CN103153612A - 多层膜 - Google Patents
多层膜 Download PDFInfo
- Publication number
- CN103153612A CN103153612A CN2011800421289A CN201180042128A CN103153612A CN 103153612 A CN103153612 A CN 103153612A CN 2011800421289 A CN2011800421289 A CN 2011800421289A CN 201180042128 A CN201180042128 A CN 201180042128A CN 103153612 A CN103153612 A CN 103153612A
- Authority
- CN
- China
- Prior art keywords
- multilayer film
- resin combination
- polylactic acid
- based polymer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
- B29C48/83—Heating or cooling the cylinders
- B29C48/832—Heating
-
- 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
-
- 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
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
-
- 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
- B32B5/18—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 features of a layer of foamed material
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/516—Oriented mono-axially
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及由脂肪族聚碳酸酯和聚乳酸基聚合物共挤出的多层膜和用于生产该多层膜的方法。根据本发明,即使没有单独的粘合层,也可以制造具有优异粘合特性的多层膜。
Description
技术领域
本发明涉及由脂肪族聚碳酸酯和聚乳酸基聚合物共挤出的多层膜和用于生产该多层膜的方法。
背景技术
脂肪族聚碳酸酯具有优异的氧阻隔特性、透明度等,但由于低Tg而难以以单层膜使用,在大多数情况下,其需要在使用时与其它树脂层合。但是,当能够粘合两种树脂的合适的粘合剂用于层合或共挤出时,为了使脂肪族聚碳酸酯与其它种类的树脂(如PE、PP等)层合,需要用于能够粘合两种树脂的连接层的树脂。
由于其可生物降解性和固有物理特性,聚乳酸基聚合物可以不同地用作膜、片、纤维等,但在需要防止由其大的氧透过性而引起酸化的包装领域中受到限制。
发明内容
技术问题
本发明的一个目的是通过共挤出脂肪族聚碳酸酯和聚乳酸基聚合物来提供界面之间具有优异的粘合特性并且不再需要单独的粘合层或连接层的多层膜。
特别地,与使用聚乳酸基聚合物的模制体相比,本发明可以赋予优异的氧阻隔特性、低温热粘合特性和可打印性,并且提供了因不需要粘合层或连接层而能够降低原材料成本以及因简化了的层构成而显著地降低了制造成本的模制体。
此外,本发明旨在提供通过在预定温度下单轴地或双轴地拉伸模制体(即,膜或片)而得到的收缩膜。
问题的解决方案
本发明涉及其中脂肪族聚碳酸酯和聚乳酸基聚合物层合的模制体,更特别地,涉及片型或膜型的多层膜。
本发明人证实,当共挤出脂肪族聚碳酸酯和聚乳酸基聚合物时,两个层彼此良好粘合并且彼此几乎不分层,即使没有粘合层和连接层也是如此,从而完成了本发明。
因此,本发明人发现,与其中单独使用聚乳酸基聚合物的情况相比,在其中脂肪族聚碳酸酯和聚乳酸基聚合物层合在多层结构中的情况下,可以提供氧阻隔特性、低温热密封特性和可打印性。在这里,因为不需要粘合树脂或连接树脂,所以可以降低原材料的成本,并且因为简化了层的构成,所以可以显著地降低制造成本。
此外,本发明人证实,当在预定温度下单轴地或双轴地拉伸如此形成的具有脂肪族聚碳酸酯和聚乳酸基聚合物的该层合结构的模制体(即,膜或片)时,其收缩在高于预定温度下发生,因而,该模制体可以被用作收缩膜,从而完成了本发明。
具体地,本发明涉及由两层或更多层组成的多层膜,其中,包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层和包含聚乳酸基聚合物的聚乳酸基聚合物层层合。
更具体地,将参照附图来描述本发明。
如图1所示,本发明的一个一般方面提供了双层结构的膜或片,其中,包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10和在脂肪族聚碳酸酯层10的一个表面上的包含聚乳酸基聚合物的聚乳酸基聚合物层20被层合。
如图2所示,本发明的另一个一般方面提供了层合的三层结构的膜或片,其中,包含聚乳酸基聚合物的聚乳酸基聚合物层20和在聚乳酸基聚合物层20的两个表面上的包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10被层合。
如图3所示,本发明的另一个一般方面提供了三层结构的膜或片,其中,包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10和在脂肪族聚碳酸酯层10的两个表面上的包含聚乳酸基聚合物的聚乳酸基聚合物层20被层合。
