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由预加工淀粉制造的成型制品

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CN1027726C
CN1027726C CN 88104981 CN88104981A CN1027726C CN 1027726 C CN1027726 C CN 1027726C CN 88104981 CN88104981 CN 88104981 CN 88104981 A CN88104981 A CN 88104981A CN 1027726 C CN1027726 C CN 1027726C
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罗伯特·弗雷德里克·托马斯·斯特普托
伊凡·汤卡
马卡斯·托马
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沃纳-兰伯特公司
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, E.G. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
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    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
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    • A61F2013/15235Properties of the article, e.g. stiffness or absorbency soluble or disintegratable in liquid by its solubility in water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2303/00Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02Starch; Degradation products thereof, e.g. dextrin

Abstract

本发明涉及由淀粉制造成形制品的方法以及其制品。该方法包括:

Description

本发明涉及由预加工淀粉制造的成形制品。

已经知道,存在于植物制品中并含有一定量水分的天然淀粉能够在高温和密闭容器的高压中加工成熔化物。这种加工可在注模机或挤压机中方便地进行。通过给料器把淀粉送入旋转的往复螺杆上。进料淀粉即沿螺杆向顶部移动,在这个过程中,通过围绕料桶外的外加热器及螺杆的剪切作用,使物料温度增高。粒状进料先在进料区,接着在压缩区逐渐熔化。然后通过使熔化物均匀化的计量区,把它送入螺杆端部。在端部用注模、挤压或加工热塑性熔化物的其它公知技术进一步处理该熔化物以制得成形制品。

欧洲专利申请号84300940.8(公开号118240)中介绍的处理方法可得到基本上变性的淀粉。其原因是在高于淀粉组分的熔融和玻璃转变温度加热淀粉,以致其组分发生吸热变化。从而,使淀粉颗粒的分子结构发生无序化和熔融,结果得到本质上变性的淀粉,由上述热塑熔融成形得到的这种基本上变性的淀粉叫做“预加工淀粉”。

虽然由天然淀粉注模而得到的制品是有用的,但已发现,这样得到的成形制品物理强度比较低。还发现由于熔化物粘度与螺旋桶内的剪切速率有很大的依赖关系,它使注模法或挤压法加工对螺旋速率、温度、压力和/或水含量诸条件变得更加灵敏,并且降低了所制得制品的平均质量,所以该方法本身具有相当高的不稳定性。

在上述的淀粉注模方法中,有二个重要的步骤,(A)变性步骤,即在高于淀粉组分的熔点和玻璃转变温度下加热淀粉颗粒,以使分子结构发生高温转变和(B)模制步骤,即用注模法得到成形制品。

现在还意想不到地发现,如果将上述两个步骤相互分开,即步骤(A)中得到的变性淀粉在它再次在螺旋桶中加热,以最后得到成形制品以前使其凝固的话,则所述困难可以克服。已经发现,将变性步骤(A)与模制步骤(B)分开时,得到的成形制品的物理性质因此而有明显改善,并且当螺旋桶中的熔化物进行步骤(B)时,会大大减少粘度对剪切速率的依赖性,并且其流动特性能得到改善,制得的成形制品的平均质量得到了提高。

本发明涉及一种由淀粉制得成型制品的方法,它包括:(a)将含有经预加工的和基本上变性的淀粉/水物料的组合物(水含量范围按组合物的重量为基计为10-20重量%)加热到足以使淀粉基本上变性的温度以形成熔化物;

