CN1072891C - 一种协同杀微生物组合物 - Google Patents
一种协同杀微生物组合物 Download PDFInfo
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Abstract
公开了一种具有协同性的杀微生物组合物，由4，5-二氯-2-n-辛基-3-异噻唑酮和一种或多种第二杀微生物剂组成，它对多种系统中的微生物的作用更有效，控制范围更大。第二杀微生物剂可选自：2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪和N，N-二甲基-N’-苯基-(N’-氟二氯甲硫基)-磺酰胺。这些组合物可对很大范围的微生物产生意想不到的协同性杀伤作用；两种化合物合并对微生物的破坏作用比两种化合物单独作用之和要大得多。
Description
本发明涉及杀生物剂，其主要应用于海洋、工业及建筑业用涂料中。
在3761488、4105431、4252694、4265899和4279762号美国专利中及其他地方都对异噻唑酮(isothiazolone)有过描述，它作为杀微生物剂的作用是已知的。
异噻唑酮可与某些其他的活性组分协同作用，详例见4990525,4964892、5236888、5292763号美国专利。
4,5-二氯-2-正辛基-3-异噻唑酮是一种特殊种类的异噻唑酮，可用于海洋、工业及建筑业用涂料。异噻唑酮是已知的皮肤激敏物，它在某些涂料中的应用受到限制是因为有效控制微生物生长所需的异噻唑酮的量要高于避免致敏作用而建议的使用限量所致。
用于文中的术语“杀微生物的”(或“抗微生物的“或“杀生物的”)，其含义包括(但不限于此)所有的杀细菌、杀真菌及杀藻类活性。
因此，本发明的目的之一是提供既能有效地控制微生物生长又能减小其对皮肤致敏作用的4,5-二氯-2-n-辛基-3-异噻唑酮杀微生物组合物。
该目的(其他将随下列阐述显而易见的目的)可通过本发明来实现，本发明一方面包括；由4,5-二氯-2-n-辛基-3-异噻唑酮和一种或多种选自2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪和N,N-二甲基-N’-苯基-(N’-氟二氯甲硫基)-磺酰胺的第二组分形成的组合物。这种组合物可对很大范围的微生物产生意想不到的协同性杀伤作用：两种化合物合并使用对微生物的破坏作用意外地要比两种化合物单独作用之和大得多。
本发明中的组合物所说明的协同作用并不是由所预知的化合物的活性或活性改良所产生。由于组合物的协同作用，所需的有效剂量降低，从而使其不仅更经济而且还提高了安全度，本发明的协同性组合物使得在许多系统中对微生物的控制更有效、范围更广。
本发明提供具有杀微生物活性的组合物，它包括4,5-二氯-2-n-辛基-3-异噻唑酮和选自于2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪和N,N-二甲基-N’-苯基-(N’-氟二氯甲硫基)-磺酰胺的一种或多种的第二组分；其中4,5-二氯-2-n-辛基-3-异噻唑酮和第二组分的重量比为约60∶1到约1∶500之间。
本发明的协同性杀微生物组合物的重要应用包括(但不限于此)：抑制软体或硬体的海洋污损生物的生长，如藻类、被囊动物、水螅、双壳类动物、苔藓、多毛线虫、海绵、藤壶，这些生物生长在水下结构物上，如船的水中部分、桥墩、码头、木桩、鱼网、热交换器、大坝以及管道结构如管道几口处的滤网；抑制工业涂料如颜料、橡胶涂料、胶粘剂、粘合剂、密封胶及嵌缝胶中的藻类、细菌及真菌的生长；木材处理，如压力或真空的渗透以及抗树液着色处理；控制在纸浆、造纸厂及冷却塔中的产粘质的藻类、细菌、真菌的生长；橡胶乳化液及胶合水泥中的应用；保护切削液；用以浸泡或喷雾处理纺织品或皮革以防止霉菌生长；保护漆膜，尤其是外层漆不为藻类所破坏，而通常漆膜暴露在外时易为藻类所污染损坏；保护甘蔗和甜菜的制糖过程中所用的设备不受粘质沉积的损害；防止微生物在工业净水供应系统中的净化器或去污系统中的繁殖与沉积；保护燃料；控制油田钻井过程中微生物在油浆混和物以及二次石油回收时的污染及沉积；防止在纸张涂层及涂层过程中细菌与真菌的生长；控制各种特质板如硬纸板、刨花板的制作过程中细菌与真菌的生长与沉积；控制细菌与真菌在粘土和各种色料浆中的生长；作为一种硬质表面消毒剂以防止细菌、真菌在墙、地板等处的生长；作为化妆品盥洗品原料、地板抛光剂、织物软化剂、家用及工业用清洗剂的防腐剂；用于游泳池中防止藻类的生长；抑制有害细菌、酵母、真菌在植物、树木、水果、种子或土壤中的生长；保护农业设施、电沉积系统、诊断与试剂产生品、医疗器械；保护动物浸水处没有微生物的繁殖；在照相冲洗过程中免受微生物的污染，等等。
本发明组合物可单独使用到任何系统中，也可制成包含其基本成分及必要时含有合适的载体或溶媒的简单混合物，或制成水乳液或分散体。
本发明也提供一种在易受细菌、真菌、藻类污染的位置抑制该类微生物生长的方法，即在易受污染处直接施用上文所定义的任何组合物，用量为足以对细菌、真菌藻类的生长产生遏制效果。
本发明的组合物可与多种有机溶剂制成溶液。该溶液一般含5-30％(重量)的活性组合物。要得到该组合物的水稀释液就更方便：只要往有机溶液中加一种乳化剂，然后用水稀释即可，或作为一种即用固体来配制。
