CN1058222A - 含基于乙烯和马来酸酐共聚物的热塑性组合物及其工业制品 - Google Patents
含基于乙烯和马来酸酐共聚物的热塑性组合物及其工业制品 Download PDFInfo
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Abstract
本发明涉及一种热塑性组合物,该组合物包括
25-80%(重量)的至少一种部分结晶的乙烯聚合物
或共聚物,其密度为0.870-0.945;15-85%(重量)的
至少一种无规共聚物,此共聚物包括83-99.7%(摩
尔)的由乙烯衍生的单元,0-14%(摩尔)的由至少一
种丙烯酸酯或甲基丙烯酸酯衍生的单元,和0.3-3%
(摩尔)的由马来酸酐衍生的单元,其熔融指数为
1-500dg/min;1-8%(重量)的至少一种橡胶;和
0-8%(重量)的滑石粉,以及该组合物的应用。
Description
本发明涉及热塑性组合物,该组合物包括基于乙烯、马来酸酐和任意的丙烯酸烷基酯或甲基丙烯酸烷基酯的共聚物,该组合物特别适用于制备具有良好粘合性能的薄膜、复合薄膜以及覆膜金属。
美国专利US-A-4,868,052介绍了一种含未交联混合物的热塑性组合物:
(A)1-80%(重量)的至少一种部分结晶的乙烯聚合物或共聚物,其密度为0.870-0.945,和
(B)20-99%(重量)的至少一种疏水的、非弹性的无规共聚物,该共聚物含:
(ⅰ)83-99.7%(摩尔)的由乙烯衍生的单元;
(ⅱ)0-14%(摩尔)的由至少一种丙烯酸酯或甲基丙烯酸酯衍生的单元;和
(ⅲ)0.3-3%(摩尔)的由马来酸酐衍生的单元;
其熔融指数为1-500dg/min。
该文献还介绍了填充的热塑性组合物,该组合物包括67-99%(重量)的(A)、1-33%(重量)的(B)和每100份(重量)(A)+(B)混合物有至多100份的至少一种无机填料。
这些组合物可制成工业品如:
-粘性薄膜,该薄膜在各种底物如玻璃、聚丙烯织物、聚氨酯泡沫塑料等等上面能显示良好的粘合性能,该薄膜通常由未填充组合物制成,共聚物(B)的熔融指数选在约1-30dg/min之间;
-具有改进的冲击强度的模制品,在此种情况中,该组合物中添加了填料;
-复合薄膜,该薄膜包括至少一层上述定义过的未填充的热塑性组合物和至少一层由其它热塑性塑料(如聚乙烯、聚丙烯、聚-1-丁烯、聚(4-甲基-1-戊烯)、聚酰胺、聚苯乙烯、聚氯乙烯和乙烯/乙烯醇共聚物)组成的其它层;和
-用所述未填充组合物组成的第一层覆盖的金属品,必要时,在第一层上还可以覆盖至少一种由其它热塑性塑料如低密度聚乙烯组成的第二层,从而提供一种对抗机械损害和/或水份侵蚀的有效保护。
现在,本公司发现,如果在上述类型的热塑料组合物(包括基于乙烯和马来酸酐的共聚物)中加入橡胶和滑石粉(适当地),可以得到具有较高粘性的薄膜以及复合薄膜和涂覆有上述二层和三层体系的金属品,此种热塑性组合物具有比美国专利第4,868,052号中所叙述的未填充的组合物更好的抗剥离或抗脱层性。
因此,本发明的主题首先是包括下述混合物的热塑性组合物:
(A)约25-80%(重量)的至少一种部分结晶的乙烯聚合物或共聚物,其密度约为0.870-0.945;
(B)约15-85%(重量)的至少一种无规共聚物,该共聚物包括:
(a)约83-99.7%(摩尔)的由乙烯衍生的单元;
(b)0-约14%(摩尔)的由至少一种丙烯酸酯或甲基丙烯酸酯衍生单元;和
(c)约0.3-3%(摩尔)的由马来酸酐衍生的单元;
其熔融指数为1-500dg/min;和
(C)约1-8%(重量)的至少一种橡胶;和
(D)约0-8%(重量)的滑石粉。
本发明组合物的聚合物(A)可以是
-在高温高压下由自由基聚合得到的聚合物,该聚合物包括至少98%(摩尔)的乙烯和不超过2%(摩尔)的极性共聚单体如一氧化碳、醋酸乙烯酯、丙烯酸烷基酯和甲基丙烯酸烷基酯,其中烷基含1-12个碳原子,此种聚合物的密度通常在约0.910-0.935之间;
-或在齐格勒型催化剂存在下获得的共聚物,其中包括至少79%(摩尔)的由乙烯衍生的单元和不超过21%(摩尔)的含3-12个碳原子的α-烯烃单元,
共聚物(A)的最小密度为0.870时通常相应的结晶度至少为5%,密度至少为0.905时通常结晶度至少为30%。
对于本发明组合物,在大部分应用场合下,共聚物(A)的溶融指数选择在约0.1-20dg/min之间较为有利,熔融指数在ASTM标准D-1238的标准条件(170℃,2.16kg加载)下测量。
本发明组合物的共聚物(B)可以通过例如在高温高压下,由乙烯、马来酸酐和丙烯酸或甲基丙烯酸酯(也可以不用)直接共聚来制备,这种方法得到的是无规共聚物。适合的高温高压法见例如英国专利第2,091,745号和美国专利US-A-4,617,366和US-A-4,644,044。
