CN1299844A - 可熔融加工的淀粉组合物 - Google Patents
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Abstract
本发明涉及一种淀粉组合物,该组合物包括淀粉,与淀粉基本上相容并且具有重均分子量至少是500,000的聚合物,以使该聚合物与相邻的淀粉分子形成有效缠结或连接,优选加入至少一种添加剂以改进熔融流动性和可熔融加工性。添加剂可以是羟基增塑剂,无羟基增塑剂,稀释剂和它们的混合物。该组合物可在常规的热塑性加工设备上熔融加工。该组合物特别适用于单轴和双轴拉伸加工方法以制成纤维,膜,泡沫体和类似产品。
Description
本发明涉及一种新颖的淀粉组合物,该组合物基本上是均匀的,并且具有所希望的流变性,因而它具有用常规的热塑性加工设备可熔融加工的特性。本发明的组合物特别适用于单轴和双轴拉伸工艺。
众所周知,淀粉分子存在两种形式:基本上线性的直链淀粉聚合物和高支化的支链淀粉聚合物。这两种形式的淀粉具有非常不同的性质,这可能是由于不同分子间的羟基缔合的结果。直链淀粉的分子结构基本上是具有2-5个比较长的支链的线性结构。支链的平均聚合度是约350个单体单元。在主要用适当的溶剂稀释,某些情况下加热稀释以提供足够的分子运动自由度的条件下,线性直链淀粉链的链被优先取向成平行的直线排列,使一个链上的羟基与邻近链上的羟基极接近。可以认为邻近直链淀粉分子的直线性便于形成分子间氢键。因此,直链淀粉分子形成剧烈聚集。相反,支链淀粉的分子结构通过1,6-α键被高度支化。支链的平均聚合度是约25个单体单元。由于高度支化的结构,因此支链淀粉分子不易自由移动,不容易成直线和不易缔合。
人们尝试在塑料工业的标准设备和现有已知技术上加工天然淀粉。由于天然淀粉通常具有粒状的结构,在像热塑性材料一样,将淀粉进行熔融加工前,需要对其“破坏(destucturized)”和/或改性。为了进行破坏,通常在一定压力条件下,将淀粉加热至高于其软化温度和熔融温度。淀粉粒的分子结构发生熔融和无序,从而得到破坏了的淀粉。还可以使用化学试剂和酶催化剂对淀粉进行破坏,氧化或衍生化。改性的淀粉已经被用于生产可生物降解的塑料,其中将改性的淀粉作为添加剂或次要的成分与石油基的或合成的聚合物共混。但是,当加工改性淀粉本身或用常规的热塑性加工技术(如模塑或挤压)将改性的淀粉作为主要成分与其它材料混合时,成品趋于具有高的瑕疵率。此外,人们还发现改性淀粉(单独地或作为混合物的主要成分)的熔融延伸性差;因此,不能成功地用单轴或双轴拉伸加工方法将改性淀粉加工成纤维,膜,泡沫等等。
先有的生产淀粉纤维的尝试主要涉及湿法纺丝方法。例如,可以从喷丝头挤压淀粉/溶剂胶体悬浮液进入纺丝浴。该方法显著地取决于直链淀粉成线性的趋势,并且形成强的缔合聚集以提供最终纤维的强度和整体性。容许任何支链淀粉作为杂质,不利于纤维纺丝加工效果和最终产品的强度。由于,众所周知天然淀粉富含支链淀粉,早期的方法包括预处理天然淀粉以得到用于纤维纺丝所希望的富含直链淀粉部分。很清楚,由于大量的淀粉(也就是支链淀粉部分)被丢弃,该方法在工业规模上的生产不经济适宜。在最近的技术发展中,可将通常是高支链淀粉含量的天然淀粉湿纺成纤维。但是,该湿纺纤维是粗糙的,一般纤维直径大于50微米。另外,在该方法中所使用的大量溶剂需要另外的干燥步骤,和排放物的回收和处理步骤。有关湿纺淀粉纤维的一些参考文献包括在1979年2月13日授权给Hernandez等人的美国专利No.4,139,699;在1989年8月1日授权给Eden等人的美国专利No.4,853,168;和在1981年1月6日授权给Hernandez等人的美国专利No.4,234,480。
Buehler等人的美国专利No.5,516,815和No.5,316,578涉及用于从熔融纺丝方法生产淀粉纤维的淀粉组合物。将熔融淀粉组合物从喷丝头挤过,以生产比喷丝头上的模孔直径稍大直径的长丝(即,模头膨胀效果)。接着,用拉伸设备对长丝进行形变拉伸或热形变拉伸,以降低纤维的直径。Buehler等人的淀粉组合物的主要缺点是没使用能增强淀粉组合物熔融伸长性的高分子聚合物。因此,不能成功地将Buehler等人的淀粉组合物熔融拉细,以生产25微米或更小直径的精细纤维。
在1989年8月8日授权给Sachetto等人的美国专利No.4,900,361;在1992年3月10日授权给Lay等人的美国专利No.5,095,054;在1998年4月7日授权给Bastioli等人的美国专利No.5,736,586;和由Hanna等人申请的1997年3月14日公开的PCT出版物WO98/40434中披露了其它的可热形变加工的淀粉组合物。这些淀粉组合物不含有高分子量聚合物,为了得到所需要的熔体粘度和熔体伸长性,需要高分子聚合物,高分子聚合物是生产精细纤维,薄膜或薄壁泡沫的关键性的材料特征。
现有技术表明需要从天然淀粉得到廉价的和可熔融加工的组合物。在加工操作过程中,这类可熔融加工的淀粉组合物不需要蒸发大量的溶剂或产生大量的排放物。此外,这类淀粉组合物应具有适用于常规塑料加工设备的熔体流变性。
现有技术还表明需要用于单轴和双轴拉伸加工方法的淀粉组合物,以生产纤维,膜,片,泡沫,成形制品等等,并且经济效益好和效率高。特别是,淀粉组合物具有适于在熔融相以基本上连续的方式(即无过量的熔体破坏或其它瑕疵)进行单轴和双轴拉伸加工的熔体流变性。
本发明涉及一种淀粉组合物,在常规的热塑加工设备上,该组合物可被熔融加工。特别是,可通过单轴和双轴拉伸的力对该淀粉组合物成功地进行加工,以提供具有良好强度的最终产品。此外,该淀粉组合物具有适用于熔融拉细加工方法的流变性,以实现一般用其它方法(包括喷射或机械伸长加工方法)不能得到的非常高的单轴或双轴拉伸。
本发明涉及包括淀粉、聚合物和优选使用至少一种以改进熔体流动性和可熔融加工性的添加剂的淀粉组合物,该聚合物基本上与淀粉是可相容的,并且具有足够高的分子量以与邻近的淀粉分子形成有效缠结或缔合,在此特别使用具有重均分子量至少500,000的聚合物。添加剂可以是羟基增塑剂,无羟基增塑剂,稀释剂或它们的混合物。
本发明的淀粉组合物具有所希望范围内的熔体强度和熔体粘度(剪切和拉伸),使该组合物专门地适用于熔融拉伸加工工艺。本发明的淀粉组合物具有熔融剪切粘度一般在约0.1-约40Pa·s,所以可在常规加工设备上对该组合物进行混合,传送或其它加工,常规加工设备包括螺杆挤出机,搅拌釡,泵,喷丝头等等。由于加入了高分子聚合物,本发明的淀粉组合物通常具有增强的熔体拉伸粘度。
图1表示用于生产本发明的精细淀粉纤维的具有熔喷模头的转矩流变仪装置。
图2表示用于通过纺粘法生产淀粉纤维网的转矩流变仪装置。
图3a以200微米比例表示的本发明的精细淀粉纤维的扫描电镜图。
图3b以20微米比例表示的本发明的精细淀粉纤维的扫描电镜图
在本发明中所用的术语“包括”是指在本发明的实施中可以结合使用各种成份、配料或步骤。因此术语“包括”包含更进一步限制性的术语“基本上由……组成”和“由……组成”。
在本发明中所用的“结合水”是指在使淀粉与其它成分混合制备本发明组合物前,在淀粉中发现的天然存在的水。术语“自由水”是指在制备本发明组合物的过程中加入的水。本领域的普通技术人员知道一旦将各组分混合在组合物中,就不能再区分出水的来源。
在本发明中所用的所有的百分含量,比和比例是指组合物的重量百分含量,除非有另外的具体说明。淀粉组合物
通常天然存在的淀粉是D-葡萄糖单元的线性直链淀粉和枝化的支链淀粉聚合物的混合物。直链淀粉基本上是通过(1,4)-α-D键结合了的D-葡萄糖单元的线性聚合物。支链淀粉是在支化点上通过(1,4)-α-D键和(1,6)-α-D键结合了的D-葡萄糖单元的高枝化的聚合物。天然存在的淀粉通常含有相对高含量的支链淀粉,例如玉米淀粉(64-80%支链淀粉),含蜡玉米(93-100%支链淀粉),米(83-84%支链淀粉),土豆(约78%支链淀粉),和小麦(73-83%支链淀粉)。尽管在本发明中可以用所有的淀粉,但是本发明最常使用源自农产品的具有高支链淀粉的天然淀粉,农产品的资源丰富,容易补给并且便宜。
本发明中适于使用任何天然存在的未改性均淀粉和改性的淀粉;可以通过物理、化学或生物加工方法,或它们的混合方法对淀粉进行改性。对于本发明选择未改性的或改性的淀粉取决于最终所需要的产品。本发明中还适于使用各种淀粉的混合物,以及支链淀粉的含量在所希望的范围内的直链淀粉或支链淀粉成分的混合物。在本发明中所使用的淀粉或淀粉混合物一般具有支链淀粉的含量占淀粉或其混合物的约20%-约100%,优选从约40%-约90%,更优选从约60%-约85%。
适用的天然存在的淀粉包括但不限于玉米淀粉,土豆淀粉,蕃薯淀粉,小麦淀粉,西谷叶纤维淀粉,木薯淀粉,米淀粉,大豆淀粉,木薯淀粉,支链淀粉,欧洲蕨淀粉(bracken),藕淀粉,含蜡玉米淀粉,高支链淀粉玉米淀粉。对于天然存在的淀粉,特别优选的淀粉聚合物是玉米淀粉和小麦淀粉,这是由于它们经济且易得。
可以对淀粉进行分子内改性或分子间改性的物理改性。分子内改性包括降低分子量和/或分子量分布,改变聚合物链结构等等。分子间改性包括熔融和/或无序化淀粉分子,降低结晶度、晶体尺寸和颗粒尺寸等等。可以通过输入能量(如热能,机械能,热机械能,电磁能,超声波能等等),压力,水分,分离及其结合完成这些物理改性。
淀粉的化学改性一般包括酸或碱的水解和氧化断链以降低分子量和分子量分布。适用于淀粉化学改性的化合物包括有机酸如柠檬酸,乙酸,乙醇酸,和己二酸;无机酸如盐酸,硫酸,硝酸,磷酸,硼酸,和偏多元酸盐例如KH2PO4,NaHSO4;Ⅰa族和Ⅱa族的金属氢氧化物如氢氧化钠,氢氧化钾;铵;氧化剂如过氧化氢,过氧化苯酰,过硫酸铵,高锰酸钾(potassium permagnate),碳酸氢钠,次氯酸盐等等;和它们的混合物。本发明优选的化学试剂包括过硫酸铵,硫酸,盐酸及其混合物。
化学改性还可以包括通过淀粉的OH基与烯化氧类,和其它的醚-,酯-,氨基甲酸乙酯-,氨基甲酸酯或异氰酸酯形成物质以衍生化淀粉。优选化学改性淀粉是羟烷基淀粉,乙酰基淀粉或氨基甲酸酯淀粉或其混合物。化学改性淀粉的取代度是0.05-3.0,优选0.05-0.2。
淀粉的生物改性包括碳水化合物键的细菌分解或用酶如淀粉酶,支链淀粉酶等等进行酶水解。
淀粉通常具有结合水的含量约为淀粉重量的5%-16%。特别优选水的含量约为淀粉重量的8%-12%。淀粉中直链淀粉的含量一般为淀粉重量的0-约80%,优选约20%-约35%。
天然的、未改性的淀粉通常具有非常高的平均分子量和宽的分子量分布,(例如天然的玉米淀粉具有平均分子量约10,000,000和分子量分布大于1000)。通过链断裂(氧化反应或酶催化),水解(酸或碱性催化),物理/化学降解作用(例如通过向加工设备中输入热机械能),或它们的结合,可将本发明淀粉的平均分子降低至所需要的范围。这些反应还可降低淀粉的分子量分布至小于约600,优选小于约300。热机械方法和氧化反应方法提供另外的优点在于能在熔融纺丝加工中就地实施热机械方法和氧化反应方法。
在一个实施方案中,在酸(如盐酸或硫酸)存在下天然淀粉被水解,以此降低分子量或分子量分布。在另一个实施方案中,可以往熔融的可纺丝的淀粉组合物中加入断链剂,以使基本上在淀粉与其它成分混合的同时发生断链剂反应。适合本发明的非限制性的氧化断链剂的例子包括过硫酸铵,过氧化氢,次氯酸盐,高锰酸钾和它们的混合物。通常,将加入有效量的断链剂以使淀粉的平均分子量降低至所需要的范围。例如,对于单轴或双轴熔融拉细加工工艺,淀粉应该具有平均分子量从约1,000至约2,000,000,优选从约1,500至约800,000,更优选从约2,000至约500,000。具有在上述分子量范围的改性淀粉的组合物有适合的熔融剪切粘度,因此改进了可熔融加工性。改进了可熔融加工性可明显减少工艺的中断(例如减少断裂,闪光效应,疵点,意外停机)并且产品的表面外观和强度较好。
本发明组合物通常包括约20%-约99.99%重量,优选约30%-约95%重量,更优选约50%-约85%重量的未改性和/或改性的淀粉。在组合物中淀粉的重量包括淀粉和它的天然结合水。公知的是,作为极性溶剂或增塑剂而加入的另外的自由水,并不包括在淀粉的重量中。
也可使用基本上与本发明所用的淀粉相容的高分子量聚合物(下文称“高聚物”)。所适合的聚合物分子量应该足够高以实现与淀粉分子的缠结和/或缔合。尽管具有短的(C1-C3)支链的线性链或具有1至3个长支链的支化的链也适用于本发明,但是优选高聚物具有基本上线性的链结构。本发明所用的术语“基本上相容”是指当将温度加热至高于组合物的软化温度和/或熔融温度时,高聚物能与淀粉形成基本上均匀的混合物,即用裸眼观察组合物,组合物呈现透明或半透明。
用希尔德布兰德(Hildebrand)溶解度参数(δ)评估淀粉和聚合物之间的相容性。通常,当溶解度参数近似时,两种材料之间可能基本上相容。众所周知,具有δ水值为48.0MPa1/2的水是最常用溶剂,这可能是由于水具有强的氢键。通常淀粉的δ淀粉值与纤维素的δ纤维素值(约34MPa1/2)近似。
不受理论约束,可以认为,为了形成基本上相容的混合物,优选本发明所适用的聚合物与淀粉分子在分子级上相互作用。相互作用范围从强度,化学型相互作用(如聚合物和淀粉之间的氢键)至聚合物和淀粉之间仅仅是物理缠结。本发明所用的聚合物优选是高分子量、基本上线性分子链的聚合物。由于在单个分子内支链近似,因此支链淀粉的高支化结构有利于支链的分子内相互作用。因此,可以认为支链淀粉分子与其它的淀粉分子(特别是其它支链淀粉分子)之间的缠结/相互作用差或无效。与淀粉的相容性使适用的聚合物能够与支化的支链淀粉分子均匀混合和化学相互作用和/或物理缠结,通过聚合物使支链淀粉分子与另一个支链淀粉分子连接。高分子量的聚合物能够同时与几个淀粉分子相互作用和/或物理缠结。即高聚物对于淀粉分子起分子连接的作用。对于高支链淀粉含量的淀粉,高聚物的连接作用特别重要。淀粉和聚合物之间的缠结和/或连接提高了淀粉组合物的熔融伸长率,使组合物适于拉伸加工。在另一实施方案中,组合物可被单轴熔融拉细至非常高的拉伸比(大于1000)。
为了有效地与淀粉分子形成缠结和/或连接,本发明所用的高聚物应该具有重均分子量至少为500,000。通常聚合物的重均分子量的范围从约500,000至约25,000,000,优选从约800,000至约22,000,000,更优选从约1,000,000至约20,000,000,最优选从约2,000,000至约15,000,000。优选高分子量聚合物是由于高分子量聚合物能同时与几个淀粉分子相互作用,因此提高了拉伸熔体粘度并降低了熔体破裂。
适合的高聚物具有这样的δ聚合物∶δ淀粉和δ聚合物之间的差小于约10MPa1/2,优选小于约5Pa1/2,和更优选小于约3Pa1/2。适用高聚物的非限制性的例子包括聚丙烯酰胺及其衍生物,如羧基改性的聚丙烯酰胺;丙烯酸聚合物和共聚物包括聚丙烯酸,聚甲基丙烯酸和它们的不完全的酯;乙烯基聚合物包括聚乙烯醇,聚乙酸乙烯酯,聚乙烯基吡咯烷酮,聚乙烯-乙酸乙烯酯,聚乙烯亚胺等;聚氧化亚烷基如聚环氧乙烷,聚环氧丙烷,聚环氧乙丙烷,及其混合物。由选自任何一种上述所提到聚合物的单体的混合物制成的共聚物也适用于本发明。其它高聚物的例子包括水溶性多糖类如海藻酸(盐),角叉菜,果胶及其衍生物,壳多糖及其衍生物等等;树胶如古尔胶,黄原胶,琼脂,阿拉伯树胶,刺梧桐树胶,黄耆胶,刺槐豆胶等树胶;水溶性纤维素衍生物如烷基纤维素,羟烷基纤维素,羧烷基纤维素等等;和它们的混合物。
对于某些聚合物(例如聚丙烯酸,聚甲基丙烯酸)通常不能得到高分子量范围(即500,000或更高)的聚合物。可以加入少量的交联剂以增加本发明所适用的高分子量支化的聚合物。
往本发明的组合物中加入有效量的高聚物以在纺丝工艺中明显地减少熔体破裂和毛细管破裂,使得可熔体纺基本上连续的具有相对恒定直径的纤维。在组合物中,通常这些聚合物存在的量是从约0.001%-约10%重量,优选从0.005%-约5%重量,更优选从0.01%-约1%重量,最优选从0.05%-约0.5%重量。令人惊讶地发现,较低浓度的这些聚合物能极大地改进淀粉组合物的熔体拉伸性。
淀粉组合物可选择性地包括添加剂以增强熔体流动性和可熔融加工性,特别是在可熔融加工的条件下提高组合物的拉伸性。添加剂可以起增塑剂和/或稀释剂的作用以降低淀粉组合物的熔体剪切粘度。往本发明的组合物中加入有效量的高聚物增塑剂以提高流动性,因此可熔融加工。增塑剂还可改进最终产品的挠性,可以认为是由于增塑剂降低了组合物的玻璃转化温度的缘故。应该优选与本发明聚合物的成分基本上相容的增塑剂,以使增塑剂可以有效地改进组合物的性能。本发明所用的术语“基本上相容”是指当将温度加热至高于组合物的软化温度和/或熔融温度时,增塑剂能与淀粉形成基本上均匀的混合物(即用裸眼观察,组合物呈现透明或半透明)。
本发明所适用的羟基增塑剂是具有至少一个羟基,优选多羟基的有机化合物。不受理论约束,可以认为,通过与淀粉基质材料形成氢键,增塑剂的羟基提高相容性。所用羟基增塑剂的非限制性例子包括糖类如葡萄糖,蔗糖,果糖,棉子糖,麦芽糖醇,半乳糖,木糖,麦芽糖,乳糖,甘露糖,赤藓糖,甘油,和季戊四醇;糖醇类如赤藓醇,木糖醇,麦芽糖醇,甘露糖醇,山梨糖醇;多醇类如乙二醇,丙二醇,二乙二醇,丁二醇,己三醇等等,和它们的聚合物;和它们的混合物。
本发明还可使用的羟基增塑剂是poloxomers(聚氧乙烯/聚氧丙烯嵌段共聚物)和poloxamines(乙二胺的聚氧乙烯/聚氧丙烯嵌段共聚物)。可适用的“poloxomers”包括具有下列结构的聚氧乙烯/聚氧丙烯嵌段共聚物:HO-(CH2-CH2-O)x-(CHCH3-CH2-O)y-(CH2-CH2-O)z-OH其中X的值从约2-约40,y的值从约10-约50,和Z的值是从约2-约40,和优选X和Z具有相同的值。这些共聚物是以Pluronic_从BASFCorp.,Parsippany,NJ购得的。适合的poloxamers和poloxamines是以Synperonic_从ICI Chemicals,Wilmington,DE,或以Tetronic_从BASFCorp.,Parsippany,NJ购得的。
本发明还可适用的无羟基增塑剂是不具有羟基而由其它氢键形成的有机化合物,包括脲和脲衍生物;糖醇如脱水山梨糖醇的酐;动物蛋白如动物胶;植物蛋白如向日葵蛋白,大豆蛋白,棉子蛋白;和它们的混合物。所有的增塑剂可以单独使用,或以混合物使用。
通常,淀粉组合物中包括羟基增塑剂从约1%-约70%重量,更优选从约2%-约60%重量,最优选从约3%-约40%重量。通常,淀粉组合物中包括无羟基增塑剂从约0.1%-约70%重量,更优选从约2%-约50%重量,最优选从约3%-约40%重量。
在一个实施方案中,使用羟基增塑剂和无羟基增塑剂的混合物,其中羟基增塑剂是糖类如蔗糖,果糖,和山梨糖醇,和无羟基增塑剂是脲和脲衍生物。在本发明的淀粉组合物中,脲和脲衍生物具有强的结晶趋向,即甚至在快速冷却的条件下发生脲和脲衍生物的结晶作用,快速冷却条件如熔喷,纺粘,熔体挤出,湿纺等等。因此,脲和脲衍生物可用作对本发明淀粉组合物改性和控制固化速度的固化剂。在优选的方案中,往淀粉/聚合物组合物中加入有效量的蔗糖和脲的混合物,以得到所需要的可熔融加工性和固化速率。
可以在本发明的淀粉组合物中加入稀释剂如极性溶剂以调节淀粉组合物的熔融剪切粘度和提高淀粉组合物的可熔体纺丝性。通常,随着稀释剂含量的增加熔融剪切粘度呈线性降低。一般在整个组合物中加入稀释剂的量是从约5%-约60%重量,优选从约7%-约50%重量,更优选从约10%-约30%重量。
本发明所适用的稀释剂是极性稀释剂,它具有溶解度参数δ值范围从约19-约48MPa1/2,优选从从约24-约48MPa1/2,和更优选从约28-约48MPa1/2。非限制性的例子包括水,C1-C18线性或支链的醇,DMSO(二甲基亚砜),甲酰胺和衍生物如N-甲基甲酰胺,N-乙基甲酰胺,乙酰胺和衍生物如甲基乙酰胺,Cellosolv_(乙二醇烷基醚)和衍生物如丁基Cellosolv_,苄基Cellosolv_,Cellosolv_乙酸酯(所有的Cellosolv_及其衍生物可从J.T.Baker,Phillipsburg,NJ购得),肼,和氨。通过体积平均各个溶剂的δ值测定溶剂混合物的δ值也是公知的。因此,具有δ值在上述确定范围(从约19-约48MPa1/2)内的混合溶剂也适用于本发明。例如,具有组成90/10 v/v的DMSO/水的混合溶剂δ值为约31.5;这种混合溶剂体系适用于本发明。
极性溶剂能形成氢键更能有效地降低组合物的熔融粘度。照这样,较少量的极性溶剂足以将粘度调节至熔体纺丝所需要的范围。使用较少量的极性溶剂的另外的优点是,在熔融加工步骤期间或之后的步骤中减少了对蒸发步骤的需要,其结果有利于生产费用降低,如较低的能量损耗费用和较低的溶剂回收费用,以及符合环境/限制所需费用较低。
淀粉组合物还可以选择性地包括液体或可挥发性的加工助剂,加工助剂的主要起熔融组合物的粘度改性剂的作用。加工助剂基本上在熔融加工阶段是可被蒸发的或被去掉的,使其在最终产品中只有残余/痕量保留。因此,加工助剂对最终产品的强度,模量,或其它性能没有负面的影响。上述所公开的极性溶剂还可以起可挥发加工助剂的作用。其它非限制性的例子包括碳酸盐如碳酸氢钠。
可以选择性地往可纺丝的淀粉组合物中加入其它配料以改进可加工性和/或改进最终产品的物理性能如弹性,拉伸强度和模量。非限制性的例子包括氧化剂,交联剂,乳化剂,表面活性剂,剥离剂,润滑剂,其它加工助剂,莹光增白剂,抗氧剂,阻燃剂,染料,颜料,填料,蛋白及其碱性盐,可生物降解的合成聚合物,蜡,低熔融的合成热塑性聚合物,增粘树脂,增量剂,湿强度树脂和它们的混合物。在组合物中这些选择性配料的含量可以是从约0.1%-约70%,优选从约1%-约60%,,更优选从约5%-约50%,最优选从约10%-约50%。
可生物降解的合成聚合物的例子包括聚己酸内酯;多羟基链烷酸酯包括多羟基丁酸酯,和多羟基戊酸酯;聚交酯;和它们的混合物。
可以进一步加入润滑剂化合物以改进在本发明的生产加工过程中所用淀粉材料的流动性。润滑剂组合物可以包括动物或植物脂肪,优选氢化的动物或植物脂肪,特别是那些在室温下是固体的的动物或植物脂肪。另外的润滑剂材料包括单甘油酯类和二甘油酯类,和磷酯,特别是卵磷酯。本发明优选的润滑剂化合物包括单甘油酯类和单硬酯酸甘油酯。
另外的添加剂包括无机颗粒如镁、铝、硅、和钛的氧化物可以作为廉价的填料或增量剂加入。因此可以使用添加剂如包括碱金属盐,碱土金属盐,磷酸盐等等的无机盐。
根据所预期的产品的最终特殊用途加入所需要的其它添加剂。例如,在一些产品如卫生纸,一次性抹布,面巾纸和其它类似的产品中,湿强度是属于所需要的。因此,经常需要将本领域公知的作为“湿强度”树脂的交联剂加入到淀粉聚合物中。
可以在TAPPI monograph series No.29,Wet Strength in Paper andPaperboard,Technical Association of the Pulp and Paper Industry(NewYork,1965)中发现关于在造纸领域实用的湿强度树脂的类型的主要研究报告。通常最有用的湿强树脂是阳离子性的。已经发现聚酰胺-表氯醇树脂是最有用的阳离子聚酰胺-表氯醇湿强树脂。在1972年10月24日授权与Keim的美国专利No.3,700,623和1973年11月13日授权与Keim的美国专利No.3,772,076中描述了这类适合的树脂的类型,在此引入这两篇专利作为参考。可从Hercules,Inc.of Wilmington,Delaware买到所用聚酰胺-表氯醇树脂,该公司以商标Kymene_销售这类树脂。
还发现乙醛酸聚丙烯酰胺树脂可用作湿强度树脂。在1971年1月19日授权与Coscia等的美国专利No.3,556,932和1971年1月19日授权与Williams等的美国专利No.3,556,933中描述了这些树脂,在此引入这两篇专利作为参考。可从Cytec Co.of Stanford,CT买到乙醛酸聚丙烯酰胺树脂,该公司以商标Parez_631 NC销售这类树脂。
人们发现,当使用交联剂如Parez_631 NC时,在酸性条件下将其加入到本发明的淀粉组合物中。组合物为水不可溶的。也就是,用下文所述的实验方法测得组合物的水溶解度小于30%,优选小于20%,更优选小于10%,最优选小于5%。从该类组合物制成的产品如纤维和膜也是水不可溶的。
在本发明中有用的另外的水可溶性的阳离子树脂是脲醛树脂和三聚氰胺甲醛树脂。这些多官能团树脂中更常用的官能团是含有氮的基团如氨基和连接到氮上的羟甲基。还发现在本发明中可以使用聚哌嗪(polyethylenimine)型树脂。此外,可以在本发明中使用临时湿强度树脂如Caldas_10(由Japan Carlit生产)和CoBond_1000(由National Starch and Chemical Company生产)。
对于本发明,往组合物中加入的适用的交联剂的量是从约0.1%-约10%重量,更优选从约0.1%-约3%重量。淀粉组合物的流变性
对于选择合适的材料和生产设备/工艺来讲,淀粉组合物的流变性相当重要。组合物的流变性归因于许多因素,包括所用各聚合物成分的类型和量,各成分的分子量和分子量分布,添加剂(例如增塑剂,加工助剂)的量和类型,工艺条件如温度,压力,形变速度,和相对湿度,和非牛顿材料的情况,形变函数(例如时间或形变时间函数关系曲线)。
本发明的淀粉组合物通常具有高的固含量(即浓度高于临界浓度C),使之形成动态的或波动的缠结网,其中淀粉分子和高聚物分子暂时地连接和不连接。连接可以是物理缠结形式的连接,范得华力,或化学相互作用如氢键。具有缠结网结构的淀粉组合物呈现典型的非牛顿流体的熔体流动性。
本发明的淀粉组合物可以呈现应变硬化性,也就是拉伸粘度随应变或形变增加而增加。通常,牛顿流体在应力和/或力与应变之间呈现线性关系。也就是在牛顿流体中没有应变硬化性。另一方面,在较高应变(即形变硬化性)下,非牛顿流体力加大,而在较低应变(即类牛顿流体)下,显示线性关系的力-应变。
在非牛顿流体中流体单元所经过的应变取决于它的动力学函数,也就是,时间或相应的应变叫作亨基应变量(εH).对于理想的均匀单轴伸长,每个流体单元所经过的应变速率等于所施加应力赋予的形变,如通过仪器,设备或工艺所施加的外部应力。在这种理想情况下,亨基应变量直接与样品变形/伸长有关εH=In(L/L0)在牛顿流体中,能最经常观察到响应所施加应力的这类理想的应变。
经常用Trouton比(Tr)表示拉伸流动性。被定义为拉伸粘度(ηe)和剪切粘度(ηs)之间的比,Tr=ηe(ε·,t)/ηs其中拉伸粘度ηe取决于形变速率(ε·)和时间(t)。对于牛顿流体,单轴拉伸Trouton比具有恒定值3。对于非牛顿流体,拉伸粘度取决于形变速率(ε·)和时间(t)。
剪切粘度(ηs)与使用标准的聚合物加工技术淀粉组合物的可熔融加工性有关,标准的聚合物加工技术如挤出,吹塑,压缩模塑,注塑等等。在本发明的熔融拉细加工方法中,使用按照下文公开的测试方法测量的具有剪切粘度小于约30Pa·s,优选从约0.1Pa·s至约10Pa·s,更优选从1Pa·s至8Pa·s的淀粉组合物。本发明的某些淀粉组合物可以具有低熔融粘度,通常用于粘性流体的传统聚合物加工设备(如装有计量泵和喷丝头的静态混合器)能使它们混合,输送或其它的加工。通过使用一定量的增塑剂和/或溶剂,改进淀粉的分子量和分子量分布,高聚物的分子量,可以有效地改进淀粉组合物的剪切粘度。还发现降低淀粉的平均分子量是降低组合物剪切粘度的有效途径。
在传统的热塑性加工如注塑和挤出方法中,熔融剪切粘度是用于评价材料的可熔融加工性的材料性能。对于常规纤维纺丝的热塑材料如聚烯烃,聚酰胺和聚酯来讲,这些常用热塑性材料及其共混物的剪切粘度和拉伸粘度之间板相关。也就是,即使可纺性主要是由熔融拉伸粘度控制的性能,也可以简单地用熔融剪切粘度测量材料的可纺性。这种十分强的相关性使纤维工业能依赖于熔融剪切粘度选择和配制可熔体纺丝的材料。熔融拉伸粘度极少用作工业筛选的手段。
由此人们惊奇地发现,本发明的淀粉组合物不具有这种剪切粘度和拉伸粘度之间的相关性。特别是当往淀粉组合物中加入按照本发明选择的高聚物时,组合物的剪切粘度仍然相对地没有变化,甚至稍稍降低。按照常规的思维,这种淀粉组合物应该显示降低的可熔体纺丝性,并且不适用于熔融拉伸工艺。但是,令人惊奇地发现,甚至当加入少量高聚物时,本发明的淀粉组合物显示拉伸粘度显著提高。因此,本发明的淀粉组合物具有增强的可熔融拉伸性,并且适用于熔融拉伸工艺如吹塑,纺粘,吹塑薄膜,泡沫模塑等。
拉伸粘度或伸长粘度(ηe)与组合物的熔融拉伸有关,对于拉伸工艺如制纤维,膜或泡沫的工艺特别重要。拉伸粘度包括三类形变:单轴或简单的拉伸粘度,双轴拉伸粘度,和纯的剪切拉伸粘度,对于单轴拉伸工艺如纤维纺丝,熔喷,和纺粘工艺来讲,单轴拉伸粘度是重要的。对于双轴拉伸或制膜、泡沫、片材或部件的成形工艺来将,其它两种拉伸粘度是重要的。人们发现高聚物的性能对熔融拉伸粘度有重要的影响。通常用于提高本发明淀粉组合物的可熔融拉伸性的高聚物是高分子量的,基本上是线性的。此外,在提高淀粉组合物的可熔融拉伸性方面,与淀粉基本上相容的高聚物是最有效的。
人们已经发现,当将选择的高聚物加入到组合物中时,通常用于可熔融加工工艺的淀粉组合物所具有的拉伸粘度提高至少10倍。通常,当加入所选择的高聚物时,本发明的淀粉组合物显示拉伸粘度增加约10至约500,优选20至约300,更优选约30至约100。
人们还已经发现,本发明的可熔融加工的组合物通常具有Trouton比至少为3。一般地,当在90℃和700s-1测量时,Trouton比范围从约10至约5,000,优选从约20至约1,000,更优选从约30至约5,00。
当对本发明的淀粉组合物进行单轴拉伸时,以(D0 2/D2)表示拉伸比,其中D0表示拉伸前丝的直径,D表示拉伸的纤维的直径,可容易获得拉伸比大于1000。本发明的淀粉组合物通常得到拉伸比从约100至约10000,优选大于约1000,更优选大于约3000和最优选大于约5000。更具体的是,本发明的淀粉组合物具有足够的可熔融拉伸性,可以被拉伸成具有确定平均直径小于50微米,优选小于25微米,更优选小于15微米,甚至更优选小于10微米,和最优选小于5微米的精细纤维。
当对本发明的淀粉组合物进行双轴拉伸时,增强的可熔融拉伸性的组合物可以被熔融拉伸成具有确定平均厚度(caliper)小于0.8密耳,优选小于0.6密耳,更优选小于0.4密耳,甚至更优选小于0.2密耳,和最优选小于0.1密耳的膜。
在可流动态下加工本发明的淀粉组合物,通常可流动态出现在温度等于或高于其熔融温度态。因此,加工温度范围被淀粉组合物的熔融温度控制,按照下文详述的试验方法测量熔融温度。本发明的淀粉组合物的熔融温度范围从约80-180℃,优选从约85-160℃,更优选从约90-140℃。某些淀粉组合物不可能显示纯“熔融性”是可以理解的。本发明中所用的术语“熔融温度”是指温度或温度范围达到或高于组合物熔融温度或软化温度的温度。
适于淀粉组合物的单轴拉伸工艺的例子包括熔体纺丝,熔喷法,和纺粘法。在1977年12月27日授权给Akiyama等人的美国专利No.4,064,605;在1983年11月29日授权给Blackie等人的美国专利No.4,418,026;和在1989年8月8日授权给Bourland等人的美国专利No.4,855,179;在1990年3月20日授权给Cuculo等人的美国专利No.4,909,976;在1992年9月8日授权给Jezic等人的美国专利No.5,145,631;和在1996年3月14日授权给Buehler等人的美国专利No.5,516,815;和在1994年8月30日授权给Rhim等人的美国专利No.5,342,335中详细描述了这些方法。在此引入所有上述技露的内容作为参考。所得到的产品可用于空气过滤器,油与水;真空吸尘过滤器,锅炉过滤器;面罩;咖啡滤波器,茶或咖啡袋;保温材料和隔音材料;用于一次性使用的卫生产品的无纺织物如尿布,妇女卫生巾,失禁用物品;为了改进吸水性和穿着柔软的可生物降解的纺织品,如微细纤维或可呼吸的织物;为了收集和去掉灰尘的放静电、结构化的基料;为了硬化纸所用的补强剂和基料(web),硬化纸如包装纸,信纸,白报纸,皱纹纸板,和用于薄纸级的基料,薄纸如卫生纸,纸毛巾,餐巾与面巾;医疗用的如外科绷带,伤口涂剂(wound dressing),绷带(bandage),皮肤修复膜(dermal patches)和自溶解缝线;牙科使用的如牙线和牙刷毛。纤维质基料还可以包括气味吸附剂,白蚁驱避剂,杀虫剂,杀鼠剂,等等特殊用途。所得到的产品吸收水和油,并且可用在清理溢出的油或水,或在农业或园艺应用方面用于控制水的保持与释放。还可以往所得到的淀粉纤维或淀粉基料中加入其它材料如锯末,木质纸浆,塑料,和混凝土以形成复合材料,该复合材料可用作建筑材料如墙壁,支承梁,承压板,干燥墙壁与衬垫,和天花板铺瓦(砖);另外的医用如铸塑,夹板,舌压器;和装饰和/或燃烧用的壁炉。
本发明淀粉组合物的熔融流变性还使它适用于常规的双轴拉伸热性塑性工艺。由于具有合适的熔融剪切粘度和双轴拉伸粘度,本发明的淀粉组合物可以基本上减少发生撕裂,表面缺陷,和其它破损或使连续工艺中断和产生不满意产品的缺陷。这些方法包括吹塑,吹塑薄膜挤出或共挤出,真空成形,压力成形,压模法,传递模塑(transfer molding)和注塑法。在1995年4月11日授予Stepto等人的美国专利NO.5,405,564;1995年11月21日授予Yazaki等人的美国专利NO.5,468,444;1995年10月31日授予Bastioli等人的美国专利NO.5,462,982中详细描述了这些方法的非限制性的例子。在此引入所有上述披露的内容作为参考。用这些方法生产的制品包括板材,膜,涂敷层,叠层,管,棒,袋,和成形制品(如瓶子,容器)。这类制品可用作袋子如购物袋,杂货袋,和垃圾袋;用于食品存贮或烹调盒;用于冷冻食品的可微波容器;和药物用途如药物的胶囊或糖衣。用于食品包装,收缩包装或窗口式信封的膜可以基本上是透明的。还可以进一步加工这类膜用作其它材料如种子或肥料的廉价、可生物降解的载体。用于另外的用途如标签,可以往膜或板材上涂粘合剂。
还可以通过控制挥发成分(例如水,极性溶剂)的去除,将本发明的淀粉组合物制成泡沫。但是通常加入发泡剂或膨胀剂以生产具有发泡的或多孔的内部结构的制品。发泡剂或膨胀剂的例子包括二氧化碳,正戊烷,和碳酸盐类如碳酸氢钠,或者单独成分或与具有侧羧基(例如,聚丙烯酸,乙烯-丙烯酸共聚物)的聚合酸的混合物。在1994年2月22日授予Bastioli等人的美国专利NO.5,228,765;1996年3月5日授予Chinnaswamy等人的美国专利NO.5,496,895;1998年1月6日授予Tomka的美国专利NO.5,705,536;1998年4月7日授予Bastioli等人的美国专利NO.5,736,586中详细描述了发泡工艺和成形工艺的非限制性的例子。在此引入所披露的内容作为参考。所得到的产品可以用于鸡蛋纸板;用于热饮料的发泡杯;用于快餐食品的容器;肉托架;一次性使用的如野餐或聚会用的盘和碗;包装材料,松散填料或模制成适合包装品(例如计算机运输包装)的材料;保温材料;和防噪音材料或吸音材料。测试方法A.剪切粘度
使用旋转粘度计(由Rheometrics制造的Model DSR 500)测量组合物的剪切粘度。将预热的样品组合物加载到流变仪的样品桶(使用约60克样品)中。将样品桶保持在90℃的试验温度。加载样品后,通常有空气鼓泡至表面,空气不会对操作产生影响。对于较粘的样品,在开始测试前,压缩样品以去掉熔融样品内的气泡。程序控制粘度计,以直线上升地施加从10达因/厘米到5000达因/厘米的应力。用应变仪测量样品所经历的应变。从中得出组合物的表观粘度。作出log(表现粘度)与log(剪切速率)的关系曲线,并且用幂函数式η=Kγn-1校正曲线,其中K是材料常数,y是剪切速率。所报告的本发明淀粉组合物的剪切粘度是用幂函数关系式外推法至剪切速率700s-1处的值。B.拉伸粘度
使用毛细管流变仪(由Geottfert制造的Model Rheograph2003)测量拉伸粘度。使用具有直径D为0.5mm,长L为0.25mm(即L/D=0.5)的孔板模头进行测量。模头与保持在90℃的试验温度的样品桶的较低末端相连。将预热的样品组合物加载到流变仪的样品桶中,基本上填满样品桶。加载样品后,通常有空气鼓泡至表面,空气不会对操作产生影响。对于较粘的样品,在开始测试前,压缩样品以去掉熔融样品内的气泡。以选择的速率程序控制活塞,将样品从样品桶推至孔板模头。随着样品从样品桶推至孔板模头,样品经受压降。从压降和通过孔板模头的样品流速得到表观粘度。通常按现有技术已知的程序对表观粘度进行校正。用剪切校正因子和Cogswell方程校正拉伸粘度。记录在剪切速率700s-1处的校正的拉伸粘度值。
众所周知,按照本文描述的方法使用孔板模头并应用校正因子可以测量拉伸粘度。有关拉伸粘度测量的更详细的内容被披露在S.H.Spielberg等的TheRole Of End-Effects On Measurements Of Extensional Viscoisty InFilament Stretching Rheometers,Journal of Non-Newtonian FluidMechanics,Vol.64,1996,p.229-267;Bhattacharya等的UniaxialExtensional Viscosity During Extrusion Cooking From Entrance PressureDrop Method,Journal of Food Science,Vol.59,No.1,1994,p.221-226中,在此引入这两篇的内容作为参考。还公知的是可以用双曲线模头(hyperbolicdie)或半双曲线模头测量拉伸粘度。用双曲线模头或半双曲线模头测量拉伸粘度的详细内容公开在1994年10月25日授权与Collier的美国专利No.5,357,784中,在此引入其公开内容作为参考。C.分子量和分子量分布
使用混合床柱,用凝胶渗透色谱(GPC)测量淀粉的重均分子量(Mw)和分子量分布(MWD)。仪器的配件如下:
泵 Waters Model 600E
系统控制器 Waters Model 600E
自动进样器 Waters Model 717Plus
柱子 具有长600mm和内径7.5mm的PLgel20μmMixed A柱
(凝胶分子量从1,000至40,000,000)。
检测器 Waters Model 410差示折光仪
GPC软件 Waters Millenium_软件
用具有分子量245,000;350,000;480,000;805,000;和2,285,000的葡聚糖标准样校正柱子。可从American Polymer Standards Corp.,Mentor,OH.购得这些葡聚糖标准样。通过将标准样溶解在流动相中,以制得约2mg/ml的校正标准样。然后使用注射器(5ml,Norm-Ject,可从VWR得到的)通过注射器过滤器(5μl尼龙膜,Spartan-25可从VWR得到)对它轻轻地旋流和过滤。
淀粉样品的制备,首先加热在自来水中有40%重量淀粉的混合物,直到混合物胶化。然后,将1.55g胶化的混合物加入到22g流动相中以制3mg/ml溶液,该溶液是通过搅拌5分钟,把混合物放到105℃烘箱中加热1小时,从烘箱中移出混合物,并冷却至室温制成的。用上述的注射器和注射器过滤器过滤溶液。
用自动进样器加入过滤了的标准样品或样品溶液以冲洗在100μl注射回路中存在的先前测试材料,并将当前测试材料注入柱子。保持柱子在70℃。以流动相为背景,用保持在50℃、灵敏度范围设定在64的差示折光指数检测器测量流出柱子的样品。流动相是溶解了0.1%w/vLiBr的DMSO。流速设定在1.0ml/min,并且无梯度洗脱(即,在测定过程中流动相是恒定的)。每个标准样或样品在GPC上测定三次,取平均值。
高聚物的平均分子量由材料供应商提供。D.热性能
使用TA Instruments DSC-2910(已经用铟金属标准样校正的)测定本发明淀粉组合物的热性能,如化学文献所报道的铟金属标准样具有熔融温度(起始)156.6℃,每克熔融热6.80卡。按照生产商的操作手册进行标准DSC操作程序。由于在DSC测试过程中,挥发性的物质进一步(例如,水蒸汽)从淀粉组合物中挥发,因此,使用装有O型环密封的大体积盘以防止挥发性物质从样品盘中逸出。在控制条件下,以相同速率加热样品和内标(一般是空盘)。当在样品中发生实际上的或假的相变化时,DSC仪器测量相对于内标而出入样品的热流量。仪器界面用计算机控制试验参数(例如加热/冷却速率),并收集、计算和记录数据。
将称重的样品放入盘中并用O型环和盖封住。通常样品的尺寸是25-65mg。将封住的盘放在仪器中,并设定用于测量热的计算机程序如下:1.在0℃平衡;2.在0℃保持2分钟;3.以10℃/min加热至120℃;4.在120℃保持2分钟;5.以10℃/min冷却至30℃;6.在室温平衡24小时,从DSC仪器中移出样品盘,并将其放在30℃控制条件下;7.把样品盘放回DSC仪器中,并在0℃平衡;8.保持2分钟;9.以10℃/min加热至120℃;10.在120℃保持2分钟;11.以10℃/min冷却至30℃且平衡;12.移出所用的样品。
计算机计算和记录热分析结果为对于温度或时间的差热流量(ΔH)。一般差热流量是标准化的和基于单位重量记录的(例如cal/mg)。而当样品显示假的相变如玻璃转化时,可以用ΔH对时间/温度曲线的差以更容易地测量玻璃转化温度。E.水可溶性
通过加热混合各成分制成样品组合物,并搅拌至形成基本上均匀的混合物。通过将熔融组合物涂到Teflon_板上并在室温冷却,铸塑成薄膜。然后在100℃烘箱完全干燥(例如在膜/组合物中没有水)该膜。然后将干燥的膜平衡至室温。把平衡后的膜碾成粒。
为了测定在样品中的%固体含量,将2至4克碾碎的样品放进预称重的金属盘中,记录盘和样品的总重。将称重后的盘和样品放置在100℃的烘箱中2小时,然后取出并立即称重。按照下式计算%固体含量:
为了测定样品的溶解度,在250ml烧杯中称10g碾碎的样品。加入去离子水至总重100g。在搅拌盘上将样品和水混合5分钟。搅拌后,往离心管中倾入至少2ml搅拌后的样品。在10℃以20,000g离心1小时。取离心样品的上层液,并测量折光率。按照下式计算样品的%溶解度:F.厚度(caliper)
测试前,将样品置于相对湿度48%-50%和温度22℃至24℃条件下,直到得到含水量约5%至约16%的样品。通过热电电流分析TGA(Thermo GravimetricAnalysis)测定水的含量。为了进行热电电流分析,使用自TA Instruments的高分辨TGA2950热电电流分析仪。称约20mg样品并加入到TGA盘中。按照生产商的说明,将样品和盘插入到装置中,并以10℃/min的速率升温至250℃。按下式,用失重和起始重量测量样品的%含水量:
使用被切成大于基座(foot)尺寸的事先准备的样品,以测量厚度。所使用的基座是面积3.14平方英寸的圆(circle)。
将样品放在一水平的平直表面上,固定在水平表面和具有水平负载表面的负载基座之间,其中加载基座负载表面具有约3.14平方英寸的圆表面积,并对样品施加约15g/cm2(0.21psi)的控制压力。厚度是平直表面和加载基座负载表面之间的缝隙。在从Thwing-Albert,Philadelphia,Pa得到的VIRElectronic Thickness Tester ModelⅡ上能获得这种测量结果。重复测量厚度并记录至少5次。结果以密耳(mil)表示。用厚度试验得到的所记录读数的总值除以记录的读数次数。结果以密耳(mil)表示。
实施例
在实施例中所用的原料如下:
具有重均分子量100,000的改性淀粉晶胶_;具有重均分子量2,000的改性淀粉Nadex_;具有重均分子量800,000的改性淀粉Instant-n Oil_;所有这些原料购自National Starch and Chemical Corp.,Bridgewater,NJ。
购自Cytec Co.,Stamford,CT的具有平均分子量12,000,000至14,000,000的羧基化的聚丙烯酰胺Superfloc_A-130。
购自Scientific Polymer Products,Inc.,Ontario,NY的具有平均分子量分别为15,000,000和5,000,000至6,000,000的非离子聚丙烯酰胺PAM-a和PAM-b。
购自Aldrich Chemical Co.,Milwaukee,WI的具有重均分子量分别为750,000的聚乙烯亚胺。
购自Cytec Co.,Stamford,CT的低分子量乙醛酸化的聚丙烯酰胺Parez_631NC,和低分子量乙醛酸化的脲醛树脂Parez_802。
购自BASF corp.,Parsippany,NJ.的Pluronic_F87非离子poloxomer。
购自Aldrich Chemical Co.,Milwaukee,WI的脲、蔗糖和乙二醛(40%水溶液)。实施例1
通过混合45%重量淀粉(晶胶),40.5%重量脲,4.5%重量蔗糖,和9.8%重量自由水,并用手搅拌以形成浆料,制成本发明可熔融加工的组合物。在水中溶解聚丙烯酰胺(PAM-a,Mw=15,000,000)以形成PAM含水溶液。往浆料中加入等份的聚合物/水溶液。然后蒸发在浆料中的水,直到在最后的混合物中聚丙烯酰胺的重量百分含量是0.2%重量为止。
组合物在90℃和700s-1具有剪切粘度0.65Pa·s,和拉伸粘度1863.2Pa·s。对比实施例1b
按照实施例1制备对比淀粉组合物,所不同的是没有往组合物中加入聚丙烯酰胺。组合物在90℃和700s-1具有剪切粘度1.35Pa·s,和拉伸粘度43.02Pa·s。实施例1和对比实施例1b表明加入少量的高聚物稍稍地降低了剪切粘度,和显著地增加了拉伸粘度。实施例2
通过混合50%重量淀粉(晶胶),30%重量脲,1.5%重量蔗糖,和18.5%重量自由水,并用手搅拌以形成浆料,制成本发明可熔融加工的组合物。在水中溶解聚丙烯酰胺(Superfloc A-130,Mw=12-14,000,000)以形成PAM含水溶液。往浆料中加入等份的聚合物/水溶液。然后蒸发在浆料中的水,直到在最后的混合物中聚丙烯酰胺的重量百分含量是0.003%重量为止。
组合物在90℃和700s-1具有剪切粘度1.12Pa·s,和拉伸粘度46.0Pa·s。对比实施例2b
按照实施例2制备对比淀粉组合物,所不同的是没有往组合物中加入聚丙烯酰胺。组合物在90℃和700s-1具有剪切粘度1.23Pa·s,和拉伸粘度0.69Pa·s。实施例2和对比实施例2b表明加入少量的高聚物稍稍地降低了剪切粘度,和显著地增加了拉伸粘度。实施例3
用具有熔融吹塑模头的转矩流变仪加工实施例1的组合物。转矩流变仪如图1所示。转矩流变仪装置100包括驱动单元110(购自HAAKE GmbH的ModelRheocord 90),分成四个温度区122,124,126和128的样品桶120,进料口121,和熔融纺丝模头装置130。双螺杆部件160(购自HAAKE GmbH的modelTW100)与驱动单元110连接,并且被排布在样品桶120中。通过泵140,6英寸宽的熔融吹塑模头装置130(购自JM Laboratories,Dawsonville,GA)与样品桶的末端相连。模头装置具有喷丝板,喷丝板具有每线性英寸52个孔,并且孔直径0.015”(0.0381cm),周围有0.02”宽的空气通道152,高速空气流150撞击刚刚出喷丝板的挤出丝。空气流有效地将丝吹离喷丝头的同时也拉细了丝。
按照实施例1所描述的,通过混合45%重量淀粉(晶胶),0.2%重量聚丙烯酰胺(PAM-a),40.5%重量脲,4.5%重量蔗糖,和9.8%重量水,制备组合物。通过进料口121将混合物重力加料到转矩流变仪中。设定转矩流变仪和模头装置如下:
料桶温度
122区 70℃
124区 90℃
126区 90℃
128区 90℃
转矩 100rpm
模头温度 126.7℃
空气温度 126.7℃
空气压力 35psi
泵 40rpm
通过泵将混合物从挤出机输送到熔融吹塑模头中。本发明得到具有纤维直径从8至40微米拉细的丝(或精细纤维)。
值得注意的是,在可熔融加工组合物中淀粉的重量百分含量包括淀粉的重量和结合水(其平均占淀粉的约8%)的重量。可以理解的是如此制备的组合物可用于单轴和双轴拉伸工艺。但是,在熔融加工过程中失掉了大量的水,得到的淀粉纤维,膜或类似产品含有少量水或没有水。得到的产品确实含有某些结合水(可能从环境吸收的微量水)。因此可用固体成分(基于干燥固体计算)准确地表示所得组合物产品。例如按照实施例3制成的纤维混合物基于干燥固体计算,9.8%重量自由水来自整个组合物和8%的结合水来自淀粉,那么余量是100%固体含量。因此,基于干燥固体计算实施例3的纤维组合物有淀粉固体(没有结合水)47.8%重量,聚丙烯酰胺0.23%重量,脲46.8%重量和蔗糖5.2%重量。实施例4
将实施例2的组合物熔融吹塑成本发明的精细纤维。图3a是用实施例3所描述的工艺,从实施例2的组合物制得的以200微米比例表示的精细淀粉纤维的扫描电镜图。图3b是以20微米比例表示的相同淀粉纤维的扫描电镜图。这两张图显示出,实施例4的淀粉纤维具有约5微米的相当恒定的纤维直径。实施例5
在80℃,将15g淀粉(晶胶,Mw=100,000),和15g自由水混合在一起,用手搅拌直至混合物变成基本上均匀或稠化。在自由水中溶解高聚物(PAM-a,Mw=15,000,000)以形成已知浓度的PAM含水溶液。往淀粉/水混合物中加入等份的聚合物/水溶液,使整个的混合物含有O.006gPAM-a。然后加热整个混合物以蒸发水,直到最后的混合物(淀粉,PAM-a和水)的重量等于30g为止。该混合物主观上显示出适合于拉伸纤维的可熔融拉伸性。实施例6-8
用与实施例5相同的方式制备淀粉(晶胶),高聚物和水的混合物。这些混合物的最终组合物如下所示。
Mw | 实施例-6 | 实施例-7 | 实施例-8 | |
淀粉晶胶100,000 | %重量 | 49.99 | 49.99 | 46.92 |
聚丙烯酰胺12-14,000,000 | %重量 | 0.02 | ||
SuperflocA-130 | %重量 | |||
PAM-b5-6,000,000 | %重量 | 0.02 | ||
聚乙烯亚胺750,000 | %重量 | 6.17 | ||
水 | %重量 | 49.99 | 49.99 | 46.91 |
这些混合物主观上显示出适合于拉伸纤维的可熔融拉伸性。实施例9-11
按照与实施例1相同的方式制备下列的组合物。
Mw | 实施例-9 | 实施例-10 | 实施例-11 | ||
淀粉晶胶 | 100,000 | %重量 | 41.54 | 20.77 | 20.77 |
Nadex | 2,000 | %重量 | 20.77 | ||
Instant-n Oil | 800,000 | %重量 | 20.77 | ||
聚丙烯酰胺PMA-a | 15,000,000 | %重量 | 0.08 | 0.08 | O.08 |
脲 | %重量 | 6.23 | 6.23 | 6.23 | |
蔗糖 | %重量 | 6.23 | 6.23 | 6.23 | |
Parez 631 NC | %重量 | 1.04 | 1.04 | 1.04 | |
水 | %重量 | 44.88 | 44.88 | 44.88 |
本预期发明的这些组合物具有适合于拉伸纤维的可熔融拉伸性。并且基于本发明所公开的试验方法,已经将水调节至PH2,预期得到的纤维具有水溶解度小于30%。实施例12
通过混合45%重量淀粉(晶胶),0.2%重量聚丙烯酰胺(PAM-a),40.5%重量脲,4.5%重量蔗糖,和9.8%重量水以形成浆料,制备可熔融加工的组合物。按照与实施例3所描述相同的方式,使用如图1所示的转矩流变仪,将组合物熔融吹塑成精细纤维,所不同的是用加料计将混合物加入转矩流变仪中。设定转矩流变仪和模头装置如下:
料桶温度
122区 70℃
124区 90℃
126区 90℃
128区 90℃
转矩 140rpm
加料速度 16g/min
模头温度 137.8℃
空气温度 137.8℃
空气压力 50psi
泵 40rpm
本发明得到具有纤维直径从10至30微米拉细的丝(或精细纤维)。纤维被气流成网法植入纸中制成在美国专利No.4,637,859中公开的织物,以及美国专利No.5,857,498,5,672,248,5,211,815和5,098,519中的织物。在此引入所有内容作为参考,也可以判断为适用于该目的。实施例13
测试从实施例12的气流成网法工艺得到的网对于油的吸收能力。为了比较油吸收能力,分别将一滴购买的马达油(SAE 20级,Society of AutomobileEngineers’指定的)放置到网上,和市场上购得的纸巾上。在如下方面网显示出改进的油吸收能力比市场上购得的纸巾强:(1)网比市场上购得的纸巾吸油快,显示出在网表面上保留时间较短;和(2)30秒后,网的斑点直径尺寸是市场上购得的纸巾的斑点直径尺寸的约1.5至2倍。实施例14
该实施例所说明的本发明的淀粉组合物能被制成建筑材料,例如压板。通过混合60%重量淀粉(晶胶),0.1%重量聚丙烯酰胺(SP2),2%重量脲,2%重量蔗糖,1.5%重量Parez 631 NC和34.4%重量水(用硫酸调节至PH2),以形成浆料,制成可熔融加工的组合物。将浆料加入到如图1所示的转矩流变仪(ModelRheocord 90)中,并在如上述实施例12所述条件下操作,所不同的是用单毛细模头(具有1mm直径和温度90℃)代替熔融纺丝模头。当还是湿的和粘性时,挤出条被撒上锯末或刨花。将被撒的条压到一起以形成圆木。以40℃强力空气加热2小时以去掉淀粉组合物中的残余水,圆木被干燥了。最后的产品是47.8%重量锯末和52.2%重量淀粉组合物的圆木。实施例15
该实施例说明,可在本发明中加入结构材料作为补强剂。该实施例使用从组合物制成的纤维,而不使用高聚物。可以认为当使用本发明的组合物时,产品会显示较好的或相当的性能。
按照下列步骤制备对比泥样品:将5份市售Quikrete Anchoring水泥与1.5份清洁的自来水混合,直至得到一致性的浓浆。为了得到用于评估的恒定尺寸的样品,在5分钟内混合,将水泥加入到圆筒型模子中。通过从底部堆起糊状水泥混合物,填满薄壁模子5”长和内径0.23”(例如市场购得的麻茎(straws))。该填充方法消除了成品样品中的空气。在评价前,使样品老化5天。在外表面上仔细刻划(scored on)模子,以不损坏里面的样品,然后剥离模子以再(retrieved)装入对比样品(实施例15b)。
通过混合45%重量淀粉(购自National Starch and ChemicalsCorp.,Bridgewater NJ的Durabond_),15%重量脲,15%重量山梨糖醇,25%重量水以形成浆料,制成可熔融加工的组合物。将浆料加入到如图1所示的转矩流变仪(Model Rheocord 90)中,并在如上述实施例14所述条件下操作。纤维直径是约0.02”,并且将纤维切成1”长用于本发明。按照下列步骤将水泥加入到挤压的像意大利面条的条样中:将5份市售Quikrete Anchoring水泥与1.5份清洁的自来水和0.5%(基于干重)淀粉纤维混合。需要另外加入一定量的水,以得到与上述对比实施例相一致的可对比样。填满样品模,并使样品(实施例15)固化和以与上述相同的方式再装入样品。
通过用手使之弯曲至不能再弯,主观地评价样品。主观评价实施例15比实施例15b稍弱。实施例15具有表观密度1.46克/线性英寸,而对比实施例15b具有表观密度1.48克/线性英寸。因此,证明实施例15提供重量轻并较低费用(基于体积)的产品。实施例16
该实施例说明,当该材料与盆栽土壤混合时,本发明的组合物可被预先制成控制水释放的材料。控制水释放有利于园艺植物和农业植物在相对低湿环境和/或稀少浇水的环境茁壮成长。
通过混合50%重量淀粉(购自National Starch and ChemicalsCorp.,Bridgewater NJ的Durabond_),0.1%重量聚丙烯酰胺(SP2_),15%重量脲,15%重量山梨糖醇,1.5%Parez_,18.4%重量水以形成浆料,制成可熔融加工的组合物。将浆料加入到如图1所示的转矩流变仪(Model Rheocord 90)中,并在如上述实施例14所述条件下操作。在与盆栽土壤混合前,将组合物挤压成像薄的意大利面条的样条。淀粉基样条与盆栽土壤的比取决于各种类型植物的需要。通常,10%重量淀粉基样条的盆栽土壤显示满意的水保持/释放结果。
实施例17-19使用从组合物制成的膜,而没有使用高聚物。可以认为当在这些每个实施例中使用本发明的组合物时,得到的产品显示有益改进了的各性能,例如较薄厚度,较高挠性。实施例17
该实施例说明,使用具有L/D比为40的Werner&Pfleiderer ZSK-30共旋转双螺杆挤压机,将本发明的组合物制成薄膜。螺杆配置由四个捏合区域和五个输送区域组成。由一个未加热的进料区接着七个加热区组成的挤压机样桶被指定为连续的A区,B区,1区,2区,3区,4区,和5区。控制样桶的整个温度如下,并设定螺杆速度150rpm。
区域 A B 1 2 3 4 5
温度 50 50 50 95 95 95 95℃
通过用K2V-T20体积进料器(从K-Tron Inc.,Pitman,NJ购得)计量固体材料加入到挤压机中,和用微型泵(从Milton-Roy,Ivyland,PA购得)计量液体材料加入到挤压机的1区中,制备可熔融加工的组合物。各成分是:44%重量淀粉(购自National Starch and Chemicals Corp.,Bridgewater NJ的Durabond_),18%重量脲,18%重量蔗糖,20%重量水。以流速33cm3/min将混合物从挤压机输送至Zenith B-9000齿轮泵,进入6英寸宽的平幅膜模头(从Killion Extruders,Cedar Grove,NJ购得),其中齿轮泵保持在96℃,膜模头保持在94℃和模头开口设定在15密耳。将所得到的膜挤压到37℃的12英寸宽急冷辊(从Killion Extruders购得)上。然后以5fpm速度将膜卷到纸芯上。得到的膜约1密耳厚,手感稍粘,并且具有良好的挠性,例如可被重复弯曲180度而不断裂或形成死褶。实施例18
该实例说明,从实施例17得到的膜可被制成用于农业的种子载体。按照该事实例制成的种子载体膜提供一种廉价的材料,能铺设该材料以有效地覆盖和播种大面积种子。该材料保湿有利于种子发芽,并且该材料是可生物降解的,不需要回收和处理。将实施例17的膜放到单面释放纸上,并撒上草子(从Midwestern Supply购得,或从其它园艺供应商店购得)。将另一片单面释放纸放到种子上。将该装置放在1/4英寸(0.635cm)铝板之间,并且将其插入到6英寸×6英寸(15.24cm×15.24cm)预热到207℃的Carver热压机中。在低/接触压力下平衡该装置1分钟,然后将压力提高到6000磅最大压力。使该装置在最大压力下保持1分钟,并且快速减压。从热压机中取出该装置,并将其冷却到室温。所得到的膜复合材料显示出膜和种子之间的良好结合,可处理膜复合材料而不损失种子。实施例19
该实例说明,从实施例17得到的膜是可熔化的,能将膜制成基本上透明的用作可密封食品的储存袋,购物袋,杂货袋,和垃圾袋等等的袋子/小袋。重叠两片4英寸×4英寸(10.16cm×10.16cm)膜,用一片释放纸插入其间。释放纸应该比膜小,所以至少膜的三个边彼此直接接触。用Vertrod脉冲密封机(Model 24LAB-SP)密封重叠膜的三个边。将密封机设定在50%电压,60Psi压力,采样时间(1秒接触,5秒分开)6秒,和总共密封时间1分钟。所得到的袋子显示均匀的三面焊接密封。可选择性地密封第四面,以形成完全的密封袋。实施例20
该实施例说明本发明的水可溶的淀粉组合物。通过混合50%重量淀粉(晶胶),交联添加剂(交联添加剂的类型和用量如下表所示),和余量的水(已用硫酸调节至PH2)。其中使用乙二醛(40%水溶液),不需要调节水pH值。按照上面所述用于水溶解度的试验方法制备组合物和试验样品。结果如下表所示:
溶解度%添加剂 Parez631 乙二醛 Parez802
0.00% 37% 37% 37%
0.12% 16%
0.20% 10%
0.25% 28% 48%
0.32% 11%
0.40% 7%
0.50% 16% 16%
0.75% 14% 9%
1.00% 14% 6%
1.50% 11% 4%
在此引入贯穿全说明书的所有专利,专利申请(任何授权的,以及任何相应公开的外国专利申请),和所提到文献的公开内容作为参考。不特别地承认,但是在此引入作参考的任何文件教导或公开本发明。
除了说明和描述本发明的特殊试验方案外,可以进行的另外的各种变化和改进对于本领域普通技术人员是显而易见的,不背离本发明的精神和范围。
Claims (24)
1.一种组合物,它包括
(a)约20%-约99.99%重量淀粉,其中淀粉具有重均分子量约1,000至约2,000,000;和
(b)约0.001%-约10%重量高聚物,其中高聚物与淀粉基本上是相容的,并且高聚物的重均分子量至少是500,000。
2.权利要求1的组合物,其中约20%-约99%重量淀粉是支链淀粉。
3.权利要求2的组合物,其中淀粉的重均分子量为约1,500至约800,000。
4.权利要求1的组合物,其中高聚物的重均分子量为约800,000至约22,000,000。
5.权利要求4的组合物,其中高聚物的溶解参数和淀粉的溶解度参数之差小于10MPa1/2。
6.权利要求5的组合物,其中高聚物选自聚丙烯酰胺及其衍生物;聚丙烯酸,聚甲基丙烯酸和它们的酯;聚乙烯醇;聚乙烯亚胺;从上述所提到聚合物的单体的混合物制成的共聚物;和它们的混合物。
7.权利要求1的组合物,进一步包括至少一种添加剂,该添加剂选自具有至少一个羟基的羟基增塑剂,无羟基增塑剂,稀释剂和它们的混合物。
8.权利要求7的组合物,其中添加剂进一步包括选自氧化剂,交联剂,乳化剂,表面活性剂,剥离剂,润滑剂,加工助剂,莹光增白剂,抗氧剂,阻燃剂,染料,颜料,填料,蛋白及其碱性盐,可生物降解的合成聚合物,蜡,低熔融的合成热塑性聚合物,增粘树脂,增量剂,湿强度树脂和它们的混合物的材料。
9.权利要求7的组合物,其中淀粉的重均分子量为约1,500至约800,000,高聚物的重均分子量为约800,000至约22,000,000和高聚物的溶解参数和淀粉的溶解度参数之差小于10MPa1/2。
10.权利要求9的组合物,其中高聚物选自聚丙烯酰胺及其衍生物;聚丙烯酸,聚甲基丙烯酸和它们的酯;聚乙烯醇;聚乙烯亚胺;从上述所提到聚合物的单体的混合物制成的共聚物;和它们的混合物。
11.一种通过混合下列材料制备的组合物:
(a)约20%-约99.99%重量淀粉,其中淀粉具有重均分子量约1,000至约2,000,000;和
(b)约0.001%-约10%重量高聚物,其中高聚物与淀粉基本上是相容的,并且高聚物的重均分子量至少是500,000。
12.一种制备组合物的方法,该方法包括下列步骤:
(a)提供一种具有重均分子量约1,000至约2,000,000的淀粉;
(b)提供一种与淀粉基本上相容的高聚物,并且高聚物的重均分子量至少是500,000;
(c)提供至少一种选自具有至少一个羟基的羟基增塑剂,无羟基增塑剂,稀释剂和它们的混合物的添加剂;
(d)一起混合淀粉,高聚物和添加剂以形成混合物,
其中该混合物包括约20%-约99.99%重量淀粉,约0.001%-约10%重量高聚物,和余量的添加剂。
13.权利要求12的方法,其中步骤(d)包括将演粉、高聚物和添中剂加入到挤出机中,并挤出它们的混合物的步骤。
14.一种包括淀粉,高聚物和至少一种添加剂的组合物,其中该组合物具有:
(a)熔融剪切粘度小于50Pa·s;和
(b)拉伸粘度比没有高聚物的对比组合物的拉伸粘度高至少10倍。
15.权利要求14的组合物,其中该组合物具有单轴拉伸比为约5至约6000。
16.权利要求14的组合物,其中该组合物具有熔融温度范围为约80℃至约180℃。
17.权利要求12的组合物,其中添加剂选自具有至少一个羟基的羟基增塑剂,无羟基增塑剂,稀释剂和它们的混合物。
18.一种纤维,包括:
(a)约20%-约99.99%重量淀粉,其中淀粉具有重均分子量约1,000至约2,000,000;
(b)约0.001%-约10%重量高聚物,其中高聚物与淀粉基本上是相容的,并且高聚物的重均分子量至少是500,000。
19.权利要求18的纤维,其中纤维的平均直径小于50微米。
20.一种膜,包括:
(a)约20%-约99.99%重量淀粉,其中淀粉具有重均分子量约1,000至约2,000,000;
(b)约0.001%-约10%重量高聚物,其中高聚物与淀粉基本上是相容的,并且高聚物的重均分子量至少是500,000。
21.权利要求20的膜,其中膜厚度小于0.8密耳。
22.权利要求8的组合物,其中添加剂是包括乙醛酸化的聚丙烯酰胺的交联剂。
23.权利要求18的纤维,进一步包括乙醛酸化的聚丙烯酰胺。
24.权利要求20的膜,进一步包括乙醛酸化的聚丙烯酰胺。
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CN00106877A Pending CN1299844A (zh) | 1999-03-08 | 2000-03-08 | 可熔融加工的淀粉组合物 |
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Cited By (7)
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---|---|---|---|---|
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US9546296B2 (en) | 2014-12-15 | 2017-01-17 | Ppg Industries Ohio, Inc. | Coating compositions, coatings and methods for sound and vibration damping and water resistance |
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US10100216B2 (en) | 2014-12-15 | 2018-10-16 | Ppg Industries Ohio, Inc. | Coating compositions, coatings and methods for sound and vibration damping and water resistance |
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Families Citing this family (151)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ503231A (en) | 1999-03-08 | 2001-09-28 | Humatro Corp | Absorbent, flexible structure comprising pseudo-thermoplastic starch fibers, plasticizer (such as sorbitol, PVA) |
MXPA00012782A (es) * | 2000-03-07 | 2005-05-12 | Procter & Gamble | Composiciones de almidon procesables por fusion. |
AU2003201370B8 (en) * | 2000-03-07 | 2006-07-13 | The Procter & Gamble Company | Melt Processable Starch Compositions |
NZ517459A (en) * | 2000-03-07 | 2002-09-27 | Humatro Corp | Starch product comprising starch and a plasticiser or diluent |
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 |
ZA200007425B (en) * | 2000-12-12 | 2002-09-25 | Humatro Corp | Electro-spinning process for making starch filaments for flexible structure. |
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KR100402549B1 (ko) * | 2000-12-20 | 2003-10-22 | 휴마트로 코포래이션 | 가요성 구조물을 위한 전분 필라멘트의 전기방사 제조공정 |
US20030148690A1 (en) | 2001-05-10 | 2003-08-07 | Bond Eric Bryan | Multicomponent fibers comprising a dissolvable starch component, processes therefor, and fibers therefrom |
US6783854B2 (en) | 2001-05-10 | 2004-08-31 | The Procter & Gamble Company | Bicomponent fibers comprising a thermoplastic polymer surrounding a starch rich core |
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 |
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US20030077444A1 (en) | 2001-05-10 | 2003-04-24 | The Procter & Gamble Company | Multicomponent fibers comprising starch and polymers |
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EP1338405B1 (de) * | 2001-12-17 | 2006-07-26 | HB-Feinmechanik GmbH & Co.KG | Verfahren zur Herstellung von Formkörpern aus natürlichen Polymeren |
US6723160B2 (en) | 2002-02-01 | 2004-04-20 | The Procter & Gamble Company | Non-thermoplastic starch fibers and starch composition for making same |
CN1292111C (zh) * | 2002-02-01 | 2006-12-27 | 宝洁公司 | 非热塑性淀粉纤维和淀粉组合物及其制备方法 |
KR20020029050A (ko) * | 2002-03-29 | 2002-04-17 | 주식회사 나선하이테크 | 분해성 수지 및 그 제조방법 |
CN1172983C (zh) * | 2002-10-28 | 2004-10-27 | 汕头市奇佳机械厂有限公司 | 以淀粉为基料的全降解仿纸材料及其制备方法 |
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 |
US7947766B2 (en) | 2003-06-06 | 2011-05-24 | The Procter & Gamble Company | Crosslinking systems for hydroxyl polymers |
US7714065B2 (en) * | 2003-12-17 | 2010-05-11 | The Procter & Gamble Company | Polymeric structures comprising a hydrophile/lipophile system |
BRPI0417659A (pt) * | 2003-12-18 | 2007-04-03 | Procter & Gamble | processos de fiação giratória para a formação de fibras contendo polìmero de hidroxila |
WO2005087857A1 (ja) * | 2004-03-10 | 2005-09-22 | Agri Future Joetsu Co., Ltd. | 澱粉配合樹脂組成物、その成形品及びその製造方法 |
US20050238774A1 (en) * | 2004-04-22 | 2005-10-27 | Gold Medal Products Co. | Cotton candy machine |
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 |
US7281541B2 (en) * | 2004-06-16 | 2007-10-16 | Lorch Leonard G | Dental floss |
EP1799762B1 (en) * | 2004-10-05 | 2017-07-05 | Plantic Technologies Limited | Mouldable biodegradable polymer |
US20060134410A1 (en) | 2004-12-20 | 2006-06-22 | Mackey Larry N | Polymeric structures comprising an unsubstituted hydroxyl polymer and processes for making same |
US7572504B2 (en) | 2005-06-03 | 2009-08-11 | The Procter + Gamble Company | Fibrous structures comprising a polymer structure |
US7772391B2 (en) * | 2005-06-16 | 2010-08-10 | The Procter & Gamble Company | Ethersuccinylated hydroxyl polymers |
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 |
US8921244B2 (en) * | 2005-08-22 | 2014-12-30 | The Procter & Gamble Company | Hydroxyl polymer fiber fibrous structures and processes for making same |
US20160138225A1 (en) * | 2005-08-22 | 2016-05-19 | The Procter & Gamble Company | Hydroxyl Polymer Fiber Fibrous Structures and Processes for Making Same |
EP1792932B1 (de) * | 2005-12-01 | 2011-06-01 | R. Nussbaum AG | Medienführendes Bauelement |
DE602005023671D1 (de) * | 2005-12-15 | 2010-10-28 | Kimberly Clark Co | Biologisch abbaubare mehrkomponentenfasern |
AU2006341586B2 (en) | 2006-04-07 | 2011-05-12 | Kimberly-Clark Worldwide, Inc. | Biodegradable nonwoven laminate |
WO2007136552A2 (en) * | 2006-05-09 | 2007-11-29 | Jeffrey Jacob Cernohous | Compatibilized polymer processing additives |
DE602006018078D1 (de) | 2006-07-14 | 2010-12-16 | Kimberly Clark Co | Biologisch abbaubarer aliphatisch-aromatischer copolyester zur verwendung in vliesstoffen |
MX2009000527A (es) * | 2006-07-14 | 2009-01-27 | Kimberly Clark Co | Acido polilactico biodegradable para su uso en telas no tejidas. |
WO2008008067A1 (en) | 2006-07-14 | 2008-01-17 | Kimberly-Clark Worldwide, Inc. | Biodegradable aliphatic polyester for use in nonwoven webs |
CN101506291B (zh) * | 2006-08-04 | 2013-12-04 | 普朗蒂克科技有限公司 | 成型性的生物降解性聚合物 |
US7909003B2 (en) * | 2006-08-07 | 2011-03-22 | J. W. Pet Company, Inc. | Chew toys comprising biologically degradable material |
US10507083B2 (en) | 2006-12-28 | 2019-12-17 | Woodwelding Ag | Affixing an artificial element to a surface of dentine, enamel, bone, or a corresponding substitute material |
WO2008080239A1 (en) * | 2006-12-28 | 2008-07-10 | Woodwelding Ag | Method for affixing an artificial element to a surface of dentine, enamel, bone, or a corresponding substitute material, and set for carrying out the method |
EP2131808A1 (en) | 2007-03-01 | 2009-12-16 | Bioneedle Technologies Group B.V. | Implant containing destructurized starch |
EP2115008B1 (en) | 2007-03-01 | 2019-09-18 | De Staat der Nederlanden, vert. door de Minister van Volksgezondheid, Welzijn en Sport, namens de Minister, Projectdirectie ALT, het INTRAVACC | Biodegradable material based on opened starch |
KR100816497B1 (ko) * | 2007-05-23 | 2008-03-31 | 에스엔비환경주식회사 | 생분해성 고분자 수지 조성물로 이루어진 성형재의제조방법 |
US20090022960A1 (en) * | 2007-07-17 | 2009-01-22 | Michael Donald Suer | Fibrous structures and methods for making same |
US20090022983A1 (en) | 2007-07-17 | 2009-01-22 | David William Cabell | Fibrous structures |
US10024000B2 (en) | 2007-07-17 | 2018-07-17 | The Procter & Gamble Company | Fibrous structures and methods for making same |
US7972986B2 (en) * | 2007-07-17 | 2011-07-05 | The Procter & Gamble Company | Fibrous structures and methods for making same |
US8852474B2 (en) * | 2007-07-17 | 2014-10-07 | The Procter & Gamble Company | Process for making fibrous structures |
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 |
DE102008027261A1 (de) * | 2008-06-06 | 2009-12-10 | Martin-Luther-Universität Halle-Wittenberg | Verfahren zur Verbesserung der physikalisch-chemischen Eigenschaften bioabbaubarer Werkstoffe |
US8841386B2 (en) | 2008-06-10 | 2014-09-23 | Kimberly-Clark Worldwide, Inc. | Fibers formed from aromatic polyester and polyether copolymer |
FR2934272B1 (fr) * | 2008-07-24 | 2013-08-16 | Roquette Freres | Procede de preparation de compositions a base de matiere amylacee et de polymere synthetique. |
EP2370503B1 (en) * | 2008-12-03 | 2017-11-08 | EcoSynthetix Ltd. | Process for producing biopolymer nanoparticle biolatex compositions having enhanced performance and compositions based thereon |
US8194138B2 (en) * | 2008-12-17 | 2012-06-05 | Getac Technology Corporation | Portable electronic device and camera module thereof |
US20100159777A1 (en) * | 2008-12-18 | 2010-06-24 | Kimberly-Clark Worldwide, Inc. | Thermoplastic Starch Formed from an Enzymatically Debranched Starch |
FR2947557B1 (fr) * | 2009-07-03 | 2011-12-09 | Ulice | Procede de production de materiau biodegradable |
US8980059B2 (en) * | 2009-08-12 | 2015-03-17 | Nanopaper, Llc | High strength paper |
US8207651B2 (en) | 2009-09-16 | 2012-06-26 | Tyco Healthcare Group Lp | Low energy or minimum disturbance method for measuring frequency response functions of ultrasonic surgical devices in determining optimum operating point |
CA2775492C (en) * | 2009-09-29 | 2015-12-29 | Lbp Manufacturing, Inc. | Method for making seed-containing materials for packaging |
WO2011053906A1 (en) * | 2009-11-02 | 2011-05-05 | The Procter & Gamble Company | Polypropylene fibrous elements and processes for making same |
JP5292517B2 (ja) * | 2009-11-02 | 2013-09-18 | ザ プロクター アンド ギャンブル カンパニー | 繊維性構造体及びその作製方法 |
EP2496737A1 (en) * | 2009-11-02 | 2012-09-12 | The Procter & Gamble Company | Fibrous elements and fibrous structures employing same |
US20110104970A1 (en) * | 2009-11-02 | 2011-05-05 | Steven Lee Barnholtz | Low lint fibrous structures and methods for making same |
US8466337B2 (en) * | 2009-12-22 | 2013-06-18 | Kimberly-Clark Worldwide, Inc. | Biodegradable and breathable film |
US8573018B2 (en) * | 2010-01-15 | 2013-11-05 | Essex Group, Inc. | System for manufacturing wire |
CA2795139C (en) | 2010-03-31 | 2018-05-08 | The Procter & Gamble Company | Fibrous structure with absorbency, barrier protection and lotion release |
US8536087B2 (en) | 2010-04-08 | 2013-09-17 | International Imaging Materials, Inc. | Thermographic imaging element |
BRMU9000890U2 (pt) * | 2010-06-14 | 2012-02-28 | Aparecida Do Amaral Fátima | absorvente feminino descartável e biodegradável (ecologicamente correto) |
WO2011156878A1 (pt) * | 2010-06-14 | 2011-12-22 | Fatima Aparecida Do Amaral | "fralda descartável biodegradável (ecologicamente correta)". |
EP2588589B2 (en) * | 2010-07-02 | 2023-07-19 | The Procter & Gamble Company | Process for the production of a detergent product |
WO2012003349A2 (en) * | 2010-07-02 | 2012-01-05 | The Procter & Gamble Company | Dissolvable fibrous web structure article comprising active agents |
RU2541949C2 (ru) * | 2010-07-02 | 2015-02-20 | Дзе Проктер Энд Гэмбл Компани | Филаменты, содержащие активный агент, нетканые полотна и способы их получения |
BR112013000099A2 (pt) * | 2010-07-02 | 2016-05-17 | Procter & Gamble | filamentos compreendendo mantas de não tecido com agente ativo de não perfume e métodos de fabricação dos mesmos |
EP2588655B1 (en) | 2010-07-02 | 2017-11-15 | The Procter and Gamble Company | Method for delivering an active agent |
US20180163325A1 (en) | 2016-12-09 | 2018-06-14 | Robert Wayne Glenn, Jr. | Dissolvable fibrous web structure article comprising active agents |
JP5961611B2 (ja) | 2010-08-05 | 2016-08-02 | アルトリア クライアント サービシーズ リミテッド ライアビリティ カンパニー | 構造繊維と交絡させたタバコを含むファブリック |
US8978661B2 (en) | 2010-08-05 | 2015-03-17 | Altria Client Services Inc. | Composite smokeless tobacco products, systems, and methods |
US9315710B2 (en) | 2010-09-01 | 2016-04-19 | Reg Synthetic Fuels, Llc | Plastic phase change material and articles made therefrom |
US9102080B2 (en) | 2010-09-01 | 2015-08-11 | Reg Synthetic Fuels, Llc | Low cost process for manufacture of form-stable phase change material |
US8641311B2 (en) | 2010-10-11 | 2014-02-04 | The Procter & Gamble Company | Cleaning head for a target surface |
CN103210033B (zh) | 2010-11-23 | 2016-05-04 | 宝洁公司 | 热塑性淀粉组合物 |
US8889945B2 (en) | 2010-12-08 | 2014-11-18 | Kimberly-Clark Worldwide, Inc. | Elastic film containing a renewable starch polymer |
US9277976B2 (en) | 2011-01-24 | 2016-03-08 | Leonard G. Lorch | Dental floss |
US8381742B2 (en) | 2011-01-24 | 2013-02-26 | Leonard G. Lorch | Dental floss |
US10206765B2 (en) | 2011-01-24 | 2019-02-19 | Leonard G. Lorch | Dental floss |
US9277977B2 (en) | 2011-01-24 | 2016-03-08 | Leonard G. Lorch | Dental floss |
US8726444B2 (en) | 2011-03-28 | 2014-05-20 | The Procter & Gamble Company | Starch head for cleaning a target surface |
US8763192B2 (en) | 2011-03-28 | 2014-07-01 | The Procter & Gamble Company | Starch head having a stiffening member |
RU2617366C2 (ru) * | 2011-11-18 | 2017-04-24 | Рокетт Фрер | Меловальные краски на основе частично растворимых высокомолекулярных декстринов |
US11090900B2 (en) * | 2012-02-22 | 2021-08-17 | The Procter & Gamble Company | Embossed fibrous structures and methods for making same |
AU2013249341A1 (en) | 2012-04-19 | 2014-10-30 | The Procter & Gamble Company | Fibrous elements comprising fast wetting surfactants and methods for making same |
WO2013163139A1 (en) | 2012-04-23 | 2013-10-31 | The Procter & Gamble Company | Fibrous structures and methods for making same |
CA2875659A1 (en) | 2012-06-15 | 2013-12-19 | Nanopaper, Llc | Additives for papermaking |
EP2719826A1 (en) * | 2012-10-09 | 2014-04-16 | Metso Paper Inc. | Process for producing a fiber web and arrangement for producing a fiber web |
US20140259486A1 (en) * | 2013-03-14 | 2014-09-18 | Church & Dwight Co., Inc. | Plastic bristles infused with carbonate |
US9462827B2 (en) | 2013-03-14 | 2016-10-11 | Altria Client Services Llc | Product portion enrobing process and apparatus, and resulting products |
CA3152453A1 (en) | 2013-03-15 | 2014-09-18 | Shannon Maxwell Black | Methods and machines for pouching smokeless tobacco and tobacco substitute products |
EP2984217A1 (en) * | 2013-04-12 | 2016-02-17 | The Procter & Gamble Company | Fibrous structures comprising polysaccharide filaments |
JP6527861B2 (ja) * | 2013-10-16 | 2019-06-05 | ソルベイ アセトウ ゲーエムベーハー | アシル化方法 |
CA3181428A1 (en) | 2014-03-14 | 2015-09-17 | Altria Client Services Llc | Polymer encased smokeless tobacco products |
EP3597052B1 (en) | 2014-03-14 | 2023-12-27 | Altria Client Services LLC | Product portion enrobing process and apparatus |
US9827173B2 (en) | 2014-05-05 | 2017-11-28 | The Procter & Gamble Company | Porous dissolvable solid structure with two benefit agents and methods of forming an aqueous treatment liquor therefrom |
US9937111B2 (en) | 2014-05-05 | 2018-04-10 | The Procter & Gamble Company | Consumer product comprising a fibrous web solid structure with a silicone conditioning agent coating |
US9861559B2 (en) | 2014-05-05 | 2018-01-09 | The Procter & Gamble Company | Consumer product comprising a porous, dissolvable, fibrous web solid structure with a silicone coating |
US9867762B2 (en) | 2014-05-05 | 2018-01-16 | The Procter & Gamble Company | Consumer product comprising a porous dissolvable solid structure and silicone conditioning agent coating |
US10982013B2 (en) | 2014-06-02 | 2021-04-20 | Anavo Technologies, Llc | Modified biopolymers and methods of producing and using the same |
CN104451932B (zh) * | 2014-12-16 | 2017-02-22 | 广东中烟工业有限责任公司 | 一种醋酸纤维丝线及其制备方法 |
CA2977645C (en) | 2015-02-24 | 2019-08-13 | The Procter & Gamble Company | Process for molecular weight reduction of ethersuccinylated polysaccharides |
CN104801134B (zh) * | 2015-04-03 | 2016-05-11 | 福建工程学院 | 一种利用仿生叶片提高除尘效率的多级除尘器 |
US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
US11111363B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
US10995201B2 (en) | 2015-06-30 | 2021-05-04 | BiologiQ, Inc. | Articles formed with biodegradable materials and strength characteristics of the same |
US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
US10752759B2 (en) | 2015-06-30 | 2020-08-25 | BiologiQ, Inc. | Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength |
US10920044B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Carbohydrate-based plastic materials with reduced odor |
US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
US11149144B2 (en) | 2015-06-30 | 2021-10-19 | BiologiQ, Inc. | Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material |
US10919203B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Articles formed with biodegradable materials and biodegradability characteristics thereof |
US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
US11111355B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Addition of biodegradability lending additives to plastic materials |
US9480749B1 (en) * | 2015-10-07 | 2016-11-01 | King Saud University | Method of preparing a nanocomposite film including starch nanofibers |
CA3004346A1 (en) | 2015-11-23 | 2017-06-01 | Tethis, Inc. | Coated particles and methods of making and using the same |
US10640928B2 (en) * | 2016-09-19 | 2020-05-05 | Mercer International Inc. | Absorbent paper products having unique physical strength properties |
US11666514B2 (en) | 2018-09-21 | 2023-06-06 | The Procter & Gamble Company | Fibrous structures containing polymer matrix particles with perfume ingredients |
CN109498833B (zh) * | 2018-12-12 | 2021-05-28 | 济南格莱威医疗科技有限公司 | 一种医用可吸收多聚糖复合材料及其用途 |
WO2020132120A1 (en) * | 2018-12-18 | 2020-06-25 | North Carolina State University | Fast disintegrating paper products and methods of making |
CN113747798A (zh) * | 2019-04-26 | 2021-12-03 | 三得利控股株式会社 | 粉末组合物 |
CA3134222C (en) | 2019-06-28 | 2024-01-16 | The Procter & Gamble Company | Dissolvable solid fibrous articles containing anionic surfactants |
CN114269842A (zh) | 2019-08-12 | 2022-04-01 | 索卢特姆科技有限公司 | 复合物及其用途 |
CN110670243A (zh) * | 2019-10-28 | 2020-01-10 | 福建恒安集团有限公司 | 一种竹纤维增强无纺布的制备方法及其在产妇巾的应用 |
US20220371237A1 (en) * | 2019-10-30 | 2022-11-24 | Cruz Foam, Inc. | Organic polymer processing |
AT522596B1 (de) | 2019-11-04 | 2020-12-15 | Lenzing Plastics Gmbh & Co Kg | Zahnseide |
JP2023528405A (ja) * | 2020-06-02 | 2023-07-04 | バイオロジック インコーポレイテッド | デンプンベースのポリマー材料を含む不織布材料及び繊維 |
CN113931010B (zh) * | 2020-07-13 | 2023-11-10 | 杭州特种纸业有限公司 | 一种燃油滤纸及其制备方法 |
MX2023001042A (es) | 2020-07-31 | 2023-02-16 | Procter & Gamble | Bolsa fibrosa soluble en agua que contiene granulos para el cuidado del cabello. |
CN113293515B (zh) * | 2020-08-07 | 2023-08-25 | 深圳市三雅科技有限公司 | 一种熔喷布生产装置 |
CN112127000B (zh) * | 2020-09-04 | 2023-05-02 | 河北艾科瑞纤维有限公司 | 一种远红外腈纶纤维及其制备方法 |
WO2022271595A1 (en) | 2021-06-23 | 2022-12-29 | International Imaging Materials, Inc. | Thermographic imaging element |
CN114772898B (zh) * | 2022-05-17 | 2023-06-30 | 浙江华东工程建设管理有限公司 | 一种简易絮凝脱水装置 |
Family Cites Families (191)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR587222A (fr) | 1923-12-21 | 1925-04-14 | Rhodiaseta | Perfectionnements dans les procédés et appareils destinés à la fabrication des fis ou filaments artificiels |
BE354193A (zh) | 1927-09-14 | |||
FR707191A (fr) | 1929-12-07 | 1931-07-03 | Ver Fur Chemische Ind Ag | Procédé pour fabriquer des fils artificiels |
US1855256A (en) * | 1932-01-29 | 1932-04-26 | L A Young Spring & Wire Corp | Grille |
US2116942A (en) * | 1934-11-28 | 1938-05-10 | Richard Schreiber Gastell | Method and apparatus for the production of fibers |
US2109333A (en) * | 1936-03-04 | 1938-02-22 | Richard Schreiber Gastell | Artificial fiber construction |
US2123992A (en) * | 1936-07-01 | 1938-07-19 | Richard Schreiber Gastell | Method and apparatus for the production of fibers |
US2160962A (en) * | 1936-07-01 | 1939-06-06 | Richard Schreiber Gastell | Method and apparatus for spinning |
US2158416A (en) * | 1937-07-28 | 1939-05-16 | Richard Schrelber Gastell | Method and apparatus for the production of artificial fibers |
US2187306A (en) * | 1937-07-28 | 1940-01-16 | Richard Schreiber Gastell | Artificial thread and method of producing same |
US2570449A (en) * | 1946-01-19 | 1951-10-09 | Horsak Drahomir | Method of production of synthetic material from starch or starch containing substances |
US2902336A (en) | 1957-10-22 | 1959-09-01 | Avebe Coop Verkoop Prod | Process for the production of amylose articles by extrusion of aqueous sodium hydroxide solution thereof into concentrated aqueous ammonium sulphate solution |
US3088188A (en) * | 1960-01-04 | 1963-05-07 | Monsanto Chemicals | Manufacture of shaped objects of acrylonitrile polymer by wet spinning |
NL263573A (zh) * | 1960-04-13 | 1900-01-01 | ||
BE615950A (zh) | 1961-04-03 | |||
US3280229A (en) | 1963-01-15 | 1966-10-18 | Kendall & Co | Process and apparatus for producing patterned non-woven fabrics |
DE1435461C3 (de) | 1964-02-22 | 1978-04-06 | Fa. Carl Freudenberg, 6940 Weinheim | Spinndüse zum Schmelzspinnen von Fadenscharen |
US3556932A (en) * | 1965-07-12 | 1971-01-19 | American Cyanamid Co | Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith |
US3499074A (en) | 1966-09-07 | 1970-03-03 | Department Of Agriculture & Ec | Method of making amylostic filaments and fibers |
US3556933A (en) * | 1969-04-02 | 1971-01-19 | American Cyanamid Co | Regeneration of aged-deteriorated wet strength resins |
US3700623A (en) | 1970-04-22 | 1972-10-24 | Hercules Inc | Reaction products of epihalohydrin and polymers of diallylamine and their use in paper |
US4069026A (en) * | 1970-06-29 | 1978-01-17 | Bayer Aktiengesellschaft | Filter made of electrostatically spun fibres |
US4143196A (en) * | 1970-06-29 | 1979-03-06 | Bayer Aktiengesellschaft | Fibre fleece of electrostatically spun fibres and methods of making same |
SU375282A1 (zh) * | 1970-12-18 | 1973-03-23 | ||
US3865603A (en) * | 1972-07-17 | 1975-02-11 | Nat Starch Chem Corp | Modified starch-extended gelatin compositions |
CH570493A5 (zh) | 1973-08-16 | 1975-12-15 | Battelle Memorial Institute | |
US3954361A (en) | 1974-05-23 | 1976-05-04 | Beloit Corporation | Melt blowing apparatus with parallel air stream fiber attenuation |
GB1527592A (en) * | 1974-08-05 | 1978-10-04 | Ici Ltd | Wound dressing |
JPS51125468A (en) | 1975-03-27 | 1976-11-01 | Sanyo Chem Ind Ltd | Method of preparing resins of high water absorbency |
US4064605A (en) | 1975-08-28 | 1977-12-27 | Toyobo Co., Ltd. | Method for producing non-woven webs |
CA1079016A (en) | 1976-03-25 | 1980-06-10 | Donald S. Greif | Water insensitive starch fibers and a process for the production thereof |
US4079025A (en) | 1976-04-27 | 1978-03-14 | A. E. Staley Manufacturing Company | Copolymerized starch composition |
US4069177A (en) | 1976-06-21 | 1978-01-17 | Theodore Smith | Water absorbing and urine stable step-wise grafted starch-polyacrylonitrile copolymers |
DE2634539C2 (de) | 1976-07-31 | 1983-08-25 | Hoechst Ag, 6230 Frankfurt | Verfahren zur Herstellung von saugfähigen, modifizierten Stärkeethern und deren Verwendung |
US4061611A (en) * | 1976-09-22 | 1977-12-06 | The Sherwin-Williams Company | Aqueous compositions containing starch ester dispersants |
US4243480A (en) | 1977-10-17 | 1981-01-06 | National Starch And Chemical Corporation | Process for the production of paper containing starch fibers and the paper produced thereby |
CH620483A5 (zh) | 1977-12-22 | 1980-11-28 | Battelle Memorial Institute | |
JPS54105652A (en) | 1978-02-07 | 1979-08-18 | Daikin Ind Ltd | Rankine cycle working fluid |
DE2960875D1 (en) * | 1978-04-19 | 1981-12-10 | Ici Plc | A method of preparing a tubular product by electrostatic spinning |
US4223101A (en) | 1978-07-17 | 1980-09-16 | Inmont Corporation | Method of producing fibrous structure |
DE2965672D1 (en) * | 1978-10-10 | 1983-07-21 | Ici Plc | Production of electrostatically spun products |
US4380570A (en) | 1980-04-08 | 1983-04-19 | Schwarz Eckhard C A | Apparatus and process for melt-blowing a fiberforming thermoplastic polymer and product produced thereby |
US4340563A (en) | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
US4418026A (en) | 1980-05-12 | 1983-11-29 | Courtaulds Limited | Process for spinning cellulose ester fibres |
US5720832A (en) | 1981-11-24 | 1998-02-24 | Kimberly-Clark Ltd. | Method of making a meltblown nonwoven web containing absorbent particles |
ZA828635B (en) | 1981-11-24 | 1983-10-26 | Kimberly Clark Ltd | Microfibre web product |
GB2121286B (en) | 1982-06-02 | 1985-11-06 | Ethicon Inc | Improvements in synthetic vascular grafts, and methods of manufacturing such grafts |
US4515859A (en) * | 1982-09-16 | 1985-05-07 | American Cyanamid Company | Hydrophilic, water-absorbing acrylonitrile polymer fiber |
JPS5984095A (ja) | 1982-11-04 | 1984-05-15 | Hitachi Ltd | 熱交換壁 |
JPS59102316U (ja) | 1982-12-27 | 1984-07-10 | 積水化成品工業株式会社 | 合成樹脂シ−ト用成形装置 |