本发明的组合物也可加到装饰业、工业或海洋涂料组合物中，它还包括形成膜的聚合物。在用于装饰业或工业涂料组合物中时，活性组合物占涂料组合物重量的0.05-2.0％；在用于海洋业涂料组合物时，活性组合物占涂料组合物量的0.5～15.0％。
装饰业用涂料指颜料、密封胶和油漆。工业用涂料指颜料、橡胶涂料、胶粘剂、粘合剂、密封胶和嵌缝胶。海洋用涂料指用于水下构筑物上的涂料，如船体水下部分、桥墩、码头、木桩、鱼网、热交换器、大坝以及管道结构如入口处的滤网上的涂料。
一般而言，组合物中4,5-二氯-2-n-辛基-3-异噻唑酮与第二组分的重量比为从约60∶1到约1∶500，以下实施例给出了其他具体和优选的比例。
实施例1
通过化合物的大量不同浓度、不同比例对海藻肠浒苔
(UTEX739)及海硅藻短柄曲壳藻(UTEX2077)的抗性试验，阐明了两种组分的组合物的协同作用。两种化合物按横向与纵向浓度梯度列于96孔的微量滴板上，滴板中载有人工海水介质。这样，一梯度中的每一浓度即可与其他梯度的每一浓度值对比测试，每块试验板也包含每一种化合物单独的浓度梯度。短柄曲壳藻是一种单细胞生物，将其进行涡流式搅拌后用分光光度计定量，通过滴加人工海水或短柄曲壳藻来调节样品以在660nm处标定吸光度为0.14。用荧光分析法检测培养物中的叶绿素a提取物以对肠浒苔接种物定量，这是一种常用且公认的方法，详见Lobban,C.S.；Chapman,D.J.和Kremer,B.P.所著的“Experimental Phycology,A Laboratory Manual”1988,Cambridge University Press。检测接种物提取液后与用标准叶绿素a(从Sigma公司处获得，PO.BOS 14508,st.Louis,MO63178)和接种物制成的标准曲线对照，并调至最终每毫升接种物0.01ppm的叶绿素a。
人工海水可以通过用1升的去离子水溶解40克人工海盐来制备(用于家庭水族池的人工海盐结晶的浓缩混合物，如AquariumSystems的Reef Crystals,8141 Tyler Blvd.Mentor,OH44060)。通过加水或加人工海盐的方法调节其盐度为在海水试验(Sea Test)专用比重计上读数为1.0021。然后再向该溶液中加入0.092gGuillard′s(f/2)Marine Enrichment Basal Salt Mixture(G-1775)(可从Sigma公司获得，P.B.14508,St.Louis,MO63178)足量的亚硒酸达终浓度10-8M、足量硫酸镍达10-8M、足量原矾酸钠达10-8M，以及足量的铬酸钾达最终浓度10-9M。
以每一种化合物在25℃21天后能抑制显著(可见)生长的最低浓度作为最小抑制浓度值(MIC),MIC作为活性终点。化合物A(4,5-二氯-2-n-辛基-3-异噻唑酮)与化合物B(第二组分的杀微生物剂)的混合物的终点与化合物A及B单独作用的终点相比较。协同作用可通过常用且公认的Kull,F.C.；Eisman,P.C.；Sylwe-strowicz,H.D.和Mayer.R.L.在“Applied Microbiology 9:538-541(1961)”中描述的方法测定，结果由下列比例式决定：
Qa/QA+Qb/QB=协同指数(SI)
其中QA指化合物A单独作用达到终点时的浓度(ppm)；Qa指化合物A在混合物中协同作用时达到终点的浓度值(ppm)；
Qa指化合物B单独作用达到终点时的浓度值(ppm)；Qb指化合物B在混合物中协同作用达到终点时的浓度值(ppm)
当Qa/QA与Qb/QB之和大于1时表示有拮抗作用，当Qa/QA与Qb/QB之和等于1时表示有加和性；当Qa/QA与Qb/QB之和小于1时，说明具有协同作用。
阐明杀微生物剂组合物协同作用的试验结果见表1与表2，每一表都涉及4,5-二氯-2-n-辛基-3-异噻唑酮和一其他杀微生物剂的组合，并显示：
1．第二种杀微生物剂(化合物B)的种类；
2．对肠浒苔和短柄曲壳藻的抗性试验；
3．每个单一种化合物以及它们的组合物的以MIC(ppm)测定的终点活性；
4．基于上式得出的协同指数；
5．协同作用的重量比。本领域技术人员将认识到这只是大约值。
每一种化合物单独试验的MIC值(QA和QB)是终点活性。对短柄曲壳藻进行了重复性协同试验。结果见表1与表2。
表1
化合物A=4,5-二氯-2-n-辛基-3-异噻唑酮
化合物B-1=2-甲硫基-4-叔丁卤基-6-环丙氨基-S-三嗪
| 微生物 | 终点活性(ppm) | SI | A∶B-1 | |
| 化合物A | 化合物B-1 | |||
| 肠浒苔短柄曲壳藻 | 1.5(MIC)0.80.80.8-3(MIC)0.750.751.51.5-6(MIC)1.5-6(MIC)33-6(MIC)3- | -0.20.10.050.4(MIC)-0.750.40.20.11.5(MIC)-0.20.4(MIC)-0.10.051.5(MIC)-0.050.2(MIC) | 1.030.780.660.750.520.630.570.750.570.530.75 | 4∶18∶116∶11∶12∶17.5∶115∶17.5∶130∶160∶160∶1 |
化合物A与B-1的协同作用比例范围为60∶1到1∶1
