CN101578326A - 多层脂肪族聚酯膜 - Google Patents
多层脂肪族聚酯膜 Download PDFInfo
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- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 30
- 229930182843 D-Lactic acid Natural products 0.000 claims abstract description 16
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims abstract description 16
- 229940022769 d- lactic acid Drugs 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 21
- 229920006267 polyester film Polymers 0.000 claims description 19
- 239000004626 polylactic acid Substances 0.000 claims description 19
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- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 32
- -1 polyethylene Polymers 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 210000004379 membrane Anatomy 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012793 heat-sealing layer Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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- C08L2203/00—Applications
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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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
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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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Abstract
本发明的多层脂肪族聚酯膜含有第一树脂层和层合在所述第一树脂层的一侧或两侧的第二树脂层,所述第一树脂层含有在50-100重量%范围内的量的L-乳酸的聚乳酸基聚合物,所述第二树脂层含有在5-20重量%范围内的量的D-乳酸的聚乳酸基聚合物。所述多层脂肪族聚酯膜可容易地通过用手拉而剥离,并具有改进的热粘合性、耐热性、透明性、抗冲击性、抗穿孔性和尺寸稳定性。因此,它作为包装材料,尤其是作为塑料容器的一次性膜盖是有用的。
Description
技术领域
本发明针对具有改进的热粘合性、耐热性、透明性、抗冲击性、抗穿孔性和尺寸稳定性的多层脂肪族聚酯膜。
背景技术
在包装工业中,产品通常包装在塑料膜或硬质塑料包装中然后热密封。
就常规的热密封塑料膜的性能特征而言,常规的热密封塑料膜比如聚氯乙烯、聚乙烯和聚丙烯膜并不完全令人满意。例如,聚氯乙烯膜焚烧时产生有毒污染物,而聚乙烯膜因其相对较差的尺寸和机械性能仅用作低等级包装材料。另一方面,热粘合聚丙烯膜具有令人满意的机械性能,但产生不可生物降解的分解产物。为了解决这些问题,已有使用可生物降解的脂肪族聚酯,特别是聚乳酸膜。然而,这样的膜因它们的高结晶度而具有差的热粘合性和柔韧性。
为了解决这些问题,已使用可生物降解的脂肪族聚酯,特别是聚乳酸基膜。
例如,日本特开公开号1997-157408和2004-109000公开了由聚乳酸聚合物和玻璃化转变温度(Tg)为0℃或更低的脂肪族聚酯树脂组成的多层膜。然而,这些膜因它们相对差的耐热性造成热收缩率明显高。此外,密封不能容易地通过用手拉而打开。
日本特开公开号2003-170560公开了含有非晶乳酸基树脂层作为热密封层的多层膜。然而,该膜不适合作为包装,因为在包装经热浴处理后该膜变浑浊。
发明内容
因此,本发明的目的是提供在热密封后可剥离的用于包装的多层脂肪族聚酯膜,所述聚酯膜具有改进的热粘合性、耐热性、透明性、抗冲击性、抗穿孔性(perforation resistance)和尺寸稳定性。