共聚物(B)的标准熔融指数与聚合物(A)的标准熔融指数之比最好是选在约1∶6-400∶1的范围内。当然,聚合物A和共聚物(B)的相应熔融指数的选择应适合本发明组合物的预期用途。
通常,较好的是,共聚物(B)应为非弹性的,这就是为什么将除乙烯外的单体的总份数限制在约17%(摩尔)的原因。
橡胶(C)主要选自丁基橡胶、乙丙橡胶、乙烯-丙烯-二烯橡胶及其混合物。乙丙橡胶是指65-80%(摩尔)的乙烯和20-35%(摩尔)的丙烯的共聚物,其密度为0.850-0.870,没有残余结晶度因而没有结晶熔化温度。乙烯-丙烯-二烯橡胶是指乙烯-丙烯-二烯的三元共聚物,二烯选自共轭的、线性的环状的二烯如丁二烯、异戊二烯、1,3-戊二烯、1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,9-癸二烯、5-亚甲基-2-降冰片烯、5-乙烯基-2-降冰片烯、2-烷基-2,5-降冰片二烯、5-亚乙基-2-降冰片烯、5-(2-丙烯基)-2-降冰片烯、5-(5-己烯基)-2-降冰片烯、1,5-环辛二烯、二环〔2,2,2〕辛-2,5-二烯、环戊二烯、4,7,8,9-四氢茚和异丙烯基四氢茚。可以用本发明的这类弹性三元共聚物通常包括15-60%(摩尔)的由丙烯衍生的单元的0.1-20%(摩尔)的由二烯衍生的单元。
本发明的组合物可以通过下列制备方法中的任何一种方法制备:
-通过任何已知的方法,特别是在捏和机或挤出机中,将聚合物(A)和(B)、橡胶和滑石粉同时混合;
-将丙种组分混合而成的母料与剩余组分混合;
-将聚合物(A)和事先涂覆有共聚物(B)的滑石粉混合,涂覆方法为将滑石粉加入共聚物(B)的溶液中然后将溶剂蒸发掉。在适用的共聚物(B)的组合物中,溶剂选自如含5-12个碳原子的脂族烃、环脂族烃和芳香烃、酮、氯代烃、多元醇酯和乙酸酯,在所述溶剂中,共聚物的浓度不超过约15%(重量)。
本发明还涉及应用上述定义的组合物来制备具有粘合性能的薄膜。
本发明也涉及工业制品,包括覆盖有至少一层上述的热塑性组合物的金属品。
在这些覆膜金属制品中,本发明热塑性组合物层的厚度可在约10-550μm范围内。此外,在热塑性组合物中,共聚物(B)的熔融指数应该在2-10dg/min范围内较的有利。
在一些特殊的用途中,如覆膜钢管,覆膜金属制品可以额外地包括一层树脂(在金属和第一层之间,如环氧树脂)用于改善粘合性,在这种情况中,环氧树脂可以与硬化剂(如酐或多氨基酰胺)和交联剂(也可不用)混合,然后在液态下涂覆于金属,其厚度约为10-200μm。
用第一层覆盖金属的方法包括在约140-300℃之间的温度下,用由上述热塑性组合物构成的薄膜覆盖金属底物,所述金属底物的移动速度在约1-600m/min之间,例如,如果是钢管的话,所述移动速度选择在40-600m/min之间较为有利。
金属底物可以是任何形状的,如板材、片材或管材,其厚度至少为25μm。
本发明的覆膜金属有广泛的用途。例如,本发明的覆膜铝箔可以用于食品包装工业使产品不受湿并保持其香味。又例如,本发明的覆盖方法可以运用于钢管如输油管或输气管,目的是使其免遭氧化及冲击。在后一种情况下,较好的是,在本发明热塑性组合物膜上应该再覆盖一层其它热塑性塑料(如密度在0.870-0.945之间的聚乙烯),其厚度主要约为50-5000μm,塑料可以含填料如碳黑。
本发明的另一主题是复合薄膜,包括:
(a)至少有一层包括上述热塑性组合物层,其条件是在所述组合物中,滑石粉的份数应不超过足以提供防粘作用所需的份数,即约为0.3%(重量),和
(b)至少一层其它热塑性塑料层。
此种其它热塑性塑料可以选自聚酯、聚乙烯、聚丙烯、聚-1-丁烯、聚(4-甲基-1-戊烯)、聚酰胺、聚苯乙烯、聚氯乙烯和乙烯/乙烯醇共聚物。
在这类复合膜中,本发明的层的厚度可以在约5-100μm范围内,而其它热塑性组合物层的厚度依其种类可以在约20-3,000μm范围内。例如,如果是聚乙烯、聚丙烯、聚-1-丁烯、聚酰胺和乙烯/乙烯醇共聚物,厚度通常约为20-100μm,如果是聚氯乙烯,厚度通常约为25-2,000μm,如果是聚苯乙烯、厚度通常约为100-3,000μm。在这些层中,每一层都可以通过扁平模头挤出或通过圆柱形模头挤出吹胀获得。
本发明的复合薄膜可以通过扁平模头或圆柱形模头将两种热塑性组合物共挤出来制备,速度约为2-200m/min、温度在约170-290℃范围内较好,当使用圆柱形模头时,吹胀比选择在约1-4之间较好。
下列实施例对本发明作了说明,但并不限制其范围。测量熔融指数所采用的标准是ASTM标准D 1238-73(熔融指数在190℃、2.16kg下测量,单位为dg/min)。除特别标明外,百分数以重量计。采用的试验如下:
金属上两层复合膜的剥离试验
将一块喷沙钢板和一块聚乙烯覆膜(PEc)板用10分钟的时间加热至190℃,两板的尺寸为12×7×0.2cm。
将本发明组合物层和对比组合物层施于厚度为0.32μm的钢板上,然后放置PEc板,将其通过辊筒保证其粘合力,然后在流水中冷却5分钟。
放置2小时后,取10cm宽的试样用拉力计测其剥离力,剥离速度为32mm/分钟,结果用kg/5cm(N/5cm)表示。
金属上三层组合膜的剥离试验
除在钢板上运用一层薄薄的环氧树脂(厚度为50m)外,其它方法与上述试验相同。
两层复合薄膜的脱层试验
(本发明组合物或对比组合物)-聚酯
按下述方式,用加压的方法制备三层复合薄膜。
将10g/m2的本发明组合物或对比组合物置于两块Terphane (聚酯)板之间,板的尺寸为350×350mm,厚度为170μm。在150℃、49N的压力下保持接触。放置24小时后脱模,得到厚度约为160μm的复合板。
然后用拉力计以25mm/min的速度测量一层聚酯层的剥离力(另一层作为支撑层),结果用kg/cm(N/5cm)表示。
实施例1
用热混合的方法制备下述配方(%)的组合物:
-乙烯/1-丁烯共聚物,密度为0.910,
熔融指数为1,结晶熔点为116℃,
-含92%乙烯、5%丙烯酸丁酯和3%马来酸酐的三
元聚合物,熔融指数为1.0,密度为0.940,
-丁基橡胶,门尼粘度1+8(在125℃)为50-51 3
-滑石粉 4
实施例2和3
除了用门尼粘度1+8(在127℃下)为55的乙丙橡胶(实施例2)或用门尼粘度1+8(在127℃下)为35-45的乙烯-丙烯-二烯橡胶(实施例3)取代丁基橡胶外,方法与实施例1相同。
实施例4(对比例)
除了既不用滑石粉也不用橡胶并且保留的两种组分的重量比为50∶50外,方法与实施例1相同。
剥离试验结果
*RLDPE:自由基低密度聚乙烯
**HDPE:高密度聚乙烯
实施例5
用热混合的方法制备下述配方(%)的组合物:
丁基橡胶 3
滑石粉 4
剥离试验结果
*PEcl=自由基低密度聚乙烯混合物(密度为0.923,熔融指数为0.3),其中已加入3%的碳黑,商品名为Lotrene TB3026
**PEc2=高密度聚乙烯,商品名为Hoechst
***只加热至130℃的钢板
实施例6
用热混合的方法制备下述配方(%)的组合物:
-乙烯-1-丁烯低密度共聚物,
密为0.900,熔融指数为1,1,
-含85%(重量)乙烯、12%(重量)丙
烯酸乙酯和3%(重量)马来酸酐的
三元共聚物,熔融指数为2.4,
TX8030 53
-滑石粉 3.5
-丁基橡胶 5
实施例7
用热混合的方法制备下列组合物:
-Lotader TX 8030 25
-滑石粉 3
-丁基橡胶 5
剥离试验结果
*PEc:自由基低密度聚乙烯混合物(密度为0.934,熔融指数为0.3),含有2.4%的碳黑,商品名为“Lotrene TE 3017”
实施例8
用热混合的方法制备下述配方的组合物(熔融指数1.4):
Norsoflex FW 1500 20
丁基橡胶 5
母炼胶(Masterbatch)(含30%的滑石粉
Claims (10)
1、包括下述混合物的热塑性组合物:
(A)25-80%(重量)的至少一种部分结晶的乙烯聚合物或共聚物,其密度在约0.870-0.945范围内;
(B)15-85%(重量)的至少一种无规共聚物,该共聚物包括:
(a)83-99.7%(摩尔)的由乙烯衍生的单元;
(b)0-14%(摩尔)的由至少一种丙烯酸酯或甲基丙烯酸酯衍生单元;和
(c)0.3-3%(摩尔)的由马来酸酐衍生的单元;
其熔融指数为1-500dg/min;和
(C)1-8%(重量)的至少一种橡胶;和
(D)0-8%(重量)的滑石粉。
2、根据权利要求1的热塑性组合物,其特征在于该橡胶选自丁基橡胶、乙丙橡胶、乙烯-丙烯-二烯橡胶及其混合物。
3、权利要求1和2的组合物的应用,用于制备粘性薄膜。
4、包括应用至少一层权利要求1的热塑性组合物覆盖的金属的工业制品。
5、根据权利要求4的制品,其特征在于热塑性组合物层的厚度在10-500μm范围内。
6、根据权利要求4或5的制品,其特征在于在热塑性组合物中的共聚物(B)的熔融指数在2-10dg/min范围内。
7、根据权利要求4-6的制品,其特征在于覆膜金属还包括在所述的金属和所述的组合物层之间有一环氧树脂的中间层。
8、根据权利要求4-7的制品,其特征在于在热塑性组合物层上覆盖有一层厚度为50-5000μm的其它热塑性塑料层。
9、根据权利要求8的制品,其特征在于该其它热塑性塑料是聚乙烯,其密度在0.870-0.945之间。
10、复合薄膜,包括:
(a)至少有一层包括权利要求1的热塑性组合物,其条件是在所述组合物中,滑石粉的份数不超过足以提供防粘作用所需的份数,和
(b)至少一层其它热塑性塑料层。
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FR9008571 | 1990-07-05 | ||
FR9008571A FR2664283B1 (fr) | 1990-07-05 | 1990-07-05 | Composition thermoplastique comprenant un copolymere a base d'ethylene et d'anhydride maleique, et articles industriels obtenus a partir d'une telle composition. |
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CN1058222A true CN1058222A (zh) | 1992-01-29 |
Family
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CN91104661A Pending CN1058222A (zh) | 1990-07-05 | 1991-07-05 | 含基于乙烯和马来酸酐共聚物的热塑性组合物及其工业制品 |
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US (1) | US5187016A (zh) |
EP (1) | EP0465365B1 (zh) |
JP (1) | JP2533013B2 (zh) |
KR (1) | KR920002683A (zh) |
CN (1) | CN1058222A (zh) |
AT (1) | ATE128162T1 (zh) |
CA (1) | CA2046183A1 (zh) |
DE (1) | DE69113143T2 (zh) |
DK (1) | DK0465365T3 (zh) |
ES (1) | ES2076485T3 (zh) |
FI (1) | FI913263A (zh) |
FR (1) | FR2664283B1 (zh) |
GR (1) | GR3018471T3 (zh) |
IL (1) | IL98664A (zh) |
NO (1) | NO300331B1 (zh) |
PT (1) | PT98208A (zh) |
Cited By (1)
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CN102428152A (zh) * | 2009-04-08 | 2012-04-25 | 汉高公司 | 膜状厌氧粘合剂和密封剂组合物、包含其的卷筒组合装置,及其在可配合的部件上的预涂物 |
Families Citing this family (10)
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JPH04320440A (ja) * | 1991-04-19 | 1992-11-11 | Sumitomo Chem Co Ltd | 接着性樹脂組成物 |
JPH0881522A (ja) * | 1994-07-13 | 1996-03-26 | Sumitomo Chem Co Ltd | 鋼材被覆用エチレン−α−オレフィン共重合体 |
CN1079104C (zh) * | 1999-04-28 | 2002-02-13 | 中美合资宁波安达胶带制品有限公司 | 复合型聚乙烯防腐胶粘带及制造方法 |
JP2002317080A (ja) * | 2002-04-01 | 2002-10-31 | Showa Denko Kk | ヒートシール性樹脂組成物 |
DE102005009165A1 (de) * | 2005-02-25 | 2006-08-31 | Basf Ag | Abziehbare Schutzfilme |
JP5901235B2 (ja) * | 2011-11-10 | 2016-04-06 | ユニチカ株式会社 | ドライフィルムレジスト工程用感光性樹脂積層体 |
JP5929462B2 (ja) * | 2012-04-19 | 2016-06-08 | コニカミノルタ株式会社 | 画像形成方法 |
CN107001842B (zh) * | 2014-12-11 | 2020-10-30 | Sabic环球技术有限责任公司 | 用于热喷涂的聚合物组合物 |