(b)将该熔化物转移至一个模具中,同时保持上述的水含量。

(c)在模具中,将熔化物冷却至低于其玻璃转变温度以形成固态的成形制品。

本发明还涉及用上述方法得到的成型制品。

如上所述,通过淀粉的热塑熔融成形,得到了上述的预加工淀粉/水物料。

值得注意的是上述性能的改进不是延长淀粉在螺旋桶内滞留时间的结果。如果步骤(A)和(B)分开进行,则螺旋桶内熔融态淀粉物料的同样滞留时间可使产品的质量得到提高。

“淀粉”这个词可理解为化学上基本未改性的淀粉。它一般包括主要由直链淀粉和/或支链淀粉组成的天然的、植物来源的碳水化合物。这种淀粉可以从各种植物,例如豆、大米、木薯淀粉、玉米和谷类(如黑麦、燕麦、小麦)中提取。其中土豆淀粉和玉米淀粉较好,特别是土豆淀粉。它还包括物理上改性的淀粉,如胶凝或蒸煮淀粉,和改变酸度(pH)的淀粉,例如,加入酸,使淀粉的酸度降低至约3至6的淀粉。还包括这样一种淀粉(如土豆淀粉),在这种淀粉中,与淀粉的磷酸根结合的阳离子的种类和浓度已经改变,以影响如温度和压力等的加工条件。

这种淀粉适合于在挤压机的螺旋桶中,在高于其组分的熔点和玻璃转变的温度下加热足够的时间,以达到变性,一般加热时间为3-10分钟,加热时间取决于诸加工参数。温度范围约为120℃至190℃,130℃至190℃较好,这取决于所用淀粉的种类。为了变性,最好在一个密闭容积中加热淀粉物料。密闭容积可以是密封容器或者在注模机或挤压机的螺旋装置中由未熔融进料的封闭作用形成的容积。在这个意义上,注模机或者挤压机的螺旋桶可以认为是一个密闭容器。在密闭容积中产生的压力相应于所用温度下水的蒸汽压,当然,可以在螺旋桶中施加压力和/或按通常方法产生压力。施加和/或产生的压力最好在挤压或注模加工中发生的压力范围内,即从零至150×105N/m2(牛顿/米2),从零至100×105N/m2较好,最好为从零至80×105N/m2。

将这样得到的变性淀粉的熔化物先进行挤压(步骤A),冷却凝固,然后在它进一步用于注模或压模工艺(步骤B)之前,切成颗粒。

按本发明(用于步骤B),所用的经预加工和基本上变性的淀粉/水物料中的水含量,按组合物的重量为基计,约为10%至20%,12-19%较好,最好为14-18%(重量)。

按照本发明的这种变性的淀粉/水物料实质上在高于其组合的熔点和玻璃转变温度下被加热(步骤B)。这个温度一般约为80-200℃,约120°-190℃较好,最好约为140-180℃。在此温度下,基本上可使变性的淀粉形成熔化物,即热塑性熔化物。

在步骤B中最小的压力相当于在这些温度下产生的水蒸汽压力。加工过程在上述的密封容积中进行,即在注模和挤压过程中产生的压力范围内进行,如0-150×105N/m2,0-100×105N/m2较好,最好为0-80×105N/m2。

当通过挤压形成成形制品时,其压力最好如上所述。如果将本发明的变性淀粉组合物的熔化物进行注模,注模时所用的标准注入压力范围为300×105N/m2-3000×105N/m2,最好为700×105-2200×105N/m2。

