CN1175289A - 工业与非工业用纺织品以及包装材料 - Google Patents

工业与非工业用纺织品以及包装材料 Download PDF

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CN1175289A
CN1175289A CN95197700A CN95197700A CN1175289A CN 1175289 A CN1175289 A CN 1175289A CN 95197700 A CN95197700 A CN 95197700A CN 95197700 A CN95197700 A CN 95197700A CN 1175289 A CN1175289 A CN 1175289A
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thermoplastic starch
starch
polymeric blends
textile fabrics
long filament
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J·勒克斯
W·波默兰茨
H·舒密特
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BioTec Biologische Naturverpackungen GmbH and Co KG
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00Protecting plants
    • A01G13/02Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0237Devices for protecting a specific part of a plant, e.g. roots, trunk or fruits
    • DTEXTILES; PAPER
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    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/42Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • DTEXTILES; PAPER
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    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02JFINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B1/00Constructional features of ropes or cables
    • D07B1/02Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/12Physical properties biodegradable
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2869Coated or impregnated regenerated cellulose fiber fabric
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3927Including a paper or wood pulp layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674Nonwoven fabric with a preformed polymeric film or sheet
    • Y10T442/675Ester condensation polymer sheet or film [e.g., polyethylene terephthalate, etc.]

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  • Decoration Of Textiles (AREA)
  • Artificial Filaments (AREA)
  • Auxiliary Devices For And Details Of Packaging Control (AREA)
  • Woven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明提供由完全生物可降解的再生原料制成并具有极好机械性能的工业和非工业用纺织品以及包装材料。上述制品是由一种用一种可热塑加工的淀粉和一种在可能的情况下以热塑性淀粉为主成分的生物可降解聚合物混合物制造的挤出物。举例来说,这样制得的长丝为提高其强度而用塑料工业中常用的方法予以拉伸。所述长丝或纤维适于制造各种稀松、半密或紧密组织的织物。

Description

工业与非工业用纺织品以及包装材料
本发明涉及织物与包装材料及其制造方法和所述纺织品的各种工业和非工业性用途。
不论工业或非工业应用领域的纺织品和纺织复合材料以及包装材料和类似产品,既可由天然原料制成,也可由半合成和全合成原料,如塑料制成。
除了关于服装纺织品及卫生用品的所谓皮肤亲和性的重要论据之外,生物可降解性的论据也日渐充分。有了这种生物可降解性,特别是所谓的一次性产品或所谓的用毕即弃用品可以毫无问题的销毁。在这方面,举例来说,涉及卫生用品、衬料、毛絮、网、非织造布等。这些产品有一部分是用相当贵的棉花或半合成材料,如纤维素,粘胶等做的,而全合成材料因其对皮肤的亲和性差而不太受欢迎。除天然原料通常具有足够的生物可降解性之外,同时还起决定性不利作用的则是,这些材料的机械性能一般并不突出。但机械性能好得多的合成原料由于皮肤亲和性差和可降解性差而不能解决所提出的难题。
因此本发明的目的是,提供工业和非工业使用的以及作包装材料用的纺织原料,这些原料具有良好的生物可降解性,必要时具有良好的皮肤亲和性,而且机械性能大于最低可接受值。
举例来说,由现有技术已知化学纤维的生产,由所产化纤可制得纺织原料。在化学纤维制造过程中,化学纤维直接用熔体或通过许多中间步骤纺成丝,随后进行拉伸以提高强度。另外,由塑料工业还已知热塑性合成材料的拉伸。然而,所有这些已知的人造纤维均包含不能完全生物降解的基本部分,尤其是那些为了达到一定的性能,例如特别是机械性能而附加的组成部分。
因此本发明的另一目的是为纺织原料的制造提供原始材料,例如特别是长丝、纤维、单丝等等,这些原始材料具有良好的生物可降解性,在需要的情况下具有良好的皮肤亲和性,并且机械性能大于最低可接受值。
本发明提出权利要求1全文所述,既用于工业目的又用于非工业目的纺织制品以及包装材料。
此外,还提出尤其权利要求9全文所述高强长丝、纤维及单丝和类似材料的制造方法。
提出了既用于工业又用于非工业目的的纺织制品、包装材料,以及这些纺织制品所需的原材料如长丝、纤维、单丝、非织造布、毛絮、机织物、网和类似原材料热塑性可加工淀粉和/或至少含一种聚合物混合物,这种聚合物混合物含有可热塑加工的淀粉。
由WO90/05161已知,可加工热塑淀粉或简称热塑性淀粉是由天然淀粉借助于可增塑化的材料制造的。制造时重要的是,使天然淀粉的破坏(Destrukturieren)和增塑在几乎无水的情况下进行,亦即,制造热塑性淀粉时,以淀粉/增塑剂混合物重量为准计,水含量明显在5%(重量)以下,特别在1-2%(重量)以下。特别适用的增塑剂是甘油和山梨醇,但也可以采用溶解度参数在淀粉溶解度参数范围内的其它添加剂。热塑性淀粉的制备已于上述WO90/05161中详细说明,故此不再赘述该现有技术。
适于用来制造本发明所要求保护的纺织制品、包装材料及其所用原料的,除纯净的热塑性淀粉之外,还有连同热塑性淀粉还至少含有下列一种组分的所谓的聚合物混合物或聚合物共混物:
-用作相介质(Phasenvermittler)的一种聚烯烃以及嵌段共聚物,
-一种聚烯烃以及一种乙烯丙烯酸酯马来酸酐共聚物,
