CN1015511B - 消防用水的添加剂 - Google Patents
消防用水的添加剂Info
- Publication number
- CN1015511B CN1015511B CN88102935A CN88102935A CN1015511B CN 1015511 B CN1015511 B CN 1015511B CN 88102935 A CN88102935 A CN 88102935A CN 88102935 A CN88102935 A CN 88102935A CN 1015511 B CN1015511 B CN 1015511B
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- water
- fire
- fighting
- additive
- fighting purpose
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/12—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution
- B01J13/125—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution by evaporation of the solvent
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
一种消防用水添加剂，该添加剂含有以(甲基)丙烯酸钾盐或钠盐为基质的离水可膨胀性(共)聚物构成的水不溶性极性大分子细微颗粒和一种用于包裹上述(共)聚物细微颗粒使其不至于膨胀的水溶性隔离剂。
Description
就灭火而言，主要是利用来自水管网的水进行灭火，在扑灭森林火灾时，则主要靠天然水。消防用水所起的作用，一方面是当水与燃烧物体接触时，由于它有很高的热容量和很高的蒸发热，它就能起到很有效的冷却作用，由此使得该物体的温度降至其燃烧或燃点温度以下，并由此消除了新的燃烧。另一方面，水的作用在于，当水与热物体接触时，水蒸发，所产生的水蒸汽挤掉了燃烧所必不可少的空气，并由此直接使火焰熄灭。
以惯用方式用水的主要缺点是大部分水常常不起作用就跑掉了，要么浇在没有着火的物体上，要么浸入土地。就森林大火而言，这一缺点显得尤为突出，即花巨资频频远来的水中绝大部分完全用不上。由于火焰不断吞没干燥的下层丛林（草，树叶或灌木）并使各个分散的火丛随之连成一片，因此按照传统的森林灭火方式，地面灭火是森林灭火中最为重要的方式。到目前为止，还没可能最有效地利用消防用水，具体地讲，由于森林火灾常常是在漫长的干燥期发生的，因此地面的吸水能力也就特别强。其他类型的火灾基本上也会遇到相同的问题，例如，某一建筑中的顶梁着火时，防火地板并不能将屋顶与低层分开。在这种情况中，经常出现的是水穿过地板，开口处，楼梯等流到下层，由此失去灭火作用。与此同时，由于缺水，就会造成火势从着火层向下漫延的危险。另一方面，流掉的水常常造成很大的危害，并且由此使得消防用水增加也造成了问题。
为了避免上述缺点，联邦德国公开说明书（DE-OS 3114630）提出了
在建筑物有着火危险部分（如：平面屋顶）的表面涂上胶体，以作为水之屏障，并且使之将整个区域与火灾区分开。这一措施的目的在于避免由于流失和浸入地面而造成消防用水的不必要的损耗。但是这些复盖在被保护物体上的真胶粘度很高，并在该物体上形成一厚层。由于这类胶体并不能渗入有着火危险的物体内部，所以它们的灭火作用也很弱。由于其粘度之高，也只有使用专有设备才能施用。
同一原理可用于由电离幅射而交联的聚丙烯酸钾，（US-A-3229769）介绍，该物质可用作保护易燃物品的防火保护涂料。这些高粘度溶液不能用于直接灭火，而且由于前述原因也不适于这一目的。
美国专利3，354，084介绍：为了增加粘度并收到避光的效果，采用由水膨胀性丙烯多聚体（实际上是中度交联的丙烯酰胺共聚物）与很细的二氧化钛颗粒一起组成的用于森林灭火的胶体。
为了克服前述胶体所存在的高粘度之缺点，美国专利3，404，089提出在灭火前通过低粘度聚丙烯酸分散体与碱金属盐或铵盐水溶液的反应直接产生胶体。仍然存在的缺点是：无论怎样，用来灭火的真胶粘度高而且不能渗入保护对象，因此灭火效果差。
之所以还没有广泛采用水胶防火法，一是由于所采用的方法的效果不显著，二是由于采用这种灭火方法需要特殊装置，三是它们会造成腐蚀破坏，并污染环境。
因此，本发明的目的是提供用于灭火的方法，其目的在于减少由于水引起的破坏，减少环境污染，使其能用惯用设备使用，并避免腐蚀破坏。
令人惊奇的是：当将以（甲基）丙烯酸为基的高水膨胀（共）聚合物构成的水不溶性极性大分子包裹在或分散于某种水溶性隔离剂当中，可以得到没有上述缺点的灭火用水添加剂。所说（甲基）丙烯酸为交联体，其交联程度使其以钾盐或钠盐形式存在时，它们可以吸收500倍于
其自身重量的水。所说隔离剂本身不引起前述高水膨胀（（共）聚合物颗粒的膨胀）。
例如，美国专利说明书4017653和4018951介绍了不溶于水并在水中极剧膨胀的聚合物。在这一技术领域将这些物质称之为高吸收性聚合物或通常所说的超吸收体。如联帮德国专利（DE-PS 2706135）所述，这一方法特别适用于丙烯酸或甲基丙烯酸与丙烯基酰胺，甲基丙烯酰胺和丙烯腈的共聚物。
适宜的交联剂包括至少有两个官能团的单体所有烯属类化合物，如：亚甲基-双-丙烯酰胺，二乙烯基苯，氰尿酸三烯丙酯，磷酸三烯丙酯等。众所周知，通过游离基或氧化还原聚合反应可以制得适宜的交联聚合物。