如图4所示,本发明的另一个一般方面提供了四层结构的膜或片,其中,包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20/包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20被层合。
如图5所示,本发明的另一个一般方面提供了五层结构的膜或片,其中,包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20/包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20/包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10被层合。
如图6所示,本发明的另一个一般方面提供了五层结构的膜或片,其中包含聚乳酸基聚合物的聚乳酸基聚合物层20/包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20/包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层10/包含聚乳酸基聚合物的聚乳酸基聚合物层20被层合。
然而,这些方面仅用于清楚地说明本发明的构成,但并非旨在限制本发明。本发明不仅限于具有两层或更多层的情况。
此外,还可以将合适的添加剂(如防粘剂(slip agent)、防堵剂(blocking preventing agent)等)引入多层膜的外层以赋予防粘特性和防止堵塞,其种类不受限制。
在本发明中,“层合”意指“通过共挤出形成”,因为脂肪族聚碳酸酯与聚乳酸基聚合物之间的粘合特性优异,脂肪族聚碳酸酯和聚乳酸基聚合物通过共挤出层合以提供即使没有粘合层或连接层也具有优异粘合特性的多层膜。
本发明的另一方面是通过单轴和双轴地拉伸上述多层膜而能够被用作收缩膜的多层膜。当被单轴或双轴地拉伸,然后在70℃至100℃的温水浴中浸没30秒时,本发明的多层膜在拉伸方向的收缩比为5%至70%,并且适合用作收缩膜(shrinkage film)。
在下文中,将详细描述本发明的构成。
在本发明中,可以使用通过使二氧化碳和一种或两种或更多种环氧化物化合物反应而得到的聚碳酸酯共聚物或三元共聚物作为脂肪族聚碳酸酯。这里,环氧化物化合物可以是选自以下的一种或更多种:被卤素或烃氧基取代或者未被取代的氧化(C2-C10)亚烷基;被卤素或烃氧基取代或者未被取代的氧化(C4-C20)环亚烷基;和被卤素烃氧基、烷基或芳基取代或者未被取代的氧化(C8-C20)苯乙烯。
烃氧基(alkoxy)的具体实例可包括烷基氧基(alkyloxy)、芳基氧基、芳烷基氧基等;芳基氧基的具体实例可包括苯氧基、联苯氧基、萘氧基等。烃氧基、烷基和芳基可具有选自卤素原子和烃氧基基团中的取代基。
在本发明中,环氧化物化合物的具体实例可包括:环氧乙烷、环氧丙烷、环氧丁烷、环氧戊烷、环氧己烷、环氧辛烷、环氧癸烷、环氧十二烷、环氧十四烷、环氧十六烷、环氧十八烷、一氧化丁二烯(butadienemonoxide)、1,2-环氧基-7-辛烯、环氧氟丙烷、环氧氯丙烷、环氧溴丙烷、异丙基缩水甘油醚、丁基缩水甘油醚、叔丁基缩水甘油醚、2-乙基己基缩水甘油醚、烯丙基缩水甘油醚、氧化环戊烯(cyclopenetene oxide)、氧化环己烯(cyclohexene oxide)、氧化环辛烯(cyclooctene oxide)、氧化环十二烯(cyclododecene oxide)、氧化α-蒎烯(alpha-pinene oxide)、2,3-环氧降冰片烷、氧化柠檬烯(lemonene oxide)、狄氏剂(dieldrine)、2,3-环氧丙基苯、氧化苯乙烯(styrene oxide)、氧化苯基丙烯(phenylpropyleneoxide)、均二苯乙烯氧化物(stilbene oxide)、氯代均二苯乙烯氧化物(chlorostilbene oxide)、二氯代均二苯乙烯氧化物(dichlorostilbeneoxide)、1,2-环氧基-3-苯氧基丙烷、苄氧基甲基环氧乙烷、缩水甘油基-甲基苯基醚、氯代苯基-2,3-环氧基丙基醚、epoxypropyl methodyphenylether、联苯基缩水甘油醚、缩水甘油基萘基醚等。
可以通过使用溶液聚合或本体聚合来聚合聚碳酸酯共聚物或三元共聚物,更具体地,可以通过在一种或更多种环氧化物化合物和催化剂的存在下,使用有机溶剂作为反应介质同时供入二氧化碳来聚合。可以使用选自以下的单独一种或者两种或更多种的组合作为溶剂:脂肪族烃,如戊烷、辛烷、癸烷、环己烷等;芳族烃,如苯、甲苯、二甲苯等;和卤代烃,如氯代甲烷、二氯甲烷、氯仿、四氯化碳、1,1-二氯乙烷、1,2-二氯乙烷、氯乙烷、三氯乙烷、1-氯丙烷、2-氯丙烷、1-氯丁烷、2-氯丁烷、1-氯代-2-甲基丙烷、氯苯、溴苯等。二氧化碳的压力可以为1大气压至100大气压,优选为5大气压至30大气压。共聚合反应时的聚合温度可以为20℃至120℃,优选为50℃至90℃。更优选地,可以进行使用单体本身作为溶剂的本体聚合。
脂肪族聚碳酸酯共聚物的玻璃化转变温度(Tg)可以为0℃至40℃,三元共聚物的玻璃化转变温度可以为0℃至110℃。此外,重均分子量优选为50,000至500,000,熔融指数(MI)(ASTM D-1238,150℃,5kg)为0.1g/10分钟至200g/10分钟,优选为1g/10分钟至50g/10分钟,分子量分布(Mw/Mn)为1.3或更多,优选为2.5或更多。如果MI非常高,则挤出稳定性和层形成不稳定,拉伸均匀性降低。如果MI非常低,则挤出率因过量的挤出负荷而变慢。此外,如果分子量分布变宽,则可以稳定地形成从模头排出的聚合物的熔体帘(melt curtain),挤出负荷降低,因而挤出率可以升高。
更具体地,可以使用聚碳酸亚烷基酯作为脂肪族聚碳酸酯,特别地,聚碳酸亚丙酯可以是有利的,因为其氧阻隔特性优异,并且其收缩特性可以易于调节。
