxide can be accurately controlled by changing the hydrogen peroxide content in the vapor phase or the content of the reactants exposed to the vapor. Ratio of reactants. 2. It is no longer necessary to remove the solvent from the reaction product. 3. It can form peroxide compound liquid or solid, such as powder, crystal, film, and others. 4 · It is possible to prepare peroxide compounds of easily wettable substances. The following examples further describe the synthesis method of the non-aqueous peroxide compound of the present invention. Those skilled in the art should readily understand that many of these compounds can be used as catalysts in addition to the applications described herein. The examples represent examples of the composition and preparation method of the present invention, but the scope of the present invention is not limited thereby. Example 12 The preparation method of the complex formed by anhydrous glycine and thorium peroxide is as follows: ^ anhydrous glycine (Aliqi Chemical Company (Aldrich _______ 49 (please read the note f on the back before filling in this ear)) Order-5/3 -" ·--V 'f 9 male 7 9 2 ehemical co.), Milwaukee, WI) was placed on an aluminum pan in a sterilization room with a temperature of 45 ° C and 173L. The top of the aluminum pan is covered with tyvekTM non-woven fiber to prevent the anhydrous dialysis acid from being selected from the pan when the sterilization chamber is decompressed but still breathing, and does not absorb hydrogen peroxide. Close the door of the sterilization chamber and reduce the pressure in the sterilization chamber to 0.2 Torr by pumping the air through the pump. An appropriate 70% hydrogen peroxide solution was allowed to evaporate into the sterilization chamber so that the argon peroxide roll reached 10 mg / L (FMC Corp., Philadelphia, PA). Keep the hydrogen peroxide vapor in contact with anhydrous glycine for 20 minutes. At the end of the reaction ', the pressure of the sterilization chamber was first reduced to 0.2 Torr, and then returned to atmospheric pressure. The product was removed and titrated with the following iodine to determine the weight percent of hydrogen peroxide in the product.
H202 + 2KI + H2S04 ^ I2 + K2S04 + 2H20 I2 + 2Na2S203 Na2S406 + 2NaI 在碘-硫代硫酸鈉滴定反應中以澱粉當作指示劑以提高 反應終點時的顏色變化。以下列方程式來計算過氧化氫之重 量百分比: wt% H2〇2 = [(Na2S203 之體積,ml)*(Na2S203 之當 量濃度)*1·7]/(樣品克重,g) 經濟部中央標準局貝工消费合作社印11 無水甘氨酸與過氧化氫所形成之複合物中過氧化氩重量 百分比為2 4.3 %。 篪例 許多過氧化氩之有機或無機複合物均可依範例12中的 方法加以製備。在每一製備中,反應條件均與範例12中相 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局貝工消費合作社印製 A7 __B7 五、發明説明() 同,除了以1 g表1 4所列化合物來取代無水甘氨酸。 裊14 化合物的評估和以氣相合成方法製備之複合物中 過氣化氫的重量百分比 化學物名稱 化皋結構 經過氧化物 處理後之 百分比 分頬 聚(乙烯醇) [-CH2CH(OH)-]n 18.9% 乙醇 聚(乙烯甲謎) [-CH2CH(OCH3)-]n 22.0% 乙醚 聚(乙烯甲基酮) [-CH2-CH(COCH3)-]n 13.9% 丙酮 聚(丙烯酸) [-CH2CH(COOH)-]n 5.1% 酸 甘氨酸 H2C(NH2)(COOH) 20.7% 氨基酸 L-組織胺酸 [N=CHNHCH=C]CH2CH(NH2)COOH 14.1% 氨基酸 聚(乙烯乙酯) [-CH2CH(OCOCH3)-]n 9.1% 酯 纖維素乙酸酯 10.9% 酯 藻酸鈉 27.7% 有機里類 纖維素硫酸酯鈉鹽 18.2% 有機鹽類 聚(4-乙晞也咬) [-CH2CH〇>-C5H4N)-]n 21.8% 芳香胺 組織胺 [N=CHNHCH=C]CH2CH2(NH2) 13.2% 胺 丙醯胺 (C2H5)CONH2 31.8% 醯胺 尿素 (H2N2)CO 17.9% 尿素 1,3-二甲基尿素 (H3C)HNCONH(CH3) 31.7% 尿素 縮二脒 (H3C)CO(NH)CO(NH2) 13.7% 縮二脒 聚丙浠醢胺 [-CH2CH(CONH2)-]n 30.1% 聚醯胺 聚乙晞毗咯酮 [-CH2CH(-N(CH2)3CO)-]n 29.9% 聚醯胺 尼龍6 [-NH(CH2)5CO-]n 17.1% 聚醯胺 尼龍6,6薄膜 [-NH(CH2)6NHCO(CH2)4CO-]n 16.6% 聚醯胺 51 表紙張尺度適用中國國家標準(CNS ) A4規格(2丨OX297公釐) (請先閲讀背面之注$項再填寫本頁) ,βτ A7 _B7 五、發明説明() 裊14(繼婧) 經過氧化物 處理後之 化皋物名稱 化學結構 重量百分比 分頰 聚乙醚聚胺基甲酸 [-RHNCOOR'-]n 9.5% 聚胺基甲 乙酯 酸乙酯 碳酸鈉 叫(:03 14.3% 無機 碳酸鉀 K2C03 33.9% 無機 碳酸铷 Rb2C03 37.0% 無機 氫氧化鈣 Ca(OH)2 23.4% 無機 碳酸氫鈉 NaHCOj 10.7% 無機 焦麟酸四納鹽 Na4P207 18.9% 無機 (請先閲讀背面之注意事項再填寫本頁) 所形成之有機複合物涵蓋下列能與過氧化氫形成氫鍵之 官能基:醇,醚,酮,酸,氨基酸,酯,有機鹽類,胺,醯 胺,聚醯胺,聚胺基甲酸乙酯,尿素,和縮二脲。無機複合 物包括與鈉,鉀和铷陽離子所形成之碳酸鹽,以及碳酸氫 納。此外,也製備了氩氧化約和焦嶙酸四納鹽與過氧化氫所 形成之複合物。起始物除了尼龍6,6和聚乙烯甲謎外,均為 極細的粉末或稍大的結晶物,尼龍6,6為厚度0 . 1 2 m m的 薄膜,而聚乙烯甲醚則是5 0 %的水溶液。 在測試情況下以這些物質所製得的過氧化氫複合物大部 分為固體,除了聚乙烯吡咯酮,组織胺,聚(乙晞甲醚),聚 (乙烯甲基酮),丙烯醯胺,和1,3-二甲基尿素。1,3-二甲 基尿素和丙醯胺與過氧化氫所形成之複合物為可自由流動的 液體,且在蒸氣相合成法中極易處理,因在取得終產物時少 52 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 訂 經濟部中央揉準局貝工消費合作社印製 經濟部中央標準局負工消費合作社印製 A7 ______________B7_ 五、發明説明() 了須去除溶劑的步驟。组織胺,聚乙烯吡咯酮,聚(乙埽甲 醚)’和聚(乙烯甲基酮)則為樹脂類有黏性的產物,不易處 理。 範例14和15描述了在不同的製備條件下以聚乙烯吡咯 酮來製造一可自由流動之過氧化物複合物固體的研究》 簏例14 聚乙烯p比洛酮與過氧化氫所形成之複合物的製備乃是藉 改變蒸氣相中聚乙埽吡咯酮對過氧化氩濃度的比值來改變聚 乙烯说咯酮複合物中過氧化氫所佔的百分比。這些測試的條 件與範例12中相同,除了將聚乙烯吡咯酮的重量由ig增 加至3g和5g。在所有測試中,過氧化氫濃度均保持在 1 0 m g /每升殺菌室體積。測試結果列於表15。 簏例15 聚乙烯也咯酮與過氧化氫所形成之複合物的製備,其中 所用之過氧化氫乃是由過氧化氫與尿素形成之複合物中釋放 出來的。以此方式所釋出之過氧化氫,幾乎不含任何水分。 在此測試中,將5g的聚乙烯吡咯酮置於反應室中並藉加熱 7 g約3 5 °/。之過氧化氩尿素複合物至1 1 〇 〇c,5分鐘,以傳 送濃度在l〇mg /每升殺菌室體積之過氧化氩至反應室中。 其它的測試條件與範例12中相同。聚乙埽也格明複合物中 過氧化氫的百分比及此複合物之物理狀態列於表丨5中。 (請先閲讀背面之注f項再填寫本頁) 訂 妗、!H202 + 2KI + H2S04 ^ I2 + K2S04 + 2H20 I2 + 2Na2S203 Na2S406 + 2NaI In the iodine-sodium thiosulfate titration reaction, starch is used as an indicator to improve the color change at the end of the reaction. Calculate the weight percentage of hydrogen peroxide with the following equation: wt% H2〇2 = [(Volume of Na2S203, ml) * (Concentration of Na2S203) * 1 · 7] / (gram weight, g) Central Standard of the Ministry of Economic Affairs The weight percentage of argon peroxide in the complex formed by anhydrous glycine and hydrogen peroxide was 2 4.3%. Example Many organic or inorganic compounds of argon peroxide can be prepared by the method described in Example 12. In each preparation, the reaction conditions are the same as those in the paper of Example 12 and the Chinese national standard (CNS) A4 specification (210X297 mm) is applied. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 __B7 V. Description of the invention () Same , Except for the replacement of anhydrous glycine with 1 g of the compounds listed in Table 14.袅 14 Evaluation of compounds and weight percent of over-gasified hydrogen in compounds prepared by gas phase synthesis Chemical name 皋 Structure percentage after oxide treatment Poly (vinyl alcohol) [-CH2CH (OH)- ] n 18.9% ethanol poly (ethylene formazan) [-CH2CH (OCH3)-] n 22.0% ether poly (ethylene methyl ketone) [-CH2-CH (COCH3)-] n 13.9% acetone poly (acrylic acid) [- CH2CH (COOH)-] n 5.1% acid glycine H2C (NH2) (COOH) 20.7% amino acid L-histidine acid [N = CHNHCH = C] CH2CH (NH2) COOH 14.1% amino acid poly (ethylene ethyl ester) [-CH2CH (OCOCH3)-] n 9.1% ester cellulose acetate 10.9% ester sodium alginate 27.7% organic cellulose cellulose sodium sulfate 18.2% organic salt poly (4-acetamidine) [-CH2CH〇 > -C5H4N)-] n 21.8% aromatic amine Histamine [N = CHNHCH = C] CH2CH2 (NH2) 13.2% Alanine (C2H5) CONH2 31.8% Amine urea (H2N2) CO 17.9% Urea 1,3- Dimethylurea (H3C) HNCONH (CH3) 31.7% Urea Bihalide (H3C) CO (NH) CO (NH2) 13.7% Dipyridine Polypropylamidamine [-CH2CH (CONH2)-] n 30.1% Polyfluorene Amine Polypyrrolidinone [-CH2CH (-N (CH2 ) 3CO)-] n 29.9% Polyamide nylon 6 [-NH (CH2) 5CO-] n 17.1% Polyamide nylon 6,6 film [-NH (CH2) 6NHCO (CH2) 4CO-] n 16.6% Poly The amine 51 paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 OX297 mm) (please read the note on the back before filling this page), βτ A7 _B7 V. Description of the invention () 袅 14 (Continued Jing) The chemical name of the chemically treated compound after the oxide treatment. The weight percentage of the chewing polyether polyaminocarbamate [-RHNCOOR '-] n 9.5% Polyurethane methyl ester sodium carbonate is called (: 03 14.3%). Inorganic potassium carbonate K2C03 33.9% Inorganic rhenium carbonate Rb2C03 37.0% Inorganic calcium hydroxide Ca (OH) 2 23.4% Inorganic sodium bicarbonate NaHCOj 10.7% Inorganic pyrolinic acid tetra sodium salt Na4P207 18.9% Inorganic (please read the precautions on the back first) (Fill in this page) The organic complex formed includes the following functional groups capable of forming hydrogen bonds with hydrogen peroxide: alcohols, ethers, ketones, acids, amino acids, esters, organic salts, amines, amidines, polyamines, polyamines Urethane, urea, and biuret. Inorganic complexes include carbonates with sodium, potassium, and sulfonium cations, and sodium bicarbonate. In addition, a complex formed by argon oxidation and tetra sodium pyrophosphate and hydrogen peroxide was also prepared. Except for nylon 6,6 and polyethylene nails, the starting materials are extremely fine powder or slightly larger crystals. Nylon 6,6 is a thin film with a thickness of 0.12 mm, while polyethylene methyl ether is 50. % Aqueous solution. Most of the hydrogen peroxide complexes made with these materials under test are solid, except for polyvinylpyrrolidone, histamine, poly (ethyl methyl ether), poly (ethylene methyl ketone), and acrylamide. , And 1,3-dimethyl urea. The complex formed by 1,3-dimethyl urea, propylamine and hydrogen peroxide is a free-flowing liquid, and it is extremely easy to handle in the vapor phase synthesis method, because there are fewer 52 paper sizes when obtaining the final product Applicable to China National Standard (CNS) A4 specification (210X297 mm) Ordered by the Central Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Consumers ’Cooperative, A7 ______________B7_ 5. Description of the invention () The solvent must be removed A step of. Histamine, polyvinylpyrrolidone, poly (ethyl acetomethyl ether) 'and poly (ethylene methyl ketone) are viscous products of resins and are not easy to handle. Examples 14 and 15 describe the use of polyvinylpyrrolidone to produce a free-flowing peroxide composite solid under different preparation conditions. 簏 Example 14 Composite of polyethylene p-pyrrolidone and hydrogen peroxide The preparation of the compound is to change the percentage of hydrogen peroxide in the polyethylene-pyrrolidone complex by changing the ratio of polypyrrolidinone to argon peroxide concentration in the vapor phase. The conditions for these tests were the same as in Example 12, except that the weight of polyvinylpyrrolidone was increased from ig to 3g and 5g. In all tests, the hydrogen peroxide concentration was maintained at 10 mg per liter of sterilization chamber volume. The test results are listed in Table 15. 15Example 15 Preparation of a complex formed by polyvinylpyrrolidone and hydrogen peroxide, in which the hydrogen peroxide used is released from a complex formed by hydrogen peroxide and urea. The hydrogen peroxide released in this way contains almost no moisture. In this test, 5 g of polyvinylpyrrolidone was placed in a reaction chamber and heated by 7 g of about 35 ° /. The argon peroxide-urea complex was brought to 11000c for 5 minutes to transfer argon peroxide at a concentration of 10 mg / l sterilization chamber volume to the reaction chamber. Other test conditions are the same as in Example 12. The percentage of hydrogen peroxide in the polyethylene terephthalmine compound and the physical state of the compound are listed in Table 5-5. (Please read the note f on the back before filling out this page)
• m 五、發明説明( A7 B7 表1 5 範例14 蓋乙埽也哈化箱逋熗比值鉗 座p物中過巩化氣耳分比及產物之物理狀態的影蜜 複合物中過氧 化氣之重量 J~分比(%) 29.9 23.5 範例1 5 聚乙締》»比略 酮重量(g ) 1 3 5 5 19. 產物之物理狀態 柔軟之黏性物 堅硬之黏性物 自由流動之固體 自由流動之固髏 測試結果顯示可藉控制蒸氣相中聚乙缔峨略酮對過氧化氣 比值,或是,使用幾乎無水的過氧化氳蒸氣來源,可製造 能自由流動之聚乙缔说咯明複合物固雜。 的 出 (請先Μ讀背面之注$項再填寫本頁) 訂 經濟部中央橾準局工消費合作社印製 過氧化氫無機複合物 如上述過氧化氳無機複合物也可當作過氧化 物之殺菌劑。室溫大氣壓下可由這些無機複合物 化物蒸氣。但是,如以下所述,在大氣壓及減磨 無機複合物至一特定釋放溫度也可釋出相當量之 氣。為有效的由無機複合物中釋出過氧化氩蒸氣 無機複合物之加熱速度較好是維持在5 °C/ min 少每分鐘1 〇 °C或5 0 °C / m i η ;最好則是至少每 〇C。 氫有機複合 中釋出過氧 下快速加熱 過氧化氩蒸 ,過氧化物 :更好是至 分鐘1000 -線 54 衣纸張尺度適用中國國家梂準(CNS > A4規格(210X297公釐) 五、發明説明() 表16列出這些無機複合物的-些代表,及過氧化氫重 2分比。較適宜之無機複合物為那些不會分解產生由酸的 物質。因此,特別適合的複合物中須不含由原子。也可以過 氧化物混合物做為過氧化物蒸氣的來源。這類混合物可以是 物理混:物,即混合兩種不同的過氧化物複合物預製 物’或是“化學混合物”,亦即複合物中的化合物在過氧化 物複合物製備前即已混合。 用於複σ物中決定過氧化氫重量百分比的滴定步驟如範 例12中所述。碳酸鈉過氧化氫複合物乃購自福卡化學公司 C F 1 u k a C h e m 1 c a 1 c ο r p .,r 0 n k 〇 n k 〇 m a,Ν γ )。用來合 成過氧化物無機複合物的蒸氣相方法如範例12中所述除 了以10g的固體無機物樣品來取代1_5呂之固體無機物樣 品,並進行兩次循環,而非1次。 範例1 6 液相合成過氧化氫無機複合物的反應步騍如John及其 同僚所述(J · C h e m · S 〇 c .,d a 11。n,1 2 : 2 5 2 6 - 2 5 3 2, 198〇 )。簡言之,先將無機固體溶於3〇0/〇之過氧化氩水溶 液中以形成飽和溶液,接著逐滴加入乙酵•至於草酸鉀和碳 酸铷複合物,當所加入之乙醇漸增時即可形成白色沉澱 碳酸卸’焦磷酸鉀和焦磷酸鈉而言,可將飽和溶液置於 °C下數小時以促進過氧化物複合物結晶的形成。藉真空過濾 將複合物與液體分開,以乙醇清洗至少三次益真空乾燥。 (請先閲讀背面之注意事項再填寫本寅) ir 經濟部中央標準局負工消费合作社印裝 對 10• m V. Description of the invention (A7 B7 Table 1 5 Example 14 Gai Biyao also has a box ratio ratio of perforated gas in the clamp p and the peroxidation gas in the shadow honey complex of the physical state of the product Weight J ~ Fraction (%) 29.9 23.5 Example 1 5 Polyethylene "» Weight of ketalone (g) 1 3 5 5 19. Physical state of the product Soft sticky substance Hard sticky substance Free flowing solid Free-flowing solid skull test results show that by controlling the ratio of polyethylenpeltonone to peroxide gas in the vapor phase, or by using an almost anhydrous source of hafnium peroxide vapor, a free-flowing polyethylene can be produced. The compound is solid. (Please read the note on the back before filling in this page.) Order the hydrogen peroxide inorganic compound printed by the Ministry of Economic Affairs, the Central Bureau of Standards, Bureau of Industrial and Commercial Cooperatives, as described above. Can be used as a germicidal agent for peroxides. These inorganic compound compounds can be vaporized at room temperature and atmospheric pressure. However, as described below, a considerable amount of gas can also be released at atmospheric pressure and by reducing the inorganic compound to a specific release temperature. For effective compounding by inorganic The heating rate of the inorganic compound that releases argon peroxide vapor in the substance is preferably maintained at 5 ° C / min, less than 10 ° C per minute or 50 ° C / mi η, and most preferably at least per 0 C. Hydrogen Organic compound releases fast heating under argon peroxide vaporization under peroxide, peroxide: preferably up to 1000-line 54 paper size applicable to Chinese national standards (CNS > A4 size (210X297 mm) V. Description of the invention () Table 16 lists some of these inorganic composites, and 2 weight ratio of hydrogen peroxide. The more suitable inorganic composites are those that do not decompose to produce acids. Therefore, particularly suitable composites It must not contain atoms. Peroxide mixtures can also be used as a source of peroxide vapor. Such mixtures can be physical mixtures, that is, two different peroxide compound preforms' or "chemical mixtures" ", That is, the compounds in the compound are mixed before the peroxide compound is prepared. The titration procedure used to determine the weight percent of hydrogen peroxide in the complex σ is as described in Example 12. The sodium carbonate hydrogen peroxide compound Forkat Company CF 1 uka C hem 1 ca 1 c rp., R 0 nk nk nk oma, N γ). The vapor phase method used to synthesize the peroxide inorganic composite was as described in Example 12, except that 10 g of solid The inorganic sample was used to replace the solid inorganic sample of 1-5 Lu, and two cycles were performed instead of one. Example 16 The reaction steps for the liquid phase synthesis of hydrogen peroxide inorganic compounds are as described by John and his colleagues (J. C hem Soc., Da 11.n, 12: 2 5 2 6-2 5 32, 198 0). In short, the inorganic solid is first dissolved in a 300/0 argon peroxide aqueous solution to form a saturated solution, and then acetic acid is added dropwise. As for the complex of potassium oxalate and thallium carbonate, when the added ethanol gradually increases, That is to say, a white precipitate of carbonic acid, potassium potassium pyrophosphate and sodium pyrophosphate can be formed. The saturated solution can be placed at ° C for several hours to promote the formation of peroxide complex crystals. The composite was separated from the liquid by vacuum filtration, and washed with ethanol at least three times and dried under vacuum. (Please read the notes on the back before filling in this book) ir Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives
經濟部中央樣準局貞工消费合作社印製 A7 _____B7 五、發明説明() 裊16 複合物中過氧化氫重量百分比及所評估之化合物 化學名稱 化學式 複合物中過氧化氫重量百分比(wt%) 購得物2 蒸氣3 液體3 碳酸鈉 Na2〇〇3 27.35 碳酸鉀 K2C03 7.43 22.70 碳酸铷 Rb2C03 20.31 26.78 草酸鉀 K2C204 16.13 16.42 焦磷酸鈉 Na4P2〇7 11.48 23.49 焦磷酸鉀 K4P2O7 20.90 32.76 正磷酸鈉 Na3p〇4 15.67 正磷酸鉀 K3PO4 16.11 1 .用來決定複合物中過氧化氫重量百分比的滴定步驟如先前專利申請案中所 述。 2·碳酸鈉過氧化氫複合物乃購自福卡化學公司(Fluka Chemica丨c〇rp, Ronkonkoma, NY) ® 3·以蒸氣和液相方法來合成無機複合物e 以一能量差掃描器(DSC)(Model PDSC 2920,ΤΑ and Metler-Toledo Model DSC 2 7HP instruments) 來測定釋出之過氧化氫或此無機過氧化物複合物的分解特 性。在大氣壓及各種真空壓力下,將DSC的加熱速度設定 為l〇°C/ min,溫度範圍則在30 °C至220 t之間。參見第 5圖’DSC包含一樣品室11〇,加熱盤112及壓力控制系 統。壓力控制系統包括一與壓力表116相接之壓力傳送子 114。壓力表116又與一控制器118相接,之後再和壓力 控制閥120相接。壓力傳送子U4與壓力控制閥120及真 ____56__ 本紙張尺度逋用中國鬮家棣準(CNS ) A4规格(210X297公釐) ----------# '-------1T------ (請先閲讀背面之注$項再填寫本頁) 經濟部中央標隼局®C工消費合作社印製 A7 _______B7_____ 五、發明説明() 空幫浦1 2 2之間乃是以液禮相通。 將以上述方法合成之草酸鉀過氧化氫複合物置於DSC 中’並在50 °C至170 t溫度範圍内施以一特定真空壓力。 如第6圖所示’在這樣的d S C條件及樣品盤蓋子只有一個 小洞的情況下’低壓下較利於吸熱反應的進行並可釋出較大 量的過氧化氫’而高壓下則較利於過氧化氫分解之放熱反應 的進行。但是’如第10闽所示,在大氣壓下重復此實驗但 不在盤上加蓋,則只有部分的過氧化物會釋出。因此,對某 些過氧化氮複合物而言,較開放的系統和或減壓可促進過氧 化氫由複合物中釋出。 使用過氧化物之無機複合物來殺菌時,當快速加熱時複 合物的安定性是一個非常關鍵的因素’快速加熱可藉在與過 氧化物之無機組成接觸前先行預熱鋁盤而達成.在使用過氧 化物之無機複合物時,溫度較好是高於8 6 °c。 如上述,最好是能快速加熱過氧化物之無機複合物,亦 即,1 000 °C/min或更快。可藉著讓過氧化物之無機组成與 已先行預熱之鋁盤接觸而達成。第7A圖和第7B圖為一能 達成此種快速加熱過程之較佳實施例,圖中顯示一能將過氧 化物蒸氣注入一關閉狀態下之殺菌室131的裝置125。過 氧化氫無機複合物裝在過氧化物盤132中。此盤132共計 五層:三層CSR包膜,過氧化物複合物粉末和鍍有聚丙烯 的鋁箔。盤132在其邊緣密封的情況下加熱以留住過氧化 物複合物蒸氣。將過氧化物盤1 3 2置於一孔狀銘盤丨3 〇 下,此孔狀鋁盤1 3 0藉鋁連接塊1 4 2與座1 5 〇相接。過氧 ___57_____ 本纸張歧A财SS家鮮(CNS ) A4聽 ( 210X297公嫠)" " (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局貞工消費合作社印裝 A7 _B7_ 五、發明説明() 化物盤1 3 2則以0 -形環1 5 1鬆鬆的加以固定。在引入過氧 化物蒸氣進入殺菌室前,將一個遠離過氧化物盤132之已 加熱鋁製壓板134與鋁盤136相接。箱138中的彈簧(未 畫出)將盤136向下固定在關閉的位置。當室131抽真空 時,箱138也隨著成為真空。盤136位於0 -形環148的 對面,因此可將過氧化物釋出室152與通道158加以分 開。藉由栓144,146,154和156將裝置與殺菌室131 相接並固定。 參見第7B圖,為能使鋁製壓板134往上與過氧化物盤 132相接觸’讓箱138通氣》—旦壓力增加,便會使箱 138往上移’因此推著已加熱鋁製壓板134往上與過氧化 物盤1 3 2相對。在一較佳實施例中,將鋁製壓板1 3 4預熱 至1 7 5 °C ;但其它溫度也可以。過氧化物蒸氣便會穿過 CSR層由粉末中釋出,通過孔狀鋁盤13〇上之孔160,並 進入過氧化物釋出室152。鋁製壓板134往上移動的動作 也會使過氧化物釋出室1 5 2打開,使過氧化物蒸氣能進入 以液體與殺菌室相連之通道158中。 參見第8囷,圖中顯示殺菌室17〇中含許多互成直角的 玻璃 #干 172 ° 將含振 _ 桿菌jiearoi/ierwo- 之不銹鋼刀片174和176分別置於菌室170的底 部及上方。顯示於殺菌室170右方的是用來加熱過氧化氫 複合物之裝置178,例如焦磷酸鈉(Na4P2〇7 . 3H2〇2) 和草酸鉀(K2C204 . h202)之過氧化氫複合物。裝置 178包括位於殺菌室17〇底部之派瑞氏(pyrex)碗 本紙張咖用中國國家^cNS ) A4^训咖公着) (請先閲讀背面之注$項再填寫本頁)Printed by A7 _____B7, Zhengong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () 重量 16 Weight percent of hydrogen peroxide in the compound and the chemical name of the compound being evaluated. Purchase 2 Vapor 3 Liquid 3 Sodium Carbonate Na2OO3 27.35 Potassium Carbonate K2C03 7.43 22.70 Rhenium Carbonate Rb2C03 20.31 26.78 Potassium Oxalate K2C204 16.13 16.42 Sodium Pyrophosphate Na4P2〇7 11.48 23.49 Potassium Pyrophosphate K4P2O7 20.90 32.76 Sodium Orthophosphate Na3p〇4 15.67 Potassium orthophosphate K3PO4 16.11 1. The titration procedure used to determine the weight percent of hydrogen peroxide in the complex is as described in the previous patent application. 2. The sodium carbonate hydrogen peroxide complex was purchased from Fluka Chemica Corp, Ronkonkoma, NY. 3. The vapor and liquid phase methods were used to synthesize the inorganic compound. An energy difference scanner ( DSC) (Model PDSC 2920, TA and Metler-Toledo Model DSC 2 7HP instruments) to determine the decomposition characteristics of the released hydrogen peroxide or this inorganic peroxide complex. Under atmospheric pressure and various vacuum pressures, the DSC heating rate is set to 10 ° C / min, and the temperature range is between 30 ° C and 220 t. Referring to Figure 5, the DSC includes a sample chamber 110, a heating plate 112, and a pressure control system. The pressure control system includes a pressure transmitter 114 connected to a pressure gauge 116. The pressure gauge 116 is connected to a controller 118 and then to the pressure control valve 120. Pressure transmission sub U4 and pressure control valve 120 and true __56__ This paper size is in accordance with China National Standard (CNS) A4 (210X297 mm) ---------- # '----- --1T ------ (Please read the note on the back before filling in this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs® C Industrial Consumer Cooperative A7 _______B7_____ V. Description of the invention () Air pump 1 2 2 The communication is through liquid rituals. The potassium oxalate hydroperoxide complex synthesized in the above manner was placed in DSC 'and a specific vacuum pressure was applied in a temperature range of 50 ° C to 170 t. As shown in Figure 6, 'Under such d SC conditions and the sample pan cover has only a small hole,' the endothermic reaction is more favorable at low pressure and a larger amount of hydrogen peroxide can be released ', and it is more favorable at high pressure. The exothermic reaction of decomposition of hydrogen peroxide proceeds. However, as shown in Fig. 10, if this experiment is repeated at atmospheric pressure without covering the plate, only a part of the peroxide will be released. Therefore, for some nitrogen peroxide compounds, a more open system and / or reduced pressure can promote the release of hydrogen peroxide from the compound. When using the inorganic compound of peroxide to sterilize, the stability of the compound is a very critical factor when heating rapidly. 'Fast heating can be achieved by preheating the aluminum pan before contacting the inorganic composition of the peroxide. When using a peroxide-containing inorganic composite, the temperature is preferably higher than 8 6 ° c. As described above, it is preferable that the inorganic compound capable of rapidly heating the peroxide, that is, 1 000 ° C / min or faster. This can be achieved by contacting the inorganic composition of the peroxide with a pre-heated aluminum pan. Figures 7A and 7B show a preferred embodiment capable of achieving such a rapid heating process. The figure shows a device 125 capable of injecting peroxide vapor into a closed sterilization chamber 131. The hydrogen peroxide inorganic compound is contained in a peroxide disc 132. This plate 132 has five layers: three layers of CSR coating, peroxide compound powder, and aluminum foil coated with polypropylene. The disc 132 is heated with its edges sealed to retain the peroxide compound vapor. The peroxide plate 1 3 2 is placed under a hole-shaped name plate 3 0. The hole-shaped aluminum plate 1 3 0 is connected to the seat 1 5 0 by an aluminum connection block 1 4 2. Peroxide ___57_____ This paper is different from A, SS, and Household (CNS) A4 (210X297 gong) " " (Please read the precautions on the back before filling out this page) Order by the Central Standards Bureau of the Ministry of Economic Affairs Printing A7 _B7_ V. Description of the invention () The compound plate 1 3 2 is loosely fixed with a 0-shaped ring 1 5 1. Before peroxide vapor is introduced into the sterilization chamber, a heated aluminum platen 134 away from the peroxide plate 132 is connected to the aluminum plate 136. A spring (not shown) in the box 138 holds the disc 136 down in the closed position. When the chamber 131 is evacuated, the box 138 also becomes a vacuum. The disk 136 is located opposite the 0-ring 148, so that the peroxide release chamber 152 can be separated from the channel 158. The device is connected to the sterilization chamber 131 by means of the plugs 144, 146, 154, and 156 and fixed. Referring to FIG. 7B, in order to allow the aluminum platen 134 to contact the peroxide disc 132 upwards, "let the box 138 vent"-once the pressure increases, it will move the box 138 upwards. Therefore, the heated aluminum platen is pushed 134 upwards is opposite the peroxide disk 1 3 2. In a preferred embodiment, the aluminum platen 1 3 4 is preheated to 17 5 ° C; however, other temperatures are also possible. The peroxide vapor passes through the CSR layer and is released from the powder, passes through the hole 160 in the porous aluminum plate 130, and enters the peroxide release chamber 152. The upward movement of the aluminum pressure plate 134 will also open the peroxide release chamber 152, so that the peroxide vapor can enter the passage 158 connected to the sterilization chamber by the liquid. Referring to Fig. 8A, the figure shows that the sterilization chamber 17o contains many glasses at right angles to each other. #Stem 172 ° Stainless steel blades 174 and 176 containing vibrio_bacteria jiearoi / ierwo- are placed at the bottom and above the bacterial chamber 170, respectively. Shown to the right of the sterilization chamber 170 is a device 178 for heating a hydrogen peroxide complex, such as a hydrogen peroxide complex of sodium pyrophosphate (Na4P207. 3H2O2) and potassium oxalate (K2C204.h202). The device 178 includes a pyrex bowl located at the bottom of the sterilization room 170. The paper coffee is made in China ^ cNS) A4 ^ training coffee (by reading the note on the back before filling this page)
經濟部中央橾準局貝工消费合作社印製 Α7 Β7 五、發明説明() 180。派瑞氏碗180之上則是一派瑞氏盤182。在派瑞氏 盤182上則是一內含加熱墊186之鋁盤184 ^過氧化物複 合物裝於鋁盤184中。加熱墊186上連接了電線188而招 盤184上則接了熱藕190。刀片174則置於鋁盤U4上方 兩英忖之處。 在某些實施例中,過氧化氫複合物乃是以單獨的封入物 形式來提供,此封入物則藉液體和盛裝欲殺菌物體之容器相 通。封入物和容器中的壓力可以相同也可以不同。封入物中 正差壓可促進過氧化物蒸氣由封入物中的過氧化物複合物中 釋出進入殺菌容器内。此種正差壓對大容器,例如整個房 間,而言特別有用。 在另一較佳實施例中,將粉末式的過氧化物複合物塗在 一黏性表面。較適宜之黏性表面包括高溫感黏性膠帶如 A10 和 A125 黏性勝帶(3M Corp.,Minneapolis, MN)。再以第3A,7A和8圓之裝置來加熱這些塗有粉末 式的過氧化物複合物之黏性膠帶以促進過氧化物的釋出。 參見第9圖,將含過氧化複合物粉末202之高溫感黏性 膠帶200置於鋁箔層204之上》黏性膠帶層200上再加上 一或多層CSR層206。可以個別物質之單張,或所有物質 形成之捲來作這樣的排列。 範例17和18中用來決定釋出之過氧化物量和殺菌效果 之過氧化物無機複合物乃是焦磷酸鉀(K4P2O7 . 3H2°2 : pp),草酸奸(K2C2O4 . H2〇2 ; P〇)和碳酸 鈉(Na2C03 · 1 ·5Η202 : SC )。 _59_ 本紙張又度適用中國國家標準(CNS ) Α4规格(2丨0 χ 297公釐) (請先聞讀背面之注f項再填寫本頁) 、?! 级 發明説明( 經濟部中央標準局貝工消费合作社印装 篪例 由sc ’ P0* PP中釋出過氧化物 以DSC來決定由SC,P0和pp中釋出過氧化氫之理 想溫度。以75L殺菌室及第7〜B固中的裝置在各種溫 度下測定由2g這類複合物中所釋出之過氧化氫的實際量。 pp所釋出之過氧化氣要高^由sc * p〇中所 釋出之量。雖然在l75t下由Sc中所釋出之過氧化氣量最 少’但諸品量増加時’可顯著提高所釋出之過氧化氮量。 表Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs Α7 Β7 V. Description of Invention () 180. Above Perry's Bowl 180 is a Perry's Plate 182. On the Parrish disk 182 is an aluminum disk 184 containing a heating pad 186. The peroxide compound is contained in the aluminum disk 184. An electric wire 188 is connected to the heating pad 186 and a thermal paddle 190 is connected to the signboard 184. The blade 174 is placed two inches above the aluminum plate U4. In some embodiments, the hydrogen peroxide compound is provided in the form of a separate enclosure, and the enclosure is in communication with the container containing the object to be sterilized by the liquid. The pressure in the enclosure and the container may be the same or different. Positive differential pressure in the enclosure promotes the release of peroxide vapor from the peroxide compound in the enclosure into the sterilization container. This positive differential pressure is particularly useful for large containers, such as the entire room. In another preferred embodiment, a powdered peroxide compound is applied to a sticky surface. More suitable adhesive surfaces include high temperature adhesive tapes such as A10 and A125 adhesive tapes (3M Corp., Minneapolis, MN). The devices 3A, 7A and 8 were used to heat the adhesive tape coated with the powder type peroxide compound to promote the release of peroxide. Referring to Fig. 9, a high-temperature adhesive tape 200 containing a peroxide compound powder 202 is placed on the aluminum foil layer 204. The adhesive tape layer 200 is then added with one or more CSR layers 206. This can be done as a single sheet of material or as a roll of all materials. The inorganic peroxide complexes used in Examples 17 and 18 to determine the amount of peroxide released and the bactericidal effect are potassium pyrophosphate (K4P2O7. 3H2 ° 2: pp), oxalate (K2C2O4. H2〇2; P〇 ) And sodium carbonate (Na2C03.1.5.202: SC). _59_ This paper is again applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 χ 297 mm) (Please read the note f on the back before filling out this page),?! Grade invention description (Central Bureau of Standards, Ministry of Economic Affairs) The example of the printing of the Cooper Consumer Cooperative is the ideal temperature of the release of hydrogen peroxide from SC, P0 and pp. The ideal temperature of the release of hydrogen peroxide from SC, P0 and pp is determined by DSC. The 75L sterilization chamber and the 7th ~ Bth solid The device at various temperatures measures the actual amount of hydrogen peroxide released from 2g of this type of compound. The peroxide gas released from pp is higher ^ the amount released from sc * p0. Although At l75t, the amount of peroxide gas released from Sc is the smallest, but when the product quantity is added, the amount of nitrogen peroxide released can be significantly increased.
