CN1929985A - 纵向取向的多层薄膜 - Google Patents
纵向取向的多层薄膜 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
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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
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2023/04—Polymers of ethylene
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- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0625—LLDPE, i.e. linear low density polyethylene
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- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0641—MDPE, i.e. medium density polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/065—HDPE, i.e. high density polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
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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
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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
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Abstract
本发明公开了一种制造薄膜的方法。该方法包括在多层薄膜的落镖冲击强度随牵伸比的增加而提高的牵伸比纵向取向该多层薄膜。该多层薄膜包含至少一层线形低密度聚乙烯和至少一层高密度聚乙烯或中密度聚乙烯。
Description
技术领域
本发明涉及聚乙烯薄膜。更具体地说,本发明涉及纵向取向的多层薄膜。
背景技术
聚乙烯可分为高密度聚乙烯(HDPE,密度为0.941克/立方厘米或以上)、中密度聚乙烯(MDPE,密度为0.926-0.940克/立方厘米)、低密度聚乙烯(LDPE,密度为0.910-0.925克/立方厘米)和线形低密度聚乙烯(LLDPE,密度为0.910-0.925克/立方厘米)。见ASTMD4976-98:聚乙烯塑料模塑和挤塑材料标准规范。聚乙烯也可按分子量分类。例如,超高分子量聚乙烯是指重均分子量(Mw)大于3000000的聚乙烯。见美国专利6265504。高分子量聚乙烯通常指Mw为130000-1000000的聚乙烯。
聚乙烯(HDPE、MDPE、LLDPE和LDPE)的一种主要用途是薄膜领域的应用,如杂品袋、公共饮食业和消费者用的罐头内衬、商品袋、运输袋、食品包装膜、多层袋衬、生产用袋、熟食品外包装、拉伸包装膜和收缩包装膜。聚乙烯薄膜的主要物理性能包括撕裂强度、冲击强度、拉伸强度、刚度和透明度。薄膜的刚度可用模量来量度。模量是薄膜在应力作用下的抗变形性能。
纵向取向(MDO)对于聚烯烃工业来说是已知的。当聚合物在单轴应力作用下发生应变时,聚合物分子会沿拉伸方向取向。例如,美国专利6391411介绍了高分子量(Mn和Mw都高于1000000)HDPE薄膜的MDO。然而,由于这类薄膜难以拉伸至高牵伸比,因而高分子量HDPE薄膜的MDO是受限制的。
目前聚乙烯薄膜通常需兼顾各种性能如模量、屈服强度和断裂强度,以满足包装对落镖冲击强度的要求。对于不能兼顾这些性能的聚合物薄膜,则需要改进以符合包装袋的性能要求,并提高与制造和装填包装袋有关的经济性。例如,通过提高薄膜的模量和屈服强度可制造较大的包装袋,这种大袋可包装大量的物品,并被顾客提在手中时仍能保持其形状。具有较高模量的包装袋还可使物品包装生产线的运行速度加快,从而提高整个包装过程的经济效益。