在本发明中,可以将包含80重量%或更多L-乳酸的聚乳酸基聚合物用作聚乳酸基聚合物。如果L-乳酸的含量低于80重量%,则其耐热特性显著降低。作为聚乳酸基聚合物,可以使用Nature Works Company的PLA聚合物系列等,但聚乳酸基聚合物不限于此。
在本发明中,分别制备了脂肪族聚碳酸酯树脂和聚乳酸基聚合物,并共挤出为树脂组合物。这里,可以制备母料托架(mater batch pallet)类型的树脂组合物。
根据情况需要,可以将通常用于制造膜或片(如颜料、染料、填料、抗氧化剂、紫外线阻隔剂、抗静电剂、防粘结剂(antiblocking agent)、防粘剂等)的添加剂添加到树脂组合物中,其种类不受限制。
接下来,将详细描述本发明的多层膜的生产方法。
在另一个一般方面,用于生产多层膜的方法包括:a)制备包含脂肪族聚碳酸酯的第一树脂组合物;b)制备包含聚乳酸基聚合物的第二树脂组合物;和c)使第一树脂组合物和第二树脂组合物熔融,然后使用T-模头、喷式或管式挤出机共挤出第一树脂组合物和第二树脂组合物。
此外,该方法可以进一步包括:必要时,在步骤c)之后d)单轴或双轴地拉伸共挤出片。
在本发明中,就脂肪族聚碳酸酯而言,共挤出时优选的熔融温度范围为120℃至210℃,就聚乳酸基聚合物而言为180℃至250℃。共挤出通过使用T-模头、喷式或管式挤出机来进行。如果其熔融温度低于上述温度范围,则层之间的粘合强度降低。如果其熔融温度高于上述温度范围内,则可能发生过度的热降解,从而,因片中热降解的产物而产生泡。
此外,在共挤出时,通过调节模头的形式来层合两层或更多层,层的数目不受限制。
更具体地,例如,可以层合两层的第一树脂组合物/第二树脂组合物、三层的第一树脂组合物/第二树脂组合物/第一树脂组合物、三层的第二树脂组合物/第一树脂组合物/第二树脂组合物、四层的第一树脂组合物/第二树脂组合物/第一树脂组合物/第二树脂组合物、五层的第一树脂组合物/第二树脂组合物/第一树脂组合物/第二树脂组合物/第一树脂组合物、或者五层的第二树脂组合物/第一树脂组合物/第二树脂组合物/第一树脂组合物/第二树脂组合物。
在本发明中,在60℃至90℃下以2倍至6倍的拉伸比进行拉伸,从而产生适于作为具有收缩特性的收缩膜的多层膜。这里,可以通过已知方法(如滚动拉伸或拉幅拉伸或同时双轴拉伸或连续双轴拉伸)进行拉伸。发明的有益效果
由于各树脂的优越粘合特性,本发明的多层膜不再需要粘合层或连接层,并且具有改进的物理特性。
此外,单轴或双轴地拉伸本发明的多层膜以产生收缩膜,本发明的多层膜可用作包装材料等。
附图说明
图1是根据本发明的优选实施方案具有双层结构的多层膜的横截面视图;
图2是根据本发明的另一优选实施方案具有三层结构的多层膜的横截面视图;
图3是根据本发明的又一优选实施方案具有三层结构的多层膜的横截面视图;
图4是根据本发明的另一优选实施方案具有四层结构的多层膜的横截面视图;
图5是根据本发明的另一优选实施方案具有五层结构的多层膜的横截面视图;
图6是根据本发明的又一优选实施方案具有五层结构的多层膜的横截面视图;
具体实施方式
在下文中,将参照实施例来详细描述本发明,所述实施例并非旨在限制本发明。
在下文中,通过下述方法来测量物理特性。
1.重均分子量
通过使用用四氢呋喃(THF)作为溶剂的凝胶渗透色谱来测量重均分子量(室温GPC,Agilent1200HPLC)。
2.膜厚度
测量(TOYOSEIKI厚度计B-1型)了多层膜在若干点的厚度,使用其平均值。
3.分层
将多层膜切为5cm宽和20cm长的大小,将胶带贴到膜的两面上,使得胶带重叠膜的全部宽度,并且在长度方向为5cm。然后,当在垂直于膜表面的方向上从膜的两面剥去胶带时,观察到多层膜的各层彼此分层或不分层。在多至三次试验中,其中各层彼此不层合的情况确定为不层合。
4.抗张强度,伸长率
根据ASTM D-638通过使用万能试验机(Universal Testing Machine,INSTRON4301)来测量抗张强度和伸长率。
5.雾度
将多层膜切为膜宽度为7cm、膜长度为7cm的大小。测量两次或更多次雾度,使用其平均值(雾度计:Haze Meter300A,NIPPONDENSHOKU)。
6.氧透过率
通过使用MOCON OX-TRAN装置(2161型)来测量氧透过率。
7.水蒸气透过率
通过使用MOCON PERMATRAN-W装置(3133型)来测量水蒸气透过率。
8.膜收缩比
将拉伸的多层膜切为膜宽度为6cm、膜长度为6cm的大小,然后将其在温水浴中保留预定的时间段(30秒),均匀保持温水浴的温度,然后测量其长度差。
[实施例1]
通过以下方法来生产三层膜PLA/PPC/PLA:将重均分子量为180,000的聚碳酸亚丙酯(PPC,由SK Energy Company生产,通过使二氧化碳、亚丙基氧和环己烯氧反应而得到的三元共聚物)和Natureworks Company的PLA4032D(其为聚乳酸基聚合物)放入挤出机中,接着熔融,然后通过T-模头共挤出。这里,在共挤出时,在140℃(料筒1)-170℃(料筒2)-180℃(料筒3)-180℃(模头)的挤出机温度下熔融挤出聚碳酸亚丙酯,在180℃(料筒1)-180℃(料筒2)-200℃(料筒3)-200℃(模头)的挤出机温度下熔融挤出聚乳酸基聚合物。
作为测量结果,所产生的多层膜的厚度为68.1μm。
测量所生产的膜的物理特性,结果列表于表1中。
[实施例2]
通过与实施例1相同的方法生产多层膜,不同之处在于,在共挤出时将各层的厚度调节为50μm/80μm/60μm,以及通过在85℃下使用双轴拉伸机分别在横向和纵向上以3×3倍的拉伸比拉伸所产生的片。测量所生产的膜的物理特性,结果列表于表1中。
[实施例3]
通过与实施例2相同的方法生产多层膜,不同之处在于,以3×4倍的拉伸比进行拉伸。
测量所生产的膜的物理特性,结果列表于表1中。
[表1]
如表1所示,可以看出,与未拉伸的膜相比,经双轴拉伸的膜的机械特性提高,并且雾度降低从而增加了透明度,而氧透过率和水蒸气透过率与经拉伸的膜的厚度成反比。