75L殺菌室中所含之釋出 SC 释出過氧化IL之SL度 的過氧化氫量 EQ E£ (以DSC決定) 170°C 150°c 130°C 2g樣品 在125°C下 0.3mg/L 〇.8mg/L l.Omg/L 在150°C下 1.2mg/L 2.〇mg/L 1.5mg/L 在175°C下 1.8mg/L 2.5mg/L 3.4mg/L 3g樣品 在175°C下 2.3mg/L 4g樣品 在175°C下 2.9mg/L 本紙張尺度適用中國國家糅準(CNS ) A4規格(210X297公釐) ^0 訂 線-(請先聞讀背面之注意事項再填寫本頁) A7 B7 五、發明説明() 麄例1 « 以SC,P0和PP所進行之效率測試 將 2 χ 1〇6 枯草桿菌芽胞(βα£Μ·ΠΜί75L sterilization chamber contained SC released peroxide SL released hydrogen peroxide amount EQ E £ (based on DSC) 170 ° C 150 ° c 130 ° C 2g sample at 125 ° C 0.3mg / L 0.8 mg / L 1.0 mg / L 1.2 mg / L 2.0 mg / L 1.5 mg / L at 150 ° C 1.8 mg / L 2.5 mg / L 3.4 mg / L 3 mg sample at 175 ° C 2.3mg / L 4g sample at 175 ° C 2.9mg / L at 175 ° C This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) Please fill in this page again) A7 B7 V. Description of the invention () Example 1 «The efficiency test with SC, P0 and PP will be 2 χ 106
Mked)接種在不銹鋼刀片上。將三個接種了的刀片分別 置於以SPUNGARD包復之10英吋x 21英吋χ 3 5英吋 聚苯烯氧盤之前方,中間及後端。之後再將包覆住的盤子放 在75L初壓為0.2托之真空殺菌室中β以熱將sc,SO或 pP之無機過氧化物粉末封在三層SPUNGARD和一層有聚 丙晞薄膜之鋁箔上以形成一 5.5英吋的過氧化物盤。藉著讓 此盤與一已預熱至1 7 5 t的鋁盤接觸2分鐘使過氧化物釋 出’接著使其擴散8分鐘使總曝露時間達10分鐘》處理 後,將三個刀片分別置於胰蛋白酵素黃豆培養基中,並在 32 °C下培養7天並觀察細菌生長的情形,結果總結於表18 中。 表18 效率測試結果 (請先聞讀背面之注意ί項再填寫本頁)Mked) inoculated on stainless steel blades. The three inoculated blades were placed in front of, in the middle of, and at the rear end of a 10-inch x 21-inch x 3 5-inch polystyrene oxygen disk covered with SPUNGARD. After that, the coated plate was placed in a 75L vacuum sterilization chamber with an initial pressure of 0.2 Torr, β, and the inorganic peroxide powder of sc, SO or pP was sealed on three layers of SPUNGARD and a layer of aluminum foil with polypropylene film. To form a 5.5-inch peroxide disc. By contacting this disk with an aluminum plate that has been preheated to 175 t for 2 minutes to release the peroxide, and then allowing it to diffuse for 8 minutes to achieve a total exposure time of 10 minutes, "the three blades were treated separately. It was placed in trypsin soy medium and cultured at 32 ° C for 7 days to observe the growth of bacteria. The results are summarized in Table 18. Table 18 Efficiency test results (please read the note on the back before filling this page)
>1T 線 經濟部中央橾準局貝工消费合作社印裝 過氧化物 複合物 複合物 殺菌力(正反應 複合物 重量 濃度 /樣品總教、 ΡΡ 2g 3.4 m g / L 0/3 ΡΟ 2g 2.5 m g / L 0/3 SC 2g 1 . 8 m g/L 1/3 SC 3g 2.3 m g / L 0/3 SC 4g 2 · 9 m g / L 0/3 __61 本紙張錢制t目S家樣準(CNS )八4祕(210X297公釐) 經濟部中央標準局貝工消費合作社印裝 A7 _ B7 五、發明説明() 如表18所示,除了 2gSC(l/3)組外,其餘各組均未觀 察到有細菌生長的跡象。但是,當SC的使用量増加至3g 時,便沒有細菌生長的現象了。這些結果顯示以過氧化氣無 機複合物的殺菌效力。 過氧化氫之無機複合物能被輕易的併入上述以有機過氧 化氫複合物來殺菌之殺菌步驟中。例如,可將無機複合物與 電漿殺菌法一同使用,或與能自我殺菌之封入物—同使用, 其中過氧化物能緩慢的自該封入物内之複合物中釋出。同樣 的,無機複合物也可用於具有狹長内室物趙的殺菌,其中該 内室乃與含有此無機過氧化物複合物的容器相通。此外,也 可使用壓力脈衝使蒸氣自無機過氧化物複合物中釋出.在參 考了本發明之特定範例後,其它以無機過氧化物複合物來殺 菌的範例對本領域習知技藝的人士而言,將是顯而易見的。 磷酸鹽和濃縮之磷酸過氣化物複合物之合成 表19中總結了某些磷酸鹽和濃縮之磷酸過氧化物複合 物,與本文中提到的合成方法。一般來說,這些複合物的合 成可藉混合磷酸鹽與過氧化氫水溶液(將固體加至過氧化物 水溶液中或將過氧化物水溶液加於固體上)來完成。由於反 應產生的熱可能導致過氧化氫的分解,因此嘗試著藉緩慢混 合固體與過氧化物水溶液或使用低溫(亦即,0 °C )過氧化 物水溶液來控制反應溫度。也可藉溶解磷酸鹽水合物或溶於 過氧化物水溶液中之濃縮磷酸鹽來形成過氧化物複合物。 ----- 62 本紙張尺度適用中國國家標準(CNS > M規格(2ΐ〇χ297公釐) ---------C------1T------^ (請先閲讀背面之注意事項再填寫本頁) 五、發明説明()> 1T Printed Peroxide Complex Complex Bactericidal Complex (Positive Concentration / Concentration of Samples, PP 2g 3.4 mg / L 0/3 ΡΟ 2g 2.5 mg / L 0/3 SC 2g 1. 8 mg / L 1/3 SC 3g 2.3 mg / L 0/3 SC 4g 2 · 9 mg / L 0/3 __61 This paper is made of t-membrane S household samples (CNS) Eighty-fourth secret (210X297 mm) printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 _ B7 V. Description of the invention () As shown in Table 18, except for the 2gSC (l / 3) group, the other groups were not observed There are signs of bacterial growth. However, when the amount of SC used is increased to 3g, there is no bacterial growth. These results show the bactericidal effect of the inorganic compound with peroxide gas. The inorganic compound of hydrogen peroxide can be Easily incorporated into the sterilization steps described above with organic hydrogen peroxide compounds for sterilization. For example, inorganic compounds can be used with plasma sterilization, or with enclosures that can self-sterilize—with the use of peroxides. Can be slowly released from the compound in the enclosure. Similarly, no The organic compound can also be used for sterilization of Zhao with a narrow inner chamber, where the inner chamber is in communication with a container containing the inorganic peroxide compound. In addition, pressure pulses can also be used to make steam from the inorganic peroxide compound After referring to the specific examples of the present invention, other examples of sterilization with inorganic peroxide compounds will be apparent to those skilled in the art. Phosphate and concentrated phosphate overgas compound Synthesis of certain compounds Table 19 summarizes certain phosphate and concentrated phosphate peroxide complexes with the synthetic methods mentioned in this article. Generally speaking, the synthesis of these complexes can be achieved by mixing phosphate with an aqueous hydrogen peroxide solution. (Add the solid to the aqueous solution of peroxide or add the aqueous solution of peroxide to the solid). Because the heat generated by the reaction may cause the decomposition of hydrogen peroxide, try to slowly mix the solid with the aqueous solution of peroxide or A low temperature (ie, 0 ° C) aqueous peroxide solution is used to control the reaction temperature. It can also be dissolved in phosphate hydrate or in peroxide water. Concentrated phosphate in the liquid to form a peroxide complex. ----- 62 This paper size applies the Chinese National Standard (CNS > M Specification (2ΐ〇χ297mm) --------- C ------ 1T ------ ^ (Please read the notes on the back before filling out this page) 5. Description of the invention ()
A B 經濟部中央標準局貝工消費合作社印装 裊19 起始物 合成 化學式 參考文獻 固體 過氧化氫 265% 緩慢的將Na2P207加至過氧 化氫水溶液中以將溫度控制 在低於50°C Na2P2〇7 · ΝΗ2〇2 n=2,3 或 更高 1 Na^P 2〇7 250% 使3莫耳5〇%H2〇2與1莫耳 Na4P2〇7反應,低溫下於流 床上乾燥 Na4P2〇7 · 3H2〇2 2 Na4P207 . ioh2o2 30-90% 將 Na4P2〇7 · 1〇H2〇2 加至 H2〇2溶液中並於20°C下真 空乾燥 Na4P2〇7 3H2〇2 3 Na3P04 12H2〇2 30% 將 Na3P〇4 . 12H2〇2 加至 H2〇2溶液中並於2〇°C下真 空乾燥 NajPO^ · 5H2〇2 4 Na2HP04 • 12H202 4-76% 將 Na2HP04.12H2〇2 加至 H2〇2溶液中並於20°C下真 空乾燥 Na2HP04 NH2〇2 n=l,2 4 Na5P3〇,〇 60% 在流床上於40-50 °C下將 出〇2溶液喷在NajP^OlO 上,之後在流床上乾燥 Na5p3°10 _ NH2〇2 n<l 5 K3P〇4 · 7H2〇2 65-70% 〇°c下於h2〇2溶液中溶解 Κ3Ρ04.7Η2〇2,並使溫度 保持在低於70°C K3PO4 · NH2〇2 n=l,2,4 6 K4P2〇7 60-90% 將K4P2〇7加至H2〇2溶液 中以維持溫度低於50°C ·結 果顯示當使用大量起始物 (亦即’ 174g)時,此方法 無法形成任合複合物· K4P2O7 * NH2O2 n=5.35,7 7 1. Richmond, Howard, PCT Publication No. WO 95/05431 63 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -----IT------0 (請先閲讀背面之注f項再填寫本頁) 經濟部中央橾準局貝工消費合作社印製 A7 B7 五、發明説明() 2. Xiao et al., Faming Zhuanli Shenging Gongkai Shoumingshu, CN 1,097,798, 25 Jan 1995. 3. Titova et al. Russ. J. Inorg. Chem. 40(3):384 (1995) 4. Titova et al· Russ. J. Inorg. Chem. 39(5):7544 (1994) 5. Kudo, I., Japan Kokai, (C1.C01B), Aug. 29, 1975, Appl. 74 15,389, Feb. 08, 1974. 6. Kirsanova, M.P., Bogdanov, G.A., Dymova, Z. N., Safonov, V. V., Izv. Vyssh. Ucheb. Zaved. Kjim. Khim. Tekhnol. 15(2):183-6 (19752). 7. Majewski, H.W., U.S. Patent No. 3,650,750. 噴灑法 以類似文獻中所描述之方法來決定以本方法製備磷酸鹽 及濃縮磷酸鹽之難易程度及其限制。一般來說,是以將過氧 化物溶液均勻的喷灑在鹽類固體上,並真空乾燥來製備複合 物。表2 0總結以此喷激法所合成之複合物^ N a 4 P 2 〇 7 · 3H2〇2無法以3〇%H2〇2來製備,這點與先前文獻中所述 相同。K3P〇4過氧化物複合物無法藉著在室溫下直接將過 氧化氫溶液加至無水Κ 3 Ρ Ο 4固體上來製備。詳細的合成條 件參見以下範例21至3 6。 64 本紙張尺度適用中國國家梯準(CNS ) Α4規格(210X297公釐) ^1ί1τ'^-- (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央橾準局貝工消費合作社印製 紙 本 發明説明( A.20 起始物 合成 化學式 範例 固體 過氧化氳 Na< 卩2〇7 >50% 將過氧化氩水溶液喷灑 在Na4P2〇7固體上 n»4p2°7 . nh2°2 n = 3, 或更高 丨 ----Ί. 21-27 Na4P2〇7 3 0% 脖過氧化氫水溶液喷灑 在Na4P2〇7固體上 Ν^4Ρ2〇7 · ΝΗ2Ο2 π<—2 26 Na3P〇4 3 0 - 7 0 % 將過氧化氫水溶液嘖灑 在Na3P〇4固體上 Na3P04 · 5Η2〇2 28 Na2HP04 3 0 - 7 0 % 將過氧化氩水溶液噴灑 在Na2HP04固體上 Na2HP〇4 · ΝΗ2Ο2 η=1,2 29 Na5P3O10 3 0 - 7 0% 將過氧化氩水溶液喷灑 在Na5P30丨〇固體上 Na5p3°10 * ΝΗ2Ο2 η~ 1 >2 3 0 k3P04 5 9% 無過氧化氩水溶液嘖灑 在k3P04固體上 無複合物產生 3 1 k4p2〇7 5 9 - 7 0 % 將過氧化氩水溶液喷灑 在Κ4Ρ207固體上 Κ4Ρ2°7 * ΝΗ2〇2 η=4-7 32 K2HP〇4 5 9% 將過氧化氩水溶液嘖灑 在Κ2ΗΡ〇4固體上 Κ2ΗΡ〇4 3·15Η202 3 3 KH2P〇4 5 9% 將過氧化氫水溶液喷灑 在ΚΗ2Ρ〇4固體上 ΚΗ2Ρ〇4 1Η2〇2 3 4 Ca2?2〇7 5 9% 將過氧化氩水溶液喷灑 在Ca2P2〇7固體上 Ca2P2°7 3.42Η2〇2 3 5 Mg2p2°7 5 9% 4過氧化氩水溶液嘖灑 在Mg2P2〇7固體上 Mg2p2〇7 4.60Η2〇2 36 以浚體噴灑方法來合成Na4P?〇7 · nH9〇9 一般而言,焦磷酸鈉與過氧化氫所形成之無水複合物乃 是以液體噴灑方法加上真空和或乾燥來合成。在以液艏噴激 65 JL通用中國國家樣準(CNS ) A4規格(210X297公釐) (请先聞讀背面之注$項再填寫本貫) 經濟部中央橾準局貝工消费合作社印製 A7 ______ —__Β7_ 五、發明説明() ~ '' 方法來製備焦磷酸鈞與過氧化氩之複合物時,可改變許多參 數,詳見以下範例21-27❶將濃縮之過氧化氫溶液(3〇_ 9 0%)逐滴喷灑於焦磷酸衲(98%,阿得里奇化學公司)上。 讓混合物l〇C,25°C,或45。(:下培育1_6小時,接著在 25t-6(TC下作真空乾燥或在60〇C下以烘箱進行乾燥在 以下範例中’改變過氧化氫濃度,開始時過氧化氫與 Na4P207之莫耳比,固液比,培育時間及溫度,乾燥形 式’乾燥溫度及起始物量來決定它們對產物組成的效果β 範例2 1至2 3顯示在2 5 °C下反應2小時後,乾燥方法 (分別為30°C下真空乾燥,60°C下真空乾燥,和在60°C 下以烘箱進行乾燥)對所得複合物之最終過氧化氩重量百分 比的影響。 範例2 4顯示2 5 °C下真空乾燥時反應時間的影響❹結果 顯示1小時的反應時間已足以形成焦嶙酸鈉與過氧化氮比值 為1 : 3之複合物。 範例2 5顯示反應溫度對形成過氧化物複合物的影響。 結果顯示當使用少量起始物時,仍可在低於45t的溫度下 形成焦磷酸鈉與過氧化氣比值為1:3之複合物。 範例26顯示過氧化氩濃度對以液體喷灑方法製備之過 氧化物複合物組成的影響。如表21所示,當30 % H2〇2被 噴灑在焦磷酸鈉固體上時,即使開始時之H2〇2輿SP比例 為1:4,所得複合物Na4P2〇7 . 1.64H2〇2之H2〇2與 SP比例仍低於2:1 (雙過氧水合物,bis-peroxyhydrate )。當H2〇2濃度高於45%,較好是高於50%,可行成三 _______66__—___ 一 I紙張尺度逋用中國國家揉準(CNS ) A4規格(210X297公釐) ~" I 裝-'、-----訂------線! Γ, ' (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明() 過氧水合物(tris-peroxyhydrate ,N a 4 P 2 〇 7 . 3H2〇2 ) 。h2〇2 與 SP 比例為 4:1 之 Na4P2〇7 . 4H2〇2 ’其組成僅在低於60°C的溫度下才安定。 範例27顯示當所用大量之Na4P2〇7時,無法以液體 喷灑方法來製備焦磷酸鈉三過氧水合物複合物β 範例21 3〇 °C下真空乾燥 H2〇2 (59%)與焦磷酸鈉以固液比為1:0.8,1:0.9 和1 : 1 . 1之重量比例加以混合,在2 5 °C下反應2小時後, 在30 eC下真空乾燥4小時或30。(:下真空乾燥4小時後接著 在6 0 °C下乾燥1 5小時。所得產物之產率8 4 %至9 9 %的範 圍内。結果總結於表2 1中® (請先閲讀背面之注項再填寫本頁) -訂 經濟部中央橾準局貝工消費合作社印褽 表2 1 起始化合物 25°C 下 產物重 H2〇2之重量百分比 之反應 量 時間 SP 59%¾ H2〇2/S 30°C 下 30°C下真空乾燥4 〇2 Ρ莫耳 真空乾 小時加60°C下乾 數比 燥 燥15小時 (g) (g) (g) 4小時 密閉1 開放2 l〇g 8g 3.7 2小時 13.5 26.81 26.11 26.18 l〇g Η 4.2 2小時 13.9 27.75 26.95 26.98 l〇g Hg 5.1 2小時 11.7 27.75 26.61 26.88 67 線 尺 紙 不 準 揉 冢 明 明 r 州 Λ 釐 公 97 五、發明説明( A7 B7 1. 在密閉狀況下’複合物乃是置於一密閉有蓋之塑膠瓶中; 2. 在開放狀況下’複合物乃是置於一開放的培養皿中。 簏例2 2 60 °C下真空乾燥 Η 2 Ο 2 ( 5 9 % )與焦磷酸鈉以固液比為j : 〇 8 , 1 : 〇 9 和1:1.1之重量比例加以混合,在25r下反應2小時後, 在6 0 °C下真空乾燥4小時。結果總結於表2 2中。 $ 中 央 揉 準 局 貝 J. 合 作 社 印 表22 Μ :始化合物 反應 時間 反應 溫度 H2〇2之重量百分比 SP 59% H2〇2 H2O2/ SP莫 耳數比 60°C下真空 乾燥 6(TC下其空乾 燥4小時加60 。(:下乾燥15小 時 (g) (g) (小時) ICC) 4小時 1開放 10 8 3.7 2 25 26.54 25.53 10 9 卜4.2 2 25 26.92 26.38 10 11 5.1 2 25 26.83 26.28 Jfe»j 2 3 6 0 °C下以烘箱乾燥 Η 2 〇 2 ( 5 9 % )與焦磷酸鈉以固液比為j : 〇 8,1 : 0 . S 和1 : 1 · 1之重量比例加以混合,在2 5 °c下反應.2小時後, 在6 0 °C下以烘箱乾燥6或2 1小時。結果總結於表2 3中。 ___68 本紙張尺度遑用中國國家橾準(CNS ) A4規格(210X297公釐) ---------#0-----1T------線 (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明() 表23 起始化合物 反應 時間 反應 溫度 H2〇2之重量百分比 SP 59% H2〇2 H2O2/SP 莫 耳數比 60°C下以烘箱乾燥 (g) (g) (小時) (°C) 6小時 21小時 10 8 3.7 2 25 27.22 26.83 10 9 4.2 2 25 27.10 26.87 10 11 5.1 2 25 29.57 26.74 (請先閲讀背面之注意事項再填寫本頁) 範例24 反應時間的影響 Η 2 〇 2 ( 5 9 % )與焦磷酸鈉以固液比為1 : 0 · 8之重量比 例加以混合,分別在2 5 °C下反應1,2,1 6小時並在2 5 °C 下真空乾燥4小時。結果總結於表2 4中。AB Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives. 19 Starter Synthesis Chemical Formula References Solid hydrogen peroxide 265% Slowly add Na2P207 to the aqueous hydrogen peroxide solution to control the temperature below 50 ° C Na2P2. 7 · ΝΗ2〇2 n = 2, 3 or higher 1 Na ^ P 2 07 250% react 3 Molar 50% H2O2 with 1 Molar Na4P2 07, dry Na4P2 0 on a flow bed at low temperature 3H2〇2 2 Na4P207 .ioh2o2 30-90% Na4P2〇7 · 10H2〇2 was added to the H2O2 solution and dried under vacuum at 20 ° C Na4P2 07 3H2 2 3 Na3P04 12H2 2 2 30% Add Na3P04.12H2O2 to the H2O2 solution and vacuum dry NajPO ^ at 20 ° C ^ 5H2O2 4 Na2HP04 • 12H202 4-76% Add Na2HP04.12H2O2 to the H2O2 solution Na2HP04 NH2〇2 n = 1, 2 4 Na5P3 0, 60% in a vacuum bed at 20 ° C. Spray the solution of Na2P04 on NajP ^ OlO at 40-50 ° C on a flow bed, and then Dry Na5p3 ° 10 _ NH2〇2 n < l 5 K3P〇4 · 7H2〇2 65-70% 〇3c in a h2O2 solution to dissolve KK3PO04.7Η2 02, and keep the temperature below 70 ° C K3PO4 NH2〇2 n = 1, 2,4 6 K4P2 07 60-90% K4P2 07 was added to the H2O2 solution to maintain the temperature below 50 ° C. The results show that when a large amount of starting material (i.e. ' 174g), this method cannot form any composites. K4P2O7 * NH2O2 n = 5.35,7 7 1. Richmond, Howard, PCT Publication No. WO 95/05431 63 This paper is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) ----- IT ------ 0 (Please read the note f on the back before filling this page) Printed by A7 B7, Shellfish Consumer Cooperative, Central Procurement Bureau, Ministry of Economic Affairs ) 2. Xiao et al., Faming Zhuanli Shenging Gongkai Shoumingshu, CN 1,097,798, 25 Jan 1995. 3. Titova et al. Russ. J. Inorg. Chem. 40 (3): 384 (1995) 4. Titova et al · Russ. J. Inorg. Chem. 39 (5): 7544 (1994) 5. Kudo, I., Japan Kokai, (C1.C01B), Aug. 29, 1975, Appl. 74 15,389, Feb. 08, 1974. 6. Kirsanova, MP, Bogdanov, GA, Dymova, ZN, Safonov, VV, Izv. Vyssh. Ucheb. Zaved. Kjim. Khim. Tekhnol. 15 (2): 183-6 (19752). 7. Majewski, HW, US Patent No. 3,650,750. Spraying method is similar in the literature The method described is determined to present a process for preparing phosphates and phosphate was concentrated and restrict the degree of difficulty. Generally, the composite is prepared by uniformly spraying a peroxide solution on a salt solid and drying it under vacuum. Table 2 summarizes the complexes synthesized by this spray method ^ Na 4 P 2 0 7 · 3H2O2 cannot be prepared at 30% H2O2, which is the same as described in the previous literature. The K3P04 peroxide complex cannot be prepared by directly adding a hydrogen peroxide solution to an anhydrous K 3 P 0 4 solid at room temperature. For detailed synthesis conditions, see Examples 21 to 36 below. 64 This paper size applies to China National Standards of Standards (CNS) Α4 (210X297 mm) ^ 1ί1τ '^-(Please read the precautions on the back before filling out this page) A7 B7 Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Printed paper Description of the invention (A.20 Example of the chemical formula of the starting material solid 氲 Peroxide Na < 卩 2 07 > 50% Spray an argon peroxide aqueous solution on the Na4P207 solid n »4p2 ° 7. Nh2 ° 2 n = 3, or higher 丨 ---- Ί. 21-27 Na4P2〇7 3 0% neck hydrogen peroxide solution is sprayed on Na4P2〇7 solid N ^ 4P2〇7 · ΝΗ2Ο2 π < -2 26 Na3P 〇4 3 0-70% Aqueous hydrogen peroxide solution was sprayed on Na3P〇4 solid Na3P04 · 5Η2〇2 28 Na2HP04 3 0-7 0% Aqueous argon peroxide solution was sprayed on Na2HP04 solid Na2HP〇4 · Ν 2Ο2 η = 1,2 29 Na5P3O10 3 0-7 0% Spray an aqueous solution of argon peroxide on Na5P30 丨 Solid Na5p3 ° 10 * ΝΗ2Ο2 η ~ 1 > 2 3 0 k3P04 5 9% non-argon peroxide solution is sprayed on No complex on k3P04 solids 3 1 k4p2〇7 5 9-70% Sprayed with argon peroxide solution on K4P207 solids 4Ρ2 ° 7 * ΝΗ2〇2 η = 4-7 32 K2HP〇4 5 9% Aqueous argon peroxide solution was sprayed on the K2ΚΡ〇4 solid K2ΗΡ〇4 3 · 15Η202 3 3 KH2P〇4 5 9% Hydrogen peroxide Aqueous solution is sprayed on K2P04 solid KK2P0 4 1 2202 2 4 Ca2 2 07 5 9% Aqueous argon peroxide is sprayed on Ca2P2 07 solid Ca2P2 ° 7 3.42 2 0 2 3 5 Mg2p2 ° 7 5 9% 4 Aqueous argon peroxide solution is sprayed on Mg2P2 07 solid Mg2p2 07 4.60 2 0 2 36 Synthesis of Na4P 2 by the spray method of dredging. In general, sodium pyrophosphate and hydrogen peroxide The formed anhydrous compound is synthesized by liquid spraying method plus vacuum and or drying. 