表2
化合物A=4,5-二氯-2-n-辛基-3-异噻唑酮
化合物B-2=N,N-二甲基-N′-苯基-(N′-氟二氯甲硫
基)磺酰胺
| 微生物 | 终点活性(ppm) | SI | A∶B-2 | |
| 化合物A | 化合物B-2 | |||
| 短柄曲壳藻 | 6(MIC)1.53331.51.5-3(MIC)0.75- | -502512.562512.5100(MIC)-2550(MIC) | 0.750.750.6250.560.750.50.75 | 1∶331∶81∶41∶221∶171∶81∶33 |
化合物A与B-2的协同作用比例范围是从1∶2到1∶33
从表1、表2可看出，用MIC测定，本发明组合物具有协同性杀微生物活性，其活性远大于各组合物中单一成分活性的代数和。
实施例2
对卤虫进行协同性研究。制备化合物A(4,5-二氯-2-n-辛基-3-异噻唑酮)的二甲基甲酰胺溶液，浓度为80ppm，以及化合物B-1(2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪)的二甲基甲酰胺溶液，浓度为10,000ppm，备用。
卤虫卵在25℃的Instant Ocean(IO)人工海水中孵化过夜，并保持良好通气。从未孵化卵中分离出孵化好的剑水蚤转移到盛有IO海水的罐中，在该罐的通气区中培养24小时，温度为25℃。调节
卤虫的浓度，尽量接近每10毫升溶液中有50个卤虫。用吸量管取10毫升该培养液注入到已滴入10微升杀生物备用液的玻璃管中，对照管中滴有10微升二甲基甲酰胺。
这些玻璃管在25℃温度下孵育24小时，然后记录死亡的卤虫数目。死亡的卤虫沉在管底，很容易在双筒显微镜下计数：在显微镜下观察，大约两秒钟时间不见运动的卤虫即可视为死亡。往管中加入几滴固定剂后数出全部的卤虫数目即可计算出活的卤虫数目。实际过程中，若管中只有1-2个卤虫存活(小于5％)则视为死亡率为100％。对照组的死亡率一般为5-10％(即每管有2-5个死亡的卤虫)，如果对照组的死亡率超过了15％，则放弃本次试验结果。
测定三批重复的对照组的死亡率百分值，计算出其平均对照死亡率Pc。每一次重复试验的死亡率为Po，则每一次重复试验的死亡率的修正值(PT)可用下述公式计算出： 每一种杀生物剂的平均致死率可以用三次重复的PT值计算出。化合物A与化合物B-1各自单独的平均致死率见表3：
表3
化合物A和B对卤虫的平均致死率化合物A=4,5-二氯-2-n-辛基-3-异噻唑酮化合物B-1=2-甲硫基-4-叔丁卤基-6-环丙氨基-S-三嗪
| 化合物A(ppm) | 化合物B-1(ppm) | 平均死亡率(％) |
| 0.020.040.060.08------- | ----0.020.040.060.080.11.010.0 | 018.359.786.32.302.72.35.02.35.7 |
为进行协同作用试验，重复以上实验步骤只是将分别溶于10μlDMF中的化合物A和化合物B-1都加入样品中。这样，对照管及每一个剂量管中包含了20微升二甲基甲酰胺。化合物A的试验浓度为0.02,0.04,0.06,0.08ppm，化合物B-1的试验浓度为除了与A相同值以外还有0.1,1.0及10.0ppm。
计算出组合物每次重复实验的PT值。再由三次PT值的平均值计算出组合物的平均致死率。用所观察到的该平均致死率与每一种化合物单独作用测得的平均致死率之和(称期望值)相比较，如果观察值大于期望值，则说明复合物是具有协同作用的，结果见表4。
表4
化合物A和B-1的组合物对卤虫的平均致死亡率化合物A=4,5-二氯-2-n-辛基-3-异噻唑酮化合物B-1=2-甲硫基-4-叔丁氨基-5-环丙氨基-S-三嗪
| 化合物A(ppm) | 化合物B-1(ppm) | A∶B-1 | 欲期值死亡率(％) | 观察值死亡率(％) |
| 0.020.020.020.020.040.040.040.040.060.060.060.060.080.080.080.08 | 0.020.11.010.00.040.11.010.00.060.11.010.00.080.11.010.0 | 1∶11∶51∶501∶5001∶11∶251∶251∶2501∶11∶1.71∶171∶1701∶11∶1.251∶12.51∶125 | 2.35.02.35.718.323.320.624.062.464.762.065.488.691.388.692.0 | 1.71.716.326.331.732.745.351.764.758.782.086.795.794.0100100 |
从以上数据可以看出，化合物A与化合物B-1之间的协同作用比例范围为1∶1到1∶500
实施例3
用4,5-二氯-2-n-辛基-3-异噻唑酮与N,N-二甲基-N’-苯基-(N’-氟二氯甲硫基)-磺酰胺对三种真菌：黑曲霉(Aspergillus niger)(ATCC6275)，芽枝状枝孢(Cladosporium.Cla-dosporides)(ATCC16022)及产紫青霉(Penicillium Purpurogenum)(ATCC52427)进行协同性研究。这些真菌在30℃的马铃薯-葡萄糖琼脂培养基上生长并培养5天后，用50ppm的Triton X-100水溶液洗涤，再用4层无菌纱布过滤，然后用血细胞计数器平板控制该真前的浓度标准为106个孢子/毫升。