[实施例4]
通过制备与实施例2具有相同厚度的片来生产多层膜,然后如下表2所示调节拉伸比和拉伸温度。将如此产生的膜在70℃至100℃的温水浴中浸没30秒,测量各膜的收缩比。
结果列表于表2中。
[表2]
如表2所示,可以看出,与单轴拉伸相比,双轴拉伸进一步增加了收缩比,并且以相同的拉伸比,收缩比随拉伸温度变低而增加。
[实施例5]
使用与实施例1相同的装置和树脂来制备其中PPC层变厚的片。各层的厚度为:PLA/PPC/PLA=14μm/142μm/21μm,总厚度为176μm。在60℃和70℃的拉伸温度下单轴拉伸如此产生的膜,将经拉伸的膜在70℃、80℃和90℃的温水浴中浸没30秒。然后,测量各膜的收缩比。
结果列表于表3中。
[表3]
如表3所示,可以看出,当PPC层的厚度增加时,收缩比一般增加。可以看出,如实施例4,收缩比随拉伸温度降低而增加,当收缩温度高时,收缩比大。
[实施例6]
使用与实施例1相同的设备和树脂来生产五层膜PLA/PPC/PLA/PPC/PLA。这里,在共挤出时,在140℃(料筒1)-170℃(料筒2)-180℃(料筒3)-180℃(模头)的挤出机温度下,熔融挤出聚碳酸亚丙酯,在180℃(料筒1)-180℃(料筒2)-200℃(料筒3)-200℃(模头)的挤出机温度下,熔融挤出聚乳酸基聚合物。
所生产的多层膜的厚度为105μm(20.5μm/18.2μm/20.2μm/19.1μm/21.2μm),测量所生产的膜的物理特性,结果列表于表4中。
[表4]
如实施例1与实施例6之间的比较所示,随着PPC层的厚度因PPC的多层层合而增加,氧阻隔特性和水阻隔特性改进,抗张强度提高。
工业实用性
由于各树脂的优越粘合特性,本发明的多层膜不再需要粘合层或连接层,并且具有改进的物理特性。
此外,单轴或双轴地拉伸本发明的多层膜以产生收缩膜,本发明的多层膜可用作包装材料等。
Claims (16)
1.一种多层膜,其中使至少一个包含脂肪族聚碳酸酯的脂肪族聚碳酸酯层与至少一个包含聚乳酸基聚合物的聚乳酸基聚合物层以至少两个层的形式层合。
2.根据权利要求1所述的多层膜,其中所述多层膜通过共挤出层合。
3.根据权利要求2所述的多层膜,其中所述共挤出通过以下方法来进行:在120℃至210℃下熔融挤出所述脂肪族聚碳酸酯,在180℃至250℃下熔融挤出所述聚乳酸基聚合物,然后使用T-模头、喷式或管式挤出机进行共挤出。
4.根据权利要求2所述的多层膜,其中所述多层膜在60℃至90℃下以2倍至6倍的拉伸比被单轴或双轴地拉伸。
5.根据权利要求4所述的多层膜,其中所述多层膜被单轴或双轴地拉伸之后,当在70℃至100℃的温水浴中浸没30秒时,所述多层膜的收缩比为5%至60%。
6.根据权利要求1所述的多层膜,其中包含所述聚乳酸基聚合物的所述聚乳酸基聚合物层层合在包含所述脂肪族聚碳酸酯的所述脂肪族聚碳酸酯层的一个表面上、或者包含所述聚乳酸基聚合物的所述聚乳酸基聚合物层层合在包含所述脂肪族聚碳酸酯的所述脂肪族聚碳酸酯层的两个表面上。
7.根据权利要求1所述的多层膜,其中所述脂肪族聚碳酸酯是通过使二氧化碳和一种或更多种环氧化物化合物反应而得到的聚碳酸酯共聚物或三元共聚物,所述环氧化物化合物选自:被卤素或烃氧基取代或者未被取代的氧化(C2-C10)亚烷基;被卤素或烃氧基取代或者未被取代的氧化(C4-C20)环亚烷基;和被卤素、烃氧基、烷基或芳基取代或者未被取代的氧化(C8-C20)苯乙烯。
8.根据权利要求1所述的多层膜,其中所述脂肪族聚碳酸酯共聚物的玻璃化转变温度(Tg)为0℃至40℃,所述三元共聚物的玻璃化转变温度(Tg)为0℃至110℃。
9.根据权利要求1所述的多层膜,其中所述脂肪族聚碳酸酯是聚碳酸亚丙酯。
10.根据权利要求1所述的多层膜,其中所述聚乳酸基聚合物的L-乳酸含量为80重量%或更多。
11.一种用于生产多层膜的方法,包括:
a)制备包含脂肪族聚碳酸酯的第一树脂组合物;
b)制备包含聚乳酸基聚合物的第二树脂组合物;和
c)使所述第一树脂组合物和所述第二树脂组合物熔融,然后使用T-模头、喷式或管式挤出机共挤出所述第一树脂组合物和所述第二树脂组合物。
12.根据权利要求11所述的方法,其中在共挤出时,所述第一树脂组合物和所述第二树脂组合物以两层或更多层的形式层合。
13.根据权利要求11所述的方法,还包括:
d)在步骤c)之后,单轴或双轴地拉伸共挤出片。
14.根据权利要求13所述的方法,其中进行所述共挤出以提供第一树脂组合物/第二树脂组合物的双层结构,和第二树脂组合物/第一树脂组合物/第二树脂组合物的三层结构。
15.根据权利要求11所述的方法,其中在共挤出时,在120℃至210℃下熔融挤出所述第一树脂组合物,在180℃至250℃下熔融挤出所述第二树脂组合物。
16.根据权利要求13所述的方法,其中在60℃至90℃下,以2倍至6倍的拉伸比单轴或双轴地拉伸所述多层膜。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20100086276 | 2010-09-03 | ||
KR10-2010-0086276 | 2010-09-03 | ||
KR1020110077928A KR101383665B1 (ko) | 2010-09-03 | 2011-08-04 | 다층필름 |
KR10-2011-0077928 | 2011-08-04 | ||
PCT/KR2011/006381 WO2012030129A2 (en) | 2010-09-03 | 2011-08-30 | Multilayer film |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103153612A true CN103153612A (zh) | 2013-06-12 |
CN103153612B CN103153612B (zh) | 2015-03-04 |
Family