CN105255326A (zh) * | 2015-11-27 | 2016-01-20 | 常熟市地大探矿机械厂 | 石油开采用钻具 |
CN111363486B (zh) * | 2020-04-30 | 2022-03-29 | 江苏达胜热缩防护用品有限公司 | 埋地钢制弯管防腐用辐射交联聚乙烯复合带及其制备方法 |
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JPS60138083A (ja) * | 1983-12-26 | 1985-07-22 | Mitsubishi Alum Co Ltd | 高温強度および犠牲陽極効果のすぐれた熱交換器用Al合金製複合フイン材 |
FR2574804B1 (fr) * | 1984-12-14 | 1987-01-09 | Charbonnages Ste Chimique | Nouvelles formulations a base de caoutchoucs epdm ayant une durete elevee et une bonne facilite a la mise en oeuvre |
FR2587350B1 (fr) * | 1985-04-24 | 1987-10-30 | Charbonnages Ste Chimique | Compositions ternaires rigides a resistance au choc amelioree, un procede pour leur preparation et articles obtenus |
DE3607756A1 (de) * | 1986-03-08 | 1987-09-10 | Basf Ag | Kabelisolierung auf basis von ethylenpolymerisaten mit hoher widerstandsfaehigkeit gegenueber der bildung von wasserbaeumchen |
JPH0730217B2 (ja) * | 1986-05-08 | 1995-04-05 | 住友化学工業株式会社 | 熱可塑性エラストマ−組成物 |
US4945005A (en) * | 1987-03-31 | 1990-07-31 | Dexter Corporation | Thermoplastic compositions and articles made therefrom |
EP0312664A1 (en) * | 1987-10-22 | 1989-04-26 | Elf Atochem S.A. | Impact-resistant thermoplastic composition having improved surface properties |
FR2625508B1 (fr) * | 1987-12-30 | 1992-05-22 | Charbonnages Ste Chimique | Compositions polymeres ignifugees et leur application au revetement de cables electriques |
JP2570358B2 (ja) * | 1988-02-03 | 1997-01-08 | 住友化学工業株式会社 | 熱可塑性エラストマー組成物 |
WO1989007624A1 (en) * | 1988-02-22 | 1989-08-24 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polymer composition |
US4957968A (en) * | 1988-08-09 | 1990-09-18 | Monsanto Company | Adhesive thermoplastic elastomer blends |
-
1990
- 1990-07-05 FR FR9008571A patent/FR2664283B1/fr not_active Expired - Fee Related
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- 1991-07-03 DE DE69113143T patent/DE69113143T2/de not_active Expired - Fee Related
- 1991-07-03 AT AT91401840T patent/ATE128162T1/de not_active IP Right Cessation
- 1991-07-03 ES ES91401840T patent/ES2076485T3/es not_active Expired - Lifetime
- 1991-07-03 EP EP91401840A patent/EP0465365B1/fr not_active Expired - Lifetime
- 1991-07-03 DK DK91401840.3T patent/DK0465365T3/da active
- 1991-07-04 NO NO912628A patent/NO300331B1/no unknown
- 1991-07-04 PT PT98208A patent/PT98208A/pt not_active Application Discontinuation
- 1991-07-04 CA CA002046183A patent/CA2046183A1/fr not_active Abandoned
- 1991-07-04 FI FI913263A patent/FI913263A/fi not_active Application Discontinuation
- 1991-07-05 US US07/726,197 patent/US5187016A/en not_active Expired - Fee Related
- 1991-07-05 JP JP3165783A patent/JP2533013B2/ja not_active Expired - Lifetime
- 1991-07-05 KR KR1019910011427A patent/KR920002683A/ko not_active Application Discontinuation
- 1991-07-05 CN CN91104661A patent/CN1058222A/zh active Pending
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102428152A (zh) * | 2009-04-08 | 2012-04-25 | 汉高公司 | 膜状厌氧粘合剂和密封剂组合物、包含其的卷筒组合装置,及其在可配合的部件上的预涂物 |
CN102428152B (zh) * | 2009-04-08 | 2013-07-31 | 汉高公司 | 膜状厌氧粘合剂和密封剂组合物、包含其的卷筒组合装置,及其在可配合的部件上的预涂物 |
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Publication number | Publication date |
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NO912628L (no) | 1992-01-06 |
PT98208A (pt) | 1992-05-29 |
GR3018471T3 (en) | 1996-03-31 |
FR2664283B1 (fr) | 1994-04-15 |
NO300331B1 (no) | 1997-05-12 |
ES2076485T3 (es) | 1995-11-01 |
IL98664A (en) | 1995-12-08 |
US5187016A (en) | 1993-02-16 |
FR2664283A1 (fr) | 1992-01-10 |
JPH04226550A (ja) | 1992-08-17 |
JP2533013B2 (ja) | 1996-09-11 |
ATE128162T1 (de) | 1995-10-15 |
FI913263A0 (fi) | 1991-07-04 |
DE69113143D1 (de) | 1995-10-26 |
DK0465365T3 (da) | 1996-01-15 |
EP0465365A1 (fr) | 1992-01-08 |
CA2046183A1 (fr) | 1992-01-06 |
FI913263A (fi) | 1992-01-06 |
DE69113143T2 (de) | 1996-06-20 |
IL98664A0 (en) | 1992-07-15 |
KR920002683A (ko) | 1992-02-28 |
EP0465365B1 (fr) | 1995-09-20 |
NO912628D0 (no) | 1991-07-04 |
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