隔离剂使得胶凝剂在水渗入时不变粘，因此可以避免胶结。当按本发明所述使用隔离剂时胶凝物质的分散将不受任何影响。主要的是该隔离剂具有良好的水溶性，而其本身并不引起胶凝剂颗粒膨胀。按照本发明，该隔离剂所起的作用就是在胶凝剂颗粒之间形成屏障，从而防止胶结。
水系统中所含胶体颗粒的浓度应保证有足量的游离水存在，即类似于纯水的作用，首先要取得极佳的灭火效果，同时将水所造成的破坏降到最低，其二要在保证极佳润湿量的同时施用之。在本发明的水系统中，总水量的50-80%（重量），最好是60-70%（重量）存在于胶体颗粒中。
所说胶体颗粒由高吸水性能的共聚体制成，该共聚体的结构特性使得它们能迅速地吸收高达其自身重量500倍的水;但它们在水中不溶。如果将过量的水加入膨胀了的胶体颗粒中，过量的水仍保持纯水相，并起到胶体颗粒载体的作用，虽然应该把胶体颗粒看作是各个分散的颗粒，但实质上它仍有其粘度。
本发明中以聚丙烯酸为基础（以其纳盐或钾盐的形式）的膨胀体满
足了本发明的要求，同时又不会造成任何环境污染。
但是，如果按照本发明所述方法用水溶性隔离剂包裹胶凝剂颗粒，也可以使用极细微颗粒状胶凝物质，不致使颗粒胶结。因此，可以借助这一手段直接将胶凝物质通过喷头喷入软管。
本发明所述优选的隔离剂是聚乙二醇。与乙二醇和二乙二醇相反，胶凝物质不能吸收聚乙二醇。因此，聚乙二醇层可以起到保护胶凝剂颗粒的作用，使之在渗水时不致于彼此之间粘合太快，也不致产生胶结。此外，聚乙二醇是绝对无毒的，并且很快分解，因此，从生态学考虑，它是非污染性物质。
经证实：以胶凝物质的用量计算，加入10-100%（重量）的聚乙二醇300或400，使胶凝剂颗粒湿润是很有好处的。
此外，二磷酸二铵（diammonium biphosphate，下同）也是特别适宜的隔离剂。就远离海岸的灭火而言，如果发生了最灾难性的森林大火，通常要用海水装满水柜。由于海水中含有高浓度的氯化钠和引起硬化的盐，因此施用方法不当会使胶凝物质的膨胀容量大幅度降低。当使用二磷酸二铵盐作为隔离剂时，可以大大减少该不利作用。磷酸根离子对抗致硬物质，而铵离子则补偿了由钠离子对膨胀容量带来的付作用。以胶凝物质计算，使用20-100%（重量）的二磷酸二铵盐特别有利。
用于制备消防用水添加剂的尤为可取的方法是：在高速混合机中将50%（重量）的二磷酸二铵与胶凝物质干混合。由此将磷酸氢二铵结晶压碎。与此同时，以胶凝物质计算，将10-30%（重量）的水喷到该混合物中。胶凝物质颗粒在短时间内迅速粘着，二磷酸二铵盐牢牢地粘在胶凝剂颗粒的表面。
按照本发明，糖也可用作隔离剂，实际上单糖和二糖均可。例如，用甘露糖醇可以收到良好的效果。
如果在消防用水中加入0.1-0.4%（重量）的上述添加剂，仅测到其
粘度稍有增加。该液体完全可以用泵输送，并且在灭火期间由纯水变成加入上述膨胀体的水后，操作喷射龙头的消防人员感觉不到任何操作异常。当加入量增加时，粘度突然增加，游离水（即本发明的水系统的特征所在）迅速减少。一般粘度为100mPa.s的水可当作纯水使用，即可称之为“消防用水”。根据大规模试验测定的结果，通过在水中加入0.2%的膨胀体制得的消防用水的效果是极佳的：已发现：就标准的室内火灾而言，灭火用水量和灭火时间减少30-35%，而且从火源流失的消防用水减少85%。加入0.5-0.6%膨胀物体后，粘度大大增加然而灭火操作仍可照常进行。
为了加速膨胀过程，如有必要，在非膨胀的共聚物中加入极细分的活性硅酸和/或硅酸盐。可加的活性硅酸是由四氯化硅热水解分解制得的已知产物。具体地讲，是用作填充剂或吸收剂，例如硅酸干胶，其表面积大于30m2/g（按BET法测定），一般为几百m2/g，或者是表面积为50-450m2/g的活性硅胶（Aerosil）（按BET法测定）。就本发明的目的而言，也可用下列物质的干胶代替活性硅酸，与高吸附性聚合物合并使用。这些物质包括：按BET法则定表面积大于30m2/g，从水玻璃和相应的金属盐和可能的无机酸中沉淀出的活性硅酸盐，具体地讲是硅酸的钙盐，镁盐或铝盐。
本发明的分散胶体颗粒与惯用的增稠剂完全不同，后者可以使水的粘性增加，并由此引起粘度剧增和与之有关的许多缺点。
将pH值调至6-8，可以避免所使用的灭火器材以及在被喷射的防火物体上出现腐蚀现象。
由于粘度低，本发明用于消防用水的水系统不需要任何特殊的泵或管道。当森林灭火时或在战场灭火期间，同样可以使用一般器材。在W型灭火器和洒水器中也可使用。
当使用本发明所述的用于灭火的水系统时，所加入的胶体颗粒并不
能防止水渗入燃烧着的物体，但是它们绝不会流失。就其本身的粘合能力而言，它们仍保留在燃烧或有烧燃危险物体的表面。除此之外，如果升温很快，它们使其中含有的水很容易以蒸汽的形式逸出，这样可将所有消防用水用于冷却并形成蒸汽。因此，与惯用方法相比，灭火液体的需要量可以大大减少。此外，可以十分有效地防止火灾漫延。
就贮罐灭火而言，将罐壁冷却是十分重要的。利用本发明的水系统，在灭火操作期间，用同样的管道不时地向罐壁喷洒即可，粘着的胶体颗粒形成一恒定的喷洒过剩（sprinkling surperfluous）并使管容量的利用度更高。由于胶体颗粒粘着在经灭火过的物体上，这就减少了复燃的危险。
尽管在三组合消防车容器中，在“水弹”中或者尤其是在混合容器中，有可能产生膨胀体，但仍有必要在喷洒期间或喷洒停止后数分钟稍加搅拌或适当地用泵打出。膨胀后的胶体颗粒彼此之间并不粘着。在长期静置期间，它们可能稍有沉淀，但是将它们用泵打出或搅拌之容易是绝对没有问题的，甚至数星期之后的也是如此。然而在一般的情况下并非必需的。