ID=46130983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180042128.9A Active CN103153612B (zh) | 2010-09-03 | 2011-08-30 | 多层膜 |
Country Status (8)
Country | Link |
---|---|
US (2) | US8568636B2 (zh) |
EP (1) | EP2611610A4 (zh) |
JP (1) | JP2013540612A (zh) |
KR (1) | KR101383665B1 (zh) |
CN (1) | CN103153612B (zh) |
CA (1) | CA2807333A1 (zh) |
TW (1) | TW201210820A (zh) |
WO (1) | WO2012030129A2 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103640290A (zh) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | 高阻隔性完全生物降解复合膜 |
CN108290396A (zh) * | 2016-03-08 | 2018-07-17 | Lg化学株式会社 | 包含聚碳酸亚烷基酯的多层膜及其制造方法 |
CN115240339A (zh) * | 2022-09-23 | 2022-10-25 | 江苏睿道信息科技有限公司 | 一种医用自助智能支付设备的消毒装置 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101791215B1 (ko) * | 2010-11-19 | 2017-10-27 | 에스케이씨 주식회사 | 환경친화형 열수축 필름 |
KR101406989B1 (ko) * | 2011-01-18 | 2014-06-13 | 에스케이이노베이션 주식회사 | 다층필름 |
DK2484602T4 (da) * | 2011-02-04 | 2022-05-30 | Mosca Gmbh | Omsnøringsbånd af fornyelige råstoffer |
WO2013063310A1 (en) * | 2011-10-26 | 2013-05-02 | E. I. Du Pont De Nemours And Company | Multilayer film structure comprising renewably sourced materials |
US10853741B2 (en) * | 2013-12-16 | 2020-12-01 | MetaGovernance, Inc. | Information governance platform |
WO2017155308A1 (ko) * | 2016-03-08 | 2017-09-14 | 주식회사 엘지화학 | 폴리알킬렌 카보네이트를 포함하는 다층 필름 및 그의 제조 방법 |
RU2761017C2 (ru) | 2016-08-11 | 2021-12-02 | Кимберли-Кларк Ворлдвайд, Инк. | Усиленная пленка на основе термопластичного полиолефинового эластомера |
WO2018136207A2 (en) | 2016-12-28 | 2018-07-26 | Sabic Global Technologies B.V. | Sheets including polyphenylene and an aryl salicylate and methods of making thereof |
WO2018125855A1 (en) | 2016-12-28 | 2018-07-05 | Sabic Global Technologies B.V. | Multilayer sheets including polyphenylene and polypropylene and methods of making thereof |
CN113698646B (zh) * | 2021-08-27 | 2022-09-16 | 江南大学 | 一种透明性保湿抗菌可降解包装膜及其制备方法与应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1335807A (zh) * | 1999-10-27 | 2002-02-13 | 三菱树脂株式会社 | 生物可降解的袋子 |
Family Cites Families (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4142021A (en) * | 1977-06-01 | 1979-02-27 | Air Products And Chemicals, Inc. | Oxygen barrier laminate films including a polyalkylene carbonate adhesive |
US4643925A (en) * | 1982-09-07 | 1987-02-17 | The Goodyear Tire & Rubber Company | Multi-layer polyisophthalate and polyterephthalate articles and process therefor |
US4482586A (en) * | 1982-09-07 | 1984-11-13 | The Goodyear Tire & Rubber Company | Multi-layer polyisophthalate and polyterephthalate articles and process therefor |