65 JL common Chinese national standard (CNS) A4 size (210X297 mm) is sprayed with liquid radon (please read the back first) Note ($), then fill in the original) A7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ______ —__ Β7_ V. Description of the invention () ~ '' Method to prepare the compound of pyrophosphate and argon peroxide Change many parameters, see the following examples 21-27. Spray concentrated hydrogen peroxide solution (30—90%) dropwise on coke. Cassock acid (98%, Adelaide Aldrich Chemical Co.). Let the mixture 10 ° C, 25 ° C, or 45 ° C. (: Incubate for 1-6 hours, then vacuum dry at 25t-6 (TC or dry in an oven at 60 ° C. In the following example 'change the hydrogen peroxide concentration, the molar ratio of hydrogen peroxide to Na4P207 at the beginning , Solid-liquid ratio, incubation time and temperature, drying form 'drying temperature and amount of starting material to determine their effect on product composition β Example 2 1 to 2 3 show the reaction method at 2 5 ° C after 2 hours, drying method (respectively Is the effect of vacuum drying at 30 ° C, vacuum drying at 60 ° C, and drying in an oven at 60 ° C) on the final weight percentage of argon peroxide of the resulting composite. Example 2 4 shows a vacuum at 25 ° C Effect of reaction time during drying 干燥 The results show that a reaction time of 1 hour is sufficient to form a complex with a ratio of sodium pyrophosphate to nitrogen peroxide of 1: 3. Example 25 shows the effect of reaction temperature on the formation of a peroxide complex. The results show that when a small amount of starting material is used, a complex of sodium pyrophosphate and peroxide gas with a ratio of 1: 3 can still be formed at a temperature below 45t. Example 26 shows that the concentration of argon peroxide versus the liquid spray method Peroxide complex The effect of the composition of the compound. As shown in Table 21, when 30% H2O2 was sprayed on the sodium pyrophosphate solid, even though the H2O2 to SP ratio was 1: 4 at the beginning, the resulting complex Na4P2 07. The ratio of H2O2 to SP of 1.64H2O2 is still lower than 2: 1 (bis-peroxyhydrate). When the concentration of H2O2 is higher than 45%, preferably higher than 50%, it is feasible to become three. _______66______ One I paper size: China National Standard (CNS) A4 size (210X297 mm) ~ " I installed-', ----- ordered ------ line! Γ,' ( Please read the notes on the back before filling this page) A7 B7 V. Description of the invention () Tris-peroxyhydrate (Na 4 P 2 〇7. 3H2 〇 2). The ratio of h2〇2 to SP is 4 : 1's Na4P2 07. 4H2 2 ''s composition is stable only at temperatures below 60 ° C. Example 27 shows that when a large amount of Na4P2 07 is used, it is not possible to prepare sodium pyrophosphate tris by liquid spraying. Peroxohydrate complex β Example 21 Vacuum drying H2O2 (59%) at 30 ° C with sodium pyrophosphate in a weight-to-solid ratio of 1: 0.8, 1: 0.9 and 1: 1 After 2 hours at 25 ° C , Dry under vacuum at 30 eC for 4 hours or 30. (: Dry under vacuum for 4 hours and then dry at 60 ° C for 15 hours. The yield of the obtained product is in the range of 84% to 99%. Summary of results In Table 2 1 ® (Please read the note on the back before filling out this page)-Order printed by the Central Ministry of Economic Affairs, Central Bureau of Standards, and Shellfish Consumer Cooperatives. Table 2 1 The weight of the starting compound at 25 ° C Percent reaction time SP 59% ¾ H2〇2 / S 30 ° C vacuum drying at 30 ° C 4 〇2 Pmor vacuum drying hours plus 60 ° C dry number ratio drying 15 hours (g) (g ) (g) 4 hours closed 1 open 2 l0g 8g 3.7 2 hours 13.5 26.81 26.11 26.18 l0g Η 4.2 2 hours 13.9 27.75 26.95 26.98 l0g Hg 5.1 2 hours 11.7 27.75 26.61 26.88 67 Ruler paper is not allowed to be rubbed Tsukaki Akira r State Λ cm. 97 V. Description of the invention (A7 B7 1. In a closed condition, the 'composite is placed in a closed plastic bottle; 2. In an open state, the' composite is placed in a Open Petri Dish. Example 2 Vacuum drying at 2 60 ° C 2 0 2 (59%) and sodium pyrophosphate are mixed in a solid-liquid ratio of j: 〇8, 1: 〇9, and 1: 1.1 by weight ratio at 25r After 2 hours of reaction, it was dried under vacuum at 60 ° C for 4 hours. The results are summarized in Table 2-2. $ Chuanban Zhunbei J. Cooperative Co., Ltd. 22 Μ: Initial compound reaction time reaction temperature H2O2% by weight SP 59% H2O2 H2O2 / SP Molar number than 60 ° C vacuum drying 6 (TC at its Dry for 4 hours and add 60. (: Dry for 15 hours (g) (g) (hours) ICC) 4 hours 1 open 10 8 3.7 2 25 26.54 25.53 10 9 Bu 4.2 2 25 26.92 26.38 10 11 5.1 2 25 26.83 26.28 Jfe »j 2 3 6 0 ° C drying in an oven 〇 2 〇2 (59%) and sodium pyrophosphate in a solid-liquid ratio of j: 〇8, 1: 0. S and 1: 1 by weight ratio Mix and react at 25 ° C. After 2 hours, dry in an oven at 60 ° C for 6 or 21 hours. The results are summarized in Table 23. ___68 This paper uses the Chinese National Standard (CNS) ) A4 specification (210X297mm) --------- # 0 ----- 1T ------ line (please read the notes on the back before filling this page) A7 B7 V. Invention Description () Table 23 Reaction time of starting compound Weight percentage of reaction temperature H2O2 SP 59% H2O2 H2O2 / SP Molar ratio 60 ° C Dry in oven (g) (g) (hours) (° C ) 6 hours 21 hours 10 8 3.7 2 25 27.22 26.83 10 9 4.2 2 25 27.10 26.87 10 11 5.1 2 25 29.57 26.74 (Please read the notes on the back before filling out this page) Example 24 Effect of reaction time Η 2 〇2 (59%) Sodium phosphate was mixed at a solid-liquid ratio of 1: 0 · 8, and reacted at 25 ° C for 1, 2, 16 hours and vacuum-dried at 25 ° C for 4 hours. The results are summarized in Table 2. 4 in.
、1T 經濟部中央樣準局員工消費合作社印製 裊24 起始化合物 反應時間 反應溫度 H2〇2之重量百分比 SP 59% H2〇2 H2〇2 /SP 莫耳 數比 25t下真空 乾燥 25 °C下真空 乾燥4小時 加60°C下乾 燥15小時 (g) (g) (小時) (°C) 4小時 開放 10 8 3.7 1 25 27.45 26.77 10 8 4.2 2 25 26.81 26.18 10 8 5.1 16 25 27.01 26.96 25* 20 3.7 16 25 27.12 26.90 69 本紙張尺度適用中國國家梯準(CNS ) Α4規格(210Χ297公釐) 經濟部中央橾準局貞工消费合作社印製 A7 B7 五、發明説明()1T printed by the Consumer Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs24 Initial compound reaction time Reaction temperature H2O2% by weight SP 59% H2O2 H2O2 / SP Molar number 25 ° C under vacuum at 25 Dry under vacuum for 4 hours plus 60 ° C for 15 hours (g) (g) (hours) (° C) 4 hours open 10 8 3.7 1 25 27.45 26.77 10 8 4.2 2 25 26.81 26.18 10 8 5.1 16 25 27.01 26.96 25 * 20 3.7 16 25 27.12 26.90 69 This paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) Printed by Zhenong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs A7 B7 V. Description of invention ()
篪例2S 反應溫度的影馨 Η 2 〇 2 ( 5 9 % )與焦磷酸鈉以固液比為1 : 〇 . 8,1 : 1 . 1 和1 : 1 . 3之重量比例加以混合,分别在1 〇 »c,2 5 °C或4 5 °C下反應,並真空乾燥》結果總結於表2 5中。 裊25 7 故始化合与 h 反應 時間 反應 溫度 H2〇2之重量百分比 SP 59% H2〇2 H2〇2/SP 莫耳數比 25°C下真 空乾燥 45°C下真 空乾燥 (g) (g) (小時) (°C) 4小時 2小時 10 8 3.7 2 10 27.81 10 8 4.2 2 25 26.81 25 27 5.0 1.5 45 26.07 25 32.5 6.0 1.5 45 27.23 SUH 26 Η 2 〇 2濃度的影響 將不同濃度之Η2〇2溶液逐滴加入焦磷酸鈉(98%,阿 得里奇化學公司)中《混合物在2 5 °C下培育2小時,之後在 25C下真空乾燥4小時,接著並以烘箱在go °c下乾燥15 小時但表26最下面一列之樣品除外,此列之樣品乃是在25 C下真空乾燥4小時,接著並以烘箱在40 °c下乾燥9小 ----------裝 Π-----ΐτ—·-----0 (請先聞讀背面之注^•項再填寫本頁)篪 Example 2S The reaction temperature of Yingxin 2 〇2 (59%) and sodium pyrophosphate were mixed in a solid-liquid ratio of 1: 0.8, 1: 1, 1.1 and 1: 1.3, respectively. The reaction was performed at 10 ° C, 25 ° C or 45 ° C, and dried under vacuum. The results are summarized in Table 25.袅 25 7 Therefore, the initial compounding and h reaction time reaction temperature H2O2% by weight SP 59% H2O2 H2O2 / SP Molar number ratio vacuum drying at 25 ° C vacuum drying at 45 ° C (g) (g ) (Hours) (° C) 4 hours 2 hours 10 8 3.7 2 10 27.81 10 8 4.2 2 25 26.81 25 27 5.0 1.5 45 26.07 25 32.5 6.0 1.5 45 27.23 SUH 26 Η 2 〇2 The effect of concentration will be Η2 〇2 solution was added dropwise to sodium pyrophosphate (98%, Adrige Chemical Co., Ltd.) "The mixture was incubated at 25 ° C for 2 hours, then dried at 25 C under vacuum for 4 hours, and then in an oven at go ° c Dry for 15 hours except for the samples in the bottom row of Table 26. The samples in this column are dried under vacuum at 25 C for 4 hours, and then dried in an oven at 40 ° C for 9 hours .--------- -装 Π ----- ΐτ— · ----- 0 (Please read the note on the back ^ • before filling this page)
°?=@ηόχ¥η@·>°¥ητ==ςατ〇ίαν L??^? ι·ηός@ηύ =?ς©·?ςα¥η·00ν°©·τ〇ία η1-? ςτ Β7 五、發明説明() 時。結果總結於表2 6中,結果顯示欲製備Η 2 〇 2與S Ρ比 例約1 : 3之過氧化物複合物須要較高濃度的過氧化物。 裊26 起始化合物 複合物 SP H2〇2 之 重量 H2〇2之濃 度 H202/SP 莫 耳數比 H2〇2之重 量百分比 組成 (g) (g) (%) 10 15.8 30 3.7 15.69 他4卩2〇7 · 1.46H2〇2 10 17.2 30 4.0 17.36 Na4?2〇7 ' 1.64H2〇2 10 11 45 4.0 25.48 恤4卩2〇7 . 2·6Η202 10 8 59 3.7 26.18 Na4P2〇7 * 2.78H2〇2 10 9 59 4.2 26.98 Na4?2〇7 · 2.89H2〇2 10 12 90 5.6 27.16 你4卩2〇7 · 2.92H2〇2 10 12 90 5.6 34.44* Na4P2〇7 . 4.11H2〇2 (請先閱讀背面之注意事項再填寫本頁) 、Γ-". 訂 經濟部中央橾準局貝工消費合作社印裝 *樣品乃是在25°C下真空乾燥4小時,接著並以烘箱在40 °C下乾燥9小時。 範例27 起始物含量的影響 在室溫下緩慢的將59 %之H2〇2溶液喷灑在焦磷酸鈉 固體上;但是,混合物的溫度會升高。當59 %之H2〇2溶 71 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) A7B7 五、發明説明() 液被加到3 0 0 g的焦磷酸鈉(S P )固體上時,混合物的溫度 升高至超過60 °C。因此,使用大量SP的效果不如使用少 量S P來的好。結果總結於表2 7中。 表27 起始化合物 混合過程 中的溫度 CG) 25°C 下 之培育 時間 乾燥條件 H2〇2 之 重量百分 比 SP 59% H2〇2 H202/SP 莫 耳數比 (g) (g) (小時) 10 8 3.7 〜35 1 25°C下真空 乾燥3.5小時 加60°C下烘 箱乾燥15小 時 26.77 100 80 3.7 ~45 3 25°C下真空 乾燥3.5小時 加60°C下烘 箱乾燥15小 時 25.86 300 250 3.7 高於60 3 45°C下真空 乾燥15小時 19.98 經濟部中央樣準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 其餘過氧化物複合物之數種其它液體喷灑合成法詳述於 以下範例2 8至3 4中。 72 本紙張尺度適用中國國家標準(CNS ) A4规格(2丨0XW7公釐) 五、發明説明() SLM 28 以液體喷灑合成法來合成Na3P〇4 . 5H2〇2 將濃度為3 0 %,5 9 %,和7 0 %之過氧化氫水溶液噴灑 在具三個鹼基之正磷酸鈉固體(SPT; 96%,阿得里奇化學 公司)上以形成一泥狀物。讓混合物在2 5 °C下培育2小 時,之後於同樣溫度下真空乾燥。結果總結於表28中。 ^2J8°? = @ Ηόχ ¥ η @ · > ° ¥ ητ == ςατ〇ίαν L ?? ^? Ι · ηός @ ηύ =? Σ © ·? Σα ¥ η · 00ν ° © · τ〇ία η1-? Στ Β7 V. Description of invention (). The results are summarized in Table 26. The results show that a higher concentration of peroxide is required to prepare a peroxide compound having a ratio of Η2 02 to SP of about 1: 3.袅 26 Weight of starting compound complex H2O2 Concentration of H2O2 H202 / SP Molar ratio to H2O2 Weight percentage composition (g) (g) (%) 10 15.8 30 3.7 15.69 He 4 卩 2 〇7 · 1.46H2〇2 10 17.2 30 4.0 17.36 Na4? 2〇7 '1.64H2〇2 10 11 45 4.0 25.48 shirt 4 卩 2 07. 2 · 6Η 202 10 8 59 3.7 26.18 Na4P2 07 * 2.78H2 2 10 9 59 4.2 26.98 Na4? 2〇7 · 2.89H2〇2 10 12 90 5.6 27.16 You 4 卩 2〇7 · 2.92H2〇2 10 12 90 5.6 34.44 * Na4P2〇7. 4.11H2〇2 (Please read the back first (Please note this page and fill in this page again), Γ- ". Ordered by the Central Ministry of Economic Affairs, Central Bureau of quasi-station, shellfish consumer cooperatives * Samples are vacuum dried at 25 ° C for 4 hours, and then dried in an oven at 40 ° C Dry for 9 hours. Example 27 Effect of starting material content Slowly spray a 59% H2O2 solution on sodium pyrophosphate solids at room temperature; however, the temperature of the mixture will rise. When 59% of H2O2 is dissolved, the paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7B7 V. Description of the invention () The solution is added to 300 g of sodium pyrophosphate (SP) solid At this time, the temperature of the mixture rose above 60 ° C. Therefore, using a large amount of SP is not as effective as using a small amount of SP. The results are summarized in Table 27. Table 27 Temperature during mixing of starting compounds CG) Incubation time at 25 ° C Drying conditions H2〇2 Weight percent SP 59% H2 02 H202 / SP Molar ratio (g) (g) (hours) 10 8 3.7 ~ 35 1 Vacuum drying at 25 ° C for 3.5 hours plus oven drying at 60 ° C for 15 hours 26.77 100 80 3.7 ~ 45 3 Vacuum drying at 25 ° C for 3.5 hours plus oven drying at 60 ° C for 15 hours 25.86 300 250 3.7 Vacuum drying above 60 3 45 ° C for 15 hours. 19.98 Printed by the Shell Cooperative Consumer Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Several other liquids of peroxide compounds are sprayed. Sprinkler synthesis is detailed in Examples 28 to 34 below. 72 This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0XW7 mm) 5. Description of the invention () SLM 28 uses liquid spray synthesis to synthesize Na3P〇4. 5H2〇2 will have a concentration of 30%, 59%, and 70% aqueous hydrogen peroxide solution was sprayed on a three base sodium orthophosphate solid (SPT; 96%, Adrige Chemical Company) to form a mud. The mixture was allowed to incubate at 25 ° C for 2 hours, and then dried under vacuum at the same temperature. The results are summarized in Table 28. ^ 2J8