-一种纤维素衍生物,如纤维素醚、纤维素酯或纤维素乙酸酯-丁酸酯混合酯,
-一种憎水性生物可降解聚合物,如一种脂肪族聚酯、一种憎水性
蛋白质或聚乙烯醇,
-一种由常用二元醇和芳香族及脂肪族二元羧酸制备的芳族聚酯和
/或聚酯共聚物,
-一种聚酯酰胺。
与针对热塑性淀粉的各聚合物混合物、聚烯烃以及用作相介质的嵌段共聚物有关的内容可参阅WO91/16375。
与以热塑性淀粉为主料的聚合物混合物、聚烯烃以及乙烯丙烯酸酯马来酸酐共聚物有关的内容可参阅WO92/20740。
由热塑性淀粉及纤维素衍生物组成的各聚合物混合物,已在EP-A-542155中详细说明。
在EP-A-596437中详细解释了仍以热塑性淀粉为主料的聚合物混合物及一种生物可降解的憎水性聚合物。
就技术方案而言,本发明从这样的基本思想出发:即原料如长丝或强力丝、纤维、单丝、散纤维和类似材料,由可热塑加工的淀粉的挤出物和/或必要时由一种以热塑性淀粉为基料的生物可降解的聚合物混合物的挤出物来制造。因此,这样制造的本发明原料可完全生物降解。
热塑性淀粉与其它优选聚合物组分的组合,旨在使热塑性淀粉原本已相当好的机械性能进一步改善,并在可能情况下适应应用目的。特别是热塑性淀粉和上述其它优选聚合物混合配料的组合,旨在使热塑性淀粉原本已良好的性能进一步最优化,以满足应用上的要求。这样特别是由热塑性淀粉和脂肪族以及芳香族聚酯,聚酯氨基甲酸酯和类似化合物组成的聚合物混合物特别宜于形成结晶。有时混合物配料涉及单独不可生物降解的聚合物,例如芳香族聚酯,但是它与其它混合物配料如脂肪族聚酯和热塑淀粉组合时,还是能被生物降解。
特别是聚已内酯、聚羟基丁酸、聚乳酸、聚羟基苯甲酸、聚羟基丁酸-羟基戊酸共聚物和类似聚合物作为与热塑性淀粉特别合适的混合配料精选出来。要提及的特别还有以脂肪族二元羧酸和脂肪族二元醇为原料生成的脂肪族聚酯,例如均聚物或聚丁二酸丁二酯-己二酸丁二酯共聚物和聚丁二酸乙二酯-己二酸乙二酯共聚物。其它用于制造本发明所定义纺织原料如纺织制品的热塑性淀粉的混合配料为下列材料:
-明胶、蛋白质、玉米醇溶蛋白、多糖、纤维素衍生物、聚乳酸、聚乙烯醇、聚醋酸乙烯酯、聚丙烯酸酯、糖醇、虫膠、酪朊、聚缩醛、聚酯氨基甲酸乙酯、由脂肪族二元醇和芳香族二元羧酸生成的共聚酯,脂肪酸衍生物、卵磷酯、脱乙酰壳多糖、聚酯酰胺。
此外,还可将天然纤维加入本发明所定义、用于制造纺织原料和纺织制品的原材料,所加的天然纤维如棉花,羊毛,剑麻,苧麻,亚麻或胡麻。
当然,也可在原料中添加其它添加剂和助剂,例如在制造纤维、单丝、长丝和类似材料时常用的添加剂和助剂。
适合于制造纤维、单丝、长丝、薄膜之类的用于工业和非工业的纺织制品以及包装材料可用和优选的聚合物混合物的例子列举在下列表1中。该表中,七个实施例不仅包括已用于制造热塑性淀粉的组分,也包括制造本发明所建议聚合混合物时可用的热塑性淀粉的混合配料。此外,该表中罗列了加工条件,而且还特别罗列了聚合物混合物制造过程中挤压机内存在的水分,它无一例外地均为<0.1%(重量)。最后,在表中列举了所制聚合物混合物的优选应用可能性。不言而喻,此表只包括一些实施例,而所有在本说明开头提到的组分均适于同热塑性淀粉混合来制造工业用、非工业用纺织制品以及包括材料的原料。表1                                               实施例
    实施例编号     1     2     3     4     5     6     7
    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
    3PLA%      -      -      -      -     48.8     55.0      -
    4聚酰胺1     40.5     61.2      -      -      -      -     67.5
    5聚酯1      -      -     55.2     60.6      -      -      -
    6PCL%      -      -      -      -     4.0     2.0      -
     H2O%    <0.1    <0.1    <0.1    <0.1    <0.1    <O.1    <0.1
    7挤压     ZSK40     ZSK40     ZSK40     ZSK40     ZSK40     ZSK40     ZSK40
     T℃     220     206     203     210     215     210     220
     压力巴     6.5     2.5     1.5     1.5     6.2     7.5     0.5
     MFlg/10′     9     13     12.5     13     8.5     8.0     22
     切粒     4mm     4mm     4mm     4mm     4mm     4mm     4mm
     Gra H2O%     3.5     3.6     3.4     3.6     3.4     3.4     3.0
     应用
     吹塑薄膜      +      +      +      +      +      +      -
     平膜      +      +      +      +      +      +      -
     板      +      +      +      +      +      +      -
 注射模塑件     +     -   +     -     +     -     -
    纤维     -     +   -     +     -     +     +
1Starch(淀粉)=干燥至含3.5%H2O的天然马铃薯淀粉,
sorbitol(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,经过除气予
       以脱水按EP0397819中所述已知方法由淀粉、山梨醇和甘
       油组成的无水热塑性淀粉;
3PLA(聚乳酸树脂)=Mitsui Toatsu Chemicals LACEAH100 MFR13
                   190℃2.16kg;
4Polyamid(聚酰胺)1=Bayer BAK1095聚酯酰胺MFI2.5150℃
                     2.16kg;
5Polyester(聚酯)1=BASFZK242/108由脂肪族二元醇和脂肪族
                    /芳香族二元羧酸制得的共聚酯,190℃时
                    MVR3.0/2.16kg;
6PCL(聚己内酯)=Union Carbide Tone聚合物P-787MFI1.0125
                 ℃44psig/10min;
7Extrusion Equipment(挤压设备)=Werner & Pfleiderer ZSK40;
下面举例详细阐明本发明所定义的原料,例如制造纺织品用的高强度长丝和高强度纤维的制造。
在挤压机中改性的原料成薄膜出料和切成长丝或直接成丝条出料,进行拉伸以提高强度,并随后卷绕或用在线方法直接进而加工成机织物或类似产品。本发明长丝的最佳加工温度特别是当拉伸时约在30-40℃之间,从而大大低于通常为100℃的合成热塑性材料加工温度。当于约30-40℃温度下拉伸时,大分子得以定向,它使断裂强度提高,透明度增加,对水和水蒸汽作用的稳定性提高。出乎预料的是,经此处理,丝条的最大断裂力比同截面的未拉伸长丝约提高10次方(Zehnerpotenz)。
挤压机中由可热塑加工淀粉和以热塑性淀粉为主料的生物可降解性聚合物混合物组成的改性原料混合物,可先如DE-B-4228016中所述加工成薄膜,随后切成长丝并予以拉伸,或者直接用在线方法经多孔喷丝板挤压成许多单根丝条,随后直接予以拉伸。丝的拉伸在室温或最高至60℃的温度下单轴向进行,但优选在30-40℃下于空气或其它介质中,例如在由水和/或溶剂组成的拉伸浴中,也或在其它气相介质中进行。拉伸比基本上在1∶5和1∶20之间;优选为1∶8。由原料混合物挤压成的薄片提供以下加工的可能性:直接在薄膜挤出装置(吹塑膜或平膜)后将薄膜在线连续切成许多单根丝,形成的丝随后按上述工艺参数在线拉伸并单根以强力窄带形式卷绕在丝筒子上。这样得到的生物可降解的窄带可以窄带形式直接应用,也或可以卷绕成的单个丝筒为原料在其它机器上以一步法继续加工成机织物、网、纺织品或绳子。此外,也可由形成的单个丝筒用两步法通整经的中间工序制造上述的机织物、网、纺织品或绳子。
除此之外,薄膜原料以卷材形式在一个工序中切成丝条,将其按上述工艺参数在线进行拉伸和并轴。形成的由许多根抗断裂的单根丝组成经轴可在后续工序中加工成机织物、网、纺织品或绳子。
同样,可将按上述工艺参数单轴拉伸的薄膜用作原料(以卷材形式)。此薄膜于一工序中用机器切成单根抗断裂的丝,并加工成机织物、网、纺织品或绳子,或者以窄带形式单根卷绕成筒。
按另外的加工可能性,将薄膜原料以卷材形式在一工序中切成丝条,按上述的工艺参数拉伸并随即在线用同一机器加工成机织物、网、纺织品或绳子,或者以窄带形式单根卷成筒。
本发明长丝的优越性能可用所进行的薄膜拉伸试验来说明。由热塑性淀粉和可降解的脂肪族聚酯(Bio Flex BF102)形成的生物可降解材料制成的薄膜条,其尺寸长/宽/厚为50mm/2mm/0.025mm在温度为35℃以1∶8的比例进行拉伸。在多次的抗拉试验中确证,在所施加的断裂负荷为12.8-14.8N时,该薄膜条的断裂强度或抗拉强度或抗拉强度在216N和250N/mm2之间。与此相反,以未经拉伸的薄膜条作对比试验的断裂强度在断裂负荷为1.3-1.9N时仅约为25.1-38.1N/mm2。下面进行的薄膜抗拉试验1和2用各自所属的拉伸图1和2(图1和2)说明此结果其中h是样品厚度,Ao是样品截面积,Fmax是最大断裂负荷,δmax是以样品截面积为准计的最大断裂强度,S-(Fmax)是以mm为单位的样品总伸长值和ε-(Fmax)以%表示的原始测定长度的伸长率。比较试验3用图表3(图3)表明未拉伸长丝在拉力负荷下的结果,其中测得延伸开始时附加的拉力(F伸长)和同时作用的拉伸应力。
1.用拉伸后的薄膜进行的薄膜抗拉试验(图1)
试验参数:
样品宽度                      =2mm
测量长度                      =50mm(相应于压力板的间距)
开始测量时的予应力            =0.2N
断裂标准                      =2N
至予应力时的速度              =500mm/min
测试速度                      =500mm/min
所有三个样品都在35℃温度下以1∶8比例进行拉伸。
                  试验结果序号   h      Ao     F-max   δ-max   S-(Fmax) ε-(Fmax)
   mm     mm2      N       N/mm2     mm        %1   0.027   0.054    12.765   236.389    26.20     52.392   0.028   0.056    13.748   245.500    25.74     50.883   0.030   0.060    13.027   217.117    27.75     55.50
2.用拉伸后的薄膜进行的薄膜抗拉试验(图2)
试验参数:
试验参数相当于第1个薄膜抗拉试验的参数
                 试验结果序号   h      Ao     F-max    δ-max   S-(Fmax) ε-(Fmax)
   mm     mm2      N        N/mm2     mm        %1   0.028   0.056    13.893    248.089    26.51     52.492   0.032   0.064    13.866    216.656    27.74     55.003   0.028   0.056    14.015    250.268    26.24     51.874   0.031   0.062    14.760    238.065    26.67     53.333.用未拉伸薄膜进行的薄膜抗拉试验(图3)试验参数:试验参数相当于第1个薄膜抗拉试验的参数
              试验结果序号   标志-22       h           Ao     F-max   δ-max
    备注         mm          mm2      N      N/mm21    纵向伸长     0.025        0.050    1.257    25.142    纵向伸长     0.025        0.050    1.906    38.120序号  S-(Fmax)  ε-(Fmax)      F伸长  拉伸应力
      mm         %          N        N/mm21     209.58      419.17       0.85       172     267.92      535.84       1.05       21
正如试验所表明那样,本发明纤维或长丝可用化学纤维制造中普通的拉伸方法来加工。长丝在35℃进行拉伸就已很有效,而且明显改善了断裂强度。此外,长丝的整个制造,包括拉伸以连续且一步运行的方法来进行。由可完全生物降解的材料制成的本发明长丝或纤维例如适于制成窄带和/或单丝作为最终产品应用于农艺和园艺(种植用窄带之类),作为包装材料(包括绳子和带子之类),或作为中间产品在经轴上或单个丝筒子上继续加工成生物可降解的网、机织物、纺织品或绳子。此外,还可制成特别牢固、可完全生物降解的纤维和/或经窄带/单丝的加捻或编织制成绳子。这些特别牢固的带子和/或绳子可进而加工成网、机织物和各种纺织品。
这类产品的用途举例来说有:
-稀松或半密或紧密结构的包装袋(拉舍尔经编袋或网袋等等),
例如用于装马铃薯、柑果类、洋葱,以及玩具、家用物品以及各
种类型产物品,
-在林业或园艺中再造/新植时用于各种树木和植物的轻型护栏,例
如防止野兽啃咬或防冲蚀,
-门窗防蝇网或蚊帐,
-用于树木包装(例如圣诞树或灌木)和在园艺和农艺中用于做包
捆树根的网,
-抗张垃圾袋,
-各种滤布,
-可撕裂带卷、捆扎带卷(Umreifungsbanderolen.)之类形式的可焊
 接带子卷材,
-体育运动领域(羽毛球、乒乓球、排球之类)用网,
-家畜饲养用格网,例如兔栏,鸽棚,
-各种护网,例如用于人身保护、防范岩石塌方、防冲蚀,也用于
 坡地葡萄园种值、农业和园艺,
-网子卷材用于建筑业等等,以及家务劳动必须品(Heimwerkerbedarf),
-养鱼和捕捞/淡水捕捞业用品,
-各种纺织品,例如台布、窗帘、太阳罩、盖蓬、遮阳布蓬等等,
-农业用纺织品,例如提前收获、防风、防太阳用的盖地布,
-用于干法非织造布的纤维(气流铺网),
-热粘非织造布,
-纺织的包装带,例如用于捆扎纸箱,捆扎底板,
-超净室中用的防护服或一次性衣物,例如帽子、手套、鞋罩、罩衣和工作服。
本发明长丝在纺织领域的其它用途是加工成尿布产品。这种全可生物降解尿布的构造如下:
外封套是生物可降解的薄膜,例如同DE-B-4228016中所述者,它以轧辊粘合法粘合在一层柔软的纤维素层上。另外一些柔软的纤维素层装于其中,这些纤维素层含有SAP制品(淀粉接技高聚物形式的超强吸水剂,Superabsorber)并放置得能强力吸水。内芯是由生物可降解材料的非织造布组成的。具有上述结构的尿布可用高生产速度来制造,因为原始产品是卷材,而且各层用热熔方法叠合在一起。尿布的形状和大小例如通过冲压由卷材来制造。用热熔固定边缘和弹性腿带和腹带上的橡皮筋。尿布前部和后背部的固定采用粘合条或搭扣。
本发明长丝或纤维本身也可以制成松散材料,例如纺织纤维或长丝,并可加工成非织造布、毛毡和纺织复合材料。纤维网可通过针刺、成网眼,加捻和纤维的熔融和热融予以固定。纤维网也可通过附加的丝条、机织物或编织物加固,例如相同种类或不同种类的可降解材料,如纤维素纤维,源于棉花、木棉、剑麻、亚麻、大麻、黄麻、洋麻、苧麻、椰子的植物纤维和源于羊毛或真丝的纤维。上述的纤维网、毛毡和纺织复合材料可用于制造过滤布、人造革、用毕即弃物品,如擦尘布、抹布、尿布、工业和服装业上作绝缘材料,例如防护服。
其它纺织品、纺织半成品与成品以及由此制得的制成品,其例子为线状物如纱、亚麻布、股线、绳、索、捻线;平面状物如粘着产品、毛毡、针刺毛毡、针织品及编织品,或者膨松物品如短绒、毛絮、过滤毡和抛光用毛絮。
权利要求书
按照条约第19条的修改
1.工业及非工业用的纺织品,其中含热塑性淀粉和/或至少一种含热塑性淀粉的聚合物混合物,而且所述热塑性淀粉是通过破坏天然淀粉或借助至少一种增塑剂增塑天然淀粉,同时使其水含量减至以淀粉/增塑剂混合物为准计的5%(重量)以下而得到。
2.用作包装材料的纺织品,其中含有热塑性淀粉和/或至少一种含热塑性淀粉的聚合物混合物,而且所述热塑性淀粉是通过破坏天然淀粉或借助至少一种增塑剂增塑天然淀粉,同时使其水含量减至以淀粉/增塑剂混合物为准计的5%(重量)以下而得到。
3.尤其权利要求1或2所述的纺织制品,其特征是,所述热塑性淀粉含有甘油、山梨醇和/或它们的混合物作增塑剂或软化剂。
4.尤其权利要求1至3中任一项所述的纺织制品,其特征是,所述聚合物混合物除热塑性淀粉之外还至少含有一种下列组分:
-用作相介质的一种聚烯烃以及一种嵌段共聚物,
-一种聚烯烃及一种乙烯丙烯酸酯-马来酸酐共聚物,
-一种纤维素衍生物,如纤维素酯、纤维素醚或者一种纤维素乙酸酯丁酸酯混合酯,
-一种憎水性生物可降解聚合物,例如
-脂肪族聚酯如聚己内酯、聚羟基丁酸、一种聚羟基丁酸-羟基戊酸共聚物和/或聚乳酸,
-一种以聚葡糖酸、聚乳酸、聚羟基丁酸、聚己内酯、聚羟基苯甲酸、聚酯聚氨酯为主成分的脂肪族共聚酯,
-由脂肪族二元醇和芳香族二元酸形成的聚酯,
-一种憎水性蛋白质如玉米醇溶蛋白和/或未100%水解的聚乙烯醇。
5.尤其权利要求1至3中任一项所述的纺织制品,其特征是,所述聚合物混合物除热塑性淀粉外还至少含有下列一种组分:
明胶、多糖、聚交酯、聚乙酸乙烯酯、聚丙烯酸酯、糖醇、虫膠、酪朊、脂肪酸衍生物,卵 磷酯、脱乙酰壳多糖、合成生物聚合物(Xant an)和/或一种聚酯酰胺。
6.尤其权利要求1至5中任一项所述的纺织制品,其特征是,所述热塑性淀粉和/或含有热塑性淀粉的聚合物混合物至少含有下列的一种添加剂:
一种天然染料、一种憎水剂、一种乳化剂、瓜耳豆胶、一种交联剂、一种填料和/或一种溶胀剂或增塑剂。
7.尤其权利要求1至6中任一项所述的纺织制品,其特征是,所述热

Claims (20)

1.工业及非工业用纺织制品,其中包含热塑性淀粉和/或至少一种含有热塑性淀粉的聚合物混合物。
2.用作包装材料的纺织制品,其中包含热塑性淀粉和/或至少一种含有热塑性淀粉的聚合物混合物。
3.尤其权利要求1或2所述的纺织制品,其特征是,所述热塑性淀粉含有甘油、山梨醇和/或它们的混合物作增塑剂或软化剂。
4.尤其权利要求1至3中任一项所述的纺织制品,其特征是,所述聚合物混合物除热塑性淀粉之外还至少含有一种下列组分:
-用作相介质的一种聚烯烃以及一种嵌段共聚物,
-一种聚烯烃及一种乙烯丙烯酸酯-马来酸酐共聚物,
-一种纤维素衍生物,如纤维素酯、纤维素醚或者一种纤维素乙酸酯丁酸酯混合酯,
-一种憎水性生物可降解聚合物,例如
-脂肪族聚酯如聚己内酯、聚羟基丁酸、一种聚羟基丁酸-羟基戊酸共聚物和/或聚乳酸,
一种以聚葡糖酸、聚乳酸、聚羟基丁酸、聚己内酯、聚羟基苯甲酸、聚酯聚氨酯为主成分的脂肪族共聚酯,
-由脂肪族二元醇和芳香族二元酸形成的聚酯,
-一种憎水性蛋白质如玉米醇溶蛋白和/或未100%水解的聚乙烯醇。
5.尤其权利要求1至3中任一项所述的纺织制品,其特征是,所述聚合物混合物除热塑性淀粉外还至少含有下列一种组分:
明胶、多糖、聚交酯、聚乙酸乙烯酯、聚丙烯酸酯、糖醇、虫膠、酪朊、脂肪酸衍生物,卵 磷酯、脱乙酰壳多糖、合成生物聚合物(Xantan)和/或一种聚酯酰胺。
6.尤其权利要求1至5中任一项所述的纺织制品,其特征是,所述热塑性淀粉和/或含有热塑性淀粉的聚合物混合物至少含有下列的一种添加剂:
一种天然染料、一种憎水剂、一种乳化剂、瓜耳豆胶、一种交联剂、一种填料和/或一种溶胀剂或增塑剂。
7.尤其权利要求1至6中任一项所述的纺织制品,其特征是,所述热塑性淀粉和/或含有热塑性淀粉的聚合物混合物中掺加一种天然纤维,例如棉花、羊毛、西沙尔麻(剑麻)、苧麻、亚麻或长麻。
8.主要由纤维、长丝、纤维网、薄膜、短绒、毛絮、一种机织物、网、毛毡和类似材料以及这些材料相结合组成或制成的纺织品,它们至少部分由热塑性淀粉和/或一种含有热塑性淀粉的聚合物混合物制成的。
9.用于制造权利要求1至8中任一项所述的纺织制品的长丝、纤维、单丝等的方法,其特征是,对热塑性淀粉和/或以热塑性淀粉为主成分的聚合物混合物以纺织技术上已知的方法进行挤压并相应地进行加工。
10.至少部分由再生原料如热塑性淀粉组成的高强丝的制造方法,其特征是,该方法的工艺步骤为:
a)将热塑性可加工的淀粉和可能情况下以热塑性淀粉为主成分的生物可降解的聚合物混合物连续挤压成薄膜,
b)将薄膜切成长丝,
c)将长丝以1∶4至1∶20的拉伸比进行拉伸,
d)将长丝卷绕起来,并在可能有的情况下进而加工成织物或诸如此类。
11.至少部分由再生原料如热塑性淀粉组成的高强长丝的制造方法,其特征是,该方法的工艺步骤为:
a)将热塑性可加工的淀粉和可能情况下以热塑性淀粉为主成分的生物可降解的聚合物混合物连续挤压成长丝,
b)将长丝以1∶4至1∶20的拉伸比进行拉伸,以及
c)将长丝卷绕起来,并在可能情况下进而加工成织物或诸如此类。
12.尤其权利要求10或11所述的方法,其特征是,所述拉伸在小于60℃的温度下,特别是在30至40℃下进行。
13.尤其权利要求10至12中任一项所述的方法,其特征是,所述拉伸在气相或液相介质中进行。
14.尤其权利要求12所述的方法,其特征是,将所述长丝在空气或水中进行拉伸。
15.特别是按权利要求10至14中任一项所述的方法,其特征是,所述拉伸为单轴进行。
16.尤其权利要求10至15中任一项所述的方法,其特征是,所述工艺步骤a)至d)或a)至c)连续地并一步进行。
17.尤其权利要求10至15中任一项所述的方法,其特征是,将所述长丝连续并一步直接加工成织物和诸如此类产品。
18.权利要求10至17中任一项所述的高强丝作为最终产品在农艺和园艺和/或作为包装材料或制造生物可降解的网、织物、毛毡、非织造布、短绒、毛絮、稀松、半密和紧密组织的纺织品或绳索方面的应用。
19.权利要求1至8中任一项所述的纺织制品在制造卫生用品如尿布、卫生带、防备大小便失禁用产品及床垫方面的应用。
20.制造卫生产品如尿布、卫生带、防备大小便失禁用产品或床垫的方法,其特征是,在一基本上由热塑性淀粉或以热塑性淀粉为主成分的聚合物混合物组成的纤维构成的纤维网上敷覆一层纤维素短绒或一层柔软的纤维素层,随后在可能有的情况下再敷覆一层由干燥纸(Trockenpapier)组成的纤维素网及主要由热塑性淀粉或以热塑淀粉为主成分的混合物组成的短绒层或毛絮层,并最后敷覆一护层,该护层仍主要由热塑性淀粉和/或以热塑性淀粉为主成分的聚合物混合物组成。
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GR3031457T3 (en) 2000-01-31
KR980700469A (ko) 1998-03-30
AU3992195A (en) 1996-07-10
WO1996019599A1 (de) 1996-06-27
ES2137550T3 (es) 1999-12-16
ATE184333T1 (de) 1999-09-15
DE59506810D1 (de) 1999-10-14
JPH10511145A (ja) 1998-10-27
CA2208357A1 (en) 1996-06-27
EP0799335A1 (de) 1997-10-08
EP0799335B1 (de) 1999-09-08
DK0799335T3 (da) 2000-03-20
US6218321B1 (en) 2001-04-17

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