提高薄膜的屈服强度,则有可能降低包装袋在应力作用下的伸长,从而能保持其初始形状和尺寸。这样可减少薄膜因在荷重下发生屈服、变薄而引起的破裂量。同时,包装袋的印刷表面也不会发生变形,仍能保持包装的美学质量,从而提高顾客对商标的认知度。
此外,还应使不能兼顾上述性能的薄膜厚度降低从而进一步提高与该产品有关的经济效益。这些新措施是所有重载荷运输袋工业所希望的,以便制造出既具有良好性能又具有经济效益的新产品。
发明内容
本发明方法包括在能使薄膜的落镖冲击强度随牵伸比增加而提高的牵伸比下对多层薄膜进行纵向取向(MD)。该多层薄膜包括至少一层线形低密度聚乙烯(LLDPE)和至少一层高密度聚乙烯(HDPE)或中密度聚乙烯(MDPE)。
当薄膜被拉伸时,其落镖冲击强度通常会随膜变薄而降低。出乎意料地发现,当多层膜在纵向取向超过一定牵伸比时,膜的落镖冲击强度会随牵伸比的增加而提高,且取向膜的最终落镖冲击强度值高于初始薄膜的落镖冲击强度值。因此,本发明提供一种制造纵向取向(MDO)、具有高模量、高拉伸强度和高落镖冲击强度的多层薄膜的方法。
具体实施方式
本发明方法包括在能使薄膜的落镖冲击强度随牵伸比增加而提高的牵伸比下对多层薄膜进行纵向取向(MD)。该多层膜包括至少一层线形低密度聚乙烯(LLDPE)和至少一层高密度聚乙烯(HDPE)或中密度聚乙烯(MDPE)。
适用的LLDPE优选为乙烯与5重量%-15重量%长链α-烯烃如1-丁烯、1-己烯和1-辛烯的共聚物。适用的LLDPE包括密度为约0.910克/立方厘米-约0.925克/立方厘米的聚乙烯。适用的LLDPE也包括所谓很低密度聚乙烯(VLDPE)。适用的VLDPE的密度为0.865克/立方厘米-0.910克/立方厘米。
适用MDPE的优选密度为约0.926克/立方厘米-约0.940克/立方厘米,更优选为约0.930克/立方厘米-约0.940克/立方厘米。优选的MDPE为包含约85重量%-约98重量%乙烯重复单元与约2重量%-约15重量%C3-C10α-烯烃重复单元的共聚物。适用的C3-C10α-烯烯包括丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯和1-辛烯等,以及它们的混合物。
优选的是,MDPE呈双峰分子量分布或多峰分子量分布。制备双峰或多峰MDPE的方法是已知的。例如,美国专利6486270介绍了多段工艺制备MDPE的方法。
适用HDPE的优选密度为约0.941克/立方厘米-约0.970克/立方厘米,更优选为约0.945克/立方厘米-约0.965克/立方厘米,最优选为0.958克/立方厘米-约0.962克/立方厘米。
优选的是,LLDPE、MDPE和HDPE的MI2为约0.01-约1.5分克/分钟,更优选为约0.01-约1.0分克/分钟。优选的是,LLDPE、MDPE和HDPE的MFR为约50-约300。熔体指数(MI2)通常用来量度聚合物的分子量,熔体流动比率(MFR)常用来量度分子量分布。MI2较高表示分子量较低。MFR较高表示分子量分布较宽。MFR是指高载荷熔体指数(HLMI)与MI2的比值。MI2与HLMI可按照ASTM D-1238方法进行测定。MI2是在190℃、2.16千克载荷下测定的。HLMI是在190℃、21.6千克载荷下测定的。
优选的是,LLDPE、MDPE和HDPE的数均分子量(Mn)为约10000-约500000,更优选为约11000-约50000,而最优选为约11000-约35000。优选的是,LLDPE、MDPE和HDPE的重均分子量(Mw)为约120000-约1000000,更优选为约135000-约500000,而最优选为约140000-约250000。优选的是,LLDPE、MDPE和HDPE的分子量分布(Mw/Mn)为约3-约20,更优选为约4-约18,而最优选为约5-约17。
Mw、Mn和Mw/Mn是在装置有混合床GPC柱(Polymer Labs混合的B-LS)、以1,2,4-三氯苯(TCB)为流动相的Waters GPC 2000CV高温仪上以凝胶渗透色谱法(GPC)测得的。流动相的正常流速为1.0毫升/分钟,温度为145℃。不同流动相添加抗氧化剂,但用于试样溶解的溶剂中添加有800ppm BHT。聚合物试样在175℃加热2小时,同时每隔30分钟进行缓慢搅拌。试样的注入体积为100微升。
Mw和Mn是采用Waters Millennium 4.0软件提供的累积匹配%校正程序进行计算的。该程序包括首先采用窄分子量分布的聚苯乙烯标准样(PSS,Waters Corporation的产品)制作校准曲线,然后通过通用校准步骤求得聚乙烯校准曲线。
适用的LLDPE、MDPE和HDPE可通过Ziegler、单中心催化剂或任何其它烯烃聚合催化剂来制造。Ziegler催化剂是众所周知的。适用的Ziegler催化剂的实例包括钛的卤化物、钛的烷氧化物、钒的卤化物以及它们的混合物。Ziegler催化剂是与助催化剂如烷基铝化合物一起使用的。
单中心催化剂可分为金属茂和非金属茂催化剂。金属茂单中心催化剂是包含环戊二烯基(Cp)或Cp衍生物配体的过渡金属化合物。例如,美国专利4542199介绍了金属茂催化剂。非金属茂单中心催化剂包含的配体不是Cp,但具有与金属茂相同的催化特性。非金属茂单中心催化剂可包含杂原子配体,例如硼芳基、吡咯基、azaborolinyl或喹啉基。例如美国专利6034027、5539124、5756611和5637660介绍了非金属茂催化剂。
任选的是,多层薄膜可包含其它层如阻气层、粘合剂层、药物层、阻燃层等。适用作任选层的材料包括聚(偏二氯乙烯)、聚(乙烯醇)、聚酰胺(尼龙)、聚丙烯腈、乙烯-醋酸乙烯酯共聚物(EVA)、乙烯-丙烯酸甲酯共聚物(EMA)、乙烯-丙烯酸共聚物(EAA)、离子交联聚合物、马来酸酐接枝聚烯烃、K-树脂(苯乙烯/丁二烯嵌段共聚物)、聚(对苯二甲酸乙二醇酯)(PET)等,以及它们的混合物。
多层薄膜可通过共挤塑、贴合以及任何其它层合方法来制造。它们可通过铸塑薄膜或吹胀薄膜工艺来制造。吹胀薄膜工艺包括高注道工艺和型腔内(in-pocket)工艺。高注道工艺与型腔内工艺的区别在于:在高注道工艺中挤塑膜管是在挤出模头前的注道范围(即注道长度)内吹胀的,而在型腔内工艺中挤塑膜管是在膜管挤出模头出口时吹胀的。
多层薄膜是以纵向(或加工方向)进行单轴拉伸的。这就是通常所说的MDO。在进行MDO期间将由吹胀薄膜生产线或其它薄膜工艺制造的薄膜加热至取向温度。优选的取向温度在玻璃化转变温度(Tg)与熔点(Tm)之差的60%与熔融温度Tm之间。例如,如果共混物的Tg为25℃而Tm为125℃,则取向温度优选在约60°-约125℃范围内。优选采用多个加热辊来实施加热。
接着,用夹膜辊将已加热的薄膜喂入慢速牵引辊,该牵引辊的辊速与加热辊辊速相同。然后,使薄膜进入快速牵引辊。快速牵引辊的辊速比慢速牵引辊快2-10倍,快速牵引辊能连续地拉伸薄膜。
然后,经拉伸的薄膜进入退火热辊,该薄膜通过在退火热辊的高温下保持一定时间而达到应力松弛。退火温度优选为约100℃-约125℃,退火时间为约1-约2秒钟。最后通过冷却辊使薄膜冷却至环境温度。
薄膜在取向前与取向后的厚度之比称为“牵伸比”。例如,当厚度为6密耳的薄膜被牵伸至厚度为0.6密耳时,则牵伸比为10∶1。根据本发明方法,牵伸比要足够高,以使薄膜的落镖冲击强度随牵伸比增加而提高。如预期的那样,当多层薄膜进行MD取向时,该薄膜的落镖冲击值会随牵伸比增加而降低。然而,出乎意料地发现,当薄膜取向超过某一值时,落镖冲击值会随牵伸比增加而提高。当取向继续进行时,取向薄膜可具有高于未取向薄膜的最终落镖冲击值。
落镖冲击值随牵伸比提高的临界点取决于许多因素,其中包括各层的性质,薄膜加工条件和MDO条件。优选的是,牵伸比大于6∶1。更优选的牵伸比大于8∶1。最优选的牵伸比大于10∶1。优选的是,使多层薄膜取向至达到薄膜的各层开始脱层的程度,并形成多层壁薄膜。
本发明包括通过本发明方法制造的MD取向薄膜。本发明还包括通过本发明方法制造的多层壁薄膜。本发明薄膜不仅具有高模量、高拉伸强度,而且还具有高的落镖冲击强度。由于本发明薄膜既具有高模量、高拉伸强度又具有高冲击强度,因而特别适用于制造重负载包装袋。
优选的是,本发明薄膜的1%正切MD和TD(横向)模量高于150000磅/平方英寸,更优选高于200000磅/平方英寸,而最优选高于250000磅/平方英寸。模量是根据ASTM E-111-97方法测定的。
优选的是,薄膜的MD屈服拉伸强度和MD断裂拉伸强度高于30000磅/平方英寸,更优选高于35000磅/平方英寸,而最优选高于40000磅/平方英寸。拉伸强度是根据ASTM D-882方法测定的。
优选的是,薄膜的雾度低于30%,更优选低于50%。雾度是根据ASTM D 1003-92方法(Standard Test Method for Haze and LuminousTransmittance of Transparent Plastics,Oct.1992)测定的。优选的是,薄膜的光泽度大于20,更优选大于30。光泽度是根据ASTM D2457-90:Standard Test Method for Specular Gloss of PlasticFilms and Solid Plastics测定的。
下述实施例只是作为对本发明的说明。技术熟练人员都知道在本发明精神和权利要求书范围内可以有许多变体。
实施例1-6
LLDPE/MDPE/LLDPE三层薄膜的纵向取向
将中密度聚乙烯(XL3805,Equistar Chemicals的产品,LP,MI2:0.057分克/分钟,密度:0.938克/立方厘米,Mn:18000,Mw:209000)与线形低密度聚乙烯(GS707,Equistar Chemicals的产品,LP,密度:0.915克/立方厘米,MI2:0.700分克/分钟,Mn:30000,Mw:120000)进行共挤塑,并用模口间隙为2.5毫米的1000毫米模头加工成厚度为14.0密耳的等厚三层(LLDPE/MDPE/LLDPE)叠层膜。将该膜在型腔内以吹胀比(BUR)2∶1吹胀成薄膜。
然后,按照实施例1-6分别以4、5、6、7、8和9.3∶1的牵伸比对薄膜进行纵向拉伸成为更薄的薄膜。牵伸比9.3∶1是取向设备限制的最大牵伸比而不是聚合物薄膜的最大牵伸比。薄膜的性能列于表1中。数据显示,在较低牵伸比时,落镖冲击值如预期的那样随牵伸比增加而降低。在一特定的牵伸比之后,落镖冲击值开始随牵伸比增加而提高并明显地超过初始薄膜的落镖冲击值。
表1多层薄膜性能与牵伸比的关系
实施例 | 牵伸比 | 落镖冲击强度F 50克 | MD模量kpsi | TD模量kpsi | MD拉伸屈服强度kpsi | MD拉伸断裂强度kpsi | 光泽度 | 雾度% |
1 | 4∶1 | 136 | 122 | 149 | 8.85 | 13.8 | 22 | 39 |
2 | 5∶1 | 128 | 144 | 155 | 16.5 | 20.2 | 26 | 34 |
3 | 6″1 | 134 | 170 | 160 | 24.3 | 26.7 | 29 | 31 |
4 | 7∶1 | 155 | 200 | 164 | 32.0 | 33.0 | 31 | 30 |
5 | 8∶1 | 190 | 236 | 167 | 39.5 | 39.5 | 32 | 30 |
6 | 9.3∶1 | 258 | 293 | 171 | 47.9 | 47.9 | 31 | 33 |
对照实施例7-11
HDPE单层薄膜的纵向取向
重复实施例1-6,但薄膜是单层HDPE结构(L5005,EquistarChemicals产品,LP,密度:0.949克/立方厘米,MI:0.057分克/分钟,Mn:12600,Mw:212000)。薄膜性能列于表2中,数据显示,落镖冲击值随牵伸比增加而明显地下降,并未观察到如在实施例1-6多层膜中所见到的落镖冲击值急剧上升的现象。牵伸比7.9∶1是取向设备限制的最大牵伸比而不是聚合物薄膜的最大牵伸比。
表2单层薄膜性能与牵伸比的关系
实施例 | 牵伸比 | 落镖冲击强度F 50克 | MD模量kpsi | TD模量kpsi | MD拉伸屈服强度kpsi | MD拉伸断裂强度kpsi | 光泽度 | 雾度% | |||
C7 | 4∶1 | 137 | 218 | 234 | 6.53 | 15.3 | 12 | 60 | |||
C8 | 5∶1 | 105 | 239 | 236 | 7.17 | 20.1 | 14 | 56 | |||
C9 | 6∶1 | 86 | 261 | 238 | 7.81 | 25.0 | 16 | 52 | |||
C10 | 7∶1 | 81 | 286 | 240 | 8.45 | 29.8 | 19 | 48 | |||
C11 | 7.9∶1 | 88 | 310 | 241 | 9.02 | 34.1 | 23 | 44 |
对照实施例12-19
由MDPE-LLDPE共混物制成的单层薄膜的纵向取向
重复实施例1-6,但薄膜是由MDPE(XL 3805,Equistar Chemicals产品,LP,MI2:0.057分克/分钟,密度:0.938克/立方厘米,Mn:18000,MW:209000)和LLDPE(GS707,Equistar Chemicals产品,LP,密度:0.915克/立方厘米,MI2:0.700分克/分钟,Mn:30000,Mw:120000)的共混物制成的单层薄膜。共混物中各组分的比例要使整个薄膜中每种材料的百分比分别与实施例1-6多层薄膜中两种材料的百分比相同。薄膜的性能列于表3中,数据显示,落镖冲击值随牵伸比增加而明显地下降,并未观察到如实施例1-6多层膜中所见到的落镖冲击值急剧上升的现象。牵伸比10.6∶1是取向设备限制的最大牵伸比而不是聚合物薄膜的最大牵伸比。
表3MDPE-LLDPE共混物单层薄膜性能与牵伸比的关系