其协同作用研究用微量滴板试验进行，培养基为马铃薯-葡萄糖肉汤。用该法在微量滴板的96孔中对化合物的浓度进行2倍的连续稀释，从而可对很大范围的浓度值进行试验。所有液体培养基的转移均采用标准单管或多向性数字移液管进行。用合适的溶媒配制化合物的备用液并混合到生长培养基中。所进行的连续稀释都用适当的生长培养基进行；每一个孔中液体的体积为100微升。在每块滴板上沿不同方向对两种化合物采用等量连续稀释，同时每块板上还包括对每一种化合物的对照组，所以也可测得每一种化合物的MIC值。
其协同作用的结果见表5。
表5化合物A=4,5-二氯-2-n-辛基-3-异噻唑酮化合物B-2=N,N-二甲基-N′-苯基-(N′-氟二氯甲硫基)磺酰胺
化合物A与化合物B-2之间的协同作用比例范围为从12∶1到1∶79。
| 微生物 | 终点活性(ppm) | SI | A∶B-2 | |
| 化合物A | 化合物B-2 | |||
| 黑曲霉芽枝状枝孢产紫青霉 | 6(MIC)30.8-12(MIC)60.8-12(MIC)63-12(MIC)60.8-6(MIC)33-12(MIC)60.8- | -263125 (MIC)-0.634590(MIC)-43263(MIC)-863125(MIC)-41663(MIC)-0.51632(MIC) | 0.520.620.500.560.560.750.560.560.560.750.520.56 | 1.5∶11∶7910∶11∶561.5∶11∶101∶1.31∶791∶1.31∶512∶11∶20 |
本发明组合物的协同作用活性对藻类、细菌、真菌、污损生物及其混合物有效。因此，这种组合物不仅降低了杀生物剂的使用量，而且扩大了作用范围。尤其对单独使用某一种化合物时由于其对某些生物的作用较弱而显得效果不佳的地方更为有用。
Claims (12)
1．一种组合物，包括至少两种组分，第一种是4,5-二氯-2-正辛基-3-异噻唑酮，第二种为选自下列化合物中的一种或多种：2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪和N,N-二甲基-N′-苯基-(N′-氟二氯甲硫基)磺酰胺；其中第一种与第二种组分之间有协同作用，且存在的第一种与第二种组分之间重量比范围是从60∶1到1∶500。
2．权利要求1的组合物，其中第一组分化合物与第二组分化合物2-甲硫基-4-叔-丁氨基-6-环丙氨基-S-三嗪之间重量比范围是从2∶1到60∶1。
3．权利要求1的组合物，其中第一组分化合物与第二组分化合物N,N-二甲基-N′-苯基-(N′-氟二氯甲硫基)-磺酰胺之间的重量比范围是从12∶1到1∶79。
4．权利要求1的组合物，其中第一组分化合物与第二组分化合物N,N-二甲基-N′-苯基-(N′-氟二氯甲硫基)-磺酰胺之间的重量比范围是从1∶4到1∶8。
5．权利要求1的组合物，它还含有一种乳化剂和水。
6．权利要求1的组合物，它呈含有成膜聚合物的涂料形式。
7．权利要求6的组合物，其中所述涂料为颜料、橡胶涂料、胶粘剂、粘合剂、密封胶、嵌缝胶或油漆形式。
8．一种保护海洋或淡水构筑物以免受海洋或淡水生物污损的方法，包括施用权利要求1的组合物。
9．一种抑制细菌、真菌、藻类在易受其污染的位点生长的方法，包括在该位点以能有效地控制细菌、真菌、藻类生长的用量施用权利要求1-5任一项的组合物。
10．权利要求9方法，其中所述位点是一种水中环境，且这种组合物是权利要求5的组合物。
11．权利要求9方法，其中所述位点是木材。
12．一种保护海洋或淡水中构筑物免受海洋或淡水生物污损的方法，包括施用权利要求6的一种涂料组合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/237,538 US5466382A (en) | 1994-05-03 | 1994-05-03 | Synergistic microbicidal combinations containing 4,5-dichloro-2-n-octyl-3-isothiazolone and certain commercial biocides |
| US237538 | 1994-05-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116041A CN1116041A (zh) | 1996-02-07 |
| CN1072891C true CN1072891C (zh) | 2001-10-17 |
Family
ID=22894163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95105413A Expired - Lifetime CN1072891C (zh) | 1994-05-03 | 1995-05-02 | 一种协同杀微生物组合物 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5466382A (zh) |
| EP (1) | EP0680695B1 (zh) |
