CN1098157C - 布状完全可生物降解的和/或可堆肥化处理的复合材料及其制造方法 - Google Patents

布状完全可生物降解的和/或可堆肥化处理的复合材料及其制造方法 Download PDF

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CN1098157C
CN1098157C CN98803666A CN98803666A CN1098157C CN 1098157 C CN1098157 C CN 1098157C CN 98803666 A CN98803666 A CN 98803666A CN 98803666 A CN98803666 A CN 98803666A CN 1098157 C CN1098157 C CN 1098157C
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compostization
lactic acid
polymer
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CN1251068A (zh
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吴百湶
菲利普·埃雷
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Fiber Networks France
Clopay Plastic Products Co Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2555/00—Personal care
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    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet

Abstract

完全可生物降解和/或可堆肥化的膜(30)和完全可生物降解和/或可堆肥化的无纺织物的一种完全可生物降解和/或可堆肥化的软布状复合材料(110)及其制造方法。完全可生物降解和/或可堆肥化的无纺织纤维网(40)和完全可生物降解和/或可堆肥化的膜(30)被层压在一起。层压件以增量方式由拉伸机(80)拉伸生产出完全可生物降解和/或可堆肥化的复合材料(110)，它比当可生物降解和/或可堆肥化无纺织网粘结于可生物降解和/或可堆肥化膜时所生产的复合材料要更软一些。本发明的软布状特征是许多应用所需要的，其中包括尿布，裤子，外科长上衣，床单，服饰，医用产品等。

Description

布状完全可生物降解的和/或可堆肥化处理的复合材料及其制造方法
本发明的领域
本发明涉及完全可生物降解和/或可堆肥化处理的且具有布状手感的无纺织物和塑料膜的复合材料，以及涉及它们的制造方法。
本发明的背景
可生物降解和/或可堆肥化产品有助于保护环境资源并且防止附加废物的产生。制造商和消费者都知道有限量的掩埋空间和其它废弃场所，并坚定不移地寻求可生物降解和/或可堆肥化的产品取代非生物降解和/或非堆肥化的产品。生物降解性和/或堆肥化处理性的需要对于一次性、高频率使用的产品如婴儿尿布、妇女卫生巾产品、医院手术室用挡帷(hospital drapes)等是尤其重要的。然而，除可生物降解和/或可堆肥化处理性之外，重要的是该产品具有软布状手感达到舒适和美感的目的。
可生物降解和/或可堆肥化的膜的生产在现有技术中是已知的。US专利5,407,979公开了由三种组分构成的可生物降解的热塑性膜：链烷酰基聚合物，变性淀粉，和乙烯共聚物。这些组分能够被挤出并且膜可被拉伸而形成透气性的膜。US专利5,200,247公开了含有链烷酰基聚合物/聚乙烯醇(PVA)共混物的可生物降解的热塑性膜。US专利5,196,247公开了可堆肥化的聚合物复合片材及其制造方法或堆肥化方法。该复合材料含有第一层和第三层水不溶性聚合物和中间层的水溶性聚合物。
可生物降解的和/或可堆肥化的无纺织物的生产在现有技术中也是已知的。US专利申请序列号No.08/284,001，连同法国专利2.709.500的主题，公开了从乳酸得到的熔融稳定性聚合物用于生产无纺织物材料的用途。所有的单丝纤维都是基于从L乳酸和D乳酸得到的聚合物。聚合物借助于单螺杆挤出机或双螺杆挤出机进行熔融和挤出，并转移至纺丝泵。熔化的聚合物然后通过过滤器，然后通过喷丝板进行纺丝，冷却和拉伸。冷却可借助于冷空气进行，拉伸可借助于空气的抽吸作用或吹气来进行。拉伸比一般是2-12倍。纺丝系统之后接着是铺层装置，后者将单丝纤维随机铺列在传送带上。传送带将无纺织网输送至加热轧光机使单丝纤维粘结在一起并形成无纺织物。所得到的无纺织物用作一次性制品的唯一组件或部分组件。
熔融稳定的丙交酯聚合物(lactide polymer)的生产公开于US专利5,539,081。该′081专利公开了在催化剂存在下将丙交酯聚合物链与稳定剂结合以形成熔融稳定的丙交酯聚合物。熔融稳定的聚合物是这样一种聚合物，在实际的设备中进行加工的熔体加工温度下具有足够低的粘度和具有充分低的降解速度，以使得降解不影响其物理性能或引起设备结垢。该反应能够很好地表征；反应的水和丙交酯单体副产物可通过对聚丙交酯进行脱挥发分而除去，并且为了在熔体加工步骤中减少解聚，稳定剂是必需的。
US专利5382461公开了一种纺粘纤维和挤出的热塑性膜的增量 拉伸的层压件。公开了用于该网和膜的各种不同的材料，其中的一 些是可生物降解的。
然而，仍然需要生产完全可生物降解和/或可堆肥化的复合材料，当然还要保持软布状手感。这一类型的复合材料可用于卫生织物，例如婴儿尿布，成人尿失禁用品，妇女卫生用品和抹布；用于医用织物，例如长上衣，挡帷，防护衣，头和鞋覆盖物，以及流体和颗粒阻隔材料；以及用于园艺和农业覆盖物，例如用于育种的保护地膜，其中产品的所需环境和触觉性能都是人们所要寻求的。
本发明概述
本发明涉及一层或多层完全可生物降解的和/或可堆肥化的塑料膜和一层或多层完全可生物降解和/或可堆肥化的无纺织物网的完全可生物降解和/或可堆肥化复合材料。该复合材料以增量方式逐渐拉伸得到软布状手感。
完全可生物降解的和/或堆肥化的复合材料是通过配制一种完全可生物降解的和/或可堆肥化的塑料膜组合物，将组合物挤出形成膜，和将该膜层压到完全可生物降解和/或可堆肥化的无纺织物宋制得的。层压件以增量方式主要沿其长度和宽度方向并在其整个深度上逐渐拉伸，产生软布状手感。
附图的简述
图中显示了形成完全可生物降解和/或可堆肥化的复合材料的制造步骤。
详细叙述
A.可生物降解的和/或可堆肥化的膜聚合物
完全可生物降解和/或可堆肥化的成膜聚合物，如链烷酰基聚合物和聚乙烯醇(PVA)的共混物描述在US专利5,200,247。还有，链烷酰基聚合物，变性淀粉和乙烯共聚物的共混物可用作微孔性成形聚合物，以及可生物降解和/或可堆肥化的组合物描述在US专利5,407,979中。适合于实施本发明的许多热塑性聚合物是正常呈固体的氧化链烷酰基聚合物或二链烷酰基聚合物，其代表有聚己内酯(PCL)与淀粉聚合物或PVA的可成膜的共混物。具体地说，该完全可生物降解和/或可堆肥化的塑料膜组合物选自由聚乙烯醇(PVA)，聚己内酯(PCL)，淀粉，淀粉和PVA的共混物，淀粉和PCL的共混物，PCL和PVA的共混物，PLA、淀粉、聚酯、和其混合物(PHBV)的共混物所组成的组，所述聚酯选自聚羟基(丁酸酯)(PHB)、聚羟基(戊酸酯)(PHV)。
B.可生物降解和/或可堆肥化的无纺织物
可生物降解和/或可堆肥化的无纺织物40优选是在US专利5,539,081中描述的那些类型的熔融稳定性丙交酯聚合物，即，聚丙交酯无纺织物(PLA)。该无纺织物的所有的单丝纤维是完全由乳酸，即L乳酸，D乳酸，或L乳酸和D乳酸的混合物得到的聚合物或聚合物混合物制成的。其它可生物降解和/或可堆肥化处理的无纺织物包括棉类无纺织物，纤维素无纺织物，和它们的共混物。由此，该完全可生物降解和/或可堆肥化的无纺织物包括选自由全L乳酸的聚合物，全D乳酸的聚合物，L乳酸和D乳酸的共聚物，以及L乳酸和D乳酸各自聚合物的共混物所组成的组中的聚合物。
从乳酸得到的聚合物或聚合物混合物有利地具有100,000g/mol和200,000g/mol之间的分于量以及约1和约3之间的多分散性。还有，它们的玻璃化转变温度在45℃和55℃之间，熔点在165℃-180℃之间。
举例来说，用于生产本发明的无纺织物的聚合物A能够通过在反应器中让乳酸与辛酸锡形式的催化剂反应(辛酸锡与乳酸混合的比率是0.11wt％)来获得。聚合物A，当离开反应器时处于209℃的温度下，具有132,000g/mol的重均分于量，1.9的多分散性值，51.5℃的玻璃化转变温度，和170℃的熔点。
通过使用以上指定的操作条件，还有可能获得从乳酸形成的聚合物B，该聚合物能够用于生产本发明的无纺织物并具有158,000g/mol的重均分子量，2.1的多分散性值，49℃的玻璃化转变温度，和171.6℃的熔点。
正如在已转让于Fiberweb France的法国专利2.709.500中和在US专利申请序列号No.08/284.001中(两文献被引入本文共参考)所公开的，从乳酸得到的聚合物或聚合物混合物的固体物料被加入到加热挤出机中。物料在被处理的同时进行可控方式的加热，获得显示出所确定粘度的均匀熔体。熔体被输送至模头装置以形成单丝纤维。如此获得的单丝纤维被冷却，拉伸和铺列，无需优先的取向，在传输收集带上以形成片材或无纺织物网。如果合适，这些单丝纤维在它们的交叉点的至少一部分上相互粘接在一起和/或由压延操作台和/或对应的处理操作台(网或无纺织物片材在成形之后通过这些操作台)通过浸泡。涂敷。浸渍或喷雾进行处理。
C.挤出层压
对于本发明的目的和参考附图，上述可生物降解和/或可堆肥化的热塑性膜配方的挤出是通过使用挤出机10和模头20进行的。模头温度对于PCL/淀粉共混物是在约240°F-300°F (115.56-148.89℃)范围内，但该温度这取决于聚合物。膜是使用2″ (6.35cm)挤出机10在简体温度大约200°F-300°F (93.33-148.89℃)下通过缝形模头挤出，该温度再次取决于聚合物。典型地，取决于挤出条件，本发明的可生物降解和/或可堆肥化处理的膜10被挤出加工成约1-20密耳(25.4-508μm)，优选1-10密耳 (25.4-254μm)的膜。当2″ (6.35cm)挤出机10以大约50rpm的螺杆速度使用时，上述聚合物的膜能够在大约65fpm (15.24m/min)线速度下生产。可生物降解的和/或可堆肥化的膜30的下面所述实例是根据这一操作程序制造的。应该理解的是挤出技术对于本技术领域中熟练人员来说是众所周知的，因此在这些不需进一步详细讨论。D.增量方式拉伸(Incremental Stretching)
复合材料70通过使用对角线相互串套，横向(CD)相互串套，或纵向(MD)相互串套式拉伸方法来进行增量拉伸，如US专利5,200,247，US专利5,202,173，US专利5,382,461和US专利5,422,172中所公开的，它们全部转让于本发明的受让人，这些公开物的每一件以其全部内容被引入本文供参考。
通过拉伸挤出的可生物降解和/或可堆肥化处理的复合材料，膜的分子结构会断裂，产生微孔或微隙。微隙的形成会引起可生物降解和/或可堆肥化热塑性膜中产生透气性。透气性允许空气和水汽进出或通过该膜。此外，通过拉伸膜得到的增加表面积因此增强了膜的可生物降解性和/或可堆肥化处理性。
各种类型的拉伸技术可用来改变透气性和增强生物降解性和/或堆肥化处理性。经拉伸后，无需添加任何不透明剂如二氧化钛，半透明的膜变不透明。膜的不透明性是光线被吸收在由可生物降解和/或可堆肥化处理的膜的分子断裂导致的微隙或微孔中的结果。
可生物降解和/或可堆肥化的复合材料能够根据US专利5,202,173(1993年4月13日授权于Wu等人)中描述的增量拉伸技术来进行拉伸，该文献被引入本文供参考。其中公开的一种拉伸机和技术被描述如下：1.对角线相互串套拉伸机
对角线相互串套拉伸80由平行轴上方的一对左手和右手螺旋形齿轮状元件组成。该轴位于两片机器侧板之间，下面的轴位于固定轴承内，上面的轴位于垂直滑动型机构中的轴承内。滑动型机构可借助于调节螺钉带动的楔形元件在垂直方向上进行调节。将楔子拧出或拧进可使垂直滑动机构分别向下或向上垂直运动，从而进一步使上串套(intermeshing)辊的齿轮状齿与下串套辊的齿咬合或离开。安装在侧框上的测微计可用于指示串套辊的齿的咬合深度。
气筒用于保持滑动机构在它们较低的咬合位置上紧靠在调节楔子上，以抵制由被拉伸材料施加的向上的力。这些气筒也可回缩来使上下串套辊相互分离开以便穿引(threading)该材料通过串套设备或与安全电路结合，该电路在开通时将打开所有机器夹持点。
驱动装置典型地用于驱动静态串套辊。如果出于机器穿引(threading)或安全方面的考虑分离开上串套辊，优选在上下串套辊之间使用消隙的齿轮排列，以确保在再次咬合时一只串套辊的齿总是落在另一串套辊的齿之间，并避免了串套齿的齿顶之间的潜在的损害性物理接触。如果串套辊保持恒定的咬合，则上串套辊典型地不需要驱动。驱动可通过驱动串套辊来完成，通过该辊将材料拉伸。
串套辊非常象细螺距的螺旋形齿轮。在优选的实施方案中，辊具有5.935″(15.075cm)直径，45°螺旋角，0.100″(0.254cm)法向节距，30径向节距，14°压力角，且基本上是长的齿顶齿轮。这将得到窄而深的齿构型，允许有大约0.090″(0.229cm)的串套咬合且在齿的侧边有大约0.005″ (0.0127cm)的缝隙作为材料的厚度。齿不是设计来传送旋转扭矩并且在正常串套拉伸操作中不会使金属-金属接触。2.横向串套拉伸机
横向串套拉伸设备等同于对角线串套拉伸机，但在串套辊的设计上和下面指出的其它较小的方面上有差异。由于CD串套元件能够具有大的咬合深度，重要的是该设备采用了当顶轴升高或下降时引起两串套辊的轴保持平行的装置。这需要确保一只串套辊的齿总是落在另一串套辊的齿之间并避免了串套齿之间的潜在的损害性物理接触。平行运动可由齿条和齿轮排列来确保，其中静态齿轮齿条连接于毗邻该垂直滑动机构的每一侧框上。轴横穿侧框并在每一垂直滑动性机构的轴承内活动。停留在该轴的每一端上并与齿条咬合进行操作，以产生所需平行运动。
CD串套拉伸机的驱动必须同时操作上下两串套辊，但这对于有较高摩擦系数的材料的串套拉伸的情况是例外的。驱动不必是消隙的，然而，因为少量的纵向不重合或驱动滑动将不会引起问题。从针对CD串套元件的叙述可更清楚这一理由。
CD串套元件可从固体材料加工制造，但是最佳被描述为两种不同直径盘的交替堆积。在优选的实施方案中，串套盘将具有6″(15.24cm)直径，0.031″ (0.0787cm)厚度，并在它们的边缘具有全半径。隔离串套盘的间隔盘将具有5″ (13.79cm)的直径和0.069″(0.175cm)的厚度。这一构型的两辊能够串套至多0.231″ (0.587cm)以便为所有侧边上的材料预留0.019″ (0.0483cm)缝隙。对于对角线串套拉伸机，这一CD串套元件构型将具有0.100″ (0.254cm)的螺距。3.纵向串套拉伸机
MD串套拉伸设备等同于对角线串套拉伸机，但例外的是串套辊的设计不同。MD辊串套辊非常象细螺距的正齿轮。在优选实施方案

Claims (9)

1、包括一层或多层完全可生物降解的和/或可堆肥化的塑料膜和一层或多层完全可生物降解的和/或可堆肥化的无纺织物网的一种完全可生物降解的和/或可堆肥化的软布状的复合材料，该复合材料具有以增量方式主要沿其长度和宽度方向并在其整个深度上拉伸的部分，以提供复合材料软布状手感。
2、权利要求1的复合材料，其中
(a)该完全可生物降解和/或可堆肥化的无纺织物包括选自由全L乳酸的聚合物，全D乳酸的聚合物，L乳酸和D乳酸的共聚物，以及L乳酸和D乳酸各自聚合物的共混物所组成的组中的聚合物；并且
(b)该完全可生物降解和/或可堆肥化的塑料膜组合物选自由聚乙烯醇(PVA)，聚己内酯(PCL)，淀粉，淀粉和PVA的共混物，淀粉和PCL的共混物，PCL和PVA的共混物，PLA、淀粉、聚酯、和其混合物(PHBV)的共混物所组成的组，所述聚酯选自聚羟基(丁酸酯)(PHB)、聚羟基(戊酸酯)(PHV)。
3、一种生产完全可生物降解和/或可堆肥化的软布状复合材料的方法，包括：配制一种完全可生物降解的和/或可堆肥化的塑料膜组合物；将该组合物挤出成膜；将该膜层压到完全可生物降解和/或可堆肥化的无纺织网上以形成完全可生物降解性和/或可堆肥化的层压件；和沿其长度和宽度方向并在其整个深度上以增量方式拉伸该层压件的各部分，从而生产出软布状的复合材料。
4、权利要求3的方法，其中完全可生物降解和/或可堆肥化的无纺织网包括选自由全L乳酸的聚合物，全D乳酸的聚合物，L乳酸和D乳酸的共聚物，以及L乳酸和D乳酸各自聚合物的共混物所组成的组中的聚合物。
5、权利要求3或4的方法，其中完全可生物降解和/或可堆肥化的塑料膜组合物选自由聚乙烯醇(PVA)，聚己内酯(PCL)，淀粉，淀粉和PVA的共混物，淀粉和PCL的共混物，PCL和PVA的共混物，PLA、淀粉、聚酯和其混合物(PHBV)的共混物所组成的组，所述聚酯选自聚羟基(丁酸酯)(PHB)和聚羟基(戊酸酯)(PHV)。
6、权利要求3的方法，其中塑料膜组合物是通过将80％PCL和20％淀粉聚合物共混而形成的，并且其中完全可生物降解和/或可堆肥化的无纺织网是从聚丙交酯形成的。
7、权利要求3、4和6之一的方法，其中塑料膜组合物是由缝形模头挤出的方法挤出成厚度约1.0-1.2密耳(25.4-30.48μm)的膜。
8、权利要求3、4和6之一的方法，其中该层压件在横向以增量方式拉伸。
9、权利要求3、4和6之一的方法，其中该层压件在纵向以增量方式拉伸。
CN98803666A 1997-03-27 1998-03-02 布状完全可生物降解的和/或可堆肥化处理的复合材料及其制造方法 Expired - Fee Related CN1098157C (zh)

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AU6677198A (en) 1998-10-22
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ATE294708T1 (de) 2005-05-15
WO1998043810A1 (en) 1998-10-08
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US5851937A (en) 1998-12-22
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