实施本发明的一般方法是喷洒或喷射含有成形胶体颗粒的水系统。如有必要，可以用喷管短时加入非膨胀态的膨胀体。尽管不能利用该胶体颗粒高粘性这一优点来保护仍未着火的物体，但是它可以迅速而有效地防止由水引起的破坏，其原因是迅速膨胀后的颗粒可以封闭裂缝和接头处。一旦形成胶体密封层，就可以连续用纯水操作，就此而论显然是有利的。就森林火灾而言，由于粘合性，部分胶体留在树上，可以很好地防止火灾从一树丛向其他树丛漫延。就多层建筑火灾而言，所形成的水层可以防止火灾漫延到该建筑的其他各个部分。
本发明的其他用途在于制做灭火毯，这种灭火毯可以帮助人们（以包裹形式）逃离处于大火危险的工厂和大厦（如：酒店）。
这种灭火毯含有已膨胀的膨胀体。为了避免损失湿气，可将它们封闭在塑料袋或包中。
Claims (6)
1、一种消防用水的添加剂，其中含有
a)以(甲基)丙烯酸为基质的高水溶胀性(共)聚合物构成的水不溶性极性大分子细微颗粒，其达到的交联程度使其钾盐或钠盐形式可以吸收高至其自重500倍的水，和
b)按该胶凝剂计，含20%至100%(重量)的二磷酸二铵(diammoniumbiphosphate，下同)。
2、按权利要求1所述的消防用水添加剂，其特征在于该大分子是多聚阴离子型丙烯酸共聚物。
3、按权利要求1所述的消防用水添加剂，其特征在于它含有硅酸和（或）硅酸盐。
4、按权利要求2所述的消防用水添加剂，其特征在于它含有硅酸和（或）硅酸盐。
5、使用权利要求1至4中任一权利要求所述的消防用水添加剂用于消防用水分散体，其中溶胀后的颗粒中所含水的量占水总重量的50-80%（重量），最好是60-70%（重量）。
6、使用权利要求1至4中任一权利要求所述的消防用水添加剂用于灭火器或消防喷洒装置中的消防用水分散体。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873716304 DE3716304A1 (de) | 1987-05-15 | 1987-05-15 | Loeschwasserzusatz |
| DEP3716304.3 | 1987-05-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88102935A CN88102935A (zh) | 1988-12-14 |
| CN1015511B true CN1015511B (zh) | 1992-02-19 |
Family
ID=6327637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102935A Expired CN1015511B (zh) | 1987-05-15 | 1988-05-14 | 消防用水的添加剂 |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0295412B1 (zh) |
| JP (1) | JP2756563B2 (zh) |
| KR (1) | KR960008612B1 (zh) |
| CN (1) | CN1015511B (zh) |
| AT (1) | ATE79044T1 (zh) |
| AU (1) | AU602766B2 (zh) |
| CA (1) | CA1307393C (zh) |
| DE (2) | DE3716304A1 (zh) |
| DK (1) | DK167175B1 (zh) |
| ES (1) | ES2034007T3 (zh) |
| FI (1) | FI882239A (zh) |
| GR (1) | GR3005617T3 (zh) |
| NO (1) | NO175520C (zh) |
| PT (1) | PT87404B (zh) |
| SG (1) | SG42593G (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5496475A (en) * | 1992-10-30 | 1996-03-05 | Ciba-Geigy Corporation | Low viscosity polar-solvent fire-fighting foam compositions |
| DE4336319A1 (de) * | 1993-10-25 | 1995-04-27 | Oeko Tec Umweltschutzsyst Gmbh | Löschmittel und Verfahren zu seiner Herstellung |
| GR1002790B (el) | 1996-07-22 | 1997-10-17 | Μεθοδος και προιοντα κατασβεσης πυρκαιων. | |
| NL1007738C2 (nl) * | 1997-12-08 | 1999-06-09 | Univ Delft Tech | Toepassing van hydrofiele, gelvormende polymeren als brandblusmiddel. |
| EP1056519B1 (en) | 1998-02-27 | 2005-04-27 | Astaris Llc | Fire retardant concentrates and methods for preparation thereof and use |