| JP (1) | JPH0892016A (zh) |
| KR (1) | KR100341713B1 (zh) |
| CN (1) | CN1072891C (zh) |
| AT (1) | ATE172844T1 (zh) |
| AU (1) | AU695345B2 (zh) |
| CA (1) | CA2148189A1 (zh) |
| DE (1) | DE69505727T2 (zh) |
| ES (1) | ES2123912T3 (zh) |
| SG (1) | SG46939A1 (zh) |
| TW (1) | TW353014B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08301704A (ja) * | 1995-05-10 | 1996-11-19 | Mitsubishi Corp | 工業用防腐防カビ剤組成物及び水中防汚剤組成物 |
| JPH10109912A (ja) * | 1996-10-04 | 1998-04-28 | Akio Suganuma | 抗菌組成物 |
| DE19651351A1 (de) * | 1996-12-10 | 1998-06-18 | Riedel De Haen Ag | Mikrobizide Gemische |
| US6069142A (en) * | 1998-12-23 | 2000-05-30 | Calgon Corporation | Synergistic antimicrobial combination of 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one and a mixture of a chlorinated isocyanurate and a bromide compound and methods of using same |
| US7713279B2 (en) | 2000-12-20 | 2010-05-11 | Fox Hollow Technologies, Inc. | Method and devices for cutting tissue |
| US7708749B2 (en) | 2000-12-20 | 2010-05-04 | Fox Hollow Technologies, Inc. | Debulking catheters and methods |
| US6299622B1 (en) | 1999-08-19 | 2001-10-09 | Fox Hollow Technologies, Inc. | Atherectomy catheter with aligned imager |
| US8328829B2 (en) | 1999-08-19 | 2012-12-11 | Covidien Lp | High capacity debulking catheter with razor edge cutting window |
| ES2436668T3 (es) | 2000-12-20 | 2014-01-03 | Covidien Lp | Catéter para retirar material oclusivo ateromatoso o trombótico |
| US8246640B2 (en) | 2003-04-22 | 2012-08-21 | Tyco Healthcare Group Lp | Methods and devices for cutting tissue at a vascular location |
| WO2004098289A1 (en) * | 2003-05-07 | 2004-11-18 | Laboratorios Miret S.A. | Synergistic antimicrobial composition with terbutryn |
| JP4025735B2 (ja) * | 2003-08-21 | 2007-12-26 | ローム アンド ハース カンパニー | 水性系を処理する方法 |
| US20070276419A1 (en) | 2006-05-26 | 2007-11-29 | Fox Hollow Technologies, Inc. | Methods and devices for rotating an active element and an energy emitter on a catheter |
| US8784440B2 (en) | 2008-02-25 | 2014-07-22 | Covidien Lp | Methods and devices for cutting tissue |
| US8414604B2 (en) | 2008-10-13 | 2013-04-09 | Covidien Lp | Devices and methods for manipulating a catheter shaft |
| BRPI1014721A2 (pt) | 2009-04-29 | 2016-04-12 | Tyco Healthcare | métodos e dispositivos para cortar e raspar tecido |
