CN1181098A - 生物可降解的聚合物混合物 - Google Patents
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Abstract
生物可降解的聚合物混合物作为组分具有至少一种以再生原料为基础制备的生物聚合物和一种选自下列物质的聚合物:芳族聚酯,聚酯-共聚物(其中聚酯-共聚物具有脂族和芳族的嵌段),聚酰胺酯,聚乙二醇,聚酯尿烷和/或其混合物。
Description
本发明涉及生物可降解的聚合物混合物,其制备方法以及加工本发明聚合物混合物的方法。
由大量的专利文献和文章已知制备生物可降解的聚合物混合物的建议。通常聚合物混合物很大的问题在于,这些混合物(它们具有优异的生物可降解性)在工程塑料领域内仅有有限的使用性,由此说明至今相对成果不大。具有改善性能的聚合物混合物或是生物性不足或是可降解时化费高,或是太贵。
由EP-535994已知一种聚合物混合物,主要是由淀粉和脂族的聚酯组成的,例如聚己内酯,其中淀粉优选是用水分解的。
与此相对并认识到用水分解淀粉的不足时在DE-4237535中建议对生物可降解的聚合物混合物使用热塑性淀粉,这种淀粉是在隔绝水和使用适宜的增塑剂情况下制备的。这种建议的聚合物混合物含有热塑性淀粉,疏水的聚合物以及相介质,其中作为优选的混合物建议使用具有聚己内酯的热塑性淀粉。
脂族聚酯本身是制备生物可降解的聚合物混合物的适合的混合组分,因为它具有好的生物可降解性。然而脂族聚酯只具有中等的物料性能,例如熔点,拉伸强度等,因此相应的混合物在使用以再生原料为基础制备的聚合物,例如热塑性淀粉的条件下也只具有中等的性能,对此在工程塑料领域内这种使用性再次成了问题。
因此本发明的任务是,提出一种生物可降解的聚合物混合物,它不仅是完善地生物可降解,并附加地具有好的力学和热的性能,由此可考虑作为工程塑料或作为大宗塑料使用。适合作为大宗塑料的另一前提条件还在于,按照建议的聚合物混合物生产费用达到可接收的程度。
按照本发明上述这种任务利用按照权利要求1的生物可降解的聚合物混合物可得到解决。
许多在现有技术中建议的生物聚合物或生物可降解的聚合物混合物大部分是以淀粉构成的或使用了淀粉,其中尽简天然的淀粉作为工业可用的聚合物几乎是不适宜的。但因为淀粉是可很好生物降解的,具有适宜的价格并由于是以再生原料为基础而不依赖石油产物,所以建议使用淀粉。由于天然淀粉作为“工程塑料”的适宜性很差本发明建议使用所谓的热塑性淀粉,它们例如在PCT/WO90/05161中被建议。取得这些热塑性淀粉的方法是天然淀粉利用增塑剂或溶胀剂在熔融状态加工成均匀的物质,其中溶胀剂或增塑剂的含量通常可在10和约40%之间,以混合物的总重量为基计。此外适宜的溶胀剂或增塑剂(如在权利要求4中所说明)例如是甘油或山梨醇。
由于热塑性淀粉用于大宗塑料始终受限制的性能按照本发明建议,热塑性淀粉与至少一种其他的聚合物混合,如与芳族聚酯,与聚酯共聚物(其中聚酯共聚物是由通常的二醇和由芳族和脂族二羧酸制备的),与聚酰胺酯,聚环氧乙烷聚合物或聚乙二醇,聚酯尿烷和/或其混合物混合。对于热塑性淀粉的非常中等的物料性能的改进证实特别是各种各样的聚酯和共聚酯或聚乙二醇可作为适宜的物料。在现有技术中建议的脂族聚酯虽然具有好的生物可降解性,但由于它的同样中等的物料性能即熔点和拉伸性而不是特别适合对改善热塑性淀粉本身的物料性能作出贡献。与此相对芳族聚酯表现出优异的物料性能,但其生物可降解性是非常一般的。另外与此相反以芳族和脂族二羧酸为基础的聚酯共聚物,聚酰胺酯以及聚酯尿烷不仅具有突出的物料性能,而且也具有快速的生物可降解性,因此它们特别适合用在具有热塑性淀粉的聚合物混合物中。
本发明建议的聚酯共聚物可由石化的大宗产物,如己二酸、癸二酸、对苯二甲酸和二醇,利用缩聚合制备,其中作为二醇使用通常市售品如1,2-乙二醇,1,3-丙二醇,1,4-丁二醇和/或1,6-己二醇。重要的是,不仅使用芳族的而且也使用脂族的二-羧酸,利用它们例如借助贯常的缩聚方法制备无规的聚酯共聚物。
由脂族和芳族二-羧酸组成的无规共聚酯,含有例如约35-55mol%的芳族酸,例如对苯二甲酸,该共聚酯是在生物可降解性和物料性能之间的理想的平衡体(compromise),因此它们在混合物中与热塑性淀粉是特别适合的。这种无规共聚酯的生物可降解性在8-12周内处于肥料和泥土中。在美国专利US5446079中已指出这一点,其中已详述了脂族-芳族共聚酯的制备。
为制备本发明的淀粉/聚酯-共聚物混合物举例来说聚对苯二酸亚烷基酯和聚对苯二酸乙二醇酯已经证实是适宜的共聚酯,它是由脂族二醇和芳族二羧酸制备的。
除本发明建议的并上面记述的淀粉/聚酯-共聚物混合物外已表明,用淀粉或热塑性淀粉掺合的或填充的酯含量在30至70重量%之间的聚酰胺酯表现出好的力学性能,即使用于制造薄膜时,和具有好的可降解性或可堆肥性。建议使用例如具有平均分子量在10-300,000之间,优选20-150,000之间的聚酰胺酯。此外可参考欧洲的专利申请EP-A-641817,其中已详细记述了本发明建议的聚酰胺酯的合成。只不过应提到,本发明的聚酰胺酯可以是由下面组的单体构成:
-二元醇如乙二醇,1,4-丁二醇,1,3-丙二醇,1,6-己二醇,二甘醇以及其他等等;和/或
-二元羧酸如乙二酸,琥珀酸,己二酸以及其他等等,还可以是其各自的酯形式(甲基-,乙基-等);和/或
-羟基羧酸和内酯如己内酯以及其他等等;和/或
-氨基醇如乙醇胺,丙醇胺等等;和/或
-环状内酰胺如∈-己内酰胺或月桂内酰胺等等,和/或
-ω-氨基羧酸如氨基己酸等等,和/或
-由二羧酸如己二酸,琥珀酸等等和二胺如六亚甲基二胺,二氨基丁烷等等组成的混合物(1∶1盐)。
当聚合物混合物很大程度上以热塑性淀粉和芳族聚酯,脂族-芳族共聚酯或聚酰胺酯为基础时,添加脂族聚酯或共聚酯例如己内酯作为另外的组分,是有利的。从而这种例如芳族聚酯相对差的生物可降解性通过脂族聚酯优异的可降解性得以均衡。其实例可述及由热塑性淀粉,至少一种聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸亚烷基酯以及聚己内酯组成的聚合物混合物。脂族聚酯或共聚酯的其他例子是聚乳酸,聚羟基丁酸,聚羟基苯甲酸,聚羟基丁羧/羟基戊酸共聚物和/或其混合物。
视如何进行制备聚合物混合物的情况而定有利的是,这种聚合物混合物附加含有一种嵌段共聚物作为相介质,以在热塑性淀粉和聚酯形式的疏水聚合物之间形成连续的均匀相。这样的相介质例如可以是反应混合物,通过热塑性淀粉或必要时自然的或分解的淀粉与脂族或芳族聚酯或共聚酯,与芳族/脂族共聚酯,与聚酰胺酯和/或聚酯尿烷的基本无水的混合可以得到。
含有上面提到的增塑剂或溶胀剂的热塑性淀粉的含量在本发明建议的聚合物混合物中可以是在10-95重量%之间,以总重为基,优选使用30-75重量%的热塑性淀粉。热塑性淀粉的含量一方面与使用的聚酯或共聚酯有关以及另一方面与聚合物混合物的使用目的有关,如注射成型,挤压,薄膜吹制。对物料性能的要求也影响热塑性淀粉的含量。例如若物料的力学和热性能提出较高要求时,则争取优选热塑性淀粉含量在40-65重量%范围内,这样混合物的价格始终也是可接收的。
本发明的主题还是含有90-30,特别是80-40重量%的可热塑加工的聚酰胺酯的混合物,聚酰胺酯由30-70重量%脂族酯和70-30重量%的脂族酰胺结构组成,其中进一步优选含有10-90重量%,特别是20-60重量%的淀粉或热塑性淀粉。
加入其他的添加剂,如增塑剂,稳定剂,阻燃剂以及其他的生物可降解的聚合物,如纤维素酯,纤维素乙酸酯,纤维素,聚羟基丁酸,疏水的蛋白,聚乙烯醇等,是可能的并是取决于对要制备的聚合物混合物的要求以及自然也取决于相应组分的可用性。作为添加剂还可考虑下面述及的聚合物,如明胶,蛋白,玉米蛋白,多糖,纤维素衍生物,聚丙交酯,聚乙烯醇,聚乙酸乙烯酯,聚丙烯酸酯,山梨醇,虫胶,酪蛋白,脂肪酸衍生物,植物纤维,卵磷脂,壳聚糖酐,聚酯多尿烷以及聚酰胺酯。应述及的还有聚酯混合物,它们是由热塑性淀粉,本发明建议的脂族/芳族聚酯以及作为其他组分的共聚物(选自乙烯/丙烯酸共聚物和乙烯/乙烯醇共聚物)组成的。
作为填料特别适合的还有有机填料,是由再生原料,例如纤维素纤维得到的。
其中R=在C12-C24范围内的直链饱和烷基。通常在聚合物混合物中这样的润湿剂的浓度为约0.05-2%(以重量为基)的干的热塑性淀粉含量,优选0.1-1重量%。建议的烷基烯酮二聚物此时与淀粉聚合物的羟基进行反应。
本发明建议的聚合物混合物制备方法是使淀粉,优选如热塑性淀粉,与芳族聚酯和/或含有芳族及脂族组分的芳族聚酯或聚酯-共聚物一起在熔融状态混合,其中在混合前或混合时使混合物的水份含量减少到低于1重量%,以混合物的重量为基计。
尤其在只使用芳族聚酯与热塑性淀粉一起用于制备聚合物混合物的情况证实在制备时另外添加一种脂族聚酯是有利的。例如适合的脂族聚酯是聚己内酯,聚乳酸等,如上已提到的。其他适合的脂族聚酯是例如聚丁二酸乙二醇酯(PESU)和聚丁二酸丁二醇酯(PBSU)。后面提到的脂族聚酯通过乙二醇与脂族二羧酸和其他的酸反应生成并具有下面的通式结构式:
总之按照本发明方法的优选实施方案建议,在熔体混合期间降低水份含量至低于0.5重量%,优选甚至到低于0.1重量%,以混合物的总重量为基。
在制备本发明建议的聚合物混合物时一开始热塑性淀粉作为所谓的分散相存在,在此期间聚酯或共聚酯即聚酰胺酯或聚酯尿烷,一种疏水的聚合物,以基本粘连的连续相存在。现容易猜想到,在隔绝水的情况下在二种聚合物混合时在聚酯或共聚酯等的分子链中嵌入的酯基与热塑性淀粉进行酯化反应,这样反应的分子链与淀粉形成相介质,相介质能使两相进行分子连接,并由此形成连续相。在有湿度的情况这种反应以下列方式受到竞争,即在水存在时酯基不是与淀粉反应形成相介质,而是发生了水解。因此阻碍了相介质的形成,由此不能构成完好的分散或均匀化。自然可以从一开始就使用相介质,如嵌段共聚物,它至少包括二种嵌段,其中一种嵌段在疏水的聚酯相中至少很大程度是溶解的并另一种嵌段至少很大程度在淀粉相中是溶解的。对此可参阅DE-4237535.5。
按使用的芳族,脂族,芳族/脂族共聚酯即聚酰胺酯和/或聚酯尿烷,混合是在熔融状态在温度在120-260℃之间实施的,优选在140-160℃。必须这样选择混合温度,即不能损害使用的聚酯或共聚酯。热塑性淀粉与一种或多种聚酯组分,必要时与其他的添加剂和组分一起混合优选在挤压机中或捏合机中进行,该种机械优选具有脱气设备,用于连续抽走湿气、以达到要求的无水程度。已表明,在热塑性淀粉与一种或多种聚酯混合时形成水,它例如会导致上述的酯基与淀粉形成相介质的反应。在通过喷咀离开挤压机或捏合机时熔体具有极微小的水含量,优选<0.5或<0.1重量%。在由喷咀抽出后熔体优选在水浴中冷却并调节,以接着例如使其成粒。若使干燥的熔体本身在水浴中冷却,从而使其以数量级为2-约6重量%吸收水,以总重为基,以保证完好的造粒,这种情况证明是有益的。
本发明制备的聚合物混合物至少含有热塑性淀粉和例如由芳族和脂族嵌段组成的聚酯-共聚物,在所谓的“工程塑料”的范围内极适合作为广泛应用的大宗塑料。所以在注射成型方法中加工以及通过挤压和薄膜吹制加工是可能的。不过在加工本发明的聚合物混合物时下述情况已证明是有利的,例如使作为颗粒存在的聚合物混合物在加工前或用水或用增塑剂,如甘油或其混合物进行调节处理。例如通常在加工聚酯时,努力争取水含量为约1-6重量%,以总重为基,优选3-5重量%。还有制备的注塑件,挤压件或薄膜优选在其制备后直接放入相对湿度至少为40%,优选至少45-50%的环境中。
可能的和优选的聚合物混合物的实施例(至少含有淀粉或热塑性淀粉和疏水的聚合物,如在从属权利要求2-17之一中要求的或按在权利要求18-24之一阐明的方法制备的)列举在下述表1-4中。这些实施例通过附加的试验29得以补充。
此全部29个述及的实施例其中不仅包括,那些用于制备热塑性淀粉的增塑剂或溶胀剂意义上的组分在内,而且也包括用于制备本发明建议的聚合物混合物的热塑性淀粉的可能的聚合物的混合组分。此外这些表中含有加工条件和特别是在挤压机中制备聚合物混合物期间存在的水含量,该水含量一律<0.1重量%。另外在表中列举了例如制备聚合物混合物优选的应用可能性。自然表中只含有实施例并所有开始提到的组分都是适于与淀粉或热塑性淀粉混合用于制备本发明定义的工业及非工业应用的原料聚合物混合物。
表1 实施例
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
1淀粉% | 42.2 | 24.0 | 29.9 | 24.0 | 33.0 | 38.0 | 21.5 |
1山梨醇% | 14.0 | 8.0 | 9.5 | 8.0 | 9.9 | 11.8 | 6.9 |
1甘油% | 9.5 | 6.0 | 6.5 | 6.0 | 7.9 | 9.3 | 2.1 |
2TPS% | 60.5 | 34.9 | 42.0 | 34.9 | 46.7 | 54.5 | 27.8 |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
3PLA% | - | - | - | - | 40.0 | 10.9 | - |
4聚酰胺1 | 34.3 | 50.0 | - | - | 9.2 | - | 69.5 |
5聚酯1 | - | - | 54.1 | 45.0 | - | 30.0 | - |
6PCL% | - | 12.0 | - | 17.0 | - | - | - |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
7挤压机 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 |
T℃ | 212 | 225 | 210 | 210 | 215 | 210 | 200 |
压力,巴 | 8.5 | 2.0 | 2.5 | 2.5 | 6.2 | 7.5 | 0.5 |
MFIg/10’ | 9 | 13 | 11.5 | 13 | 8.5 | 8.0 | 29 |
颗粒 | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm |
颗粒H2O% | 3.0 | 3.6 | 3.4 | 3.6 | 3.4 | 3.4 | 3.0 |
应用 | |||||||
吹制薄膜 | + | + | + | + | + | + | - |
平薄膜 | + | + | + | + | + | + | - |
板片 | + | + | + | + | + | + | - |
注塑件 | +<0.4%* | - | - | - | - | - | - |
纤维 | - | + | - | + | - | - | + |
1淀粉=干燥的天然马铃薯淀粉3.5%H2O,山梨醇=山梨醇LGDHR71%,甘油99.5%;
2TPS=热塑性淀粉=淀粉+山梨醇+甘油<0.1%H2O。-通过脱气的水含量,按已知方法EP0397819无水的TPS由淀粉,山梨醇和甘油组成;
3PLA(聚乳酸树脂)=Mitsui Toatsu Chemicals LACEA H100MFR13 190℃ 2.16kg;
4聚酰胺1=Bayer BAK1095聚酰胺酯MFI2.5 150℃2.16kg;
5聚酯1=BASFZK242/108由脂族二醇和脂族/芳族二羧酸组成的共聚酯在190℃/2.16kg的MVR为3.0;
6PCL(聚己内酯)=Union Carbide Tone Polymer P-787 MFI1.0 125℃44磅/10分;
7挤压机=Werner&Pfleiderer ZSK40;
*0.1-0.4%水含量
表2实施例
实施例 | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
1淀粉% | 38.2 | 24.6 | 29.2 | 24.6 | 30.7 | 28.0 | 21.5 |
1山梨醇% | 12.8 | 8.2 | 9.4 | 8.8 | 9.1 | 8.8 | 6.9 |
1甘油% | 8.5 | 6.0 | 6.2 | 6.0 | 7.4 | 6.2 | 4.1 |
2TPS% | 54.5 | 35.5 | 41.1 | 36.0 | 43.5 | 39.5 | 29.7 |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
3PPDX% | 34.0 | - | - | 6.5 | - | - | 33.8 |
4PT-C300 | - | - | 45.1 | - | - | - | - |
5PT-T8-200 | - | 32.5 | - | - | 47.0 | 57.0 | - |
6BAK | 65 | 28.7 | 10.1 | 54.1 | 5.8 | - | 33.7 |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
7挤压机 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 |
T℃ | 220 | 214 | 240 | 215 | 215 | 210 | 205 |
压力,巴 | 6.5 | 3.5 | 5.5 | 7.5 | 4.5 | 7.5 | 0.5 |
MFIg/10’ | 8 | 13 | 2.5 | 11.5 | 8.5 | 8.0 | 30 |
颗粒 | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm |
颗粒H2O% | 3.9 | 3.6 | 3.5 | 3.3 | 3.4 | 3.6 | 3.2 |
应用 | |||||||
吹制薄膜 | + | + | - | + | + | + | - |
平薄膜 | + | + | + | + | + | + | - |
板片 | + | + | + | + | + | + | - |
注塑件 | +<0.15* | - | +<0.4* | - | - | - | - |
纤维 | - | - | - | - | - | - | + |
1淀粉=干燥的天然马铃薯淀粉3.5%H2O,山梨醇=山梨醇LGDHR71%,甘油99.5%;
2TPS=热塑性淀粉=淀粉+山梨醇+甘油<0.1%H2O。-通过脱气的水含量,按已知方法EP0397819无水的TPS由淀粉,山梨醇和甘油组成;
3PPDX,聚对二氧六环酮(Polypara dioxanone),ShellInternational Chemicals Ltd.峰熔点110℃;
4PT-C300ZT,环保塑料,Plantet Polymers,维卡软化点89℃,聚环氧乙烷聚合物;
5PT-T8-200DL环保塑料C,Plantet Polymers,聚环氧乙烷聚合物;
6聚酰胺酯,BAK1095,Bayer Ag,MFI2.5 150℃,2.16kg;
7挤压机=Werner & Pfieiderer ZSK40;
*0.1-0.4%水含量
表3实施例
实施例 | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
1淀粉% | 20.9 | 24.6 | 20.4 | 24.6 | 9.2 | 9.2 | 9.2 |
1山梨醇% | 7.0 | 8.2 | 6.6 | 8.8 | 2.7 | 2.7 | 2.7 |
1甘油% | 4.7 | 6.0 | 4.4 | 6.0 | 2.2 | 2.2 | 2.2 |
2TPS% | 29.9 | 35.5 | 28.6 | 36.0 | 13.0 | 13.0 | 13.0 |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
3填料% | 26.9 | - | 25.0 | - | 60.0 | - | 60.0 |
4聚酰胺1 | 40.5 | 36.2 | - | - | 25.9 | 27.9 | - |
5聚酯1 | - | - | 43.6 | 35.6 | - | - | 25.9 |
6填料% | - | 25.0 | - | 25.0 | - | 58.0 | - |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
7挤压机 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 |
T℃ | 203 | 206 | 220 | 215 | 205 | 205 | 220 |
压力,巴 | 156.5 | 21 | 15 | 22 | 35 | 40 | 35 |
MFIg/10’ | 13 | 9 | 12.5 | 8.5 | 3 | 2.8 | 2.2 |
颗粒 | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm |
颗粒H2O% | 3.5 | 3.6 | 3.4 | 3.6 | 3.4 | 3.4 | 3.0 |
应用 | |||||||
吹制薄膜 | - | - | - | - | - | - | - |
平薄膜 | (+) | (+) | (+) | (+) | - | - | - |
板片 | + | + | + | + | + | + | + |
注塑件 | +<0.2%* | +<0.2%* | +<0.2%* | +<0.2%* | +<0.2%* | +<0.2%* | +<0.2%* |
纤维 | - | - | - | - | - | - | - |
1淀粉=干燥的天然马铃薯淀粉3.5%H2O,山梨醇=山梨醇LGDHR71%,甘油99.5%;
2TPS=热塑性淀粉=淀粉+山梨醇+甘油<0.1%H2O,-通过脱气的水含量,按已知方法EP0397819无水的TPS由淀粉,山梨醇和甘油组成;
3填料,微细化的纤维素;
4聚酰胺1=Bayer BAK1095聚酰胺酯MFI2.5 150℃2.16kg;
5聚酯1=BASFZK242/108由脂族二醇和脂族/芳族二羧酸组成的共聚物在190℃/2.16kg的MVR为3.0;
6填料:微细化的棉花;
7挤压机=Werner & Pfpeiderer ZSK 40;
*0.1-0.4%水含量
表4实施例
实施例 | 22 | 23 | 24 | 25 | 26 | 27** | 28** |
1淀粉% | 34.5 | 35.5 | 40.5 | 50.5 | 60.7 | 70.3 | 67.8 |
1山梨醇% | - | - | - | - | - | - | - |
1甘油% | 16.3 | 16.5 | 12.0 | 7.1 | 4.0 | 4.5 | - |
2聚酰胺1 | 25.0 | 23.5 | 47.5 | 42.4 | 35.3 | 25.2 | 32.2 |
3TPS% | 74.8 | 74.4 | 98.6 | 98.5 | 98.2 | 87.4 | 87.8 |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
4PLA% | 24.2 | - | - | - | - | - | - |
5聚酯1 | - | 24.5 | - | - | - | - | - |
6 | - | - | - | - | - | - | - |
H2O% | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
7挤压机 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 | ZSK40 |
T℃ | 200 | 206 | 190 | 170 | 160 | 155 | 155 |
压力,巴 | 15 | 15 | 20 | 26 | 31 | 35 | 37 |
MFIg/10’ | 12 | 14 | 122.5 | 10 | 6 | 5 | 5.5 |
颗粒 | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm | 4mm |
颗粒H2O% | 2.1 | 2.1 | 2.2 | 2.6 | 0.4 | 0.4 | 0.3 |
应用 | |||||||
吹制薄膜 | + | + | + | + | + | + | + |
平薄膜 | + | + | + | + | + | + | + |
板片 | + | + | + | + | + | + | + |
注塑件 | - | - | - | (+) | +<0.15%* | +<0.2%* | +<0.2%* |
纤维 | - | - | - | - | - | - | - |
1淀粉=干燥的天然马铃薯淀粉3.5%H2O,山梨醇=山梨醇LGDHR71%,甘油99.5%;
4聚酰胺1=Bayer BAK 1095聚酰胺酯在150℃2.16kg的MFI为2.5;用作增塑剂;
2TPS=热塑性淀粉=淀粉+山梨醇+甘油和/或BAK1095,<0.1%H2O,-通过脱气的水含量,按已知方法EP0397819,27**+28**淀粉=天然的马铃薯淀粉18%H2O;
3PLA(聚乳酸树脂)=Mitsu Toatsu Chemicals LACEAH100在190℃2.16kg的MFR为13;
5聚酯1=BASFZK242/108由脂族二醇和脂族/芳族二羧酸组成的共聚酯在190℃/2.16kg的MVR为3.0;
6PCL(聚己内酯)=Union Carbide Tone Polymer P-787在125℃44磅/10分的MFI为1.0;
7挤压机=Werner & Pfleiderer ZSK 40;
*0.1-0.4%水含量
试验实施例29:
类似于试验28在实施例29中使聚酰胺酯BAK1095与10%马铃薯淀粉在双轴挤压机ZSK40中在155℃和20巴时在排出水分的情况下进行化合混合,挤出后的剩余湿度为0.15%并在聚酯束冷却后造粒。聚合物混合物在150℃/5kg时具有MFI为25g/10’并适于制备吹制薄膜和平薄膜。
利用本发明建议的聚合物混合物制备的注塑件,挤压件和薄膜除了具有较好的物料性能外还具有优异的生物可降解性,因此它们能够对急迫的垃圾问题作出重要的贡献。例如由本发明建议的聚合物混合物制备的薄膜非常适合在农业领域中的广泛应用,例如覆盖耕地,这样的薄膜使用后或者可作堆肥,或者在田里可翻耕到泥土中。这样的聚合物混合物还适合于制备堆肥袋,堆肥垃圾容器等。另外可由本发明建议的聚合物混合物利用模具吹制例如容器和瓶子。
但本发明的聚合物混合物也适合制备纺织品,例如纤维制品,单纤维制品,平面结构制品,如机织织物,缩绒,非织制织物,所谓的衬布,粘合织物,散纤维,棉絮,以及线性的结构,例如线,纱,绳,亚麻绳,等等。在实践中特别表明的是,本发明的聚合物混合物适于制作卫生用品,如襁褓,绷带,失禁产品以及床垫。另外这些卫生用品在其结构中具有非织制织物(由本发明的聚合物材料制备),因为这种聚合物材料具有很好的皮肤相容性,活跃呼吸,在同时不漏水的情况水蒸汽可以通过,并是完全可生物降解的。
此外本发明建议的聚合物混合物的大部分,如特别是含有热塑性淀粉和/或共聚酯和/或聚酰胺酯和/或聚酯尿烷的聚合物混合物适合作为粘结剂或又可用作涂层,例如纺织的机织织物的浸渍。同时业已表明,对这种应用领域适合的本发明建议的聚合物混合物优选至少部分地溶入醇的溶剂中并使用。这样例如从试验实施例29预想不到地发现,这样制备的聚合物混合物在热的醇-乙醇混合物中是溶解的。一种20%的醇溶液在制备后直接具有一粘度为100mPas。在这种情况又得出一种可能的在生物可降解的粘结剂中的应用,作为涂层或浸渍,它导致疏水性能并是可透过水蒸汽的。有关试验实施例29确定的用途也是可转移到大部分其余实施例上和其他的本发明建议的聚合物混合物上。但本发明的聚合物混合物理所当然地适合于许多别的应用,例如也适于注塑一次性使用产物,等等。
Claims (30)
1.生物可降解的聚合物混合物,其特征在于,至少一种以再生原料为基础制备的生物聚合物和一种选自下列的聚合物被用作为组分:
-芳族聚酯,
-既具有脂族嵌段又具有芳族嵌段的聚酯共聚物,
-聚酰胺酯,
-聚环氧乙烷聚合物或聚乙二醇,
-聚酯尿烷
-和/或其混合物。
2.按照权利要求1的生物可降解的聚合物混合物,其特征在于,至少淀粉,如优选热塑性淀粉作为生物聚合物存在。