起始化合物 複合物 Na3P〇4 H2〇2之重 H2〇2 之 H2〇2^Na3P〇4 之 H2〇2 之 组 量 濃度 莫耳數比 重董百分比 (g) (g) (%) ------- 5 34.6 30 10 51.70 Na3P〇7T- 5.16H2〇2 5 17.6 59 10 52.23 Na3P〇^r- 5.27H2〇2 5 14.8 70 10 48.81 Na3P〇j7 4.6〇H2〇2 1J 魏例29 張 纸 __本 經濟部中央梂準局貞工消費合作杜印製 以液體喷灑合成法來合成 Na2HP〇4 . H2〇2 和 Na2HP〇4 . 2H2〇2 將磷酸鈉之二鹼基固體(99.5%,阿得里奇化學公司) 溶於過氧化氫水溶液中並讓混合物在2 5 〇c下培育1小時, 之後於同樣溫度下進行真空乾燥》得到一 Na2HP〇4〆 H2〇2比例為1:2之明膠類產物。將此膠狀物進一步乾燥以 得一 N a 2 Η P 0 4 / Η 2 〇 2比例為1 : 1之粉末。結果總結於表 73 1適用中國躅家梂準(CNS ) Α4规格(2丨0X297公釐 B7 五、發明説明() 29中。 表29 起始化合物 複合物 Na2HP04 H2〇2 之重量 H2〇2 之濃度 H2〇2/Na 2HP〇4之 莫耳數比 H2〇2 之重量 百分比 組成 H2〇2 之重量 百分比 組成 (g) (g) (%) , 明丹 於形式 粉末形式 5 12.0 30 3.0 20.37 Na2HP〇4 · 1.07H2〇2 5 19.8 30 5.0 33.72 Na2HP〇4 · 2.12H2〇2 23.01 Na2HP04 · 1.25H2〇2 5 6.1 59 3.0 27.88 Na2HP〇4 · 1.61H2〇2 22.28 Na2HP04 -1.20H2〇2 5 10.2 59 5.0 35.33 Na2HP04 · 2.28H2〇2 20.85 Na2HP04 · 1.10H2〇2 5 5.1 70 3.0 31.31 Na2HP04 · H2〇2 5 8.5 70 5.0 35.13 Na2HP〇4 · 2.26H2〇2 21.49 Na2HP04 * 1.14H2〇2 (請先閱讀背面之注$項再填寫本頁) • 1'·-,<··_ -β 經濟部中央橾準局員工消费合作社印裝 簏例30 以液趙喷灑合成法來合成Na5P3〇10 . 1·2Η2〇2 將濃縮之過氧化氮水溶液逐滴噴灑在三聚磷酸鈉之固體 (8 5 %,阿得里奇化學公司)(S Ρ Τ )上。讓混合物在2 5 °C 下培育1小時,之後於同樣溫度下進行真空乾燥,並在60 °C下以烘箱乾燥。結果總結於表3 0中。 74 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 五、發明説明() 袅30 起始化合物 複合物 Na5p3°10 H2〇2 之 重量 H2〇2 之 濃度 Η2〇2/Ν&5Ρ3〇10 之 莫耳數比 Η2〇2 之 重量百分比 組成 (g) (g) (%) 10 13.0 30 5.0 10.58 Na5p3°10 * 1.4H2〇2 10 6.6 59 5.0 1 · 12.58 Na5p3°10 ' 1.62H2〇2 10 5.6 70 5.0 13.40 Na5p3°10 · 1.73H2〇2 (請先閲讀背面之注意事項再填寫本頁) 簏例31 以液體噴灑合成法來合成K3P〇4 . nH2〇2 在室溫•下將59%之H2〇2溶液逐滴加到磷酸鉀之三鹼 基固體上(9 7 %,阿得里奇化學公司)。在喷灑過程中混合 物的溫度持續升高至8 0 °C。在真空下將此泥狀混合物乾燥 4小時。結果總結於表3 1中。 訂 裊31 經濟部中央梂準局貝工消费合作社印裝 起始化合物 反應之羞物 Κ3Ρ04 H2〇2 之 重量 H2〇2 之 濃度 H202/K3P〇4 之 莫耳數比 H2〇2 之 重量百分比 组成 (g) (g) (%) 10 8 59 3.0 ' 0.34 K3PO4 * 〇.〇2Η2〇2 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印裂 五、發明説明() 簏例32 以液趙喷激合成法來合成K4P2O7 . nH2〇2 在室溫下將5 9 %或7 0 %之Η 2 〇 2溶液喷灑在焦磷酸鉀 (Ρ Ρ )之固體上(9 7 %,阿得里奇化學公司)以形成一泥狀 物,在噴灑過程中混合物的溫度約為3 0 °C至3 5 °C。讓混合 物在2 5 °C下反應2小時,之後在2 5 °C下進行真空乾燥。結 果總結於表3 2中。 裊32 起始化合物 複合物 K4P2〇7 H2〇2 之重量 H2〇2 之濃度 H2〇2 义4?2〇7 之莫耳數比 H2〇2 之 重量百分比 组成 (g) (g) (%) 10 8 59 4.6 28.74 K4P2〇7 * 3.91H2〇2 10 9.5 59 5.4 33.70 K4P2O7 · 4.74H2〇2 10 11.0 59 6.4 36.30 Κ4Ρ2〇7 * 5.6H2〇2 10 17.5 59 10 41.64 K4P2〇7 · 6.93H2〇2 10 21.0 59 12 41.48 K4P2〇7 · 6.99H2〇2 10 14.7 70 10 42.80 K4P2O7 · 7.26H2〇2 10 17.6 70 12 41.11 K4P2〇7 * 6.78H2〇2 76 本紙張尺度逋用中國國家標準(CNS > A4規格(210X297公釐) n^i I n In nn In In I I /V (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央橾準局貝工消費合作社印袈 A7 B7 五、發明説明() 簏例33 以液體噴灑合成法來合成K2HPO4 . 3H2〇2 將濃縮之H2〇2溶液逐滴噴灑在磷酸氩鉀(PHP)之固體 上(9 8❶/❶,阿得里奇化學公司)。讓混合物在2 5。(:下反應 1小時,之後在2 5 X:下進行真空乾燥。結果總結於表3 3 中。 裊33 起始化合物 複合物 Κ2ΗΡ〇4 H2〇2 之 重量 H2〇2 之濃度 H2O2/K2HPO4 之 莫耳數比 H2〇2 之 重量百分比 组成 (g) (g) (%) 5 4.97 59 3.0 38.04 K2HP〇4 . 3.I5H2〇2 簏例34 以液體噴灑合成法來合成KH2P〇4 · H2〇2 將濃縮之Η 2 〇2溶液逐滴喷灑在磷酸二氫鉀(PDHP)之 固體上(98%,阿得里奇化學公司)。讓混合物在25t下 反應1小時,之後在2 5 t下進行真空乾燥》結果總結於表 34中。 _ 77 本紙張尺度適用中國國家標準(CNS > A4规格(210X297公釐) " ^ 訂 (請先Μ讀背面之注意事項再填寫本頁)Starting compound complex Na3P〇4 H2O2 weight H2O2 H2O2 ^ Na3P0 4 H2O2 Group concentration Concentration Molar Specific gravity% (g) (g) (%) --- ---- 5 34.6 30 10 51.70 Na3P〇7T- 5.16H2〇2 5 17.6 59 10 52.23 Na3P〇 ^ r- 5.27H2〇2 5 14.8 70 10 48.81 Na3P〇j7 4.6〇H2 02 2J Wei Zheng 29 sheets __The Ministry of Economic Affairs, Central Bureau of Quasi-Institute of the Ministry of Economic Affairs and the Consumers Cooperation Du Yin produced a liquid spray synthesis method to synthesize Na2HP〇4. (Adrige Chemical Co., Ltd.) was dissolved in an aqueous hydrogen peroxide solution and the mixture was allowed to incubate at 25 ° C for 1 hour, and then vacuum-dried at the same temperature to obtain a Na2HP04H2 02 ratio of 1: 2 of gelatin products. This gum was further dried to obtain a powder having a ratio of N a 2 Η P 0 4 / Η 2 02 of 1: 1. The results are summarized in Table 73. 1 Applicable to China National Standard (CNS) A4 specification (2 丨 0297mm B7 V. Description of the invention) 29. Table 29 Weight of the starting compound complex Na2HP04 H2 02 H2 02 The molar number of the concentration H2〇2 / Na 2HP〇4 is more than the weight percentage of H2O2. The weight percentage of H2O2 is composed of (g) (g) (%). It is in powder form 5 12.0 30 3.0 20.37 Na2HP 〇4 · 1.07H2〇2 5 19.8 30 5.0 33.72 Na2HP〇4 · 2.12H2〇2 23.01 Na2HP04 · 1.25H2〇2 5 6.1 59 3.0 27.88 Na2HP〇4 · 1.61H2〇2 22.28 Na2HP04 -1.20H2 02 2 10.2 59 5.0 35.33 Na2HP04 · 2.28H2〇2 20.85 Na2HP04 · 1.10H2〇2 5 5.1 70 3.0 31.31 Na2HP04 · H2〇2 5 8.5 70 5.0 35.13 Na2HP〇4 · 2.26H2〇2 21.49 Na2HP04 * 1.14H2 02 (Please read the back first Please fill in this page if you want to add $.) • 1 '·-, < ·· _ -β Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, Example 30. Spraying synthesis method of liquid Zhao to synthesize Na5P30.1. 1 · 2Η2 0 2 Drop the concentrated aqueous solution of nitrogen peroxide dropwise on the solid sodium tripolyphosphate (85%, Adriatic Company) (SPT). The mixture was allowed to incubate at 25 ° C for 1 hour, then vacuum dried at the same temperature, and dried in an oven at 60 ° C. The results are summarized in Table 30. Paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 5. Description of the invention () 袅 30 Starting compound complex Na5p3 ° 10 H2O2 weight H2O2 concentration 22002 / N & 5P3. Molar number of 10 than weight percentage composition of Η202 (g) (g) (%) 10 13.0 30 5.0 10.58 Na5p3 ° 10 * 1.4H2〇2 10 6.6 59 5.0 1 · 12.58 Na5p3 ° 10 '1.62H2〇2 10 5.6 70 5.0 13.40 Na5p3 ° 10 · 1.73H2〇2 (Please read the precautions on the back before filling this page) Example 31 Synthesis of K3P〇4 by liquid spray synthesis method. NH2〇2 at room temperature • 59 % H2O2 solution was added dropwise to a potassium base tribasic solid (97%, Adrige Chemical Co.). The temperature of the mixture continued to rise to 80 ° C during spraying. This slimy mixture was dried under vacuum for 4 hours. The results are summarized in Table 31. Order 31 The weight of the reaction of the starting compound KK3P04 H2〇2 The concentration of H2 02 H202 / K3P04 The mole ratio of H202 / K3P〇4 is the weight percentage of H2 02 (g) (g) (%) 10 8 59 3.0 '0.34 K3PO4 * 〇.〇2Η2〇2 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm), printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention () Example 32 Synthesis of K4P2O7 by liquid Zhao spray synthesis method. NH2〇2 At room temperature, a 59% or 70% solution of Η2 〇2 was sprayed on potassium pyrophosphate (PP). ) On solids (97%, Adrige Chemical Co.) to form a mud, the temperature of the mixture during spraying was about 30 ° C to 35 ° C. The mixture was allowed to react at 25 ° C for 2 hours, and then vacuum-dried at 25 ° C. The results are summarized in Table 32.袅 32 Compound weight of starting compound K4P2 0 7 H 2 0 2 H 2 0 2 H 2 0 2 Mole ratio of H 2 0 2% by weight Composition (g) (g) (%) 10 8 59 4.6 28.74 K4P2〇7 * 3.91H2〇2 10 9.5 59 5.4 33.70 K4P2O7 · 4.74H2〇2 10 11.0 59 6.4 36.30 K4P2〇7 * 5.6H2 02 10 17.5 59 10 41.64 K4P2〇7 · 6.93H2 02 10 21.0 59 12 41.48 K4P2〇7 · 6.99H2〇2 10 14.7 70 10 42.80 K4P2O7 · 7.26H2〇2 10 17.6 70 12 41.11 K4P2〇7 * 6.78H2〇2 76 This paper uses the Chinese National Standard (CNS > A4 specification (210X297 mm) n ^ i I n In nn In In II / V (Please read the notes on the back before filling out this page) Order the seal of the Central Laboratories Bureau of the Ministry of Economic Affairs, Paiger Consumer Cooperative, A7 B7 V. Invention Explanation () Example 33 Synthesis of K2HPO4 by liquid spray synthesis. 3H2O2 The concentrated H2O2 solution was sprayed dropwise onto a solid potassium argon phosphate (PHP) (98❶ / ❶, Adrige Chemical Co., Ltd.). ). The mixture was allowed to react at 25 ° C for 1 hour, and then dried under vacuum at 25 ° C. The results are summarized in Table 33. 33 Starting compound complex K2HP04 H2O2 weight H2O2 concentration H2O2 / K2HPO4 mole ratio to H2O2 weight percentage composition (g) (g) (%) 5 4.97 59 3.0 38.04 K2HP. 4. 3. I5H2〇2 Example 34 Synthesis of KH2P〇4 · H2〇2 by liquid spray synthesis The concentrated solution of Η2 〇2 was sprayed dropwise on the solid potassium dihydrogen phosphate (PDHP) (98% , Adrige Chemical Co., Ltd.) The mixture was allowed to react at 25t for 1 hour, and then dried under vacuum at 25t. The results are summarized in Table 34. _ 77 This paper size applies Chinese National Standard (CNS > A4 specification) (210X297 mm) " ^ Order (Please read the precautions on the back before filling in this page)
A B 五、發明説明() 裊34 起始化合物 複合物 KH2P〇4 H2〇2 之 重量 H2〇2 之 濃度 H202/KH2P〇4 之 莫耳數比 H2〇2 之 重量百分比 組成 (g) (g) (%) 5 6.23 59 3.0 20.18 ΚΗ2Ρ〇4 · H2〇2 簏例35 以液體噴灑合成法來合成Ca2P2〇7 . 3·42Η2〇2 將59 %之Η2〇2溶液喷灑在焦磷酸鈣固體上(阿得里 奇化學公司)。讓混合物在2 5 °C下反應1小時,之後在2 5 t下進行真空乾燥。結果總結於表3 5中。 (諳先閲讀背面之注意事項再填寫本頁) 訂 裊35 起始化合物 複合物 匸32卩2〇7 H202 之 重量 H2〇2 之 濃度 H2〇2/Ca2p2〇7 之 莫耳數比 H2〇2 之 重量百分比 組成 (g) (g) (%) 5 10 59 8.82 31.41 Ca2P2〇7 · 3.42H2〇2 經濟部中央標準局貝工消費合作社印製 簏例36 以液體噴灑合成法來合成Mg2P2〇7 . 4·6Η2〇2 將59 %之Η2〇2溶液噴灑在焦磷酸鎂固體上(阿得里 奇化學公司)。讓混合物在2 5 °C下反應1小時,之後在2 5 °C下進行真空乾燥。結果總結於表3 6中。 78 本紙張尺度適用中國國家標準(CNS > A4規格(210X297公釐〉 A7 B7AB 5. Description of the invention () 袅 34 Starting compound complex KH2P〇4 H2〇2 H20 concentration H202 / KH2P〇4 Molar ratio to H2 02 wt% (%) 5 6.23 59 3.0 20.18 ΚΗ2Ρ〇4 · H2〇2 Example 35 Synthesis of Ca2P2 07 by a liquid spray synthesis method. 3.42Η2 02 Spray a 59% solution of Η2202 on a calcium pyrophosphate solid (Adrige Chemical Company). The mixture was allowed to react at 25 ° C for 1 hour, and then dried under vacuum at 25 t. The results are summarized in Tables 35. (Please read the precautions on the reverse side before filling out this page) Order 35 Start compound complex 32 32 07 H202 Weight H2 02 Concentration H2 02 / Ca2p2 07 Molar ratio H2 02 Weight percentage composition (g) (g) (%) 5 10 59 8.82 31.41 Ca2P2 07 · 3.42H2 02 Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Example 36 Synthesis of Mg2P2O7 by liquid spray synthesis 4.6.202 Spraying a 59% solution of Η202 on magnesium pyrophosphate solids (Adrige Chemical Co.). The mixture was allowed to react at 25 ° C for 1 hour, after which it was dried under vacuum at 25 ° C. The results are summarized in Table 36. 78 This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) A7 B7
經濟部中央梯準局員工消費合作社印I 五、發明説明() 裊36 起始化合物 複合物 Mg2P2〇7 H2〇2 之 重量 H2〇2 之 濃度 H2〇2/Mg2P2〇7 之 莫耳數比 H2〇2 之 重量百分比 组成 (g) (g) (%) 5 10 59 7.72 41.28 Mg2p2〇7 · 4.60H2〇2 雖然以上描述了數種過氧化物之磷酸複合物,但能製備 安定複合物的通用合成方法目前仍付諸關如。過氧化氫溶液 與磷酸鹽或濃縮磷酸鹽之間的反應乃屬放熱反應。由此放熱 反應中所產生的熱會導致過氧化氫的分解。因此,複合物變 得不安定,或是導致所得產物中過氧化物與磷酸鹽或濃縮磷 酸鹽之比值較低。當欲大量製備複合物時,此問題就會變得 較嚴重。 泥狀法 在一項試圖控制過氧化氫溶液與磷酸鹽或濃縮鱗睃鹽反 應所產生之熱能的嚐試中,我們發現了數種合成方法。其中 的一種被我們稱為“泥狀法",因開始時碟酸鹽或濃縮鱗酸 里與水形成泥狀物而得名。此用來合成過氧化氣無機複合物 之泥狀物-液髏合成法包括將所要的無機化合物與水混合產 生一柔軟的泥狀物。讓此泥狀物冷卻後,加入過氧化氣水溶 液》將混合物乾燥以除去水分,所得即為過氧化氫無機複合 物。 此合成法的主要優點乃是雖然無機化合物與水之間的反 79 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐) d丨 (請先閲讀背面之注$項再填寫本頁) 訂 線 經濟部中央橾準局貝工消費合作社印裝 A7 _________B7____ 五、發明説明() 應乃屬放熱反應’但在形成過氧化物無機複合物的過程中僅 有少量熱能產生’因此可避免合成過程中過氧化氫的分解。 相對於以前的方法中因大量熱能的生成導致過氧化氫分解, 此乃是一大進展。所得過氧化氫無機複合物之晶體極細且較 其它方法所得更為安定,而且可使用較低濃度之過氧化氫。 為不欲受任何特定理論或作用機制之限制,我們相信在 泥狀物形成之初乃是先形成一水合物,之後這些水合物中的 水分子再被過氧化物所取代以產生過氧化物之無機複合物。 在範例37和38中提供了製備兩種不同過氧化物磷酸複合 物的範例方法。 範例37 使用不同濃度之過氧化氩於泥狀物-液體合成法中 合成 Na4P2〇7 · 2·3Η2〇2 緩緩的將焦磷酸鈉固體(9 8 %,阿得里奇化學公司)與去 離子水挽拌混合以形成一柔軟的泥狀物。由於為放熱反應, 因此讓此泥狀物冷卻至室溫。再將不同濃度之過氧化氫水溶 液與泥狀物混合。此時溫度並不會上升。讓混合物在25〇c 下反應1小時,之後在25°C下進行真空乾燥。將真空乾燥 的樣品進一步以烘箱在60 °C下乾燥以除去任何殘留的水 分。結果總結於表37中· (請先閲讀背面之注f項再填寫本頁}Printed by the Consumers Cooperative of the Central Government Bureau of the Ministry of Economic Affairs I. 5. Description of the invention () 袅 36 Starting compound compound Mg2P2 0 7 H2 2 Weight H2 2 H2 0 2 / Mg 2 P 2 0 Molar ratio H 2 〇2 weight percentage composition (g) (g) (%) 5 10 59 7.72 41.28 Mg2p2〇7 · 4.60H2〇2 Although the phosphate complexes of several peroxides have been described above, they can be used to prepare stable complexes. The synthesis method is still relevant. The reaction between hydrogen peroxide solution and phosphate or concentrated phosphate is exothermic. The heat generated during the exothermic reaction will cause the decomposition of hydrogen peroxide. As a result, the complex becomes unstable or causes a lower ratio of peroxide to phosphate or concentrated phosphate in the resulting product. This problem is exacerbated when complexes are to be prepared in large quantities. Mud method In an attempt to control the thermal energy generated by the reaction of a hydrogen peroxide solution with a phosphate or concentrated scalefish salt, we discovered several synthetic methods. One of them is called the "mud-like method", which is named for the formation of a mud-like substance with water in dishate or concentrated scale acid. This is used to synthesize a mud-like compound of peroxide gas- The liquid-skull synthesis method includes mixing a desired inorganic compound with water to produce a soft mud. After the mud is allowed to cool, an aqueous solution of a peroxide gas is added. The mixture is dried to remove water, and the obtained hydrogen peroxide inorganic compound is obtained. The main advantage of this synthesis method is that although the inverse between the inorganic compounds and water 79 paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) d 丨 (Please read the note on the back before you read (Fill in this page) Printed by A7 _______B7____, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs of the Ordering Department 5. Description of the invention () Should be an exothermic reaction 'but only a small amount of thermal energy is generated in the process of forming the peroxide inorganic complex' Therefore, the decomposition of hydrogen peroxide during the synthesis process can be avoided. Compared with the previous method, the decomposition of hydrogen peroxide due to the generation of a large amount of thermal energy is a major progress. The obtained hydrogen peroxide has no The crystals of the composite are extremely fine and more stable than those obtained by other methods, and lower concentrations of hydrogen peroxide can be used. In order not to be limited by any specific theory or mechanism of action, we believe that the formation of mud is the first step. Monohydrates are formed, after which the water molecules in these hydrates are replaced by peroxides to produce inorganic complexes of peroxides. Examples 37 and 38 provide examples of preparing two different peroxide phosphate complexes Method 37. Synthesizing Na4P2 07 · 2 · 3〇2202 in a mud-liquid synthesis method using argon peroxide of different concentrations in a slowly synthesized sodium pyrophosphate solid (98%, Adrige Chemical Co., Ltd.) Mix with deionized water to form a soft mud. Because it is an exothermic reaction, allow the mud to cool to room temperature. Then, mix different concentrations of hydrogen peroxide aqueous solution with the mud. At this temperature Does not rise. Allow the mixture to react at 25 ° C for 1 hour, and then vacuum-dry at 25 ° C. The vacuum-dried sample is further dried in an oven at 60 ° C to remove any residual moisture. The results are summarized in Table 37. (Please read note f on the back before filling this page}
、1T "! 80, 1T "! 80