| JP5281195B2 (ja) | 2009-05-14 | 2013-09-04 | コヴィディエン リミテッド パートナーシップ | 簡単に清掃され得るアテレクトミー用カテーテルおよび使用の方法 |
| JP5561462B2 (ja) * | 2009-09-17 | 2014-07-30 | 日東化成株式会社 | 漁網防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜の形成方法、および該塗膜を表面に有する漁網、漁網用具又は水中構造物 |
| KR20120079479A (ko) | 2009-12-02 | 2012-07-12 | 타이코 헬스케어 그룹 엘피 | 조직 절단 장치 및 방법 |
| US20110144673A1 (en) | 2009-12-11 | 2011-06-16 | Fox Hollow Technologies, Inc. | Material removal device having improved material capture efficiency and methods of use |
| EP2742881B1 (en) | 2010-06-14 | 2015-10-07 | Covidien LP | Material removal device |
| US8920450B2 (en) | 2010-10-28 | 2014-12-30 | Covidien Lp | Material removal device and method of use |
| JP5302368B2 (ja) * | 2010-11-04 | 2013-10-02 | ダウ グローバル テクノロジーズ エルエルシー | フルメツラムまたはジクロスラムとイソチアゾロンとの相乗的組み合わせ |
| KR101518151B1 (ko) | 2010-11-11 | 2015-05-06 | 코비디엔 엘피 | 촬영용 가요성 디벌킹 카테터와, 사용 및 제조 방법 |
| US8992717B2 (en) | 2011-09-01 | 2015-03-31 | Covidien Lp | Catheter with helical drive shaft and methods of manufacture |
| US9532844B2 (en) | 2012-09-13 | 2017-01-03 | Covidien Lp | Cleaning device for medical instrument and method of use |
| US9943329B2 (en) | 2012-11-08 | 2018-04-17 | Covidien Lp | Tissue-removing catheter with rotatable cutter |
| WO2015200702A1 (en) | 2014-06-27 | 2015-12-30 | Covidien Lp | Cleaning device for catheter and catheter including the same |
| US10314667B2 (en) | 2015-03-25 | 2019-06-11 | Covidien Lp | Cleaning device for cleaning medical instrument |
| US10292721B2 (en) | 2015-07-20 | 2019-05-21 | Covidien Lp | Tissue-removing catheter including movable distal tip |
| US10314664B2 (en) | 2015-10-07 | 2019-06-11 | Covidien Lp | Tissue-removing catheter and tissue-removing element with depth stop |
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| EP0431752A2 (en) * | 1989-11-03 | 1991-06-12 | Rohm And Haas Company | Synergistic microbicidal combinations |
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| US4325201A (en) * | 1967-03-09 | 1982-04-20 | Rohm And Haas Company | Seed treatment with 3-isothiazolones |
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| US5334389A (en) * | 1992-10-15 | 1994-08-02 | Duke University | Antifouling coating and method for using same |