3.按照权利要求1或2之一的生物可降解的聚合物混合物,其特征在于,淀粉作为热塑性淀粉存在,主要是通过无水混合天然淀粉和至少一种数量级为10-40重量%,优选20-36重量%的增塑剂或溶胀剂(以具有天然淀粉或其衍生物的混合物为基计)得到的,其中增塑剂或溶胀剂是适宜将淀粉或衍生物至少溶胀或部分溶解。
4.按照权利要求3的生物可降解的聚合物混合物,其特征在于,热塑性淀粉含有至少下列物质的一种作为溶胀剂或增塑剂:山梨醇,甘油,羟基酸,如乳酸或其低聚物和/或其盐,聚乙烯醇,脂族聚酯,如优选低分子的脂族聚酯,以及低分子的聚乳酸或聚己内酯,聚酰胺酯,优选低分子的聚酰胺酯和/或其混合物。
5.按照权利要求1-4之一的生物可降解的聚合物混合物,其特征在于,聚酯-共聚物除多元醇外是由芳族或脂族二羧酸制备的。
7.按照权利要求1-6之一的生物可降解的聚合物混合物,其特征在于,聚酯-共聚物是通过下列化合物的缩聚制备的:一方面至少一种二醇,来自1,2-乙二醇,1,3-丙二醇,1,4-丁二醇和/或1,6-己二醇;另一方面至少一种芳族二羧酸,例如对苯二甲酸和必要时至少一种脂族二羧酸,如己二酸和/或癸二酸。
8.按照权利要求1-7之一的生物可降解的聚合物混合物,其特征在于,聚酯-共聚物是聚对苯二甲酸亚烷基酯或聚对苯二甲酸乙二醇酯。
9.按照权利要求1-8之一的生物可降解的聚合物混合物,其特征在于,作为另外的组分考虑脂族聚酯或共聚酯,例如聚乳酸,聚羟基丁酸,聚羟基苯甲酸,聚羟基丁酸/羟基戊酸-共聚物或聚己内酯。
10.按照权利要求9的生物可降解的聚合物混合物,其特征在于热塑性淀粉,至少一种聚对苯二甲酸乙二醇酯或一种聚对苯二甲酸亚烷基酯以及聚己内酯。
11.按照权利要求1-10之一的生物可降解的聚合物混合物,其特征在于,混合物含有嵌段共聚物作为相介质,例如通过无水混合淀粉或热塑性淀粉与至少一种下面的聚合物并在熔融状态反应而得到:
-带有脂族和芳族嵌段的聚酯-共聚物,
-芳族聚酯,
-脂族聚酯,
-聚酰胺酯和/或
-聚酯尿烷。
12.按照权利要求1-11之一的生物可降解的聚合物混合物,其特征在于,包含至少一种其他的组分,如添加剂,附加料或填料,如增塑剂,稳定剂,阻燃剂,一种其他的生物可降解的生物聚合物,如纤维素酯,纤维素,聚羟基丁酸,一种疏水的蛋白质,聚乙烯醇,明胶,玉米蛋白,多糖,聚丙交酯,聚乙酸乙烯酯,聚丙烯酸酯,山梨醇,虫胶,酷蛋白,脂肪酸衍生物,植物纤维,卵磷酯或壳聚糖酐。
13.按照权利要求1-12之一的生物可降解的聚合物混合物,其特征在于,聚合物混合物含有至少一种由再生原料,特别是如纤维素纤维组成的有机填料。
15.按照权利要求1-14之一的生物可降解的聚合物混合物,其特征在于,含有增塑剂或溶胀剂的热塑性淀粉含量为10-95重量%,优选30-75重量%,以混合物的总重为基。
16.按照权利要求1-15之一的生物可降解的聚合物混合物,其特征在于热塑性淀粉在混合物中的含量为40-65重量%。
17.按照权利要求1-7之一的生物可降解的聚合物混合物,其特征在于热塑性淀粉,具有脂族和芳族嵌段的聚酯-共聚物以及选自乙烯/丙烯酸-共聚物和乙烯/乙烯醇-共聚物的一种共聚物。
18.按照权利要求1-17之一的聚合物混合物的制备方法,其特征在于,淀粉,特别是如热塑性淀粉,与至少一种下面的聚合物进行混合:
-芳族聚酯
-具有芳族和脂族嵌段的聚酯-共聚物,
-聚酰胺酯,
-聚环氧乙烷聚合物或聚乙二醇,
-聚酯尿烷
-和/或混合物,其中熔体进行混合并在混合前和/或在混合时水含量降低至<1.0重量%,以混合物的重量为基计。
19.按照权利要求18的方法,其特征在于,附加地在熔体中添加脂族聚酯。
20.按照权利要求18或19之一的方法,其特征在于,水含量在混合前或在混合当中降至<0.5重量%,优选<0.1重量%。
21.按照权利要求18-20之一的方法,其特征在于,熔体的混合在温度为120-260℃进行,优选在约140-160℃。
22.按照权利要求18-21之一的方法,其特征在于,混合在挤压机或捏合机中进行,并从喷咀抽出熔体后使其在水浴中冷却并进行调节,以接着例如进行造粒。
23.按照权利要求1-17之一的聚合物混合物的加工方法,其特征在于,这种例如作为颗粒存在的聚合物混合物在通过注射,挤压或吹制加工前用增塑剂,如甘油,山梨醇等和/或水进行调节处理。
24.按照权利要求23的方法,其特征在于,作为颗粒存在的聚合物混合物使其水含量调节到1-6重量%,并接着注射,挤压或吹制成薄膜,同时制备的注塑件或挤压件或薄膜优选在制备后直接贮放在较潮湿的环境中,相对湿度>40%。
25.一层或多层薄膜,至少含有一个由按照权利要求1-17之一的聚合物混合物组成的层。
26.利用模具吹制制备的容器或瓶,主要由按照权利要求1-17之一的聚合物混合物组成。
27.纺织产品,如纤维,单纤维,纱,绳,亚麻绳,散纤维,棉絮,机织织物,缩绒,非织制织物,主要由按照权利要求1-17之一的聚合物混合物组成。
28.具有至少一层非织制织物和/或一层衬布的卫生物品,如襁褓,绷带,失禁产品,床垫等主要由按照权利要求1-17之一的聚合物混合物组成。
29.粘结剂,主要由按权利要求1-17之一的聚合物混合物或其醇溶液组成。
30.涂层,特别是如浸渍剂主要由按照权利要求1-17之一的聚合物混合物或其醇溶液组成。
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DE19513237.8 | 1995-04-07 | ||
DE1995113237 DE19513237A1 (de) | 1995-04-07 | 1995-04-07 | Biologisch abbaubare Polymermischung |
DE19515013.9 | 1995-04-24 | ||
DE19515013 | 1995-04-24 |
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Families Citing this family (168)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69730852T2 (de) * | 1996-11-05 | 2005-09-22 | Novamont S.P.A. | Biologisch abbaubare polymerzusammensetzungen, die stärke und ein thermoplastisches polymer enthalten |
KR20010014036A (ko) * | 1997-06-20 | 2001-02-26 | 바이오-텍 바이오로지슈 내츄어버파큰겐 게엠베하 앤드 캄파니 카게 | 군사설비 내지는 폭약설비 및 조립식도로, 통과보조물 및통행보조물의 생물학적으로 분해되는 재료로 제조된마모성 제품 |
DE19822979A1 (de) * | 1998-05-25 | 1999-12-02 | Kalle Nalo Gmbh & Co Kg | Folie mit Stärke oder Stärkederivaten und Polyesterurethanen sowie Verfahren zu ihrer Herstellung |
AU4054199A (en) * | 1998-06-17 | 2000-01-05 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Foamed thermoplastic film made from biodegradable materials |
ITTO980524A1 (it) * | 1998-06-17 | 1999-12-17 | Novamont Spa | Composizioni contenenti amido aventi elevata resistenza all'invecchiam ento. |
DE19860836C1 (de) * | 1998-12-30 | 2000-05-18 | Haller Formholz | Verfahren und Vorrichtung zum kontinuierlichen Herstellen von Formkörpern |
US6440364B1 (en) * | 1999-02-16 | 2002-08-27 | Ethicon, Inc. | Method of degassing absorbable suture products |
EP1035239B1 (en) * | 1999-03-08 | 2005-05-11 | The Procter & Gamble Company | Absorbent, flexible, structure comprising starch fibers |
US6632925B1 (en) * | 1999-05-04 | 2003-10-14 | Iowa State University Research Foundation, Inc. | Biodegradable plant protein composites and related methods |
US6515054B1 (en) | 1999-11-02 | 2003-02-04 | Nippon Shokubai Co., Ltd. | Biodegradable resin composition and its molded product |
US6231970B1 (en) * | 2000-01-11 | 2001-05-15 | E. Khashoggi Industries, Llc | Thermoplastic starch compositions incorporating a particulate filler component |
KR20010081685A (ko) * | 2000-02-18 | 2001-08-29 | 윤여생 | 생분해성 방습 플라스틱 용기 |
US20020028857A1 (en) * | 2000-03-31 | 2002-03-07 | Holy Norman L. | Compostable, degradable plastic compositions and articles thereof |
DE10027905A1 (de) * | 2000-06-06 | 2001-12-13 | Bayer Ag | Biologisch abbaubare Formmassen mit sehr guter Fließfähigkeit sowie deren Herstellung und Verwendung |
CN1446247A (zh) * | 2000-08-11 | 2003-10-01 | 生物技术生化学自然包装两合公司 | 生物可降解的聚合物共混物 |
US6573340B1 (en) † | 2000-08-23 | 2003-06-03 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials |
JP2002088161A (ja) * | 2000-09-14 | 2002-03-27 | Sony Corp | 生分解性樹脂組成物の弾性率向上方法 |
CN1121452C (zh) * | 2000-11-23 | 2003-09-17 | 许浩 | 生物降解环保型餐具的配方及生产工艺 |
US7402618B2 (en) * | 2000-11-23 | 2008-07-22 | Hao Xu | Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same |
US7029620B2 (en) * | 2000-11-27 | 2006-04-18 | The Procter & Gamble Company | Electro-spinning process for making starch filaments for flexible structure |
US6811740B2 (en) | 2000-11-27 | 2004-11-02 | The Procter & Gamble Company | Process for making non-thermoplastic starch fibers |
US20030203196A1 (en) * | 2000-11-27 | 2003-10-30 | Trokhan Paul Dennis | Flexible structure comprising starch filaments |
US7241832B2 (en) * | 2002-03-01 | 2007-07-10 | bio-tec Biologische Naturverpackungen GmbH & Co., KG | Biodegradable polymer blends for use in making films, sheets and other articles of manufacture |
US7297394B2 (en) * | 2002-03-01 | 2007-11-20 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials |
US7094817B2 (en) * | 2001-04-18 | 2006-08-22 | Plantic Technologies Ltd. | Biodegradable polymer |
US20030077444A1 (en) * | 2001-05-10 | 2003-04-24 | The Procter & Gamble Company | Multicomponent fibers comprising starch and polymers |
US20020168912A1 (en) * | 2001-05-10 | 2002-11-14 | Bond Eric Bryan | Multicomponent fibers comprising starch and biodegradable polymers |