A7 B7 五、發明説明() 表37 起始化合物 複合物 SP H2〇之 重量 H2〇2 之重量 H2〇2 之濃度 h2o2/sp 莫耳數比 H2〇2之重 量百分比 組成 (8) (g) (g) (%) 5 5 24.4 12 4.6 26.60 Na4p2〇7 . 2.84H2〇2 5 5 9.8 30 4.6 27.92 Na4p207 . 3.03H2〇2 5 5 2.4 59 2.2 17.16 Na4?2〇7 · 1.62H2〇2 5 5 3.0 59 2.8 19.67 Na4P2〇7 · 1.92H2〇2 5 5 3.2 59 3.2 24.43 他4卩2〇7 2.53H2〇2 5 5 4 59 3.7 26.02 Na4P2〇7 · 2.75H2〇2 5 5 5 59 4.6 28.10 ^a4^2®7 * 3.06H2〇2 50* 50 50 59 4.6 27.40 Na4p2°7 * 2.95H2〇2 200* 200 200 59 4.6 28.31 Na4?2〇7 ' 3.01H2〇2 *樣品被用於範例3 8之熱安定試驗中。 --------->------ΐτ------^ (請先閱讀背面之注$項再填寫本頁) 經濟部中央標準局w:工消費合作社印策 表3 7列出了以泥狀法製備過氧化氫複合物的數項優點: 1. 製備焦嶙酸鈉三過氧水合物(Na4P2〇7 . 3H2〇2)時, 過氧化氫之起始濃度不須一定要大於50%,甚至12 %之 過氧化氮溶液也可用於複合物的製備。 2. 也可使用大量起始物(例如,200g SP)來製備 _81_ 本紙張尺度適用中國國家梯準(CNS > A4规格(210X:297公釐) 五、發明説明() —— -A7 B7 V. Description of the invention Table 37 The weight of the starting compound complex SP H20, the weight of H2O2, the concentration of H2O2, h2o2 / sp, and the mole percentage of H2O2 (8) (g) (g) (%) 5 5 24.4 12 4.6 26.60 Na4p2〇7. 2.84H2〇2 5 5 9.8 30 4.6 27.92 Na4p207. 3.03H2〇2 5 5 2.4 59 2.2 17.16 Na4? 207 · 1.62H2〇2 5 5 3.0 59 2.8 19.67 Na4P2〇7 · 1.92H2〇2 5 5 3.2 59 3.2 24.43 He 4 卩 2〇7 2.53H2〇2 5 5 4 59 3.7 26.02 Na4P2〇7 · 2.75H2〇2 5 5 5 59 4.6 28.10 ^ a4 ^ 2®7 * 3.06H2〇2 50 * 50 50 59 4.6 27.40 Na4p2 ° 7 * 2.95H2〇2 200 * 200 200 59 4.6 28.31 Na4? 2〇7 '3.01H2〇2 * Sample was used in Example 3 of 8 Thermal stability test. --------- > ------ ΐτ ------ ^ (Please read the note on the back before filling in this page) Central Standards Bureau of the Ministry of Economic Affairs w: printed by Industrial and Consumer Cooperatives Table 3 7 lists several advantages of using the mud-like method to prepare hydrogen peroxide composites: 1. When preparing sodium pyrophosphate triperoxy hydrate (Na4P207. 3H2O2), the rise of hydrogen peroxide The initial concentration does not have to be greater than 50%, and even a 12% nitrogen peroxide solution can be used for the preparation of the composite. 2. Can also be prepared with a large amount of starting materials (for example, 200g SP)
Na4P2〇7 · 3H2〇2,因為在過氧化氣水溶液與sp水 的泥狀物混合過程中並不會有溫度升高的現象。 3.可藉著控制起始物中h2〇2與81>之莫耳數比來製備具有 不同組成之過氧化物複合物。 範》】3 8 以泥狀物-液體合成法合成K3p〇4 . nH2〇2 緩緩的將蹲酸钟三驗基固體(97%,阿得里奇化學公 司)(PPT)與去離子水攪拌混合以形成一柔軟的泥狀物,並 使其冷卻至室溫。將5 9 %之過氧化氫水溶液與泥狀物混 合。此時溫度並不會上升。讓混合物在25 t下反應2小 時,之後在25°C下進行真空乾燥。結果總結於表38中。可 以液體喷灑法(參見範例31)來製備用於大多數磷酸過氧 化物複合物合成過程中的磷酸鉀過氧化物。當過氧化氫溶液 被噴在磷睃鉀固體上時,反應溫度會立刻上升至8 0 °C左 右。此高溫會使得過氧化氫分解因此使能與磷酸鉀複合之過 氧化氩量減少。很顯然的,在製備K3P〇4 . 3H2〇2上’ 泥狀物要優於液體喷灑法。 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央揉準局貝工消费合作社印裝 本紙張尺度適用中國國家揉準(CNS ) A4规格(210X297公釐) 經濟部中央梂準局貝工消費合作社印袈 83 A7 B7 五、發明説明() 起始化合物 複合物 K3P〇4 H20 h2°2 H2〇2 h2o2/k3po H2〇2 之 组成 之重量 之重量 之濃度 4之莫耳數比 重量百分比 (g) (g) (g) (%) 5 2 6.6 59 5.0 34.57 Κ3Ρ〇4 · 3.34Η2〇2 範例39 以喷}麗法和泥狀法合成 之Na4p2〇7 . 3H2〇2之熱安定性 將約2g之複合物樣品儲存於5rlU的未蓋(開放,條件 1)或密封(密閉,糾2)《塑膠瓶中。將未加蓋或密封 疋塑膠瓶置於23°C,50%相對濕度(RH)之培養槽或6〇〇c 之烘箱内。測定複合物中h2〇2之含量。結果總結於表仞 中。 t紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐Na4P20.7 · 3H2O2, because there is no temperature rise during the mixing of the peroxide gas solution with the sp water mud. 3. Peroxide complexes with different compositions can be prepared by controlling the molar ratios of h2O2 to 81 > in the starting materials. "Fan"] 3 8 K3p〇4. NH2〇2 was synthesized by a mud-liquid synthesis method. Slowly solid acid (97%, Aldrich Chemical Co., Ltd.) (PPT) and deionized water Stir to form a soft mud, and allow to cool to room temperature. Mix 59% aqueous hydrogen peroxide solution with the mud. The temperature does not rise at this time. The mixture was allowed to react at 25 t for 2 hours, after which it was dried under vacuum at 25 ° C. The results are summarized in Table 38. A liquid spray method (see Example 31) can be used to prepare potassium phosphate peroxides for use in the synthesis of most phosphate peroxide complexes. When a hydrogen peroxide solution is sprayed on the solid potassium phosphate, the reaction temperature immediately rises to about 80 ° C. This high temperature causes the decomposition of hydrogen peroxide and therefore reduces the amount of argon peroxide that can be combined with potassium phosphate. Obviously, the preparation of K3P04. 3H2 02 'mud is better than the liquid spray method. (Please read the notes on the back before filling this page.) Order the paper size printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). Shellfish Consumer Cooperatives Co., Ltd. Seal 83 A7 B7 V. Description of the invention () The starting compound complex K3P〇4 H20 h2 ° 2 H2 02 h2o2 / k3po H2〇2 The weight ratio of the molar ratio of 4 Weight percent (g) (g) (g) (%) 5 2 6.6 59 5.0 34.57 Κ3Ρ〇4 · 3.34Η2〇2 Example 39 Na4p207.3H2O2 heat synthesized by spray method and mud method Stability Store approximately 2 g of the composite sample in an uncovered (open, condition 1) or sealed (closed, correct 2) plastic container of 5 rU. Place the uncapped or sealed 疋 plastic bottle in a 23 ° C, 50% relative humidity (RH) incubator or 600 ° C oven. The content of h2O2 in the composite was measured. The results are summarized in Table 仞. t Paper size applies to China National Standard (CNS) A4 (210X297 mm)
A7 B7 五、發明説明( * 合成法 储存條件* 測試條件 Η9〇7之重量 lw 2w 3w 4w 6w ⑴ 23〇C,50% RH 26.35 27.04 26.10 26.38 N/A 60t之烘箱 25.76 24.57 20.39 21.22 N/A 噴灑法 (2) 23eC,50% RH 26.86 26.71 26.87 26.81 26.84 60°C之烘箱 26.70 25.10 23.61 21.33 17.70 (1) 23TC.50% RH 26.85 26.93 26.73 26.64 26.98 60t之烘箱 26.84 26.29 25.58 24.78 23.73 泥狀物法 (2) 23ΐ,50% RH 27.15 27.04 26.98 26,72 27.33 60ΐ之烘箱 26.87 27.74 26.17 26.10 25.71 1^—· ^^1 ^^1 m HI I /1>- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央搮準局貝工消費合作社印製 *儲存條件:(1)未加蓋之塑膠瓶;(2)密封之塑膠瓶。 比較表3 9中之結果’在6 〇。〇下以喷灑法所得之複合物 其安疋度較泥狀物法所得之複合物來的低。但是,在2 3 °C ’ 5 0 %相對濕度下則兩者之安定度相去不遠。因此,在較 不利之儲存條件下,例如一般運送過程中,泥狀物法能提供 複合物一些預期外的安定性。 水合物法 如上述,我們深信泥狀物法在反應之初乃是產生一磷酸 II或漢縮磷酸鹽的水合物。對許多磷酸鹽或濃縮磷酸鹽化合 物而言,水合物可以此領域中眾所熟知的技術來製造或由市 面上購得。因此,我們嚐試跳過泥狀物法開始時形成泥狀物 __ __84____ 本紙張尺度適用中國國家梯準(CNS ) A4^ ( 2丨0X297公釐) 4 A7 B7 五、發明説明() 的步驟,以水合物法來合成過氧化物複合物。因一般相信在 泥狀物法中’水合物中的水分子乃為過氧化物所取代。以下 範例4 0提供了水合物合成法之範例。 feW 40 以水合物法來合成Na4P2〇7 . 3H2〇2 將含有十分水之焦磷酸鉤固體(9 9 %,阿得里奇化學八 司)與1 2 %,3 0 %或5 9 %之過氧化氩水溶液混合,在2 5 t 下反應1小時,之後在2 5。(:下進行真空乾燥。結果線結於 表4 0中。因此,此複合物可以低於3 〇 %之過氧化氣水落液 來製備。 ^ I-----------:1---- I%.· — 'f (請先聞讀背面之注^|^項再填寫本頁』A7 B7 V. Description of the invention (* Synthesis method storage conditions * Test conditions Η907 weight lw 2w 3w 4w 6w ⑴ 23 ° C, 50% RH 26.35 27.04 26.10 26.38 N / A 60t oven 25.76 24.57 20.39 21.22 N / A Spray method (2) 23eC, 50% RH 26.86 26.71 26.87 26.81 26.84 60 ° C oven 26.70 25.10 23.61 21.33 17.70 (1) 23TC.50% RH 26.85 26.93 26.73 26.64 26.98 60t oven 26.84 26.29 25.58 24.78 23.73 Slurry method (2) 23ΐ, 50% RH 27.15 27.04 26.98 26,72 27.33 60ΐOven 26.87 27.74 26.17 26.10 25.71 1 ^ — · ^^ 1 ^^ 1 m HI I / 1 >-(Please read the notes on the back before filling (This page) Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs * Storage conditions: (1) Uncapped plastic bottles; (2) Sealed plastic bottles. Compare the results in Table 39 to '60%. The compound obtained by the spray method below has a lower degree of stability than the compound obtained by the mud method. However, the stability of the two is not much different at 23 ° C '50% relative humidity. Therefore, under unfavorable storage conditions, such as during normal transportation, mud The chemical method can provide some unexpected stability of the complex. The hydrate method is as described above. We are convinced that the mud method at the beginning of the reaction is to produce hydrates of monophosphate II or manganese phosphate. For many phosphates or concentrated In the case of phosphate compounds, hydrates can be manufactured using techniques well known in the art or are commercially available. Therefore, we tried to skip the formation of mud at the beginning of the mud method __ __84____ This paper applies to China National Ladder Standard (CNS) A4 ^ (2 丨 0X297 mm) 4 A7 B7 5. In the steps of the invention (), the peroxide compound is synthesized by the hydrate method. It is generally believed that in the mud method, it is 'hydrated' The water molecules in it are replaced by peroxides. The following example 40 provides an example of a hydrate synthesis method. FeW 40 uses the hydrate method to synthesize Na4P2 07. 3H2 0 2 will contain a pyrophosphate hook solid (99%, Aldrich Chemical Eight Division) mixed with 12%, 30% or 59% argon peroxide solution, and reacted at 25 t for 1 hour, and then at 25. (: Vacuum dried. Results are shown in Table 40. Therefore, the complex can be prepared by dropping water with less than 30% of peroxide gas. ^ I -----------: 1 ---- I%. · — 'F (Please read the notes on the back ^ | ^ before filling this page ”
25.87 Na4P207 -Na4P2〇7 . (g) 24.5 (%) 1225.87 Na4P207 -Na4P2〇7. (G) 24.5 (%) 12
H2〇2,Na4P2〇7 之莫耳數比 訂 經濟部中央標準局員工消費合作社印裝 ν»4ρ2°7 1〇Η2〇2 (g) 8.4 8.4Molar number comparison of H2〇2, Na4P2〇7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ν »4ρ2 ° 7 1〇2202 (g) 8.4 8.4
10.0 30 200 120 59 4.6 4.6 4.6 28.04 27.5710.0 30 200 120 59 4.6 4.6 4.6 28.04 27.57
Na4P2〇7 · 2,9!ϋ?°- 準 揉 家 國 國 中 用 適 度 尺 張 紙 本 Μ 5 8 ί 公 7 9 2 A7 B7 五、發明説明() 硫酸鹽過氡化物複合物之合成 我們也合成了硫酸鹽與過氧化物之複合物以用於在此所 述之殺菌法。在範例41和4 2中提供了兩種不同硫酸鹽複 合物之詳細合成方法的範例。 範例41 以液體噴灑合成法來 合成 Na2Si03 · 1 .28H2〇2 將5 9 %之Η 2 〇 2溶液喷灑在硫酸鈉固體上(9 9 %,阿 得里奇化學公司)。讓混合物在2 5 °C下反應1小時,之後 在2 5 °C下進行真空乾燥。結果總結於表4 1中。 袅41 起始化合物 複合物 Na2S〇4 h2〇 H2〇2 H2〇2,Na2S〇4 H2〇2 之 組成 之重量 之濃度 之莫耳數比 重量百分比 (g) (g) 10 10 59 2.46 23.47 Na2S〇4 · 1.28H2〇2 經濟部中央標準局貝工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 簏例42 以液體噴灑合成法來合成K2S04 . 0.62H2〇2 將5 9 %之Η 2 〇 2溶液喷灑在硫酸鉀固體上(9 9 %,阿 得里奇化學公司)》讓混合物在2 5 °C下反應1小時,之後 86 本紙張尺度適用中國囤家標準(CNS ) Λ4規格(210X297公釐) A7 B7 五、發明説明() 在25t下進行真空乾燥。結果總結於表42中。 表42 ---- 一 ---- 起始化合物 複合物 K2S〇4 h2o H2〇2 H2〇2/K2S〇4 H2〇2 之 組成 之重量 之濃度 之莫耳數比 重量百分比 (g) (g) (%) 10 7 59 2.12 23.47 K2S04 . 〇.62H2〇2 (請先聞讀背面之注$項再填寫本頁) 經濟部中央榡準局貝工消費合作社印家 逆酸鹽過氣化物複合物之合成 我們也合成了矽酸鹽與過氧化物之複合物以用於在此所 述之殺菌法。在範例43和44中提供了兩種不同矽酸鹽複 合物之詳細合成方法的範例。 範供43 以泥狀物-液體法來合成Na2Si〇3 . nH2〇2 將矽酸鈉固體(Na2Si〇3,阿得里奇化學公司)與水混 合形成一柔軟的泥狀物’並冷卻至室溫•將12%之過氧化 氣水溶液與泥狀物混合。混合過程中溫度约為3 0 °C至3 5。〇 之間。讓混合物在25C下反應1小時,之後在25 °C下進行 真空乾燥。結果總結於表4 3中。 87 本紙張尺度適用中國國家梂準(CNS M4規格(210X297^*7 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明() 袅43 起始化合物 複合物 Na2Si〇3 h2o 之重量 H2〇2 之重量 H2〇2 之濃度 H2〇2/Na2Si〇3 之莫耳數比 H2〇2之重 量百分比 組成 (g) (g) (g) (%) 5 5 23.22 12 2.0 24.74 Na2Si〇3 · 1.18H2〇2 5 5 34.83 12 3.0 37.45 Na2Si〇3 · 2.15H2〇2 5 5 4645 12 4.0 37.64 Na2Si03 · 2.17H2〇2 簏例44 以水合物法來合成Na2Si3〇7 . 〇.68H2〇2 將59 %之H2〇2溶液喷灑在三矽酸鈉水合物固體上 (Na2Si3〇7 · χΙί2〇2,阿得里奇化學公司)。讓混合物 在2 5 t下反應1小時,之後在2 5 °C下進行真空乾燥。結果 總結於表4 4中。 88 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨0><297公廣) ---------t------,訂------缘— t (請先聞讀背面之注意事項再填寫本頁) ) 五、發明説明( A7 B7Na4P2〇7 · 2,9! Ϋ? °-quasi-kneading paper with a moderate ruler paper M 5 8 ί public 7 9 2 A7 B7 V. Description of the invention () Synthesis of sulfate perfluoride compound A complex of sulfate and peroxide was synthesized for use in the sterilization process described herein. Examples of detailed synthetic methods for two different sulfate complexes are provided in Examples 41 and 42. Example 41 Synthesis of Na2Si03 · 1.28H2O2 by liquid spray synthesis. A 59% solution of H2O2 was sprayed on a sodium sulfate solid (99%, Adrige Chemical Company). The mixture was allowed to react at 25 ° C for 1 hour, and then dried under vacuum at 25 ° C. The results are summarized in Table 41.袅 41 molar ratio of starting compound complex Na2S〇4 h2〇H2〇2 H2〇2, Na2S〇4 H2〇2 weight ratio (g) (g) 10 10 59 2.46 23.47 Na2S 〇4 · 1.28H2 〇2 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 簏 Example 42 Synthesis of K2S04 by liquid spray synthesis. % Η 2 〇2 solution was sprayed on potassium sulfate solids (99%, Adrige Chemical Co., Ltd.). The mixture was allowed to react at 25 ° C for 1 hour, and then 86 paper standards were applied to Chinese storehouse standards ( CNS) Λ4 specification (210X297 mm) A7 B7 V. Description of the invention () Vacuum drying at 25t. The results are summarized in Table 42. Table 42 ---- one ---- starting compound complex K2S〇4 h2o H2〇2 H2〇2 / K2S〇4 H2 02 composition weight concentration mole ratio to weight percentage (g) ( g) (%) 10 7 59 2.12 23.47 K2S04. 〇.62H2〇2 (please read the note on the back before filling in this page) Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, India, inverse acid overgas Synthesis of the complex We have also synthesized a complex of silicate and peroxide for the sterilization method described herein. Examples of detailed synthetic methods for two different silicate complexes are provided in Examples 43 and 44. Fan Gong 43 Synthesis of Na2Si〇3 by a mud-liquid method. NH2O2 A solid sodium silicate (Na2Si03, Adrige Chemical Co., Ltd.) was mixed with water to form a soft mud 'and cooled to Room temperature • Mix 12% aqueous solution of peroxide gas with mud. The temperature during mixing is approximately 30 ° C to 35 ° C. 〇 between. The mixture was allowed to react at 25C for 1 hour, and then vacuum-dried at 25 ° C. The results are summarized in Table 43. 87 This paper size applies to China National Standards (CNS M4 specifications (210X297 ^ * 7 printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7) 5. Description of the invention () 袅 43 Weight of the starting compound complex Na2Si〇3 h2o Weight of 〇2 Concentration of H2〇2 Molar number of H2〇2 / Na2Si〇3 Weight percentage composition of H2 02 (g) (g) (g) (%) 5 5 23.22 12 2.0 24.74 Na2Si〇3 · 1.18H2〇2 5 5 34.83 12 3.0 37.45 Na2Si〇3 · 2.15H2〇2 5 5 4645 12 4.0 37.64 Na2Si03 · 2.17H2〇2 Example 44 Synthesis of Na2Si3 07 by hydrate method. .68H2 02 will be 59 % H2O2 solution was sprayed on the sodium trisilicate hydrate solids (Na2Si3 07 · χΙί20, Adrige Chemical Co.). The mixture was allowed to react at 25 t for 1 hour, and then at 25 ° Vacuum drying was performed at C. The results are summarized in Table 4 4. 88 This paper size is applicable to China National Standard (CNS) A4 specifications (2 丨 0 > < 297 Gongguang) --------- t-- ----, order ------ fate — t (please read the notes on the back before filling this page)) 5. Description of the invention (A7 B7
經濟部中央棵準局—工消费合作社印裝 在此我們已顯示出許多種無機鹽類之過氧化氫複合物都 可以被製備出來。我們深信在此所揭露之殺菌方法中可藉 使用大量能形成氫鍵的陰離子鹽類來使過氧化氳成功的被釋 放例如那些至少含有一個氧或氮原子的陰離子。參見前述 表1 4,例如可與本發明方法合用之有機複合物和其它之無 機複合物。 鱼祓合物t釋出遇氧仆.你 前述範例中之DSC曲線,例如第6圖,乃是在大氣壓 及減壓狀況下在有一個洞的覆蓋盤中所得出的。由於蓋子上 僅有一個洞’一大氣壓下草酸鉀過氧化物複合物之DSC曲 線上可看一個放熱吸收峰。在大氣壓下重覆此實驗以測定在 更開放的系統中可釋出更多的過氧化氫,如範例4 5中所 示。 89 私紙張尺度適用中國囷家梯率{ CNS ) A4規格(210 X 297公釐) (請先閱讀背面之注f項再填寫本頁) 訂 ^. -1^1 m In ...... A7 B7 經濟部中央梯準局貝工消費合作社印装 五、發明説明() 篪例45 在大氣壓下由草酸抑過氧化物複合物中 釋出過氧化氩 以第5圖位於加熱盤丨丨2上具有2個洞之樣品盤密封蓋 或開放於大氣下之鋁盤之裝置,在大氣壓下加熱草酸鉀過氧 化物複合物(K2C2〇4.H202) »第1〇圖顯示所得之 DSC曲線《如果蓋子是打開的,則曲線上在一個大的吸熱 吸收峰之後出現一個小的放熱吸收峰,顯示只有部分的過氧 化氫被釋出。當盤上覆蓋的是有兩個洞的蓋子時,則曲線上 在一個小的吸熱吸收峰後出現一個大的放熱吸收峰,則是顯 示有一些過氧化氫被釋出,但絕大部分的過氧化氩則是已被 分解了。 範例4 5中的結果顯示在一開放沒有覆蓋的盤中,而不 是復有兩個洞的蓋子時,可釋出大量的過氧化氫•因此其餘 的試驗中’在大氣壓下我們選用沒有覆蓋的盤,而在減壓情 況下則使用有一個洞的蓋子作覆蓋,在D S C曲線中測試過 氧化氫由複合物中釋出的情形。第11至25圖中顯示一痤 無機複合物之DSC曲線,表45則總結了在DSC研究中過 氧化物複合物受熱時的反應。 第 11A 圖乃是 Na4P2〇7 . 2H2〇2 和 Na4P2〇7 ' 3Η2〇2在760托下的DSC曲線。囷上可看出一個吸熱吸 收峰,類示過氧化氩幾乎完全被釋出》 第11Β囷乃是Na4P2〇7 . 4Η2〇2在760托下的 DSC曲線。圖上可看出2個吸熱吸收峰,顯示過氧化氫幾 90 良紙張尺度適用中國固家標準(CNS ) A4规格(210X 297公釐) ---------- Γ (請先聞讀背面之注$項再填寫本頁)Printed by the Central Plant Quarantine Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives. Here we have shown that many kinds of inorganic hydrogen peroxide compounds can be prepared. We are convinced that the sterilization method disclosed here can successfully release thorium peroxide by using a large number of anion salts capable of forming hydrogen bonds, such as those which contain at least one oxygen or nitrogen atom. See the aforementioned Table 14 for examples of organic compounds and other inorganic compounds that can be used in conjunction with the method of the present invention. The release of fish mixture t meets oxygen. Your DSC curve in the previous example, such as Figure 6, was obtained in a cover plate with a hole under atmospheric pressure and reduced pressure. Since there is only one hole in the lid, an exothermic absorption peak can be seen on the DSC curve of the potassium oxalate peroxide complex at atmospheric pressure. Repeat this experiment at atmospheric pressure to determine that more hydrogen peroxide can be released in more open systems, as shown in Example 45. 89 The scale of private paper is applicable to China's family slope {CNS) A4 specification (210 X 297 mm) (Please read the note f on the back before filling this page) Order ^. -1 ^ 1 m In ...... A7 B7 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative Co., Ltd. 5. Description of the invention () Example 45 Argon peroxide released from the oxalic acid-inhibited peroxide compound at atmospheric pressure. 2 The device with a two-hole sample tray with a sealed lid or an aluminum tray opened to the atmosphere, heated the potassium oxalate peroxide complex (K2C204.H202) at atmospheric pressure »Figure 10 shows the DSC curve obtained "If the lid is open, a small exothermic absorption peak appears after a large endothermic absorption peak on the curve, showing that only part of the hydrogen peroxide is released. When the plate is covered with a lid with two holes, a large exothermic absorption peak appears after a small endothermic absorption peak on the curve, which shows that some hydrogen peroxide is released, but most of the Argon peroxide has been decomposed. The results in Example 4 5 show that a large amount of hydrogen peroxide can be released in an open and uncovered plate instead of a lid with two holes. Therefore, in the rest of the experiments, 'we chose uncovered at atmospheric pressure. The plate was covered with a holed lid under reduced pressure, and the release of hydrogen peroxide from the composite was tested in the DSC curve. Figures 11 to 25 show the DSC curves of an inorganic compound, and Table 45 summarizes the reaction of the peroxide compound when heated in the DSC study. Figure 11A is the DSC curve of Na4P2 07. 2H2 0 2 and Na4P2 07 '3Η2 02 at 760 Torr. An endothermic absorption peak can be seen on 囷, which shows that argon peroxide is almost completely released. The 11th 囷 is a DSC curve of Na4P207. 4Η202 at 760 Torr. The figure shows two endothermic absorption peaks, showing a few 90% of hydrogen peroxide. Good paper size is applicable to China Solid Standard (CNS) A4 (210X 297 mm) ---------- Γ (please first (Read the note $ on the back and fill out this page)
-、1T -線> 經濟部中央橾準局貝工消費合作社印製 A7 B7 五、發明説明() 一 乎完全被釋出。 第12圖乃是Na3P〇4‘5H2〇2在76〇耗,7托及 0.35托下的DSC曲線。複合物乃是以液禮嘴;麗法人成 的。圖上可看出在一個吸熱吸收峰之後出現一個小的放熱吸 收峰,顯示在大氣壓下有部分過氡化氩被釋出。但是在真& 下’一個較宽的吸熱效果顯示過氧化氩幾乎完全被釋出。 第 13 @ 乃是 Na2HP04 . 1H202 和 Na2Hp〇4 2H2〇2在760托下的DSC曲線。兩種複合物在Dsc曲 線上均顯出吸熱的現象,顯示在大氣壓下有幾近完全的釋 出。-、 1T -line > Printed by Shellfish Consumer Cooperative of Central Bureau of Quasi-Ministry of Economic Affairs A7 B7 V. Description of Invention () Almost completely released. Figure 12 is the DSC curve of Na3P04'5H202 at 76 ° C, 7 Torr and 0.35 Torr. The complex is based on the liquid mouth; It can be seen from the figure that a small exothermic absorption peak appears after an endothermic absorption peak, showing that part of the tritium argon is released at atmospheric pressure. But a wider endothermic effect under true & shows that argon peroxide is almost completely released. The 13th @ is the DSC curve of Na2HP04. 1H202 and Na2Hp〇4 2H2 02 at 760 Torr. Both complexes showed an endothermic phenomenon on the Dsc curve, showing that they were almost completely released at atmospheric pressure.
第14圖乃是Na5P3O10 . H2〇2在760托下的DSC 曲線。數個吸熱吸收峰顯示在大氣壓下有幾近完全的釋出。 第15圖乃是Κ3Ρ〇4.3·34Η202在760托,7把 及1.0托下的DSC曲線。大氣壓下DSC曲線上的一個吸 熱吸收峰顯示大部分的過氧化氫在大氣壓下已被分解,但是 在真空下’在放熱吸收峰之前的一個吸熱吸收峰顯示在真空 下有部分過氧化氫被釋出。 第16圖乃是K4P2O7 . 7H2〇2在760托及7托下的 DSC曲線。基於各自被取得之重量損失數據,在大氣壓下 140 °C-180 °C之溫度範固内,吸熱吸收峰可能與放熱吸收 峰互相抵消。因此,DSC曲線顯示在大氣壓下有部分過氧 化氫被釋出。真空下的數個吸熱吸收峰則顯示在此種情況下 有幾近完全的釋出》 第W閾乃是K:2HP〇4 . 3.15H202在760托及7托 -;_______91___ _ 本紙張尺度適用中固國家標车(CNS) A4^ (210x297公着) (請先聞讀背面之注f項再填寫本頁) 訂 經濟部中央棣準局貝工消费合作社印策 A7 B7 五、發明説明() 下的DSC曲線。基於各自被取得之重量損失數據,在大氣 壓下140C-180C之溫度範園内,吸熱吸收峰可能與放熱 吸收峰互相抵消。因此,DSC曲線顯示在大氣壓下有部分 過氧化氫被釋出。真空下的數個吸熱吸收峰則顯示在此種情 況下有幾近完全的釋出。 第18圖乃是KH2PO4 . H2〇2在760托下的DSC曲 線。圖中可觀察到兩個吸熱吸收峰,顯示在大氣壓下有幾近 完全的釋出。 第Μ圖乃是Na2C〇3 · 1.5H2〇2在760托及7托 下的DSC曲線。在90_100t溫度範圍下觀察到的吸熱吸 收锋分別是在大氣壓及真空下釋出過氧化氫所造成的。在大 氣壓下1 5 0 °C所看到的放熱吸收♦則大部分是由於過氧化氩 分解所造成的。但是’在真空下此放熱吸收峰則轉成一吸熱 吸收峰,並接著一個小的放熱吸收辛,顯示大部分的過氧化 氫均已被釋出。 第2〇圖乃是Ca2P2〇7.3.42H2〇2在760托下的 DSC曲線。圖中之吸熱吸收峰,顯示過氧化氫幾乎完全被 釋出。 第,21囷乃是Mg2p2〇7 . 4.6H2〇2在760托及7托 下的DSC曲線。在吸熱吸收峰後緊接著一個放熱吸收峰顯 示在大氣壓下有部分的過氧化氫被釋出,但是在真空下所看 到的較大的吸熱吸收峰則顯示大部分的過氧化氩均已被釋 出。 第22囷乃是Na2S04 . 1·28Η202在760托下的 92 本紙張尺度逋用中國國家梯準(CNS ) Α4規格(210X297公釐) ---------裝,-------1T------^ .( {請先閱讀背面之注$項再填寫本頁) A7 B7 五、發明説明() DSC曲線。圖中之吸熱吸收峰,顯示在大氣壓下過氧化氩 幾乎完全被釋出。 第23圖乃是K2S〇4.〇.62H2〇2在760托下的 DSC曲線。囷中之吸熱吸收峰,顯示在大氣壓下過氧化氫 幾乎完全被釋出。 第 24 圖乃是 Na2Si〇3 . 2.15H2〇2 在 76〇 托,1 托 及0.5托下的DSC曲線。放熱吸收峰顯示在真空及大氣壓 下大部分的過氧化氫均已被分解。 第25囷乃是Na2Si3〇7 · 〇.68H2〇2在760托下的 DSC曲線。放熱吸收峰顯示在大氣壓下大部分的過氧化氫 均已被分解。 表4 5總結在D S C研究中過氧化物複合物受熱時的反 應。 {請先閲讀背面之注$項再填寫本頁) -%Figure 14 is the DSC curve of Na5P3O10.H2O2 at 760 Torr. Several endothermic absorption peaks show a nearly complete release at atmospheric pressure. Figure 15 shows the DSC curve of K3PO4.3.34Η202 at 760 Torr, 7 Torr and 1.0 Torr. An endothermic absorption peak on the DSC curve at atmospheric pressure shows that most of the hydrogen peroxide has been decomposed at atmospheric pressure, but an endothermic absorption peak under vacuum 'before the exothermic absorption peak shows that some hydrogen peroxide is released under vacuum Out. Figure 16 is the DSC curve of K4P2O7. 7H2O2 at 760 Torr and 7 Torr. Based on the weight loss data obtained, the endothermic absorption peak and the exothermic absorption peak may cancel each other out in the temperature range of 140 ° C-180 ° C at atmospheric pressure. Therefore, the DSC curve shows that part of the hydrogen peroxide is released at atmospheric pressure. Several endothermic absorption peaks under vacuum show almost complete release in this case. The W threshold is K: 2HP〇4. 3.15H202 at 760 Torr and 7 Torr-; _______91___ _ This paper size applies Zhonggu National Standard Car (CNS) A4 ^ (210x297) (Please read the note f on the back before filling out this page) Order the Ace B7 Printing Policy of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy ) DSC curve. Based on the weight loss data obtained, the endothermic absorption peak and the exothermic absorption peak may cancel each other out in the temperature range of 140C-180C at atmospheric pressure. Therefore, the DSC curve shows that part of the hydrogen peroxide is released at atmospheric pressure. Several endothermic absorption peaks under vacuum show almost complete release in this case. Figure 18 shows the DSC curve of KH2PO4.H2O2 at 760 Torr. Two endothermic absorption peaks can be observed in the figure, showing almost complete release at atmospheric pressure. Figure M is the DSC curve of Na2C03.1.5H2O2 at 760 Torr and 7 Torr. The endothermic absorption fronts observed in the temperature range of 90 to 100t are caused by the release of hydrogen peroxide under atmospheric pressure and vacuum. The exothermic absorption seen at 150 ° C at atmospheric pressure is mostly due to the decomposition of argon peroxide. But 'this exothermic absorption peak turns into an endothermic absorption peak under vacuum, followed by a small exothermic absorption peak, showing that most of the hydrogen peroxide has been released. Figure 20 is the DSC curve of Ca2P20.7.3.42H2O2 at 760 Torr. The endothermic absorption peak in the figure shows that hydrogen peroxide is almost completely released. No. 21 is the DSC curve of Mg2p207. 4.6H202 at 760 Torr and 7 Torr. Immediately after the endothermic absorption peak, an exothermic absorption peak shows that part of the hydrogen peroxide is released at atmospheric pressure, but the larger endothermic absorption peak seen under vacuum shows that most of the argon peroxide has been removed. Release. No. 22 is Na2S04. 92 paper sizes of 1.28Η202 under 760 Torr, using China National Standard (CNS) Α4 size (210X297 mm) --------- install, ---- --- 1T ------ ^. ({Please read the note on the back before filling in this page) A7 B7 5. Description of the invention () DSC curve. The endothermic absorption peak in the figure shows that argon peroxide is almost completely released at atmospheric pressure. Figure 23 shows the DSC curve of K2S04.0.0.62H2O2 at 760 Torr. The endothermic absorption peak in tritium shows that hydrogen peroxide is almost completely released at atmospheric pressure. Figure 24 is the DSC curve of Na2Si〇3. 2.15H2O2 at 7600 Torr, 1 Torr and 0.5 Torr. The exothermic absorption peak shows that most of the hydrogen peroxide has been decomposed under vacuum and atmospheric pressure. The 25th line is the DSC curve of Na2Si30.7.68H2O2 at 760 Torr. The exothermic absorption peak shows that most of the hydrogen peroxide has been decomposed at atmospheric pressure. Table 4 5 summarizes the reaction of the peroxide complexes when heated in the DSC study. (Please read the note on the back before filling this page)-%
,1T --i·· · 經濟部中央標準局貝工消费合作社印装 93 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨0X297公釐) 經濟部中央橾準局員工消費合作社印製 五、發明説明() 裊45 複合物 在DSC研究中受熱時的反應 圖形編號 1大氣壓下(760 托) 真空下 K2C2°4 ' 1H2°2 吸熱+放熱 吸熱 10 Na4P2〇7 NH2〇2 n=2,3,4 吸熱 吸熱 11A 及 11B Na3P〇4 * 5H2〇2 吸熱+放熱 吸熱 12 Na2HP〇4 · nH2〇2 n=l,2 吸熱 吸熱 13 Na^P^OjQ NH2O2 n=1.2 吸熱 吸熱 14 K3PO4 * 3.34H2〇2 放熱 吸熱+放熱 15 K4P2O7 · 7H2〇2 吸熱+放熱 吸熱 16 K2HPO4 · 3.15H2〇2 吸熱+放熱 吸熱 17 KH2P〇4 · lH2〇2 吸熱 吸熱 18 Na2C03 · 1.5H2〇2 放熱 吸熱+放熱 19 匸&2卩2〇7 , 3,42H2〇2 吸熱 吸熱 20 Mg2?2〇7 ' 4.60H2〇2 吸熱+放熱 吸熱 21 Na2S〇4 · 1.28H202 吸熱 吸熱 22 K2S04 · 0.62H2〇2 吸熱 吸熱 23 Na2Si03 · 2.15H2〇2 放熱 放熱 24 Na2Si3〇7 O.68H2O2 放熱 放熱 25 效率測試結果 前述範例,如範例1 7和1 8,顯示以在此所述及其它地 方提到的技術的支援下,過氧化物無機複合物能被用於真空 下殺菌。為顯示這些過氧化物無機複合物在大氣壓下也能殺 94 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) -* 經濟部中央橾準局貝工消費合作社印製 A7 B7_ 五、發明説明() 菌,我們測試了許多化合物的殺菌效率。範例46A乃是在 一大氣壓下其DSC曲線有一吸熱吸收峰之複合物,在一大 氣壓及低溫(S6(TC)下的殺菌結果。範例46B乃是在一 大氣壓下其DSC曲線同時具有吸熱及放熱吸收♦之複合 物’在一大氣壓及低溫(各60X:)下的殺菌結果。範例 46C乃是在一大氣壓下其DSC曲線有一放熱吸收峰之複合 物’在一大氣壓及低溫(S60°C)下的殺菌結果。範例47 乃是在一大氣壓下加熱一 DSC曲線僅有一吸熱吸收嘩之複 合物’其在一大氣壓下的殺菌結果。範例48則是在一大氣 壓下加熱一 DSC曲線同時具有吸熱及放熱吸收峰之複合 物,其在一大氣壓下的殺菌結果。如下列,在這些情況下, 使用這些複合物,即使是在其DSC曲線中僅有一放熱吸收 峰之複合物,也可在大氣壓下達到有效的殺菌•如上述,一 般相信在某些情況下,在相同的溫度範困内,吸熱吸收峰可 能被:放熱吸收峰所掩蓋,因此可解釋以DSC曲線中僅有一 放熱吸收峰之複合物所作得殺菌測試效果·, 1T --i ··· Printed by the Bayer Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 93 This paper size applies to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) V. Description of the invention () The reaction pattern of the 袅 45 compound when heated in DSC studies is numbered at 1 atmosphere (760 Torr) under vacuum K2C2 ° 4 '1H2 ° 2 endothermic + exothermic 10 Na4P207 NH2〇2 n = 2 , 3,4 Endothermic 11A and 11B Na3P〇4 * 5H2〇2 Endothermic + Exothermic 12 Na2HP〇4 · nH2〇2 n = 1, 2 Endothermic 13 Na ^ P ^ OjQ NH2O2 n = 1.2 Endothermic 14 K3PO4 * 3.34H2〇2 exothermic + exothermic 15 K4P2O7 · 7H2〇2 endothermic + exothermic 16 K2HPO4 · 3.15H2 02 endothermic + exothermic 17 KH2P〇4 · lH2 02 endothermic 18 Na2C03 · 1.5H2 02 exothermic + exothermic 19 匸 & 2 卩 2〇7, 3,42H2〇2 endothermic endotherm 20 Mg2 ~ 2〇7 '4.60H2〇2 endothermic + exothermic endotherm 21 Na2S〇4 · 1.28H202 endothermic endotherm 22 K2S04 · 0.62H2 02 endothermic 23 Na2Si03 2.15H2〇2 exothermic 24 Na2Si3〇7 68. H2O2 exothermic exothermic 25 Efficiency test results The previous examples, such as Examples 17 and 18, show that with the support of the techniques described here and elsewhere, peroxide inorganic composites can be used for sterilization under vacuum. In order to show that these peroxide inorganic composites can also kill 94 at atmospheric pressure. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)-* Ministry of Economy A7 B7 printed by the Central Bureau of quasi-speciality Shellfish Consumer Cooperatives V. Description of the invention () bacteria, we tested the bactericidal efficiency of many compounds. Example 46A is a compound whose DSC curve has an endothermic absorption peak at atmospheric pressure, and sterilization results at atmospheric pressure and low temperature (S6 (TC). Example 46B is a DSC curve with both endothermic and exothermic absorption at atmospheric pressure ♦ The sterilization result of the compound 'at atmospheric pressure and low temperature (each 60X :). Example 46C is a compound whose DSC curve has an exothermic absorption peak at atmospheric pressure' at atmospheric pressure and low temperature (S60 ° C) Bactericidal results. Example 47 is a compound that has a DSC curve with only one endothermic absorption wave when heated at atmospheric pressure. Its sterilization result at one pressure. Example 48 is a DSC curve that has both endothermic and exothermic heating at one pressure. The compounds of absorption peaks have sterilization results at atmospheric pressure. As shown below, in these cases, using these compounds, even the compounds with only one exothermic absorption peak in their DSC curve can be effectively effective at atmospheric pressure. Sterilization • As mentioned above, it is generally believed that in some cases, the endothermic absorption peak may be masked by the exothermic absorption peak within the same temperature range. Cover, which can explain the sterilization test effect of the compound with only one exothermic absorption peak in the DSC curve.
篪例46A 以KH2P〇4 . H2〇2過氧化物複合物來作殺菌 (1大氣壓及低溫)Example 46A: KH2P04. H2O2 peroxide compound is used for sterilization (1 atmosphere and low temperature)
將一自助式殺菌袋以下列方式來组裝:將表面含7.7 X 鋼刀片放在一殺菌的培養皿(60 X 15 1111«)上。將2g的 KH2PO4 · H2〇2複合物粉末(内含20.31%H2〇2)放進另 __95 本紙張尺度適用中0國家標率(〇^)八4%^(21()><297公釐) " (請先閲讀背面之注f項再填寫本頁) 訂 .崠' 經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明() 一培養皿中。將兩個培養皿一起放 λ 入由 TYVEKtm/MYLARTM 製成的 1()〇 X 25 0 mni 之趣菌袋 中。將殺菌袋密封後分別置於室溫(約2 3 °C ) , 4〇v c (在 培育箱中)和60 °C (在烘箱中)下一段不同的時間。 結果 總結於表4 6 A中。Assemble a self-service sterilization bag in the following manner: Place a 7.7 X steel blade on the surface on a sterilized petri dish (60 X 15 1111 «). Put 2g of KH2PO4 · H2O2 composite powder (containing 20.31% H2O2) into another __95. This paper scale is applicable to 0 national standard rate (0 ^) 8 4% ^ (21 () > < 297 mm) " (Please read note f on the back before filling out this page) Order. 崠 'Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention () in a petri dish. Put two petri dishes together into a 1 () × 25 0 mni fungus bag made of TYVEKtm / MYLARTM. After the sterilization bag was sealed, it was placed at room temperature (about 23 ° C), 40 v c (in the incubator) and 60 ° C (in the oven) for different periods of time. The results are summarized in Table 4 6 A.
袅46A 溫度 曝露時間(正反應/相 ----〜 5·品總數、 1小時 2小時 4小時 6小時 ---^ 23°C (室溫) + + - - 4(TC + + - - •K 6 0 °C + - -袅 46A temperature exposure time (positive reaction / phase ---- ~ 5 · total number of products, 1 hour 2 hours 4 hours 6 hours --- ^ 23 ° C (room temperature) + +--4 (TC + +--- • K 6 0 ° C +--
簏例46B 以K2C2O4 . H2〇2過氧化物複合物來作殺菌 (1大氣壓及低溫) 將一自助式殺菌袋以下列方式來组裝:將表面含134 X 1〇6 枯草样菌芽跑(Baci!!uS Var. 之不銹鋼刀片放在一殺菌的培養皿(60 x 15 mm)上。將 2g 的 KH2PO4 · h2〇2 複合物粉末(内含 l4.21%H2〇2) 放進另一培養皿中。將兩個培養贝一起放入由 Μ Y L A R Τ Μ / μ Y L A R T Μ 製成的 1 〇 〇 χ 2 5 〇 m m 之殺菌袋 中。將殺菌袋密封後分別置於4〇°c (在培育箱中)和6〇r (在烘箱中)下一段不同的時間。結果總結於表4 6 b中。 96 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐) (請先聞讀背面之注$項再填寫本頁) 訂 A7 ____ B7 厂 I -- ____ - 五、發明説明()Example 46B: K2C2O4.H2O2 peroxide compound is used for sterilization (1 atmosphere and low temperature). A self-service sterilization bag is assembled in the following way: the surface containing 134 X 106 subtilis-like sprouts is run ( A stainless steel blade of Baci !! uS Var. Is placed on a sterilized petri dish (60 x 15 mm). 2g of KH2PO4 · h2〇2 composite powder (containing 14.1% H2〇2) is placed in another In a petri dish, put two culture shells together in a 100 × 25 mm sterilization bag made of MYLAR TM / μ YLART Μ. Seal the sterilization bags and place them at 40 ° C ( (In the incubator) and 60 (in the oven) for a different period of time. The results are summarized in Table 4 6 b. 96 This paper size applies to China National Standard (CNS) A4 (210X297 mm) (please First read the note $ on the back and fill in this page) Order A7 ____ B7 Factory I-____-V. Description of Invention ()
A 46B 溫度 睡·霪時間ί正反應/樣品總數) 8小時 1 6小時 2 4小時 4 8小時 7 2小時 4 0eC N/A N/A + + - 6 0°C + - - -A 46B Temperature Sleep and sleep time (positive reaction / total number of samples) 8 hours 1 6 hours 2 4 hours 4 8 hours 7 2 hours 4 0eC N / A N / A + +-6 0 ° C +---
簏例4 6 C 以Na2C〇3 . i 5H2〇2過氧化物複合物來作殺菌 (1大氣壓及低溫) 將一自助式殺菌袋以下列方式來組裝:將表面含1.34 X 10 枯草桿菌芽胞να/*. 容er)) 之不銹鋼刀片放在一殺菌的培養ϋα(60 x 15 mm)上。將 2g的Na2c〇3 . 15H202複合物粉末(内含27.78% H2〇2 ’福卡化學公司)放進另一培養μ中。將兩個培養μ 一起放入由 Μ Y L A R Τ Μ / μ Y L A R Τ Μ 製成的 1 〇 〇 X 2 5 〇 mm之殺菌袋中。將殺菌袋密封後置於60 °C (在烘箱中) 下一段不同的時間。結果總結於表4 6 c中· &J-------1T------^ XMmi (請先閏讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消費合作社印«. A 46C 溫度 曝露時間(正反應/樣品總數) 2 4小時 4 8小時 7 2小時 6 0°〇 + - * 簏例47 97 本紙張尺度通用中國國家標準(CNS ) A4規格(210X297^^7 經濟部中央標準局貝工消費合作社印製 A7 _B7_ 五、發明説明() 以Na4P2〇7 . 3H2〇2過氧化物複合物來作殺菌 (1大氣壓及提高的複合物溫度下) 以Na4p2〇7 · 3H2〇2(重量百分比= 27%)用於第8圈 的裝置中。殺菌時所用參數如下:殺菌内室大小= 6.25" X 6.25" X 7" (4.5升);殺菌室溫度=40 °C ;殺菌室壓力 =760托,加熱溫度=175-180。〇。以每個刀片上含1.5 x 1〇6 振顫桿菌芽胞ί_/ί·ί/·ϊ jpora)之濃度 作為接種濃度。結果總結於表47A及47B中。如表47A 所示,僅使用O.Olg之複合物位即可使位於加熱裝置兩英 吋上方的不銹鋼刀片達到完全殺菌的效果。相反的,已接種 且位於殺菌室底端的刀片,則須〇 . 3 g之複合物方能達到完 全殺菌的效果。Example 4 6 C Use Na2C03.i 5H2O2 peroxide compound for sterilization (atmospheric pressure and low temperature) A self-service sterilization bag is assembled in the following way: 1.34 X 10 Bacillus subtilis να on the surface / *. 容 er)) 's stainless steel blade was placed on a sterilized culture ϋα (60 x 15 mm). 2 g of Na2co3. 15H202 complex powder (containing 27.78% H2O2'Foka Chemical Co., Ltd.) was put into another culture μ. The two culture μs were put together in a 100 × 25 mm sterilization bag made of M Y L AR T Μ / μ Y L AR T Μ. Seal the sterilization bag and place at 60 ° C (in an oven) for a different period of time. The results are summarized in Table 4 6 c. &Amp; J ------- 1T ------ ^ XMmi (Please read the precautions on the back before filling out this page) Printed by a consumer cooperative «. A 46C Temperature exposure time (positive reaction / total number of samples) 2 4 hours 4 8 hours 7 2 hours 6 0 ° 〇 +-* Example 47 97 This paper is in accordance with China National Standard (CNS) A4 specifications ( 210X297 ^^ 7 Printed by A7 _B7_, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention () Use Na4P207. 3H2O2 peroxide compound for sterilization (at 1 atmosphere and elevated temperature of the compound) Na4p2 07 · 3H2 02 (weight percentage = 27%) was used in the device of the eighth circle. The parameters used in sterilization were as follows: sterilization inner chamber size = 6.25 " X 6.25 " X 7 " (4.5 liters); Sterilization chamber temperature = 40 ° C; Sterilization chamber pressure = 760 Torr, heating temperature = 175-180. 〇. Each blade contains 1.5 x 1〇6 Vibrio bacillus spores. The concentration was used as the inoculation concentration. The results are summarized in Tables 47A and 47B. As shown in Table 47A, only the compound level of O.Olg can be used to achieve the effect of complete sterilization of the stainless steel blade located two inches above the heating device. In contrast, a blade that has been inoculated and located at the bottom of the sterilization chamber requires 0.3 g of the compound to achieve the full sterilization effect.
表47A 殺菌效果(正反應/樣品總數) 樣品位於加熱盤上方兩英对處 複合物重量 2/ 1 0循環* 2 / 1 5楯環 2/3 0循環 O.Og 2/2 2/2 2/2 O.Olg 0/2 0/2 0/2 0.0 3 g 0/2 0/2 0/2 0 · 0 5 g 0/2 0/2 0/2 :循環時間=加熱時間(分鐘)/全部曝露的時間(分鐘)Table 47A Bactericidal effect (positive reaction / total number of samples) The sample is located on the top of the heating plate. The weight of the compound is 2/1 0 cycle * 2/1 5 ring 2/3 0 cycle O.Og 2/2 2/2 2 / 2 O.Olg 0/2 0/2 0/2 0.0 3 g 0/2 0/2 0/2 0 · 0 5 g 0/2 0/2 0/2: Cycle time = heating time (minutes) / Total exposure time (minutes)
表47B _________98 本紙張尺度適用中國國家標準(CNS > A4規格(210X297公釐) ---------------訂------咮:- (請先聞讀背面之注^^ίm·項再填寫本頁) A7 B7 五、發明説明() 殺菌效果(正反應/樣品總數) 樣品位於殺菌室底部 複合物重量 2/ 1 0循環* 2 / 1 5循環 2/3 0循環 0 · 0 g 2/2 2/2 2/2 0 · 1 g 2/2 2/2 2/2 〇.2g 1/2 1/2 1/2 〇.3g 0/2 0/2 0/2 0.5 g 0/2 0/2 0/2 (請先閲讀背面之注^ΡΙ·項再填寫本頁) * :循環時間=加熱時間(分鐘)/全部曝露的時間(分鐘)Table 47B _________98 This paper size applies to Chinese National Standards (CNS > A4 size (210X297mm) --------------- Order ------ 咮:-(please listen first Read the note on the back ^ ^ m · item and fill out this page again) A7 B7 V. Description of the Invention 2/3 0 cycle 0 · 0 g 2/2 2/2 2/2 0 · 1 g 2/2 2/2 2/2 〇. 2g 1/2 1/2 1/2 〇. 3g 0/2 0 / 2 0/2 0.5 g 0/2 0/2 0/2 (Please read the note on the back ^ ΡΙ · before filling out this page) *: Cycle time = heating time (minutes) / total exposure time (minutes)
Jfe 例 48Jfe case 48
、1T 一令·*'—· 以K2C2〇4 . H2〇2過氧化物複合物來作殺菌 (1大氣壓及提高的複合物溫度下) 以〖2〇2〇4.1^〇2(重量百分比=16.3%)用於第8阐 的裝置中。殺菌時所用參數如範例47所示,但加熱溫度改 用155-160。(:。在此實驗中,將接種了細菌芽胞的刀片置 於加熱盤上方•結果總結於表48中。 經濟部中央標準局WC工消費合作杜印製 i·1T 1 ** '— · Use K2C2O4. H2O2 peroxide compound for sterilization (at 1 atmosphere and elevated compound temperature) to [2〇2〇4.1 ^ 〇2 (weight percentage = 16.3%) was used in the device explained in 8. The parameters used for sterilization are shown in Example 47, but the heating temperature is changed to 155-160. (:. In this experiment, the blade inoculated with bacterial spores was placed above the heating plate. The results are summarized in Table 48. WC Industrial Consumption Cooperation by the Central Standards Bureau of the Ministry of Economic Affairs
A7 ____ B7 五、發明説明() 蠱48 殺菌效果(正反應/樣品總數) 樣品位於加熱盤上方兩英叶處 複合物重量 2/10循環* 2/1 5循環 2/30循環 Ο.Οβ 2/2 2/2 2/2 〇·〇1ε 1/2 1/2 0/2 —_0〇3g 0/2 0/2 0/2 〇 . 0 5 g 0/2 0/2 0/2 0 . 1 g 0/2 0/2 0/2 0.2 g 0/2 0/2 0/2 (請先閲讀背面之注$項再填寫本頁) :循環時間==加熱時間(分鐘)/全部曝露的時間(分鐘) 使用草酸鉀複合物殺菌時,須O.Olg及30分鐘的殺菌 時間始能達成完全殺菌。在所有三種殺菌循環中,使用 0-〇3g之複合物均可達到完全殺菌。 總言之,過氧化氫可在大氣壓及室溫下由複合物中釋 出。可藉提高溫度及減壓來促進過氧化氫的釋出。 過氣化氤禎合物中釋出蒎氣的系統 在第7A囷及第7B圖中所用的裝置可當作一種使過氧 化氫蒸氣由過氧化氩複合物中釋出的系統。此種裝置可與形 成碟狀的過氧化物複合物一同使用◎但是,我們發現使用粉 末狀的複合物可使過氧化氫蒸氣更迅速完全的釋出。以第 100 本紙張尺度ϋΛ中國國家揉準《CNS > A4規格(210X297公釐) """"" 訂 -ff ! 經濟部中央標準局貝工消费合作社印製 A7 ___—__B7_ 五、發明説明() 7A及7B圖中所述之方式將複合物粉末放入裝置中但 是,另一種引入複合物粉末的方式乃是先將複合物粉末放在 高溫下有黏著性的膠帶上。例如,3M公司製造的高溫膠帶 9469,其上所用的乃是其公司出產的a丨〇黏著劑。可將複 合物粉末灑在黏著劑及膠帶上後,再將其置入殺菌室中使過 氧化氫蒸氣釋出。可用的另一種黏性膠帶的例子乃是3 Μ公 司以Α25黏著劑製造的膠帶9485。 結論 本發明之範_並不僅限於上述之實施例。任何仍保有本 發明精神之實施例均視其仍隸屬本發明之範国内β然而本 發明之範疇乃受以下申請專利範園之限制。 (請先聞讀背面之注項再填寫本I ) -訂 經濟部中央標準局貝工消费合作社印製 一張 紙 I本 準 樣 家 一羁 一國 I中 I用 14 Α4 釐 29A7 ____ B7 V. Description of the invention () 蛊 48 Sterilization effect (positive reaction / total number of samples) The sample is located at the two leaves above the heating plate. The weight of the compound is 2/10 cycles * 2/1 5 cycles 2/30 cycles 〇β β 2 / 2 2/2 2/2 0 · 〇1ε 1/2 1/2 0/2 —_0〇3g 0/2 0/2 0/2 0. 0 5 g 0/2 0/2 0/2 0. 1 g 0/2 0/2 0/2 0.2 g 0/2 0/2 0/2 (Please read the note on the back before filling in this page): Cycle time == heating time (minutes) / all exposed Time (minutes) When using potassium oxalate compound for sterilization, complete sterilization must be achieved with O.Olg and 30 minutes. In all three sterilization cycles, complete sterilization can be achieved using 0-03 g of the complex. In summary, hydrogen peroxide can be released from the complex at atmospheric pressure and room temperature. The release of hydrogen peroxide can be promoted by increasing the temperature and reducing the pressure. System for releasing radon gas from pergassed admixture The device used in Figs. 7A and 7B can be regarded as a system for releasing hydrogen peroxide vapor from an argon peroxide compound. This type of device can be used with a peroxide compound that forms a dish. However, we have found that the use of a powder-like compound allows the hydrogen peroxide vapor to be released more quickly and completely. With the 100th paper standard, the Chinese government has approved the "CNS > A4 Specification (210X297 mm) " " " " " Order -ff! A7 printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ___— __B7_ V. Description of the invention () The composite powder is put into the device in the way described in 7A and 7B. However, another way to introduce the composite powder is to first put the composite powder on an adhesive tape with high temperature. on. For example, the high-temperature tape 9469 manufactured by 3M Company uses an ao0 adhesive produced by its company. The compound powder can be sprinkled on the adhesive and tape, and then placed in a sterilization chamber to release the hydrogen peroxide vapor. An example of another type of adhesive tape that can be used is 3845's adhesive tape 9585 made with A25 adhesive. Conclusion The scope of the present invention is not limited to the embodiments described above. Any embodiment that still retains the spirit of the present invention is regarded as still belonging to the scope of the present invention. However, the scope of the present invention is limited by the following patent application parks. (Please read the note on the back before filling in this I)-Order a piece of paper printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative, a copy of the paper, a sample, a home, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, a country, and a country. 14 A4% 29
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