本发明的淀粉物料可以含有或者可以与添加剂混合,该添加剂如增充剂,润滑剂,增塑剂和/或着色剂。

这些添加剂可以在变性步骤(步骤A)前或后加入,即与变性淀粉的固态颗粒混合,这主要取决于变性淀粉的预定用途。

这样的添加剂可为各种增充剂,例如明胶,植物蛋白质如葵花蛋白质,大豆蛋白质,棉籽蛋白质,花生蛋白质,油菜籽蛋白质,血液蛋白质,鸡蛋蛋白质,丙烯酸酯化蛋白质;水溶性多糖类,如藻酸盐,角叉菜聚糖,瓜耳胶,琼脂,阿拉伯树胶和有关的树胶(印度胶、刺梧桐树胶、横蓍树胶)果胶;水溶性纤维素的衍生物;烷基纤维素,羟烷基纤维素和羟烷基烷基纤维素,如甲基纤维素,羟甲基纤维素,羟乙基纤维素,羟丙基纤维素,羟乙基甲基纤维素,羟丙基甲基纤维素,羟丁基甲基纤维素,纤维素酯和羟烷基纤维素酯,如:乙酰邻苯二甲酸纤维素(CAP),羟丙基甲基纤维素(HPMCP);羟烷基纤维素,羧烷基烷基纤维素,羧烷基纤维素酯如:羧甲基纤维素和它们的碱金属盐类;水溶性合成聚合物,如聚丙烯酸和聚丙烯酸酯,聚甲基丙烯酸和聚甲基丙烯酸酯,聚乙酸乙烯酯,聚乙烯醇,聚乙烯乙酸邻苯二甲酸酯(PVAP),聚乙烯吡咯烷酮,聚巴豆酸;还有邻苯二甲酸酯化明胶,凝胶琥珀酸酯,交联凝胶,紫胶,淀粉的水溶性化学衍生物,具有叔氨或季氨基团的阳离子改性的丙烯酸酯和甲基丙烯酸酯,如需要时,可为季铵化的二乙氨乙基基团;和其它类似的聚合物。

这些增充剂可按需要量随意加入,按所有组分的重量为基计,其加入量为小于和等于50%,最好为3-10%(重量)。

另外的添加剂是无机填充物,如镁、铝、硅、钛等的氧化物,按所有组分的重量为基计,其浓度约为0.02-3%,最好为0.02-1%(重量)。

其它的添加剂是增塑剂,包括聚烯化氧,如聚乙二醇、聚丙乙醇,聚乙-丙二醇;低分子量的有机增塑剂,如甘油,单乙酸甘油酯,二乙酸甘油酯或三乙酸甘油酯;丙二醇,山梨醇,二乙基磺基丁二酸钠,柠檬酸三乙酯,柠檬酸三丁酯等,按所有组分的重量为基计,其加入浓度为0.5-15%最好为0.5-5%(重量)。

着色剂的例子包括已知的偶氮染料,有机或无机颜料,或者天然来源的着色剂。最好用无机颜料,如铁或钛的氧化物,这些氧化物的加入浓度按所有组分的重量为基计为0.001-10%,最好为0.5-3%(重量)。

增塑剂和水含量的总和,按所有组分的重量为基计,应以不超过25%为好,最好应不超过20%。

还可以加入其它的化合物以改善淀粉物料的流动性,这些化合物如动物或植物脂肪,以脂肪的氢化形式为好,最好是室温下呈固态的脂肪。这些脂肪的熔点最好为50℃或更高。最好用带有C12-,C14-,C16-,和C18-脂肪酸的甘油三酯。

这些脂肪可以单独加入,而不加入增充剂或增塑剂。

这些脂肪可以方便地单独加入或者和甘油-酯和/或甘油二酯或磷脂,最好是卵磷脂一起加入。甘油一酯和甘油二酯最好从上述的、即带有C12-,C14-,C16-和C18-脂肪酸的脂肪中得到。

所用的脂肪,甘油一酯,甘油二酯和/或卵磷脂的总量,按组合物的总量为基计,至多为5%,最好约为0.5-2%(重量)。

最好还加入二氧化硅或二氧化钛,其浓度按组合物的总量为基计约为0.02%-1%(重量)。这些化合物可用作增稠剂。

本文中的上述物料在加热与在密闭容器中,即在被控制的水含量和压力条件下,形成具有热塑性的熔化物。这样的熔化物如同热塑性材料一样可以在各种工艺中使用。这些工艺包括注模、吹塑、挤压和复合挤压(棒,管和膜挤压)、压模,以得到用这些工艺制成的公知制品。这些制品包括瓶、片,膜,包装材料,管、棒,层压材料,包,袋,药用胶囊。