根据本发明,提供了多层脂肪族聚酯膜,所述聚酯膜含有第一树脂层和层合在所述第一树脂层的一侧或两侧上的第二树脂层,其中:
所述第一树脂层含有在50-100重量%范围内的量的L-乳酸的聚乳酸基聚合物,所述第二树脂层含有在5-20重量%范围内的量的D-乳酸的聚乳酸基聚合物;且
在85℃经热浴处理30分钟后,所述多层脂肪族聚酯膜的熔化热(ΔHm)为0.5-20J/g,雾度为20%或更小,并且所述多层脂肪族聚酯膜的热粘合强度为300-1500gf/英寸。
根据本发明的多层脂肪族聚酯膜含有第一树脂层和层合在所述第一树脂层的一侧或两侧的第二树脂层。所述第一树脂层含有在50-100重量%,优选为70-100重量%范围内的量的L-乳酸的聚乳酸基聚合物。所述第二树脂层含有在5-20重量%,优选为5-9重量%范围内的量的D-乳酸的聚乳酸基聚合物。
当所述第一树脂层的L-乳酸的量小于50重量%时,所述膜会具有差的机械性能和高的热收缩率,而当所述第二树脂层(热密封层)的D-乳酸的量超过20重量%时,得到的膜的耐热性和雾度不会让人满意。
在所述第一树脂层中还可使用的聚乳酸基聚合物可以是在0-50重量%,优选为0-30重量%范围内的量的D-乳酸,在所述第二树脂层中还可使用的聚乳酸基聚合物可以是在80-95重量%,优选为91-95重量%范围内的量的L-乳酸。
在85℃经热浴处理30分钟后,根据本发明的聚酯膜的熔化热为0.5-20J/g,优选为1-10J/g。当所述膜的熔化热超过20J/g时,热粘合强度会变差,并且得到的膜的抗穿孔性和抗冲击性变得令人不满意,而当小于0.5J/g时,所述膜的表面因耐热性退化而变浑浊。
根据本发明的聚酯膜的粘合强度为300gf/英寸-1500gf/英寸,优选为400gf/英寸-800gf/英寸。当所述膜的热粘合强度超过1500gf/英寸时,所述膜在不破坏膜本身的完整性时不能容易地剥离,而当小于300gf/英寸时,所述密封可以容易地打开,使内含物漏出。
此外,在85℃经热处理30分钟后,根据本发明的聚酯膜的雾度为20%或更小,优选为10%或更小。
根据本发明的聚酯膜每单位厚度的冲击吸收能为0.5kgf-cm/μm或更大。当所述膜每单位厚度的冲击吸收能小于0.5kgf-cm/μm时,用所述膜热密封的包装会因外部冲击例如在储存和运输期间而容易破裂。
根据本发明的聚酯膜的穿孔强度为0.8kgf或更大。当所述膜的穿孔强度小于0.8kgf时,得到的膜会因另一包装的锋利边缘而容易被撕裂。
在100℃经热空气处理5分钟后,根据本发明的聚酯膜在纵向或横向的热收缩率为5%或更小,优选为3%或更小。当所述膜的热收缩率超过5%时,所述膜的可印性变差。
根据本发明,所述多层脂肪族聚酯膜可通过共挤出第一树脂层和第二树脂层,并通过常规方法沿纵向和横向拉伸,继之以热处理而制备。
得到的膜的厚度在5-300μm的范围内,所述第一树脂层∶第二树脂层的厚度比可在1∶1到20∶1,优选为5∶1到9∶1的范围内。当第二树脂层太厚时,因结晶度差而尺寸稳定性变得令人不满意,而当第一树脂层太厚时,所述膜的热粘合强度可能低到不令人满意。
如上所述,本发明的多层脂肪族聚酯膜可容易地通过用手拉而剥离,并具有改进的热粘合性、耐热性、透明性、抗冲击性、抗穿孔性和尺寸稳定性。因此,它作为包装材料,尤其是作为用于塑料容器的一次性膜盖是有用的。
具体实施方式
下列实施例仅出于说明的目的而给出,不旨在限制本发明的范围。
实施例1
通过将第一树脂(A)即含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)和第二树脂(B)即含有94.5重量%的L-乳酸和5.5重量%的D-乳酸的聚乳酸基树脂(4042D,NatureWorks LLC.)引入两个挤出机各自的供料区将它们熔化-挤出以获得第一树脂层和第二树脂层的厚度比为5∶1的层合物。将由此获得的层合物通过T模具并在冷却辊上冷却以获得双层共挤出片材。
由此获得的共挤出片材在70℃沿着纵向以3.0的拉伸率和在85℃沿着横向以3.8的拉伸率拉伸,在140℃热固化,并经松弛至3%的程度,以获得厚度为20μm的双轴拉伸的聚酯膜。
实施例2
重复实施例1的过程,除了使用含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)作为第一树脂层(A),并使用含有91重量%的L-乳酸和9重量%的D-乳酸的聚乳酸基树脂(4050D,Nature Works LLC.)作为第二树脂(B),以获得双层(A/B)共挤出片材。
由此获得的双层共挤出片材在75℃沿着纵向以3.0的拉伸率和在80℃沿着横向以3.8的拉伸率拉伸,在130℃热固化,并经松弛至3%的程度,以获得厚度为20μm的双轴拉伸的聚酯膜。
比较例1