实施例 | 牵伸比 | 落镖冲击强度F 50克 | MD模量kpsi | TD模量kpsi | MD拉伸屈服强度kpsi | MD拉伸断裂强度kpsi | 光泽度 | 雾度% |
C12 | 4∶1 | 140 | 104 | 129 | 7.32 | 13.4 | 27 | 32 |
C13 | 5∶1 | 120 | 120 | 135 | 12.2 | 17.5 | 30 | 29 |
C14 | 6∶1 | 105 | 139 | 140 | 17.1 | 21.6 | 34 | 27 |
C15 | 7∶1 | 93 | 161 | 145 | 22.1 | 25.7 | 36 | 25 |
C16 | 8∶1 | 87 | 186 | 148 | 27.0 | 29.9 | 38 | 24 |
C17 | 9∶1 | 84 | 215 | 151 | 32.0 | 34.0 | 39 | 24 |
C18 | 10∶1 | 86 | 249 | 154 | 36.9 | 38.1 | 39 | 25 |
C19 | 10.6∶1 | 89 | 272 | 156 | 39.9 | 40.5 | 9 | 26 |
Claims (14)
1.一种方法,包括在对于多层薄膜的落镖冲击强度随牵伸比的增加而提高的牵伸比下纵向取向该多层薄膜,其中多层薄膜包含至少一层线形低密度聚乙烯(LLDPE)和至少一层高密度聚乙烯(HDPE)或中密度聚乙烯(MDPE)。
2.权利要求1的方法,其中HDPE的密度为0.941克/立方厘米-0.970克/立方厘米。
3.权利要求1的方法,其中MDPE的密度为0.926克/立方厘米-0.940克/立方厘米。
4.权利要求1的方法,其中LLDPE的密度为0.865克/立方厘米-0.925克/立方厘米。
5.权利要求1的方法,其中薄膜是在对引起薄膜脱层有效的牵伸比下取向的。
6.权利要求1的方法,其中薄膜是在使得薄膜的落镖冲击强度高于初始薄膜的落镖冲击强度的牵伸比下取向的。
7.权利要求1的方法,其中LLDPE、HDPE和MDPE的各自重均分子量(Mw)为120000-1000000。
8.权利要求7的方法,其中Mw为135000-500000。
9.权利要求7的方法,其中Mw为140000-250000。
10.权利要求1的方法,其中LLDPE、HDPE和MDPE各自的数均分子量(Mn)为10000-500000。
11.权利要求10的方法,其中Mn为11000-50000。
12.权利要求10的方法,其中Mn为11000-35000。
13.一种通过权利要求1的方法制造的取向薄膜。
14.一种通过权利要求5的方法制造的多层壁薄膜。
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- 2005-02-15 CN CNA2005800075581A patent/CN1929985A/zh active Pending
- 2005-02-15 KR KR1020067018349A patent/KR20060129049A/ko not_active Application Discontinuation
- 2005-02-15 CA CA 2557712 patent/CA2557712A1/en not_active Abandoned
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CN104487349A (zh) * | 2012-04-18 | 2015-04-01 | 博瑞立斯有限公司 | 整理收缩膜 |
CN104582959A (zh) * | 2012-08-13 | 2015-04-29 | 北欧化工公司 | 薄膜 |
CN109153225A (zh) * | 2016-06-03 | 2019-01-04 | 博里利斯股份公司 | 多层结构 |
US11472166B2 (en) | 2016-06-03 | 2022-10-18 | Borealis Ag | Multilayer structure |
US11865818B2 (en) | 2016-06-03 | 2024-01-09 | Borealis Ag | Multilayer structure |
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US20050200046A1 (en) | 2005-09-15 |
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