下面的实例进一步说明本发明。

实例1(a)变性淀粉的制备。

将天然土豆淀粉,润滑剂/脱模剂(氢化脂肪)和熔融促流剂(卵磷脂)按一定比例在粉末混合器中混合10分钟,结果得到自由流动的粉末状混合物,它含有81.3份的天然土豆淀粉,1份氢化甘油三脂(含有C18∶C16∶C14脂肪酸百分重量比为65∶31∶4),0.7份卵磷脂和17份水。然后将该物料送入挤压机的料斗。在螺旋桶中熔融该粉料。测量桶内的温度为165℃,平均总滞留时间为12分钟(约10分钟加热时间,约2分钟处于熔融状态),并且产生的压力等于挤压机桶的容积中存在水份的蒸汽压。然后将熔化物挤压并切割成平均直径2-3毫米的颗粒。该物料是硬的、白色的、具有细泡沫结构。由于熔化物离开挤压机喷嘴时允许水逸出,所以该熔化物水含量为12%。然后调节所得粒料的水含量为17%。

(b)将上述(a)中得到的粒料送入注模机的料斗。该物料在螺旋桶内形成熔化物。温度保持在165℃,压力为75×105N/m2;平均滞留时间为7 1/2 分钟(加热时间约5分钟,熔融态约2分钟)。将熔化物注入模中,以得到适于在英斯特朗(Instron)拉伸倾斜仪上测试其物理性质(应力/应变性能)的试验片。调节样品的水含量为13.5%,并在室温下用每分钟10毫米的延伸速率测定。

图1是按实例1(b)得到的物料的应力/应变图。

图2是按实例1(b)得到的另一种物料的应力/应变图。

试验片是标准的德国工业标准设计(DIN    NO    53455)。每组都是用(a)过程得到的预加工(变性)淀粉,按(b)过程的上述相同的加工条件注模的三个样品的结果。很明显,这些试验片性质能很好重复,并且断裂延伸约为30%。它始终明显地高于比较例(2)得到的结果。其它加工条件,如注模滞留时间为600秒,螺杆转速75转/分,也得到类似的结果。

实例2(例1的比较试验)将如实施例1(a)中所述的同样的组合物原料送入注模机的料斗,在一步加工中直接得到如实施例1(b)过程中得到的试验片。螺旋桶中温度为165℃,压力为75×105N/m2,滞留时间为12 1/2 分钟(加热时间约8分钟,熔融态时间约4 1/2 分钟)。应力/应变特性如图3和图4所示。

图3为按照实施例2得到的物料的应力/应变图。

图4为按照实施例2得到的另一种物料的应力/应变图。

从这些结果可以看出得到的断裂延伸值比较低,而且不一致,此外还明显地比实施例1得到的值差。

实施例3重复实施例1和2,但是用如下组分代替实施例1(a)中的组合物原料。

天然土豆淀粉    80份润滑/脱模剂(氢化脂肪)    1.0份卵磷脂    0.7份二氧化钛    0.3份水    17.0份100.0份得到与实施例1和2类似的结果。当模拟实施例1加工时,结果如图1所示;模拟实施例2加工时,结果如图2所示。

实施例4用含有聚乙烯吡咯烷酮的组合物重复例1如2,这样得到的试验片具有如下组成:土豆淀粉    74.6%聚乙烯吡咯烷酮    10.0%氢化脂肪    1.1%卵磷脂    0.8%水    13.5%100.0%当加工类似于例1时,应力/应变性能与图1,2中所示的性能很相似,当加工类似于例2时,应力/应变性能与图3、4中所示的性能很相似。

实例5由实施例1(b)的变性淀粉和由实施例2的天然淀粉,用相同的加工条件模制另外的试验片。

调节模制片至不同的水含量(含水9.5%,10.8%,和13.5%),并测定应力/应变曲线。结果如图5和6所示。由预挤压的淀粉得到的图5的结果明显优良。在所用的所有的水含量中,物料都是均匀的。图6中的物料性能差(断裂延伸如断裂能量均较少),并且在上述各水含量中重复性差。这样的特性表明该物料的均匀性较差,粘着性较小。

实施例6(加工稳定性)当(1)按例1(b)加工时和当(2)按例2加工时,测量例1(a)所述的熔融态组合物在螺旋桶内的粘度与剪切速率的关系。在较好调整机器的情况下(Netstal机型235/90)得到了结果。利用标准注模理论由各测量值,结合再充填时间的测量值,计算出熔化物粘度与剪切速率的依赖关系。图7为按照例1的两步加工结果和按例2的一步加工结果。按照例2(一步加工)加工的物料具有较高的熔融物粘度,且对滞留时间和剪切述率有较大的灵敏性。这些较高的值和灵敏性导致较低的加工稳定性和较低的生产可重复性,这由图3、4和6中也可明显看出。

按照例1,在两步加工熔化物粘度与剪切速率的相关性与一般的热塑性材料,如聚乙烯的那种相关性相类似,众所周知聚乙烯之类的热塑性材料都能用注模法稳定地加工获得可重复的产品。

在图7中,log(η/Pas)表示在帕一秒单位中熔融物粘度值(η)的以10为底的对数;log(γ/S-1)表示在秒的倒数单位中剪切速率值的以10为底的对数。

Claims (17)

1.一种由淀粉得到成形制品的方法,该方法包括如下步骤:(a)将包括淀粉和水的固体淀粉组合物,在0-150×105N/m2的压力下加热至80-200℃的温度以形成溶化物,该组合物中以组合物重量为基水含量为10-20%(重量),其中淀粉选自如下之一种;化学上基本未改性的淀粉、物理上改性的淀粉、用酸处理过以致其pH为3-6范围内的淀粉和/或与淀粉的磷酸根基团结合的阳离子的种类和浓度已改变了的淀粉;(b)使该熔化物成形;和(c)使熔化物冷却至低于其玻璃转变温度以形成固体成形制品,其中步骤(a)所述的淀粉,是将淀粉在0-150×105N/m2的压力下加热至80-200℃,而已经预先基本变性了。
2.按照权利要求1的方法,其中淀粉是从土豆,大米,大薯淀粉,玉米,黑麦,燕麦和/或小麦中的至少一种中提取的,最好是从土豆中提取。
3.按照权利要求1的方法,其中步骤(a)所述的淀粉/水物料的水含量按组合物的重量为基计约为12%-19%,最好为14-18%(重量)。
4.按照权利要求1的方法,其中步骤(a)所述的淀粉/水物料被加热到约120-190℃,最好加热到约140-180℃,以形成熔化物。
5.按照权利要求1的方法,其中作用于熔化物的压力为0-100×105N/m2,最好为0-80×105N/m2。
6.按照权利要求1的方法,其中步骤(a)所述的淀粉/水物料含有或者混合以增充剂,润滑剂、增塑剂,无机填充物和/或着色剂。
7.按照权利要求6的方法,其中步骤(a)所述的淀粉/水物料含有或者混合以至少一种选自如下的增充剂,最好是明胶;植物蛋白质最好是葵花蛋白质,大豆蛋白质,棉籽蛋白质,花生蛋白质;水溶性的多糖类,最好为藻酸盐,角叉菜聚糖,瓜耳胶,琼脂,阿拉伯树胶,印度胶,刺梧酮树胶,黄蓍树胶,果胶;水溶性的纤维素衍生物,最好是烷基纤维素,羟烷基纤维素,羧烷基烷基纤维素,纤维素酯和羟烷基纤维素酯,羧烷基纤维素,羧烷基纤维素酯,聚丙烯酸类和聚丙烯酸酯类,聚甲基丙烯酸和聚甲基丙烯酸酯,聚乙酸乙烯酯,聚乙烯醇,聚乙烯乙酸邻苯二甲酸酯(PVAP),聚乙烯吡咯烷酮,聚巴豆酸;邻苯二甲酸酯化明胶,凝胶琥珀酸酯,交联明胶,紫胶,淀粉的水溶性化学衍生物,具有叔氨和季氨基团的阳离子改性的丙烯酸脂和/或甲基丙烯酸酯,上述增充剂的含量,按所有组分的重量为基计应小于和等于50%,最好为3-10%。
8.按照权利要求6的方法,其中步骤(a)所述的淀粉/水物料含有或者与至少一种选自如下的增塑剂混合,这类增塑剂包括聚烯化氧,最好是聚乙二醇,聚丙二醇,聚乙丙二醇;甘油,单乙酸甘油酯,二乙酸甘油酯或三乙酸甘油酯;丙二醇,山梨醇,二乙基磺基丁二酸钠,柠檬酸三乙酯,柠檬酸三丁酯,加入浓度按所有组分的重量为基计为0.5-15%,最好为0.5-5%(重量)。
9.按照权利要求6的方法,其中步骤(a)所述的淀粉含有或者与至少一种着色剂混合,着色剂选自偶氮染料、有机或无机颜料、或者天然来源的着色剂,最好是铁或钛的氧化物,上述着色剂的加入浓度按所有组分的重量为基计为0.001-10%,最好为0.5-3%(重量)。
10.按照权利要求6的方法,其中步骤(a)所述的淀粉/水物料含有或与无机填充物混合,最好是镁、铝、硅或钛的氧化物,其浓度范围按所有组分的重量为基计约为0.02-3%,最好是0.02-1%(重量)。
11.按照权利要求8的方法,其中存在增塑剂,增塑剂和水的总量按所有组分的重量为基计不超过25%,最好不超过20%(重量)。
12.按照权利要求6的方法,其中步骤(a)所述的淀粉/水物料还含有或者与一种含动物脂肪或植物脂肪的物质混合,该脂肪最好以它们的氢化形式,特别是在室温下呈固态的脂肪为好。
13.按照权利要求12的方法,其中步骤(a)所述的淀粉/水物料含有或与一种由脂肪与甘油一酯和/或甘油二脂或者磷脂,尤其是卵磷脂组成的物质混合,而所用的脂肪,甘油一脂,甘油二脂和/或卵磷脂的总量按组合物的总重量为基计不超过5%,最好约为0.5%至2%(重量)
14.按照权利要求6的方法,其中步骤(a)所述的淀粉/水物料还含有或者与二氧化硅或二氧化钛混合,其浓度按组合物的总量为基计约为0.02%至1%(重量)。
15.按权利要求1至14中任一项的方法制造的成形制品。
16.按照权利要求15的成形制品,它由选自注模、吹塑、挤压、复合挤压或压模之一种方法制成。
17.按照权利要求15或16的成形制品、其中制品为一种包装材料。
CN 88104981 1987-08-18 1988-08-09 由预加工淀粉制造的成型制品 CN1027726C (zh)

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JPH0197615A (en) 1989-04-17 application
CN1031314A (zh) 1989-03-01 application
FI93022C (fi) 1995-02-10 grant
DE3888046T2 (de) 1994-07-07 grant
FI93022B (fi) 1994-10-31 application
DK444388A (da) 1989-02-19 application
ES2051888T5 (es) 2001-02-16 grant
JP1878814C (zh) grant
EP0304401B1 (en) 1994-03-02 grant
EP0304401B2 (en) 2000-11-29 grant
EP0304401A2 (en) 1989-02-22 application
KR0130073B1 (ko) 1998-04-07 grant
US5405564A (en) 1995-04-11 grant
EP0304401A3 (en) 1990-01-24 application
FI883720A0 (fi) 1988-08-10 application
CA1328711C (en) 1994-04-26 grant
GB2208651A (en) 1989-04-12 application
GB2208651B (en) 1991-05-08 grant
DE3888046T3 (de) 2001-03-22 grant
ES2051888T3 (es) 1994-07-01 grant
FI883720A (fi) 1989-02-19 application
GB8719485D0 (en) 1987-09-23 grant
JPH066307B2 (ja) 1994-01-26 grant
DE3888046D1 (de) 1994-04-07 grant
DK171316B1 (da) 1996-09-02 grant
DK444388D0 (da) 1988-08-09 grant

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