重复实施例1的过程,除了使用含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)作为第一树脂层(A),并使用含有70重量%的L-乳酸和30重量%的D-乳酸的聚乳酸基树脂(Musashino chemical laboratory,Ltd.)作为第二树脂(B),以获得双层(A/B)共挤出片材。
由此获得的双层共挤出片材在70℃沿着纵向以3.0的拉伸率和在80℃沿着横向以3.8的拉伸率拉伸,在130℃热固化,并经松弛至3%的程度,以获得厚度为20μm的双轴拉伸的聚酯膜。
比较例2
重复实施例1的过程,除了使用含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)作为第一树脂层(A),并使用含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)作为第二树脂(B),以获得双层(A/B)共挤出片材。
由此获得的双层共挤出片材在75℃沿着纵向以3.0的拉伸率和在90℃沿着横向以3.8的拉伸率拉伸,在145℃热固化,并经松弛至3%的程度,以获得厚度为20μm的双轴拉伸的聚酯膜。
比较例3
重复实施例1的过程,除了使用含有98.5重量%的L-乳酸和1.5重量%的D-乳酸的聚乳酸基树脂(4032D,Nature Works LLC.)作为第一树脂层(A),并使用含有60重量%的L-乳酸和40重量%的D-乳酸的聚乳酸基树脂(Musashino chemical laboratory,Ltd.)作为第二树脂(B),以获得双层(A/B)共挤出片材。
由此获得的双层共挤出片材在70℃沿着纵向以3.0的拉伸率和在75℃沿着横向以3.8的拉伸率拉伸,在130℃热固化,并经松弛至3%的程度,以获得厚度为20μm的双轴拉伸的聚酯膜。
性能试验
评价在实施例1和2和比较例1到3中获得的各个聚酯膜的下列性质。结果显示于表1。
(1)热性质
在85℃经热浴处理30分钟后,以10℃/分钟的程序升温速率进行差示扫描量热仪(Perkin-Elmer DSC)分析。通过计算结晶温度中的第一个峰,和在热吸收峰中的下一个峰的峰面积确定熔化热(ΔHm,J/g)。
(2)热粘合强度
将均切成15mm(宽度)×150mm(长度)片状的两个膜样品放置,使得它们的热粘合层彼此相对,并在热梯度(40psi/秒和90℃)下施压。对熔合的膜用180°剥离试验器以300m/min进行剥离,通过剥离点的力测量热粘合强度(gf/英寸)。
(3)雾度
在85℃经热处理30分钟后用雾度仪(型号NDH-5000W,NipponDenshoku)测量膜样品的雾度(%)。
(4)冲击吸收能
根据ASTM D 3420用Film Impact Tester(Toyoseiki Inc.)测量冲击吸收能。所使用的摆锤(Pendulum)尖端是直径为1英寸的半球的形式。样品膜安装在具有直径为50mm圆孔的样品夹上。将由此测得的冲击吸收能(kgf-cm)除以样品膜厚度(μm)以确定每单位厚度的冲击吸收能(kgf-cm/μm)。取10次试验的平均值表示各个样品。
(5)穿孔强度
根据ASTM D 882用压缩模式(AGS-500D,Shimadzu)测量抗穿孔性(kgf)。所使用的尖端是以直径为1英寸的球形的形式。取10次试验的平均值表示压缩率为50mm/min下的各个样品。
(6)热收缩率
将尺寸为200mm长度和15mm宽度的样品在循环空气烘箱中维持在100℃ 5分钟,并测量膜长度的变化。使用下列等式,计算沿着纵向和横向的收缩率。
热收缩率(%)=(热处理前长度-热处理后长度)/热处理前长度×100
表1
如表1所示,本发明的多层脂肪族聚酯膜在热密封后可容易地通过用手拉而剥离,并且和比较例1到3的膜相比就热粘合性、耐热性、透明性、抗冲击性、抗穿孔性和尺寸稳定性而言显示改进的性质。
尽管本发明已通过上述具体实施例得以描述,应当认为本领域技术人员可对本发明作多种修改和变化,其同样落入由权利要求限定的本发明的范围。
Claims (6)
1.多层脂肪族聚酯膜,所述聚酯膜含有第一树脂层和层合在所述第一树脂层的一侧或两侧上的第二树脂层,其中:
所述第一树脂层含有在50-100重量%范围内的量的L-乳酸的聚乳酸基聚合物,所述第二树脂层含有在5-20重量%范围内的量的D-乳酸的聚乳酸基聚合物;和
在85℃经热浴处理30分钟后,所述聚酯膜的熔化热(ΔHm)为0.5-20J/g,雾度为20%或更小,热粘合强度为300-1500gf/英寸。
2.权利要求1的多层脂肪族聚酯膜,其中所述第一树脂层和第二树脂层的厚度比在1∶1到20∶1的范围内。
3.权利要求1的多层脂肪族聚酯膜,所述聚酯膜每单位厚度的冲击吸收能为0.5kgf-cm/μm或更大。
4.权利要求1的多层脂肪族聚酯膜,所述聚酯膜的穿孔强度为0.8kgf或更大。
5.权利要求1的多层脂肪族聚酯膜,所述聚酯膜在100℃经受热空气5分钟后在纵向和横向的热收缩率为5%或更小。
6.含有根据权利要求1到5任意一项的多层脂肪族聚酯膜的包装材料。
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