| DE10041394A1 (de) * | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Verwendung von Wasser-in-Wasser-Polymerdispersionen zur Feuerverhütung und -bekämpfung |
| DE10041395A1 (de) | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Polymerdispersionen zur Feuerverhütung und -bekämpfung mit verbesserter Umweltverträglichkeit |
| US6802994B1 (en) | 2000-11-28 | 2004-10-12 | Astaris Llc | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
| WO2002043813A1 (en) | 2000-11-28 | 2002-06-06 | Astaris Llc | Biopolymer thickened fire retardant compositions |
| US6846437B2 (en) | 2000-11-28 | 2005-01-25 | Astaris, Llc | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors |
| AU1663202A (en) | 2000-11-28 | 2002-06-11 | Astaris Llc | Fire retardant compositions with reduced aluminum corrosivity |
| CA2859477C (en) * | 2012-01-09 | 2017-12-12 | S.P.C.M. Sa | Process to stop and/or prevent the spreading of peat fires |
| CN107050699A (zh) * | 2016-12-30 | 2017-08-18 | 李小波 | 一种碱溶胀增稠剂的应用及其应用装置 |
| CN107596612A (zh) * | 2017-09-19 | 2018-01-19 | 安徽吉安消防科技有限公司 | 一种固体型灭火药剂及其制备、使用方法 |
| CN111514507B (zh) * | 2020-04-10 | 2024-06-07 | 杨根喜 | 一种森林灭火组合物的制备方法 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3229769A (en) * | 1963-01-28 | 1966-01-18 | Dow Chemical Co | Method for controlling the spread of fire |
| US3407138A (en) * | 1964-09-02 | 1968-10-22 | Dow Chemical Co | Method and composition for extinguishing and preventing fires in flammable liquids |
| US3345289A (en) * | 1965-11-01 | 1967-10-03 | Gen Aniline & Film Corp | Fire retardant composition of diammonium phosphate containing methylvinyl ether-maleic anhydride copolymer as thickener |
| US3666707A (en) * | 1970-02-20 | 1972-05-30 | Factory Mutual Res Corp | Slurry additive for ablative water fire extinguishing systems |
| US3684707A (en) * | 1970-05-19 | 1972-08-15 | William L Livingston | Slurry for ablative water systems comprising a cross-linked polymer gelling agent and a time delay carrier |
| JPS56125066A (en) * | 1980-03-05 | 1981-10-01 | Otsuka Kagaku Yakuhin | Aqueous solution-like fire-extinguishing substance |
| JPS58200758A (ja) * | 1982-05-18 | 1983-11-22 | 昭和電工株式会社 | 消火方法 |
| US4610311A (en) * | 1983-02-15 | 1986-09-09 | Sanitek Products, Inc. | Method for reducing the aerial drift of aqueous preparations |