US4851507A (en) * | 1988-03-21 | 1989-07-25 | Arco Chemical Technology, Inc. | Melt processable aliphatic polycarbonate terpolymers |
US5089318A (en) * | 1989-10-31 | 1992-02-18 | The Mearl Corporation | Iridescent film with thermoplastic elastomeric components |
GB8925785D0 (en) * | 1989-11-15 | 1990-01-04 | Ici Plc | Multilayer film |
US6203750B1 (en) * | 1992-06-05 | 2001-03-20 | Cryovac, Inc | Method for making a heat-shrinkable film containing a layer of crystalline polyamides |
US5681514A (en) * | 1995-06-07 | 1997-10-28 | Sulzer Intermedics Inc. | Method for making an implantable conductive lead for use with a cardiac stimulator |
US5849401A (en) * | 1995-09-28 | 1998-12-15 | Cargill, Incorporated | Compostable multilayer structures, methods for manufacture, and articles prepared therefrom |
US6268026B1 (en) * | 1997-10-20 | 2001-07-31 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same |
US6426128B1 (en) * | 1998-01-06 | 2002-07-30 | Hna Holdings, Inc. | Co-processable multi-layer laminates for forming high strength, haze-free, transparent articles and methods of producing same |
FI112624B (fi) * | 1998-07-07 | 2003-12-31 | Enso Oyj | Kompostoituva pinnoitettu paperi tai kartonki, menetelmä sen valmistamiseksi sekä siitä saatuja tuotteita |
US6503549B1 (en) * | 1998-09-30 | 2003-01-07 | Cryovac, Inc. | Polyester tray package with lidding film having glycol-modified copolyester sealant layer |
DE19923839A1 (de) * | 1999-05-26 | 2000-11-30 | Mitsubishi Polyester Film Gmbh | Sammelpacksystem enthaltend eine siegelfähige Polyesterfolie |
JP2001011214A (ja) * | 1999-07-01 | 2001-01-16 | Okura Ind Co Ltd | 生分解性熱収縮フィルム |
JP4118038B2 (ja) * | 2001-09-07 | 2008-07-16 | ユニチカ株式会社 | 熱収縮性ポリ乳酸系フィルムの製造方法およびその方法により得られる熱収縮性ポリ乳酸系フィルム |
KR20050023226A (ko) * | 2001-11-30 | 2005-03-09 | 제너럴 일렉트릭 캄파니 | 레조르시놀 아릴레이트 폴리에스터를 포함하는 다층 제품및 그의 제조방법 |
US6896843B2 (en) * | 2002-08-30 | 2005-05-24 | Kimberly-Clark Worldwide, Inc. | Method of making a web which is extensible in at least one direction |
US6881375B2 (en) * | 2002-08-30 | 2005-04-19 | Kimberly-Clark Worldwide, Inc. | Method of forming a 3-dimensional fiber into a web |
US7261935B2 (en) * | 2002-12-19 | 2007-08-28 | E. I. Du Pont De Nemours And Company | Co-extrudable multi-layer polymer |
JP4167107B2 (ja) * | 2003-04-02 | 2008-10-15 | ユニチカ株式会社 | ポリ乳酸系二軸延伸積層フィルム |
US7288312B2 (en) * | 2003-04-22 | 2007-10-30 | Mitsubishi Polyester Film Gmbh | Coextruded, hot-sealable and peelable polyester film having low peeling resistance, process for its production and its use |