US6743506B2 (en) | 2001-05-10 | 2004-06-01 | The Procter & Gamble Company | High elongation splittable multicomponent fibers comprising starch and polymers |
US6946506B2 (en) * | 2001-05-10 | 2005-09-20 | The Procter & Gamble Company | Fibers comprising starch and biodegradable polymers |
US6783854B2 (en) * | 2001-05-10 | 2004-08-31 | The Procter & Gamble Company | Bicomponent fibers comprising a thermoplastic polymer surrounding a starch rich core |
US6623854B2 (en) | 2001-05-10 | 2003-09-23 | The Procter & Gamble Company | High elongation multicomponent fibers comprising starch and polymers |
US20030148690A1 (en) * | 2001-05-10 | 2003-08-07 | Bond Eric Bryan | Multicomponent fibers comprising a dissolvable starch component, processes therefor, and fibers therefrom |
US20020168518A1 (en) * | 2001-05-10 | 2002-11-14 | The Procter & Gamble Company | Fibers comprising starch and polymers |
US7276201B2 (en) * | 2001-09-06 | 2007-10-02 | The Procter & Gamble Company | Process for making non-thermoplastic starch fibers |
US7071249B2 (en) * | 2001-10-05 | 2006-07-04 | William Ho | Biodegradable starch resin and method for making same |
US7077994B2 (en) * | 2001-10-19 | 2006-07-18 | The Procter & Gamble Company | Polyhydroxyalkanoate copolymer/starch compositions for laminates and films |
DE10214327A1 (de) | 2001-10-23 | 2003-05-22 | Innogel Ag Zug | Netzwerk auf Polysaccharidbasis und Verfahren zu dessen Herstellung |
US6723160B2 (en) * | 2002-02-01 | 2004-04-20 | The Procter & Gamble Company | Non-thermoplastic starch fibers and starch composition for making same |
US7217426B1 (en) | 2002-06-21 | 2007-05-15 | Advanced Cardiovascular Systems, Inc. | Coatings containing polycationic peptides for cardiovascular therapy |
US7005137B1 (en) * | 2002-06-21 | 2006-02-28 | Advanceed Cardiovascular Systems, Inc. | Coating for implantable medical devices |
US6821538B2 (en) * | 2002-07-09 | 2004-11-23 | T.F.H. Publications, Inc. | Blends of starch and aliphatic-aromatic based polyester resins |
US6830810B2 (en) * | 2002-11-14 | 2004-12-14 | The Procter & Gamble Company | Compositions and processes for reducing water solubility of a starch component in a multicomponent fiber |
DE10258227A1 (de) * | 2002-12-09 | 2004-07-15 | Biop Biopolymer Technologies Ag | Biologisch abbaubare Mehrschichtfolie |
DE10261786A1 (de) * | 2002-12-23 | 2004-07-01 | Fritz Häcker GmbH + Co.KG | Schmelzbarer Klebstoff auf Gelatinebasis |
US8791171B2 (en) | 2003-05-01 | 2014-07-29 | Abbott Cardiovascular Systems Inc. | Biodegradable coatings for implantable medical devices |
US7098292B2 (en) * | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
US6706942B1 (en) | 2003-05-08 | 2004-03-16 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
US7172814B2 (en) * | 2003-06-03 | 2007-02-06 | Bio-Tec Biologische Naturverpackungen Gmbh & Co | Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends |
US7947766B2 (en) | 2003-06-06 | 2011-05-24 | The Procter & Gamble Company | Crosslinking systems for hydroxyl polymers |
CN1906248B (zh) * | 2003-11-25 | 2010-06-16 | 旭化成化学株式会社 | 消光薄膜 |
US7368511B2 (en) * | 2003-12-22 | 2008-05-06 | Eastman Chemical Company | Polymer blends with improved rheology and improved unnotched impact strength |
US7368503B2 (en) * | 2003-12-22 | 2008-05-06 | Eastman Chemical Company | Compatibilized blends of biodegradable polymers with improved rheology |
US7160977B2 (en) * | 2003-12-22 | 2007-01-09 | Eastman Chemical Company | Polymer blends with improved notched impact strength |
WO2005079383A2 (en) * | 2004-02-16 | 2005-09-01 | Leucadia, Inc. | Biodegradable netting |
US7153569B2 (en) * | 2004-03-19 | 2006-12-26 | Kimberly-Clark Worldwide, Inc. | Biodegradable aliphatic-aromatic copolyester films |
US7776020B2 (en) * | 2004-03-19 | 2010-08-17 | Kimberly-Clark Worldwide, Inc. | Absorbent articles having an aliphatic-aromatic copolyester film |
ITMI20040720A1 (it) * | 2004-04-09 | 2004-07-09 | Novamont Spa | Sacco da film biodegradabile ad elevata respirabilita' |
US6955850B1 (en) | 2004-04-29 | 2005-10-18 | The Procter & Gamble Company | Polymeric structures and method for making same |
US6977116B2 (en) * | 2004-04-29 | 2005-12-20 | The Procter & Gamble Company | Polymeric structures and method for making same |
CA2569099C (en) * | 2004-05-07 | 2011-07-12 | Marc S. Theisen | Composite fiber environmental filtration media containing flocculant |
WO2005118434A1 (en) * | 2004-06-03 | 2005-12-15 | Novamont S.P.A. | Ventilated system for the collection of organic waste |
DE102004027673B3 (de) * | 2004-06-07 | 2006-01-19 | Universität Ulm | Biodegradables Verbundsystem und dessen Verwendung sowie Verfahren zur Herstellung eines bioabbaubaren Block-copolyesterurethans |
US7244443B2 (en) | 2004-08-31 | 2007-07-17 | Advanced Cardiovascular Systems, Inc. | Polymers of fluorinated monomers and hydrophilic monomers |
US20090160095A1 (en) * | 2004-11-19 | 2009-06-25 | Board Of Trustees Of Michigan State University | Biodegradable thermoplasticized starch-polyester reactive blends for thermoforming applications |
US7629405B2 (en) * | 2004-11-19 | 2009-12-08 | Board Of Trustees Of Michigan State University | Starch-polyester biodegradable graft copolyers and a method of preparation thereof |
US20070021515A1 (en) * | 2005-07-19 | 2007-01-25 | United States (as represented by the Secretary of Agriculture) | Expandable starch-based beads and method of manufacturing molded articles therefrom |
US7989524B2 (en) * | 2005-07-19 | 2011-08-02 | The United States Of America, As Represented By The Secretary Of Agriculture | Fiber-reinforced starch-based compositions and methods of manufacture and use |
US7666501B2 (en) * | 2005-12-07 | 2010-02-23 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) bi-constituent filaments |
US20070128459A1 (en) * | 2005-12-07 | 2007-06-07 | Kurian Joseph V | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) films |
US20070129503A1 (en) * | 2005-12-07 | 2007-06-07 | Kurian Joseph V | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) molded, shaped articles |
KR101123381B1 (ko) * | 2006-04-14 | 2012-03-23 | 비오텍 비오로기쉐 나투르페어팍쿵엔 게엠베하 운트 컴파니 카게 | 복층 필름과 그 제조 방법 |
US9028859B2 (en) | 2006-07-07 | 2015-05-12 | Advanced Cardiovascular Systems, Inc. | Phase-separated block copolymer coatings for implantable medical devices |
JP5030501B2 (ja) * | 2006-07-31 | 2012-09-19 | 関西ペイント株式会社 | 澱粉系塗料組成物 |
US7909003B2 (en) * | 2006-08-07 | 2011-03-22 | J. W. Pet Company, Inc. | Chew toys comprising biologically degradable material |
MX2009002159A (es) * | 2006-08-31 | 2009-03-11 | Kimberly Clark Co | Peliculas biodegradables con alta capacidad para respirar. |
JP2010513594A (ja) * | 2006-12-15 | 2010-04-30 | キンバリー クラーク ワールドワイド インコーポレイテッド | 繊維の形成に使用する生分解性ポリエステル |
US8592641B2 (en) | 2006-12-15 | 2013-11-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive biodegradable film |
WO2008089098A1 (en) * | 2007-01-12 | 2008-07-24 | L & P Property Management Company | Environmentally friendly polymeric textile coating |
DE102007037166A1 (de) | 2007-08-07 | 2009-02-19 | Endress + Hauser Flowtec Ag | Meßgerät |
WO2009022526A1 (ja) * | 2007-08-14 | 2009-02-19 | Toyo Seikan Kaisha, Ltd. | 蒸着膜を備えた生分解性樹脂容器及び蒸着膜の形成方法 |
US8329977B2 (en) | 2007-08-22 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable water-sensitive films |
CA2688516A1 (en) * | 2007-10-03 | 2009-04-09 | Universidad De Concepcion | Biodegradable composition, preparation method and their application in the manufacture of functional containers for agricultural and/or forestry use |
DE102007050769A1 (de) | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeres Material und Verfahren zu dessen Herstellung |
DE102007050770A1 (de) * | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeres Material und Verfahren zu dessen Herstellung |
DE102007057768A1 (de) * | 2007-11-30 | 2009-06-04 | Universität Ulm | Biodegradables Verbundsystem und dessen Verwendung |
US8227658B2 (en) | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
JP2009155531A (ja) * | 2007-12-27 | 2009-07-16 | Mitsubishi Chemicals Corp | 樹脂組成物及びその製造方法並びに該樹脂組成物からなるフィルム |
US7998888B2 (en) * | 2008-03-28 | 2011-08-16 | Kimberly-Clark Worldwide, Inc. | Thermoplastic starch for use in melt-extruded substrates |
WO2009134388A1 (en) * | 2008-04-30 | 2009-11-05 | Armstrong World Industries, Inc. | Uv/eb curable biobased coating for flooring application |
BRPI0911887A2 (pt) * | 2008-04-30 | 2015-10-13 | Armstrong World Ind Inc | produto de assoalho flexível de base biológica |
WO2009137058A1 (en) | 2008-05-06 | 2009-11-12 | Metabolix, Inc. | Biodegradable polyester blends |
US8147965B2 (en) * | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
US8338508B2 (en) * | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
US8470222B2 (en) * | 2008-06-06 | 2013-06-25 | Kimberly-Clark Worldwide, Inc. | Fibers formed from a blend of a modified aliphatic-aromatic copolyester and thermoplastic starch |
EP2291455B1 (de) * | 2008-06-18 | 2014-04-09 | Basf Se | Additive für polymerblends |
US8927617B2 (en) | 2008-06-30 | 2015-01-06 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
US8759279B2 (en) * | 2008-06-30 | 2014-06-24 | Kimberly-Clark Worldwide, Inc. | Fragranced biodegradable film |
FR2934272B1 (fr) * | 2008-07-24 | 2013-08-16 | Roquette Freres | Procede de preparation de compositions a base de matiere amylacee et de polymere synthetique. |
DE102008042893A1 (de) | 2008-10-16 | 2010-04-29 | Wacker Chemie Ag | Mischungen zur Herstellung von biologisch abbaubaren Formkörpern auf Basis von aliphatischen Polyestern und in Wasser redispergierbaren Polymerpulvern |
US8283006B2 (en) * | 2008-12-18 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Injection molding material containing starch and plant protein |
US8329601B2 (en) | 2008-12-18 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable and renewable film |
CN101525487B (zh) * | 2009-03-31 | 2012-01-11 | 武汉华丽生物材料有限公司 | 一种可环境降解的复合材料及其制备方法 |
AU2009202397A1 (en) * | 2009-06-16 | 2011-01-06 | Because We Care Pty Ltd | Biodegradable Polymeric Compositions |
FR2947557B1 (fr) | 2009-07-03 | 2011-12-09 | Ulice | Procede de production de materiau biodegradable |
IT1396597B1 (it) | 2009-11-05 | 2012-12-14 | Novamont Spa | Miscele di poliesteri biodegradabili |
IT1399031B1 (it) | 2009-11-05 | 2013-04-05 | Novamont Spa | Copoliestere alifatico-aromatico biodegradabile |
PT104846A (pt) | 2009-11-26 | 2011-05-26 | Cabopol Ind De Compostos S A | Misturas polim?ricas biocompost?veis |
US8586821B2 (en) * | 2009-12-23 | 2013-11-19 | Kimberly-Clark Worldwide, Inc. | Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester |
CN102115576B (zh) * | 2009-12-31 | 2014-09-17 | 金伯利-克拉克环球有限公司 | 天然生物聚合物热塑性膜 |
FR2957928B1 (fr) | 2010-03-25 | 2013-07-05 | Roquette Freres | Compositions a base de matiere vegetale et procede de preparation de telles compositions |
US9226524B2 (en) | 2010-03-26 | 2016-01-05 | Philip Morris Usa Inc. | Biopolymer foams as filters for smoking articles |
US20120016328A1 (en) * | 2010-07-19 | 2012-01-19 | Bo Shi | Biodegradable films |
US8907155B2 (en) | 2010-11-19 | 2014-12-09 | Kimberly-Clark Worldwide, Inc. | Biodegradable and flushable multi-layered film |
CN103210033B (zh) | 2010-11-23 | 2016-05-04 | 宝洁公司 | 热塑性淀粉组合物 |
US20120178858A1 (en) | 2011-01-10 | 2012-07-12 | Andrew Julian Wnuk | Isosorbide-Plasticized Starch And Uses Thereof |
US20120283364A1 (en) * | 2011-05-06 | 2012-11-08 | Cerestech, Inc. | Polymer blends comprising phase-encapsulated thermoplastic starch and process for making the same |
WO2012162136A2 (en) | 2011-05-20 | 2012-11-29 | The Procter & Gamble Company | Films of starch-polymer-wax-oil compositions |
CA2836876A1 (en) | 2011-05-20 | 2012-11-29 | The Procter & Gamble Company | Starch-polymer-oil compositions, methods of making and using the same |
WO2012162092A1 (en) | 2011-05-20 | 2012-11-29 | The Procter & Gamble Company | Molded articles of starch-polymer-wax-oil compositions |
MX2013013516A (es) | 2011-05-20 | 2014-02-27 | Procter & Gamble | Fibra de composiciones de almidon-polimero-aceite. |
CN102321249B (zh) | 2011-06-30 | 2013-01-16 | 无锡碧杰生物材料科技有限公司 | 一种热塑性淀粉和生物降解聚酯/淀粉复合材料及其制备 |
US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
CN102912475A (zh) * | 2011-08-04 | 2013-02-06 | 周新民 | 一种用多组分凝固浴液生产高强度壳聚糖纤维的制备方法 |
US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
US9327438B2 (en) * | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
CN104245862B (zh) * | 2012-03-28 | 2017-07-14 | 纺织和塑料研究协会图林根研究院 | 可液态应用的多功能涂层膜 |
US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
FR2992651B1 (fr) * | 2012-06-27 | 2015-07-17 | Arkema France | Utilisation d'un alliage d'amidon thermoplastique et de pof pour la fabrication d'un film ultra-fin imper-respirant adhesif. |
CN104755538B (zh) | 2012-08-17 | 2018-08-31 | Cj 第一制糖株式会社 | 用于聚合物共混物的生物基橡胶改性剂 |
JP6033008B2 (ja) * | 2012-09-03 | 2016-11-30 | 株式会社クレハ | 樹脂組成物およびその用途 |
GB201217207D0 (en) * | 2012-09-26 | 2012-11-07 | Biome Bioplastics Ltd | Bio-resins |
WO2014081791A1 (en) | 2012-11-20 | 2014-05-30 | The Procter & Gamble Company | Starch-thermoplastic polymer-grease compositions and methods of making and using the same |
US20140142225A1 (en) | 2012-11-20 | 2014-05-22 | The Procter & Gamble Company | Starch-Thermoplastic Polymer-Soap Compositions and Methods of Making and Using the Same |
US20140272370A1 (en) | 2013-03-15 | 2014-09-18 | The Procter & Gamble Company | Renewable Thermoplastic Starch-Polyolefin Compositions Comprising Compatibilizer and Flexible Thin Films Made Therefrom |
US10131783B2 (en) * | 2013-04-10 | 2018-11-20 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Polymer composition |
EP2799231A1 (en) | 2013-04-30 | 2014-11-05 | The Procter & Gamble Company | Flexible package |
EP2799232A1 (en) | 2013-04-30 | 2014-11-05 | The Procter & Gamble Company | Flexible package |
EP2999447B1 (en) | 2013-05-20 | 2019-10-23 | The Procter and Gamble Company | Nonwoven webs with visually distinct bond sites and method of making |
CN105531308B (zh) | 2013-05-30 | 2021-08-10 | Cj 第一制糖株式会社 | 回收物共混物 |
WO2015066588A1 (en) | 2013-11-04 | 2015-05-07 | The Procter & Gamble Company | Thermoplastic polymer compositions having co-continuous plate-like morphology |
CN106459544B (zh) | 2014-03-27 | 2021-10-01 | Cj 第一制糖株式会社 | 高度填充的聚合物体系 |
WO2015175445A1 (en) | 2014-05-12 | 2015-11-19 | The Procter & Gamble Company | Microtextured films with improved tactile impression and/or reduced noise perception |
ES2556680B1 (es) * | 2014-07-18 | 2016-11-03 | Moreda - Riviere Trefilerías, S.A. | Alambre recubierto, procedimiento de obtención del mismo y malla que lo comprende |
ES2765677T5 (es) | 2015-06-17 | 2023-06-05 | Hollister Inc | Sonda lavable disgregable en agua |
CN104877320A (zh) * | 2015-06-18 | 2015-09-02 | 王宏城 | 一种用于包装材料的新型pcl组合物及其制备方法 |
KR20180064535A (ko) | 2015-11-03 | 2018-06-14 | 킴벌리-클라크 월드와이드, 인크. | 고 벌크 및 저 린트를 갖는 페이퍼 티슈 |
CN106967279A (zh) * | 2017-03-22 | 2017-07-21 | 中联西北工程设计研究院有限公司 | 用于3d打印的pla、淀粉复合材料及其制备工艺 |
RU2019135307A (ru) | 2017-04-06 | 2021-05-06 | Криовак, Ллк | Пленка, упаковка и способ для созревания и сохранения сыра |
KR102626745B1 (ko) | 2017-05-26 | 2024-01-17 | 인피니트 머티리얼 솔루션즈, 엘엘씨 | 수용성 중합체 조성물 |
EP3466389B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a carded resin-bonded nonwoven web with fibers comprising antimony-free polyethylene terephthalate |
EP3466388B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a nonwoven material with antimony-free polyethylene terephthalate |
EP3466385B1 (en) | 2017-10-06 | 2020-05-27 | The Procter & Gamble Company | Absorbent article or wipe comprising a nonwoven material with bicomponent fibers comprising antimony-free polyethylene terephthalate |
US11255051B2 (en) | 2017-11-29 | 2022-02-22 | Kimberly-Clark Worldwide, Inc. | Fibrous sheet with improved properties |
GB2590316B (en) | 2018-07-25 | 2022-06-01 | Kimberly Clark Co | Process for making three-dimensional foam-laid nonwovens |
PL3689955T3 (pl) | 2019-02-01 | 2023-03-13 | United Resins - Produção De Resinas S.A. | Ulepszone, biodegradowalne polimery na bazie skrobi |
US10882977B1 (en) * | 2020-01-30 | 2021-01-05 | Edward Showalter | Earth plant compostable biodegradable substrate and method of producing the same |
US11149131B2 (en) * | 2020-01-30 | 2021-10-19 | Edward Showalter | Earth plant compostable biodegradable substrate and method of producing the same |
WO2022253731A1 (de) * | 2021-06-02 | 2022-12-08 | Periplast Werkzeugbau Und Kunststoffverarbeitung Gmbh & Co. Kg | Thermoplastisches material und verfahren zur herstellung eines formkörpers aus einem thermoplastischen material und formkörper |
CN113462021B (zh) * | 2021-07-19 | 2022-05-10 | 江南大学 | 一种天然填料及其高强高韧聚合物复合材料、制备方法和应用 |
CN116695273A (zh) * | 2023-05-17 | 2023-09-05 | 百事基材料(青岛)股份有限公司 | 含雪莲活性成分的锦纶大生物纤维及其制备方法 |
Family Cites Families (84)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3446079A (en) * | 1967-07-17 | 1969-05-27 | Singer General Precision | Linear electrostatic accelerometer |
US3867324A (en) * | 1972-07-28 | 1975-02-18 | Union Carbide Corp | Environmentally degradable-biodegradable blend of an oxyalkanoyl polymer and an environmentally degradable ethylene polymer |
US3921333A (en) * | 1972-07-28 | 1975-11-25 | Union Carbide Corp | Transplanter containers made from biodegradable-environmentally degradable blends |
US3850863A (en) * | 1972-07-28 | 1974-11-26 | Union Carbide Corp | Blends of a biodegradable thermoplastic oxyalkanoyl polymer and a naturally occurring biodegradable product |
US4076846A (en) * | 1974-11-22 | 1978-02-28 | Sumitomo Bakelite Company Limited | Protein-starch binary molding composition and shaped articles obtained therefor |
US3949145A (en) * | 1975-02-27 | 1976-04-06 | The United States Of America As Represented By The Secretary Of Agriculture | Degradable starch-based agricultural mulch film |
US4133784A (en) * | 1977-09-28 | 1979-01-09 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable film compositions prepared from starch and copolymers of ethylene and acrylic acid |
JPS6054322B2 (ja) * | 1977-09-30 | 1985-11-29 | 株式会社林原生物化学研究所 | 成形物の製法 |
US4337181A (en) * | 1980-01-17 | 1982-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable starch-based blown films |
DE3172611D1 (en) * | 1980-08-06 | 1985-11-14 | Coloroll Ltd | Plastics starch composition |
US4410571A (en) * | 1980-08-25 | 1983-10-18 | Johnson & Johnson | Absorbent products, process and compositions for immobilization of particulate absorbents |
US4394930A (en) * | 1981-03-27 | 1983-07-26 | Johnson & Johnson | Absorbent foam products |
US4482386A (en) * | 1982-03-26 | 1984-11-13 | Warner-Lambert Company | Method of conditioning a water swellable hydrocolloid |
US4655840A (en) * | 1982-03-26 | 1987-04-07 | Warner-Lambert Company | Hydrophilic polymer compositions for injection molding |
US4454268A (en) * | 1983-06-23 | 1984-06-12 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-based semipermeable films |
US4673438A (en) * | 1984-02-13 | 1987-06-16 | Warner-Lambert Company | Polymer composition for injection molding |
US4846932A (en) * | 1986-12-31 | 1989-07-11 | Kuromatsu Corporation Co., Ltd. | Water setting paper |
GB2205323B (en) * | 1987-03-09 | 1991-01-30 | Warner Lambert Co | Destructurized starch and process for making same |
GB2208651B (en) * | 1987-08-18 | 1991-05-08 | Warner Lambert Co | Shaped articles made from pre-processed starch |
US5095054A (en) * | 1988-02-03 | 1992-03-10 | Warner-Lambert Company | Polymer compositions containing destructurized starch |
GB2214918B (en) * | 1988-02-03 | 1992-10-07 | Warner Lambert Co | Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material |
US5362777A (en) * | 1988-11-03 | 1994-11-08 | Ivan Tomka | Thermoplastically processable starch and a method of making it |
IE66735B1 (en) * | 1988-11-03 | 1996-02-07 | Biotec Biolog Naturverpack | Thermoplastically workable starch and a method for the manufacture thereof |
US5043196A (en) * | 1989-05-17 | 1991-08-27 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
US4863655A (en) * | 1988-12-30 | 1989-09-05 | National Starch And Chemical Corporation | Biodegradable packaging material and the method of preparation thereof |
US5035930A (en) * | 1988-12-30 | 1991-07-30 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
IL93620A0 (en) * | 1989-03-09 | 1990-12-23 | Butterfly Srl | Biodegradable articles based on starch and process for producing them |
IT1233599B (it) * | 1989-05-30 | 1992-04-06 | Butterfly Srl | Composizioni polimeriche per la produzione di articoli di materiale plastico biodegradabile e procedimenti per la loro preparazione |
DE474705T1 (de) * | 1989-06-01 | 1992-10-15 | Goodman Fielder Wattie Australia Ltd., Gladesville, Neu Sued Wales, Au | Geformte gegenstaende aus staerke deriviert. |
IL94647A0 (en) * | 1989-07-06 | 1991-04-15 | Warner Lambert Co | Polymer base blend compositions containing destructurized starch |
YU128990A (sh) * | 1989-07-11 | 1993-05-28 | Warner-Lambert Co. | Preparati polimernih smeša koji sadrže destrukturisani skrob |
NO306471B1 (no) * | 1989-07-11 | 1999-11-08 | Warner Lambert Co | Polymerblanding omfattende strukturendret stivelse, samt anvendelse av blandingen |
HU211427B (en) * | 1989-07-18 | 1995-11-28 | Warner Lambert Co | Composition containing destructurized starch and thermoplastic destructurized-starch solid product having substantial dimensional stability |
HU208985B (en) * | 1989-07-18 | 1994-02-28 | Warner Lambert Co | Polymere-based mixture composition containing destructurated starch |
US5288765A (en) * | 1989-08-03 | 1994-02-22 | Spherilene S.R.L. | Expanded articles of biodegradable plastics materials and a method for their production |
IT1232910B (it) * | 1989-08-07 | 1992-03-05 | Butterfly Srl | Composizioni polimeriche per la produzione di articoli di materiale plastico biodegradabile e procedimenti per la loro preparazione |
US5059642A (en) * | 1989-09-14 | 1991-10-22 | Iowa State University Research Foundation, Inc. | Degradable plastics from octenyl succinate starch |
JPH03199245A (ja) * | 1989-12-27 | 1991-08-30 | Agency Of Ind Science & Technol | 微生物崩壊性熱可塑性樹脂発泡体及びその製造方法 |
EP0444880B1 (en) * | 1990-02-28 | 1997-05-07 | Director-General Of The Agency Of Industrial Science And Technology | Process for manufacture of a moldable biodegradable material |
US5108807A (en) * | 1990-03-14 | 1992-04-28 | First Brands Corporation | Degradable multilayer thermoplastic articles |
US5219646A (en) * | 1990-05-11 | 1993-06-15 | E. I. Du Pont De Nemours And Company | Polyester blends and their use in compostable products such as disposable diapers |
US5115000A (en) * | 1990-06-19 | 1992-05-19 | Iowa State University Research Foundation, Inc. | Biodegradable starch plastics incorporating modified polyethylene |
IT1240503B (it) * | 1990-07-25 | 1993-12-17 | Butterfly Srl | Miscela polimerica amidacea particolarmente per la produzione di film e simili e procedimento per la sua produzione. |
GB9017300D0 (en) * | 1990-08-07 | 1990-09-19 | Cerestar Holding Bv | Starch treatment process |
AU664831B2 (en) * | 1990-11-30 | 1995-12-07 | Eastman Chemical Company | Blends of cellulose esters and copolyesters and optionally other esters |
US5046730A (en) * | 1990-12-10 | 1991-09-10 | Bio Dynamics, Ltd. | Golf tee |
US5292782A (en) * | 1991-02-20 | 1994-03-08 | Novamont S.P.A. | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
US5186990A (en) * | 1991-04-05 | 1993-02-16 | Eagle Scientific Co. | Biodegradable and water soluble packaging material |
IT1256693B (it) * | 1992-03-10 | 1995-12-12 | Novamont Spa | Composizione polimerica amidacea filmabile, ed articoli sagomati, particolarmente film e foglie ottenibili da tale composizione, aventi elevato effetto barriera e procedimento relativo. |
US5412005A (en) * | 1991-05-03 | 1995-05-02 | Novamont S.P.A. | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
EP0525245A1 (en) * | 1991-08-01 | 1993-02-03 | NOVAMONT S.p.A. | Disposable absorbent articles |
DE539541T1 (de) * | 1991-05-03 | 1997-01-30 | Novamont Spa | Biologisch abbaubare Polymermassen auf der Basis von Stärke und thermoplastische Polymere. |
DE4116404A1 (de) * | 1991-05-18 | 1992-11-19 | Tomka Ivan | Polymermischung fuer die herstellung von folien |
WO1993000399A1 (en) * | 1991-06-26 | 1993-01-07 | The Procter & Gamble Company | Biodegradable, liquid impervious films |
DE4122212C2 (de) * | 1991-07-04 | 1994-06-16 | Inventa Ag | Thermoplastisch verarbeitbare Masse aus Stärke und Acrylatcopolymeren |
EP0524920B1 (de) * | 1991-07-26 | 1996-05-29 | Mundigler, Norbert, Dipl.-Ing. | Neuartige Formkörper |
US5256711A (en) * | 1991-10-04 | 1993-10-26 | Director-General Of Agency Of Industrial Science | Starch-containing biodegradable plastic and method of producing same |
DE4133335C2 (de) * | 1991-10-08 | 1995-11-02 | Inventa Ag | Stärkemischung, Verfahren zu ihrer Herstellung sowie Verwendung derselben |
DE4134190A1 (de) * | 1991-10-16 | 1993-04-22 | Tomka Ivan | Verfahren zur verbesserung der mechanischen eigenschaften von ein- oder mehrschichtfolien |
US5252271A (en) * | 1991-10-22 | 1993-10-12 | Bio-Products International | Biodegradable packaging foam and method of preparation |
SG47625A1 (en) * | 1991-11-14 | 1998-04-17 | Bio Tech Biolog Naturverparkun | Biodegradable mould material |
US5208267A (en) * | 1992-01-21 | 1993-05-04 | Univ Kansas State | Starch-based, biodegradable packing filler and method of preparing same |
US5248702A (en) * | 1992-01-21 | 1993-09-28 | Kansas State University Research Foundation | Starch-based, biodegradable packing filler and method of preparing same |
US5185382A (en) * | 1992-01-21 | 1993-02-09 | Kansas State University Research Foundation | Starch-based, biodegradable packing filler and method of preparing same |
US5427614A (en) * | 1992-02-14 | 1995-06-27 | Warner-Lambert Company | Starch based formulations |
US5372877A (en) * | 1992-04-16 | 1994-12-13 | Sealed Air | Biodegradable cushioning product |
US5266368A (en) * | 1992-04-16 | 1993-11-30 | International Grain & Milling Company | Biodegradable packing material and method |
DE4228016C1 (de) * | 1992-08-24 | 1994-03-31 | Biotec Biolog Naturverpack | Verfahren zum Herstellen von biologisch abbaubaren Folien aus pflanzlichen Rohstoffen |
US5308879A (en) * | 1992-09-07 | 1994-05-03 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing biodegradable resin foam |
JP3019631B2 (ja) | 1992-11-04 | 2000-03-13 | 松下電器産業株式会社 | 文書画像印字装置 |
DE4237535C2 (de) * | 1992-11-06 | 2000-05-25 | Biotec Biolog Naturverpack | Biologisch abbaubare Polymermischung, ein Verfahren und eine Folie |
US5844023A (en) * | 1992-11-06 | 1998-12-01 | Bio-Tec Biologische Naturverpackungen Gmbh | Biologically degradable polymer mixture |
US5272181A (en) * | 1992-11-18 | 1993-12-21 | Evergreen Solutions, Inc. | Biodegradable expanded foam material |
US5393804A (en) * | 1992-11-24 | 1995-02-28 | Parke, Davis & Company | Biodegradable compositions comprising starch and alkenol polymers |
KR950006538B1 (ko) * | 1992-12-31 | 1995-06-16 | 김두현 | 일회용 용기의 제조방법 |
DE4400330C2 (de) * | 1993-03-24 | 1997-10-02 | Naturpack Gmbh Verpackungen Au | Verfahren zum Herstellen eines geschäumten Produktes oder Schaumstoffmaterials aus nichtmodifizierter Stärke sowie Einrichtung zum Durchführen des Verfahrens |
US5512090A (en) * | 1993-06-24 | 1996-04-30 | Free-Flow Packaging Corporation | Compositions for resilient biodegradable packaging material products |
US5288318A (en) * | 1993-07-01 | 1994-02-22 | The United States Of America As Represented By The Secretary Of The Army | Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture |
DE4327024A1 (de) * | 1993-08-12 | 1995-02-16 | Bayer Ag | Thermoplastisch verarbeitbare und biologisch abbaubare aliphatische Polyesteramide |
US5397834A (en) * | 1993-09-03 | 1995-03-14 | Iowa State University Research Foundation, Inc. | Biodegradable thermoplastic composition of aldehyde starch and protein |
DE4335983A1 (de) * | 1993-10-21 | 1995-04-27 | Inventa Ag | Verfahren zur Erhöhung der Transparenz von Formkörpern oder Folien aus thermoplastischer Stärke oder thermoplastischem Stärke-Polymer-Blend |
US5500465A (en) * | 1994-03-10 | 1996-03-19 | Board Of Trustees Operating Michigan State University | Biodegradable multi-component polymeric materials based on unmodified starch-like polysaccharides |
DE19500756A1 (de) * | 1995-01-13 | 1996-07-18 | Basf Ag | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
DE19536505A1 (de) * | 1995-09-29 | 1997-04-10 | Biotec Biolog Naturverpack | Biologisch abbaubares Filtermaterial und Verfahren zu seiner Herstellung |
-
1996
- 1996-04-02 AU AU49522/96A patent/AU705499B2/en not_active Ceased
- 1996-04-02 CN CN96193126A patent/CN1181098A/zh active Pending
- 1996-04-02 ES ES96905977T patent/ES2201173T3/es not_active Expired - Lifetime
- 1996-04-02 DK DK96905977T patent/DK0819147T3/da active
- 1996-04-02 US US08/930,748 patent/US6096809A/en not_active Expired - Lifetime
- 1996-04-02 DE DE59610506T patent/DE59610506D1/de not_active Expired - Lifetime
- 1996-04-02 EP EP96905977A patent/EP0819147B1/de not_active Expired - Lifetime
- 1996-04-02 AT AT96905977T patent/ATE242295T1/de active
- 1996-04-02 JP JP08525223A patent/JP3107830B2/ja not_active Expired - Lifetime
- 1996-04-02 PT PT96905977T patent/PT819147E/pt unknown
- 1996-04-02 CA CA002217541A patent/CA2217541A1/en not_active Abandoned
- 1996-04-02 WO PCT/IB1996/000275 patent/WO1996031561A1/de active IP Right Grant
-
1999
- 1999-10-27 US US09/428,512 patent/US6235816B1/en not_active Expired - Lifetime
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1960923B (zh) * | 2004-06-03 | 2011-04-13 | 诺瓦蒙特股份公司 | 用于收集有机废物的通风系统 |
CN103087299B (zh) * | 2005-03-18 | 2015-04-01 | 诺瓦蒙特股份公司 | 可生物降解的脂族-芳族共聚聚酯 |
CN103087299A (zh) * | 2005-03-18 | 2013-05-08 | 诺瓦蒙特股份公司 | 可生物降解的脂族-芳族共聚聚酯 |
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WO1996031561A1 (de) | 1996-10-10 |
JP3107830B2 (ja) | 2000-11-13 |
DE59610506D1 (de) | 2003-07-10 |
US6235816B1 (en) | 2001-05-22 |
JPH10512010A (ja) | 1998-11-17 |
ATE242295T1 (de) | 2003-06-15 |
CA2217541A1 (en) | 1996-10-10 |
EP0819147A1 (de) | 1998-01-21 |
AU4952296A (en) | 1996-10-23 |
AU705499B2 (en) | 1999-05-27 |
ES2201173T3 (es) | 2004-03-16 |
US6096809A (en) | 2000-08-01 |
DK0819147T3 (da) | 2003-09-29 |
PT819147E (pt) | 2003-10-31 |
EP0819147B1 (de) | 2003-06-04 |
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