US4637859A (en) * | 1983-08-23 | 1987-01-20 | The Procter & Gamble Company | Tissue paper |
DE3401639A1 (de) | 1984-01-19 | 1985-07-25 | Hoechst Ag, 6230 Frankfurt | Vorrichtung zum herstellen eines spinnvlieses |
US4673438A (en) | 1984-02-13 | 1987-06-16 | Warner-Lambert Company | Polymer composition for injection molding |
JPS6140341A (ja) * | 1984-07-31 | 1986-02-26 | Nippon Shokuhin Kako Kk | 澱粉−ポリアクリロニトリル系高吸水性物質及びその製造方法 |
JPS6140341U (ja) | 1984-08-17 | 1986-03-14 | 株式会社ミツプス | 切離式ロ−ル巻き連続袋 |
JPH0788603B2 (ja) * | 1985-07-26 | 1995-09-27 | チッソ株式会社 | 吸水性繊維 |
GB8602115D0 (en) | 1986-01-29 | 1986-03-05 | Courtaulds Plc | Absorbent fibres |
US4818463A (en) | 1986-04-26 | 1989-04-04 | Buehning Peter G | Process for preparing non-woven webs |
GB8616416D0 (en) * | 1986-07-04 | 1986-08-13 | Ethicon Inc | Polyurethane medical prostheses |
EP0265249B1 (en) | 1986-10-21 | 1993-03-10 | Mitsui Petrochemical Industries, Ltd. | Melt blow die |
GB2205323B (en) | 1987-03-09 | 1991-01-30 | Warner Lambert Co | Destructurized starch and process for making same |
GB2206888B (en) | 1987-07-07 | 1991-02-06 | Warner Lambert Co | A destructurized starch and a process for making same |
US5277761A (en) | 1991-06-28 | 1994-01-11 | The Procter & Gamble Company | Cellulosic fibrous structures having at least three regions distinguished by intensive properties |
US4855179A (en) | 1987-07-29 | 1989-08-08 | Arco Chemical Technology, Inc. | Production of nonwoven fibrous articles |
GB2208651B (en) | 1987-08-18 | 1991-05-08 | Warner Lambert Co | Shaped articles made from pre-processed starch |
US4769081A (en) * | 1987-09-18 | 1988-09-06 | A. E. Staley Manufacturing Division Of Staley Continental, Inc. | Readily dispersible starch compositions |
US4853168A (en) | 1987-12-23 | 1989-08-01 | National Starch And Chemical Corporation | Process for spinning starch fibers |
GB2214918B (en) * | 1988-02-03 | 1992-10-07 | Warner Lambert Co | Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material |
US5095054A (en) | 1988-02-03 | 1992-03-10 | Warner-Lambert Company | Polymer compositions containing destructurized starch |
US4909976A (en) | 1988-05-09 | 1990-03-20 | North Carolina State University | Process for high speed melt spinning |
US5444113A (en) | 1988-08-08 | 1995-08-22 | Ecopol, Llc | End use applications of biodegradable polymers |
US5024789A (en) * | 1988-10-13 | 1991-06-18 | Ethicon, Inc. | Method and apparatus for manufacturing electrostatically spun structure |
US5362777A (en) | 1988-11-03 | 1994-11-08 | Ivan Tomka | Thermoplastically processable starch and a method of making it |
IT1234783B (it) | 1989-05-30 | 1992-05-27 | Butterfly Srl | Procedimento per la produzione di composizioni a base di amido destrutturato e composizioni cosi ottenute |
US5079054A (en) * | 1989-07-03 | 1992-01-07 | Ominiglass Ltd. | Moisture impermeable spacer for a sealed window unit |
US5288765A (en) | 1989-08-03 | 1994-02-22 | Spherilene S.R.L. | Expanded articles of biodegradable plastics materials and a method for their production |
EP0438585A4 (en) * | 1989-08-14 | 1992-05-13 | Board Of Regents Of The University Of Nebraska | Biodegradable polymers |
US4968238A (en) | 1989-09-22 | 1990-11-06 | E. I. Du Pont De Nemours And Company | Apparatus for making a non-woven sheet |
US5079354A (en) | 1989-10-27 | 1992-01-07 | Kimberly-Clark Corporation | Method for making absorbent starch |
US5098519A (en) * | 1989-10-30 | 1992-03-24 | James River Corporation | Method for producing a high bulk paper web and product obtained thereby |
US5211815A (en) * | 1989-10-30 | 1993-05-18 | James River Corporation | Forming fabric for use in producing a high bulk paper web |
JP2933230B2 (ja) * | 1989-12-12 | 1999-08-09 | 花王株式会社 | 衛生品用繊維状吸収体 |
US5145631A (en) | 1990-01-04 | 1992-09-08 | The Dow Chemical Company | Melt blowing process for producing microfibers of syndiotactic vinyl aromatic polymers |
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 |
JPH04100913A (ja) | 1990-08-20 | 1992-04-02 | Toray Ind Inc | 生分解性繊維、生分解性フィルムおよびそれらの製造法 |
EP0498892B1 (en) | 1990-08-29 | 1995-11-15 | Kuraray Co., Ltd. | Fiber sizing agent |
US5122048A (en) | 1990-09-24 | 1992-06-16 | Exxon Chemical Patents Inc. | Charging apparatus for meltblown webs |
JPH04146217A (ja) | 1990-10-02 | 1992-05-20 | Toray Ind Inc | 生分解性繊維 |
KR960008112B1 (ko) * | 1991-05-03 | 1996-06-20 | 노바폰트 쏘시에떼 퍼 아찌오니 | 전분 및 열가소성 고분자 기초 생물분해성 고분자 조성물 |
EP0525245A1 (en) | 1991-08-01 | 1993-02-03 | NOVAMONT S.p.A. | Disposable absorbent articles |
DE4116404A1 (de) | 1991-05-18 | 1992-11-19 | Tomka Ivan | Polymermischung fuer die herstellung von folien |
DE4117628C3 (de) | 1991-05-29 | 1999-02-11 | Inventa Ag | Verfahren und Vorrichtung zur Herstellung von Stärkeschmelze sowie nach diesem Verfahren erhältliche Produkte |
DE4119915C2 (de) | 1991-06-17 | 1994-07-21 | Inventa Ag | Stärke-Polymer-Mischung, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
DE4122212C2 (de) * | 1991-07-04 | 1994-06-16 | Inventa Ag | Thermoplastisch verarbeitbare Masse aus Stärke und Acrylatcopolymeren |
DE4136694C2 (de) * | 1991-11-07 | 1996-10-10 | Inventa Ag | Stärkefaser oder Stärke-modifizierte Faser, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
SG47625A1 (en) | 1991-11-14 | 1998-04-17 | Bio Tech Biolog Naturverparkun | Biodegradable mould material |
CA2070589C (en) * | 1991-12-19 | 2000-11-28 | Kimberly-Clark Corporation | Method of preparing a nonwoven web of poly (vinyl alcohol) fibers |
US6242102B1 (en) | 1991-12-26 | 2001-06-05 | Biotec Biologische Natuverpackungen Gmbh & Co., Kg | Single or multilayer foil having a layer containing thermoplastically processable starch |
US5427614A (en) | 1992-02-14 | 1995-06-27 | Warner-Lambert Company | Starch based formulations |
GB9210955D0 (en) * | 1992-05-22 | 1992-07-08 | Courtaulds Plc | Fibres and filaments |
US5292239A (en) * | 1992-06-01 | 1994-03-08 | Fiberweb North America, Inc. | Apparatus for producing nonwoven fabric |
US5703160A (en) | 1992-07-15 | 1997-12-30 | Solvay S.A. | Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid |
US6277899B1 (en) * | 1992-08-03 | 2001-08-21 | Novamont S.P.A. | Biodegradable polymeric composition |
IT1256914B (it) | 1992-08-03 | 1995-12-27 | Novamont Spa | Composizione polimerica biodegradabile. |
US5679145A (en) * | 1992-08-11 | 1997-10-21 | E. Khashoggi Industries | Starch-based compositions having uniformly dispersed fibers used to manufacture high strength articles having a fiber-reinforced, starch-bound cellular matrix |
US5405682A (en) | 1992-08-26 | 1995-04-11 | Kimberly Clark Corporation | Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and elastomeric thermoplastic material |
US5866251A (en) | 1992-10-16 | 1999-02-02 | Eridania Beghin-Say | Device and process for the production of fibrious starch materials |
US5844023A (en) | 1992-11-06 | 1998-12-01 | Bio-Tec Biologische Naturverpackungen Gmbh | Biologically degradable polymer mixture |
JPH06212594A (ja) | 1992-12-02 | 1994-08-02 | Honshu Paper Co Ltd | 剥離紙用原紙 |
US5368690A (en) | 1992-12-23 | 1994-11-29 | National Starch And Chemical Investment Holding Corporation | Method of papermaking using crosslinked cationic/amphoteric starches |
US5585171A (en) * | 1993-01-11 | 1996-12-17 | Graver Chemical | Adsorbent filter bed with pliant and stiff members |
NL9300245A (nl) * | 1993-02-08 | 1994-09-01 | Verstraeten Beheersmij Bv | Werkwijze voor het aanbrengen van een damwand in de bodem, alsmede een geprefabriceerd wandelement voor het toepassen van de werkwijze. |
JPH06269239A (ja) | 1993-03-22 | 1994-09-27 | Toray Ind Inc | 釣 糸 |
EP0622407A1 (en) | 1993-04-28 | 1994-11-02 | Hoechst Celanese Corporation | Polymer blend composed of cellulose acetate and starch acetate used to form fibers, films and plastic materials and a process to prepare said blends |
US5393336A (en) * | 1993-06-01 | 1995-02-28 | National Starch And Chemical Investment Holding Corporation | Water resistant high amylose corrugating adhesive with improved runnability |
SG48938A1 (en) | 1993-07-28 | 1998-05-18 | Biotec Biolog Naturverpack | Formed starch polymer |
US5357784A (en) | 1993-08-04 | 1994-10-25 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Lubricated flow elongational rheometer |
JPH0760833A (ja) | 1993-08-23 | 1995-03-07 | Mitsubishi Chem Corp | インフレーション樹脂フィルムの成形方法 |
CA2134594A1 (en) | 1994-04-12 | 1995-10-13 | Kimberly-Clark Worldwide, Inc. | Method for making soft tissue products |
US5403875A (en) * | 1994-05-12 | 1995-04-04 | Rohm And Haas Company | Melt-processed polymer blends |
US5506277A (en) * | 1994-06-30 | 1996-04-09 | Kimberly-Clark Corporation | Starch foams for absorbent articles |
JP3309886B2 (ja) | 1994-07-06 | 2002-07-29 | 特種製紙株式会社 | デンプン繊維の製造方法 |
US5489014A (en) * | 1994-08-03 | 1996-02-06 | Journomat Ag | Apparatus for checking coins and reading cards in an article vending machine |
IT1274603B (it) | 1994-08-08 | 1997-07-18 | Novamont Spa | Materiali espansi plastici biodegradabili |
DE4438961A1 (de) * | 1994-10-31 | 1996-05-02 | Hoechst Ag | Wursthüllen aus thermoplastischer Stärke und Verfahren zu deren Herstellung |
US5804605A (en) * | 1994-11-10 | 1998-09-08 | The Procter & Gamble Company | Absorbent material |
US5476616A (en) | 1994-12-12 | 1995-12-19 | Schwarz; Eckhard C. A. | Apparatus and process for uniformly melt-blowing a fiberforming thermoplastic polymer in a spinnerette assembly of multiple rows of spinning orifices |
US5688468A (en) | 1994-12-15 | 1997-11-18 | Ason Engineering, Inc. | Process for producing non-woven webs |
AU700005B2 (en) | 1994-12-22 | 1998-12-17 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Technical and non-technical textile products and packaging materials |
IT1272871B (it) | 1995-01-10 | 1997-07-01 | Novamont Spa | Composizioni termoplastiche compredenti amido ed altre componenti di origine naturale |
JPH08206250A (ja) | 1995-02-02 | 1996-08-13 | Eiwa:Kk | Pcbの分解方法 |
EP0814184A4 (en) | 1995-02-14 | 1999-04-14 | Chisso Corp | BIODEGRADABLE FIBER AND NONWOVEN TEXTILE |
JP3107830B2 (ja) | 1995-04-07 | 2000-11-13 | ビオ−テック ビオロギッシェ ナトゥーアフェアパックンゲン ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | 生物学的に分解可能なポリマー混合物 |
AT405287B (de) | 1995-05-11 | 1999-06-25 | Teich Ag | Verwendung von weichmachern für die thermoplastifizierung von stärke |
JPH0941224A (ja) | 1995-08-01 | 1997-02-10 | Tokushu Paper Mfg Co Ltd | 微細粒子複合化デンプン繊維の製造方法 |
WO1997013920A1 (fr) * | 1995-10-13 | 1997-04-17 | Uni-Charm Corporation | Voile biodegradable et hydrolysable |
US5693279A (en) | 1996-03-13 | 1997-12-02 | Hoechst Celanese Corp. | Starch acetate and blends thereof with metal chelates |
JPH09276331A (ja) * | 1996-04-09 | 1997-10-28 | Chisso Corp | 吸収性物品 |
DE19624641A1 (de) * | 1996-06-20 | 1998-01-08 | Biotec Biolog Naturverpack | Biologisch abbaubarer Werkstoff, bestehend im wesentlichen aus oder auf Basis thermoplastischer Stärke |
JP3741170B2 (ja) * | 1996-06-21 | 2006-02-01 | チッソ株式会社 | 水崩壊性複合繊維及び不織布、吸収性物品 |
ATE215969T1 (de) | 1996-08-09 | 2002-04-15 | Biotec Biolog Naturverpack | Thermoplastisch verarbeitbare stärke bzw. stärkederivat-polymermischungen |
GB9624031D0 (en) | 1996-11-19 | 1997-01-08 | Allied Colloids Ltd | Manufacture of paper |
DE19701523A1 (de) * | 1997-01-17 | 1998-07-23 | Basf Ag | Polymermodifizierte anionische Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung |
CA2285458A1 (en) | 1997-03-14 | 1998-09-17 | Gerald Biby | Degradable composite polymer and method of making such composite polymer |
US5737953A (en) | 1997-03-18 | 1998-04-14 | Aluminum Company Of America | Process for stretch forming hollow metal bodies |
US5857498A (en) * | 1997-06-04 | 1999-01-12 | Weavexx Corporation | Papermaker's double layer forming fabric |
US5945480A (en) | 1997-07-31 | 1999-08-31 | Kimberly-Clark Worldwide, Inc. | Water-responsive, biodegradable fibers comprising polylactide modified polylactide and polyvinyl alcohol, and method for making the fibers |
US6106913A (en) | 1997-10-10 | 2000-08-22 | Quantum Group, Inc | Fibrous structures containing nanofibrils and other textile fibers |
US6413505B1 (en) * | 1998-04-09 | 2002-07-02 | Nationa L Starch And Chemical Investment Holding Corporation | Nonionically derivatized starches and their use in non-aerosol, low VOC hair cosmetic compositions |
US6110590A (en) | 1998-04-15 | 2000-08-29 | The University Of Akron | Synthetically spun silk nanofibers and a process for making the same |
US6261679B1 (en) * | 1998-05-22 | 2001-07-17 | Kimberly-Clark Worldwide, Inc. | Fibrous absorbent material and methods of making the same |
US6013223A (en) | 1998-05-28 | 2000-01-11 | Biax-Fiberfilm Corporation | Process and apparatus for producing non-woven webs of strong filaments |
FR2779439B1 (fr) * | 1998-06-08 | 2000-08-25 | Roquette Freres | Composition diluante et desintegrante, son procede d'obtention et son utilisation |
US6303000B1 (en) | 1998-08-31 | 2001-10-16 | Omnova Solutions Inc. | Paper making process utilizing a reactive cationic starch composition |
WO2000043423A1 (en) | 1999-01-25 | 2000-07-27 | Kimberly-Clark Worldwide, Inc. | Modified polysaccharides containing amphiphilic moieties |
US6517678B1 (en) | 2000-01-20 | 2003-02-11 | Kimberly-Clark Worldwide, Inc. | Modified polysaccharides containing amphiphillic hydrocarbon moieties |
NZ503231A (en) | 1999-03-08 | 2001-09-28 | Humatro Corp | Absorbent, flexible structure comprising pseudo-thermoplastic starch fibers, plasticizer (such as sorbitol, PVA) |
WO2000069960A1 (en) | 1999-05-14 | 2000-11-23 | The Dow Chemical Company | Process for preparing starch and epoxy-based thermoplastic polymer compositions |
US6302997B1 (en) | 1999-08-30 | 2001-10-16 | North Carolina State University | Process for producing a pulp suitable for papermaking from nonwood fibrous materials |
EP1103655A1 (en) | 1999-11-25 | 2001-05-30 | Coöperatieve Verkoop- en Productievereniging van Aardappelmeel en Derivaten 'AVEBE' B.A. | A process for making paper |
US20030022581A1 (en) | 1999-12-29 | 2003-01-30 | Fu-Jya Daniel Tsai | Biodegradable thermoplastic nonwoven webs for fluid management |
US6231970B1 (en) | 2000-01-11 | 2001-05-15 | E. Khashoggi Industries, Llc | Thermoplastic starch compositions incorporating a particulate filler component |
US20020015854A1 (en) * | 2000-05-10 | 2002-02-07 | Billmers Robert L. | Paper coating composition comprising a blend of modified high amylose starch and polyvinyl alcohol |
US6528088B1 (en) * | 2000-06-01 | 2003-03-04 | A. E. Staley Manufacturing Co. | Highly flexible starch-based films |
US6372361B1 (en) * | 2000-07-07 | 2002-04-16 | National Starch And Chemical Investment Holding Corporation | Coating for paper products |
US6365002B1 (en) | 2000-08-07 | 2002-04-02 | National Starch And Chemical Investment Holding Corporation | Amphoteric starches used in papermaking |
US20030203196A1 (en) | 2000-11-27 | 2003-10-30 | Trokhan Paul Dennis | Flexible structure comprising starch filaments |
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 |
US6843888B2 (en) * | 2001-03-13 | 2005-01-18 | National Starch And Chemical Investment Holding Corporation | Starches for use in papermaking |
US6461999B1 (en) * | 2001-03-28 | 2002-10-08 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-containing lubricant systems for oil field applications |
US20020168518A1 (en) * | 2001-05-10 | 2002-11-14 | The Procter & Gamble Company | Fibers comprising starch and polymers |
US6946506B2 (en) * | 2001-05-10 | 2005-09-20 | The Procter & Gamble Company | Fibers comprising starch and biodegradable polymers |
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 |
US20030072731A1 (en) * | 2001-05-15 | 2003-04-17 | Cynthia Gulian | Dip coating compositions containing starch or dextrin |
US7276201B2 (en) * | 2001-09-06 | 2007-10-02 | The Procter & Gamble Company | Process for making non-thermoplastic starch fibers |
US20030099691A1 (en) * | 2001-11-16 | 2003-05-29 | Susan Lydzinski | Films containing starch |
JP4100913B2 (ja) | 2002-01-15 | 2008-06-11 | 株式会社リコー | 情報再生装置、データ管理情報取得方法、データ管理情報取得プログラム、記憶媒体、及び再生システム |
US6723160B2 (en) * | 2002-02-01 | 2004-04-20 | The Procter & Gamble Company | Non-thermoplastic starch fibers and starch composition for making same |
GB0208418D0 (en) * | 2002-04-11 | 2002-05-22 | Univ Aston | Polymeric fibre |
JP4146217B2 (ja) | 2002-11-25 | 2008-09-10 | 三洋電機株式会社 | 通信端末装置 |
US7254379B2 (en) * | 2004-07-09 | 2007-08-07 | Silicon Storage Technology, Inc. | RF receiver mismatch calibration system and method |
US20060134410A1 (en) * | 2004-12-20 | 2006-06-22 | Mackey Larry N | Polymeric structures comprising an unsubstituted hydroxyl polymer and processes for making same |
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 |
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 |
WO2012003365A1 (en) * | 2010-07-02 | 2012-01-05 | The Procter & Gamble Company | Filaments comprising an ingestible active agent nonwoven webs and methods for making same |
EP2588589B2 (en) * | 2010-07-02 | 2023-07-19 | The Procter & Gamble Company | Process for the production of a detergent product |
RU2591704C2 (ru) * | 2012-01-04 | 2016-07-20 | Дзе Проктер Энд Гэмбл Компани | Содержащие активные агенты волокнистые структуры с множеством областей |
EP3097183A1 (en) * | 2014-01-24 | 2016-11-30 | The Procter & Gamble Company | Web comprising a microorganism-containing fibrous element and method for making same |
-
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