US7144632B2 (en) * | 2003-06-11 | 2006-12-05 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyetherester compositions, articles, films, coating and laminates and processes for producing same |
US7060217B2 (en) * | 2003-06-12 | 2006-06-13 | General Electric Company | Composite articles comprising resorcinol arylate polyester and method for making thereof |
US7390558B2 (en) * | 2003-07-18 | 2008-06-24 | Mitsubishi Plastics, Inc. | Aliphatic polyester film and packaging material |
US7998385B2 (en) * | 2003-10-01 | 2011-08-16 | Kureha Corporation | Method for producing multilayer stretch-molded article |
US20050112352A1 (en) * | 2003-11-26 | 2005-05-26 | Laney Thomas M. | Polylactic-acid-based sheet material and method of making |
JP2005329557A (ja) * | 2004-05-18 | 2005-12-02 | Mitsui Chemicals Inc | 多層フィルム |
JP2005330332A (ja) * | 2004-05-18 | 2005-12-02 | Tohcello Co Ltd | 脂肪族ポリエステル組成物、それからなるフィルム及び積層フィルム。 |
CN100522557C (zh) * | 2004-05-31 | 2009-08-05 | 东丽株式会社 | 液体流的合流装置和多层薄膜的制造方法 |
JPWO2005120978A1 (ja) * | 2004-06-10 | 2008-04-10 | ユニチカ株式会社 | 生分解性ガスバリア容器およびその製造方法 |
US8075966B2 (en) * | 2004-07-22 | 2011-12-13 | Graham Packaging Company, Ltd. | Delamination-resistant multilayer container, preform, article and method with oxygen barrier formulations |
US20070014977A1 (en) * | 2005-07-12 | 2007-01-18 | Daniel Graney | Multilayer Film |
JP2009534509A (ja) * | 2006-04-27 | 2009-09-24 | ビーエーエスエフ ソシエタス・ヨーロピア | 透明ポリプロピレンカーボネート配合物 |
KR100786005B1 (ko) | 2006-08-18 | 2007-12-14 | 에스케이씨 주식회사 | 다층 지방족 폴리에스터 필름 |
JP2008195003A (ja) * | 2007-02-15 | 2008-08-28 | Matsushita Electric Ind Co Ltd | 難燃性フィルムおよびその製造方法 |
KR101235462B1 (ko) * | 2007-03-29 | 2013-02-20 | 미쓰비시 쥬시 가부시끼가이샤 | 카드용 코어 시트 |
KR20100017602A (ko) * | 2007-06-05 | 2010-02-16 | 데이진 가부시키가이샤 | 폴리카보네이트 수지 조성물 |
US8513144B2 (en) * | 2007-06-15 | 2013-08-20 | Honeywell International Inc | Property films from renewable polymers |
US7951438B2 (en) * | 2007-12-10 | 2011-05-31 | Toray Plastics (America), Inc. | Biaxially oriented polylactic acid film with high barrier |
US7678444B2 (en) * | 2007-12-17 | 2010-03-16 | International Paper Company | Thermoformed article made from renewable polymer and heat-resistant polymer |
US8246878B2 (en) * | 2008-04-30 | 2012-08-21 | Fina Technology, Inc. | Composites comprising a polymer and a layered compound and methods of preparing and using same |
US20110311794A1 (en) * | 2009-06-19 | 2011-12-22 | Qinghai Zhou | Biodegradable complex oxygen barrier film and application thereof |