| DE3515865A1 (de) * | 1985-05-03 | 1986-11-06 | Hasso von 4000 Düsseldorf Blücher | Verwendung eines waessrigen, gequollene makromolekuele enthaltenden systems als loeschwasser |
| JPS6244271A (ja) * | 1985-08-22 | 1987-02-26 | 森田ポンプ株式会社 | 消火薬剤原液 |
-
1987
- 1987-05-15 DE DE19873716304 patent/DE3716304A1/de not_active Withdrawn
-
1988
- 1988-04-12 CA CA000563917A patent/CA1307393C/en not_active Expired - Lifetime
- 1988-04-15 KR KR1019880004311A patent/KR960008612B1/ko not_active IP Right Cessation
- 1988-04-29 AU AU15333/88A patent/AU602766B2/en not_active Ceased
- 1988-05-02 NO NO881917A patent/NO175520C/no unknown
- 1988-05-04 EP EP88107121A patent/EP0295412B1/de not_active Expired - Lifetime
- 1988-05-04 ES ES198888107121T patent/ES2034007T3/es not_active Expired - Lifetime
- 1988-05-04 PT PT87404A patent/PT87404B/pt active IP Right Revival
- 1988-05-04 DE DE8888107121T patent/DE3873430D1/de not_active Expired - Lifetime
- 1988-05-04 AT AT88107121T patent/ATE79044T1/de not_active IP Right Cessation
- 1988-05-13 FI FI882239A patent/FI882239A/fi not_active Application Discontinuation
- 1988-05-13 JP JP63116759A patent/JP2756563B2/ja not_active Expired - Lifetime
- 1988-05-13 DK DK266188A patent/DK167175B1/da active
- 1988-05-14 CN CN88102935A patent/CN1015511B/zh not_active Expired
-
1992
- 1992-09-07 GR GR920401944T patent/GR3005617T3/el unknown
-
1993
- 1993-04-12 SG SG425/93A patent/SG42593G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT87404A (pt) | 1989-05-31 |
| NO881917L (no) | 1988-11-16 |
| CA1307393C (en) | 1992-09-15 |
| ES2034007T3 (es) | 1993-04-01 |
| JP2756563B2 (ja) | 1998-05-25 |
| DK167175B1 (da) | 1993-09-13 |
| AU602766B2 (en) | 1990-10-25 |
| GR3005617T3 (zh) | 1993-06-07 |
| DE3716304A1 (de) | 1988-11-24 |
| DE3873430D1 (de) | 1992-09-10 |
| PT87404B (pt) | 1992-08-31 |
| NO175520B (no) | 1994-07-18 |
| DK266188D0 (da) | 1988-05-13 |
| EP0295412A2 (de) | 1988-12-21 |
| ATE79044T1 (de) | 1992-08-15 |
| KR880013589A (ko) | 1988-12-21 |
| NO881917D0 (no) | 1988-05-02 |
| EP0295412A3 (en) | 1989-05-10 |
| FI882239A0 (fi) | 1988-05-13 |
| NO175520C (no) | 1994-10-26 |
| AU1533388A (en) | 1988-11-17 |
| SG42593G (en) | 1993-07-09 |
| KR960008612B1 (ko) | 1996-06-28 |
| EP0295412B1 (de) | 1992-08-05 |
| FI882239A (fi) | 1988-11-16 |
| JPS63309279A (ja) | 1988-12-16 |
| DK266188A (da) | 1988-11-16 |
| CN88102935A (zh) | 1988-12-14 |
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