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1994
- 1994-05-03 US US08/237,538 patent/US5466382A/en not_active Expired - Lifetime
-
1995
- 1995-04-24 ES ES95302727T patent/ES2123912T3/es not_active Expired - Lifetime
- 1995-04-24 AT AT95302727T patent/ATE172844T1/de not_active IP Right Cessation
- 1995-04-24 EP EP95302727A patent/EP0680695B1/en not_active Expired - Lifetime
- 1995-04-24 DE DE69505727T patent/DE69505727T2/de not_active Expired - Lifetime
- 1995-04-27 KR KR1019950010016A patent/KR100341713B1/ko not_active IP Right Cessation
- 1995-04-28 CA CA002148189A patent/CA2148189A1/en not_active Abandoned
- 1995-04-28 AU AU17674/95A patent/AU695345B2/en not_active Expired
- 1995-04-29 SG SG1995000366A patent/SG46939A1/en unknown
- 1995-05-02 CN CN95105413A patent/CN1072891C/zh not_active Expired - Lifetime
- 1995-05-02 JP JP7131212A patent/JPH0892016A/ja active Pending
- 1995-05-03 TW TW084104403A patent/TW353014B/zh not_active IP Right Cessation
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| US4900736A (en) * | 1986-12-16 | 1990-02-13 | Schulke Mayr, Gmbh | Salts of alkyl-2-benzimidazole-carbamate and fungicidal compositions thereof suitable for paints and plaster |
| JPH02175969A (ja) * | 1988-12-26 | 1990-07-09 | Toyobo Co Ltd | 高比重防汚性糸条 |
| EP0380984A1 (de) * | 1989-02-01 | 1990-08-08 | Riedel-De Haen Aktiengesellschaft | Flüssige algizid wirkende Zubereitung |
| EP0431752A2 (en) * | 1989-11-03 | 1991-06-12 | Rohm And Haas Company | Synergistic microbicidal combinations |
Also Published As
| Publication number | Publication date |
|---|---|
| AU695345B2 (en) | 1998-08-13 |
| EP0680695A2 (en) | 1995-11-08 |
| KR100341713B1 (ko) | 2002-11-01 |
| DE69505727D1 (de) | 1998-12-10 |
| ES2123912T3 (es) | 1999-01-16 |
| ATE172844T1 (de) | 1998-11-15 |
| CN1116041A (zh) | 1996-02-07 |
| SG46939A1 (en) | 1998-03-20 |
| US5466382A (en) | 1995-11-14 |
| JPH0892016A (ja) | 1996-04-09 |
| CA2148189A1 (en) | 1995-11-04 |
| AU1767495A (en) | 1995-11-09 |
| EP0680695A3 (en) | 1996-01-10 |
| DE69505727T2 (de) | 1999-07-08 |
| EP0680695B1 (en) | 1998-11-04 |
| KR950030806A (ko) | 1995-12-18 |
| TW353014B (en) | 1999-02-21 |
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