US20120305083A1 (en) * | 2011-06-04 | 2012-12-06 | Wlp Holding Corporation | Co-extruded oxidation-resistant polyethylene pipe and method of manufacture |
-
2011
- 2011-08-04 KR KR1020110077928A patent/KR101383665B1/ko active IP Right Grant
- 2011-08-25 US US13/218,220 patent/US8568636B2/en active Active
- 2011-08-26 TW TW100130651A patent/TW201210820A/zh unknown
- 2011-08-30 CN CN201180042128.9A patent/CN103153612B/zh active Active
- 2011-08-30 JP JP2013527008A patent/JP2013540612A/ja active Pending
- 2011-08-30 CA CA2807333A patent/CA2807333A1/en not_active Abandoned
- 2011-08-30 WO PCT/KR2011/006381 patent/WO2012030129A2/en active Application Filing
- 2011-08-30 EP EP11822104.3A patent/EP2611610A4/en not_active Withdrawn
-
2013
- 2013-10-04 US US14/046,239 patent/US20140037965A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1335807A (zh) * | 1999-10-27 | 2002-02-13 | 三菱树脂株式会社 | 生物可降解的袋子 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103640290A (zh) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | 高阻隔性完全生物降解复合膜 |
CN108290396A (zh) * | 2016-03-08 | 2018-07-17 | Lg化学株式会社 | 包含聚碳酸亚烷基酯的多层膜及其制造方法 |
CN115240339A (zh) * | 2022-09-23 | 2022-10-25 | 江苏睿道信息科技有限公司 | 一种医用自助智能支付设备的消毒装置 |
Also Published As
Publication number | Publication date |
---|---|
US8568636B2 (en) | 2013-10-29 |
KR20120023553A (ko) | 2012-03-13 |
TW201210820A (en) | 2012-03-16 |
CN103153612B (zh) | 2015-03-04 |
EP2611610A4 (en) | 2015-04-01 |
US20140037965A1 (en) | 2014-02-06 |
EP2611610A2 (en) | 2013-07-10 |
US20120058346A1 (en) | 2012-03-08 |
WO2012030129A3 (en) | 2012-06-28 |
CA2807333A1 (en) | 2012-03-08 |
WO2012030129A2 (en) | 2012-03-08 |
KR101383665B1 (ko) | 2014-04-09 |
JP2013540612A (ja) | 2013-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103153612B (zh) | 多层膜 | |
EP2665603B1 (en) | Multilayer film | |
KR101484875B1 (ko) | 성형용 수지 시트 및 성형체 | |
CN102574374B (zh) | 多层膜 | |
US8945704B2 (en) | Multi-layer film, decorative molding film and molded body | |
EP2237949B1 (en) | Multilayer articles and methods for making multilayer articles | |
EP2173794B1 (en) | Polyethylene films | |
KR20120054160A (ko) | 환경친화형 다층 필름 | |
US20120288709A1 (en) | Multilayered Film Having Excellent Barrier and Thermal Adhesion Properties | |
CN110446755B (zh) | 高分子组合物及利用其的薄膜 | |
KR102448024B1 (ko) | 고분자 조성물 및 이를 이용한 필름 | |
WO2023219866A1 (en) | Thermoplastic polyurethane and uses thereof | |
KR20220134201A (ko) | 폴리케톤계 3중 블렌드 배리어층을 포함하는 포장재용 다층 필름 및 그 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |