CN1348407A - 通过吹膜挤出法制备热塑性膜的方法及由此制得的薄膜 - Google Patents
通过吹膜挤出法制备热塑性膜的方法及由此制得的薄膜 Download PDFInfo
- Publication number
- CN1348407A CN1348407A CN00806661A CN00806661A CN1348407A CN 1348407 A CN1348407 A CN 1348407A CN 00806661 A CN00806661 A CN 00806661A CN 00806661 A CN00806661 A CN 00806661A CN 1348407 A CN1348407 A CN 1348407A
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- Prior art keywords
- water
- film
- ether
- cellulose
- polymer
- 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.)
- Pending
Links
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- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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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
- 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
- B29C48/0019—Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
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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
- 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
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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
- 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
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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
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
-
- 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
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31884—Regenerated or modified cellulose
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31884—Regenerated or modified cellulose
- Y10T428/31891—Where addition polymer is an ester or halide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
一种通过吹膜挤出法制备热塑性膜的方法包括:将熔融的热塑性聚合物从管形模头中挤出以形成一种熔融聚合物管;当熔融聚合物管脱离模头时将管的内壁与一种水溶性多糖醚的水溶液相接触;将熔融聚合物管进行充气膨胀以形成被吹胀的圆筒形薄膜,而后将被吹胀的圆筒形的薄膜消气成平膜。这种热塑性膜的表面有一层水溶性多糖醚的涂层。
Description
本发明涉及一种通过吹膜挤出制备热塑性薄膜的方法。
例如，在美国专利USP2,409,521，2,476,140，2,634,459，3,750,948，4,997,616，5,213,725以及5,700,489中，均提及和描述了吹膜挤出方法。在吹膜挤出法中，熔融的热塑性聚合物通过管形模头挤出。被挤出的熔融聚合物以无定形的聚合物管的形式脱离模头，并且在内部空气压力的作用下形成一个气囊或被吹胀的膜。吹胀的膜消气后制成平膜。典型的是，当无定形聚合物管脱离挤出机模头时，在聚合物管中引入或回流矿物油/水溶液(软管溶液(sock solution))以保持无定形聚合物管(软管(sock))的温度并使其为均一的形态。软管溶液也可以帮助减少层间空气的截留并能控制无定形管和成品膜之间的层间粘附。当无定形管被消气制成平膜时，控制层间的粘附可以限制无定形膜的边缘熔接程度。在单层缠绕膜中，软管溶液使得薄膜层可以轻易地分离并在单层膜的卷辊上进行缠绕。对于双层缠绕膜，成品膜无需分离而是以双层的形式缠绕在卷辊上，对于新制的和已制成的薄膜，软管溶液均可提供最少的边缘熔接的层间粘附。术语“层间粘附”是指，当聚合物管在最后一套夹辊之间被压平后并以双层膜形式缠绕在卷辊上时，聚合物管相对表面之间的粘附。
需要能够提供出一种在吹膜挤出法中性能优于矿物油的，可作为软管溶液使用的材料。
第一方面，本发明是一种通过吹膜挤出法制备热塑性薄膜的方法，包括将熔融的热塑性聚合物从一个管形模头中挤出以形成一种熔融聚合物管；当熔融聚合物管脱离模头时将管的内壁与一种水溶性多糖醚的水溶液相接触；将熔融聚合物管进行充气膨胀以形成一吹胀的圆筒形薄膜，而后将这个圆筒形的薄膜消气制成平膜。
第二方面，本发明是一种表面有水溶性多糖醚涂层的热塑性薄膜。
图一是本发明中所使用的设备和方法的示意图。
从图中可知，图一所示为本发明方法中所使用的常规设备10。一种热塑性聚合物12通过挤出机14被挤出，经过管形模头16后脱模。当聚合物管18脱离模头16时，管的内壁与含有一种水溶性多糖醚水溶液的软管溶液20进行接触。通过一输送管22将软管溶液20送入到聚合物管18中。聚合物管18在淬火浴24中快速冷却至5℃到20℃，使其变成无定形状态，而后将其通过第一套夹辊26进行压平。被压平的无定形管又在再加热浴28中被重新加热至25℃到30℃，而后通过位于再加热浴之外的第二套夹辊30。在第二套夹辊30和第三套夹辊40之间，向无定形管32中引入空气进行横向拉伸，将其扩张至一个更大的直径(大约为原直径的4倍)以形成一个吹胀的泡膜34。同时，第三套夹辊40以高于第二套夹辊30的速度运转，将聚合物管沿着机器方向拉伸。吹胀的泡膜34经过导向装置38被引入到第三套夹辊40后就被消气制为双层膜的平膜36。平膜再由卷绕器42卷起并且以双层形式缠绕成双层膜。在双层缠绕的双层膜的两层之间分散着一层水溶性多糖的涂层。双层缠绕的膜也能被分割成单层缠绕的、在一面上具有水溶性纤维素醚涂层的单层膜。
本发明的实施中能使用的热塑性聚合物包括偏二氯乙烯聚合物，氯乙烯聚合物，聚对苯二甲酸乙二醇酯，聚丙烯，聚苯乙烯，聚碳酸酯，聚酰胺，乙烯-乙烯醇共聚物。
在本领域中，能适用于本发明的偏二氯乙烯聚合物是众所周知的，例如在美国专利USP3,642,743和USP3,879,359。最常用的PVDC树脂是SaranTM树脂，由Dow Chemicals公司制造。本文所使用的术语“偏二氯乙烯聚合物”或“PVDC”包括偏二氯乙烯的均聚物、二元共聚物及三元共聚物，主要成分是偏二氯乙烯，剩余部分是一种或多种能与偏二氯乙烯单体共聚的单烯键式不饱和单体。
本文中所使用的术语“氯乙烯聚合物”或“PVC”包括氯乙烯的均聚物、二元共聚物及三元共聚物，主要成分是氯乙烯，剩余部分是一种或多种能与偏二氯乙烯单体共聚的单烯键式不饱和单体。
本发明的实施中使用的可制备偏二氯乙烯聚合物或氯乙烯聚合物的单烯键式不饱和单体包括氯乙烯、丙烯酸烷基酯、甲基丙烯酸烷基酯、丙烯酸、甲基丙烯酸、衣康酸、丙烯腈和甲基丙烯腈。优选的烯键式不饱和单体包括氯乙烯、丙烯腈、甲基丙烯腈、丙烯酸烷基酯和甲基丙烯酸烷基酯。
例如，在1987年第二版的Encyclopedia of Polymer Science andTechnology中提及并描述了多糖。优选的多糖有纤维素和淀粉。
在本发明的实施中所使用的制备软管溶液的多糖醚可以是，例如纤维素醚和纤维素酯或淀粉酯和淀粉醚。例如，在1987年第二版的Encyclopedia of Polymer Science and Technology中提及并描述了这类多糖醚。
例如，在1987年第二版的Encyclopedia of Polymer Science andTechnology中提及并描述了纤维素。纤维素是天然碳水化合物的高聚物(多糖)，是由以氧原子连接的葡糖酐单元组成的长链分子，基本是线型的。纤维素可以水解形成葡萄糖。聚合度可以从木浆的1000到棉纤维的3500，分子量从160000到560000。纤维素可以从植物组织(木材、草和棉花)中提取。纤维素可以以纤维的形式来使用。
本文中的术语“淀粉”是指天然碳水化合物，来源于(origin)植物，主要由直链淀粉和/或支链淀粉组成，包括未经改性的淀粉，物理改性的淀粉，例如热塑性的、胶凝化的或熟化的(cooked)淀粉，加入了酸以降低淀粉酸值在3到6之间的经酸值(pH)调节的淀粉，胶凝化淀粉，未胶凝化淀粉，交联淀粉和碎裂型(disrupted)淀粉(即非颗粒状淀粉)。淀粉可以是晶粒状、颗粒状或粉末状。它们可以从不同的植物中提取得到，例如，土豆、大米、木薯、玉米、豌豆以及谷类(例如黑麦、燕麦和小麦)。
在本发明的实施中，优选的用于制备软管溶液的水溶性多糖醚包括水溶性非离子型纤维素醚，例如甲基纤维素、乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素和类似的合成纤维素醚。最优选的非离子型纤维素醚有METHOCELTM纤维素醚，是Dow Chemicals公司的商标产品。
在本发明的实施中，可用于制备软管溶液的其它合成纤维素醚包括离子型纤维素醚，例如羧甲基纤维素、羧甲基乙基纤维素、羧甲基羟乙基纤维素以及它们的水溶性盐。
在水溶液中，水溶性的非离子型和离子型纤维素醚形成热可逆的凝胶体。在本领域中，这些纤维素醚是为人们所知的，而且使用例如美国专利USP 2,831,852和2,835,666中描述的方法就可以制备出来。
通常，可以通过将纤维素醚分散在热水中，而后将分散体加入到冷水中或将冷水加入到分散体中的方法来制备软管溶液。尽管纤维素醚的最佳使用量取决于多种因素，例如特定的纤维素醚，但通常纤维素醚按照1份纤维素醚与5到30份水的比例来使用。
纤维素醚同样可以分散在非溶剂型介质中，例如植物油、丙二醇、聚乙二醇和甘油，优选比例为5到8份非溶剂比1份纤维素醚，可以将分散体加入到冷水中或将冷水加入到分散体中。
本发明中的软管溶液同样可以用于双泡法(double bubbleprocess)。这种方法中，在主膜泡的较低的一端向膜泡的内部引入多糖软管溶液。在本领域中用双泡法制备薄膜是为人们所知的，例如美国专利USP5,674,607。通常双泡法包括通过挤出机挤出一种聚合材料，例如偏二氯乙烯聚合物。挤出的膜用传统的热吹技术来制得一吹胀的膜泡，通常称之为主膜泡。当主膜泡脱膜后进行空冷，而后在机器方向和横向进行熔融取向。将取向后的主膜泡通过第一套夹辊进行消气，而后又在一道吹泡工序中重新吹胀，使经过吹胀和消气的薄膜进行拉伸取向，以此制得在本领域所知的二次膜泡。这是通过一种传统的方法来实现的，即把空气或其它热的气体封闭在二次膜泡中，使得材料在其取向温度下横向地拉伸使材料在横向上进一步取向拉伸。二次膜泡在第二套夹辊中被消气。第二套夹辊以高于第一套夹辊的速度运转，以此使热塑性材料在机器方向或纵向拉伸取向。而后经过二次消气的膜泡从第二套夹辊上传递到卷辊上。双泡法制备薄膜是人们所知的，例如美国专利USP 5,674,607。
本发明由以下实施例进行深入说明。这些实施例只用于解释的目的，而不能用于限制本发明使用范围。除非特别指出，所有的份数和百分比均为重量比。
实施例中使用了以下原料：METHOCEL A-Dow Chemicals公司以METHOCEL K3 Premium LV出售的甲基纤维素醚。在纤维素主链上，它平均含有22％的甲氧基和8.1％的羟丙基取代基。用ASTM标准D1347和D2363测定的METHOCEL溶液的粘度大约为3厘泊。METHOCEL B-Dow Chemicals公司以METHOCEL K100 Premium LV出售的甲基纤维素醚。在纤维素主链上，它平均含有22％的甲氧基和8.1％的羟丙基取代基。用ASTM标准D1347和D2363测定的METHOCEL溶液的粘度大约为100厘泊。Saran A-偏二氯乙烯聚合物的组合物，包含有99.63％的偏二氯乙烯共聚物(大约18％的氯乙烯和82％的偏二氯乙烯以及约4％的癸二酸二丁酯和约1％的环氧大豆油)，0.2％的环氧大豆油和0.17％的脂肪酸酰氨的增滑剂和无机防粘连剂。Saran B-偏二氯乙烯聚合物的组合物，包含有99.33％的偏二氯乙烯共聚物(大约18％的氯乙烯和82％的偏二氯乙烯以及约4％的癸二酸二丁酯和约1％的环氧大豆油)，0.2％的环氧大豆油和0.47％的组合物-包括脂肪酸酰胺的增滑剂，无机防粘连剂和红色颜料。
实施例1在Saran A挤出过程中对METHOCEL A和METHOCEL B作为软管开口剂
(sock opening agent)的评价步骤：
在一系列连续挤出条件、浴以及软管温度(sock temperature)下，用矿物油作为软管溶液和Saran A作为对照。记录下对照挤出的边缘粘合量。收集对照的样品膜用于进行层间粘附的比较。随后安装液体蓄槽以及相连的管道和泵。液体蓄槽用于软管溶液的循环，并通过添加软管开口剂来增加浓度以及用排出、稀释法降低浓度的方法来控制软管溶液的浓度。使用不同浓度的METHOCEL A和METHOCEL B软管溶液制备的样品被收集起来用于层间粘附的比较。各个浓度下的边缘熔接程度也被记录下来。结果如表I所示。
本处所使用的术语“边缘熔接”或“边缘粘合”是指无定形带的两层在边缘相互粘附的趋势。当无定形膜发生非均相膨胀后通过热槽辊(warm tank nips)时，边缘粘合很快就表现出来了。
表I软管液 边缘熔接 层间粘附矿物油对照 双边均为1.5″ 1天后很微弱
冷槽＝17℃
热槽＝35℃
软管＝24℃10％METHOCEL A溶液，剂量：a)360毫升 带开口(tape opening)边缘 新制的膜粘合紧密
5″和2″的熔接b)560毫升 刚刚足够的带开口 新制的膜粘合紧密
4″和1.5″的熔接c)840毫升 更好的带开口 粘合紧密(1天的膜)
3″和1″的熔接4.3％METHOCEL B溶液，剂量：a)150毫升 优秀的带开口双边 粘合紧密(1天的膜)
均为0.5″的熔接b)4倍稀释的a)溶液 优秀的带开口双边 粘合紧密
均为0.5″的熔接c)4倍稀释的b)溶液 较好的带开口2″ 粘合紧密
和0.5″的熔接实施例2在Saran A挤出过程中METHOCEL A(5％METHOCEL A溶解于水)作
为软管开口剂的评价步骤：
在一系列连续挤出条件、浴以及软管温度下，以用矿物油作为软管溶液和Saran A作为对照。收集对照膜用于层间粘附的比较。随后安装液体槽。这个液体槽用于回流和冷却软管溶液。使用METHOCEL A软管溶液制得的样品膜被收集起来用于层间粘附的比较。
层间粘附在新制的和已制的膜上进行测定。结果如表II所示。
表II
软管溶液 层间粘附 层间粘附
矿物油对照 12克于新制膜(1天)上 15克于已制的膜(21天)上5％METHOCEL A溶液 层间粘附 层间粘附
19克于新制膜(1天)上 22克于已制的膜(21天)上
实施例3
按照实施例二的步骤，不同的是用Saran B而不用Saran A。结果如表III所示。
表III
软管溶液 层间粘附 层间粘附
矿物油对照 10克于新制膜(1天)上 12克于已制的膜(21天)上5％METHOCEL A溶液 层间粘附 层间粘附
16克于新制膜(1天)上 17克于已制的膜(21天)上
以上结果显示，作为软管溶液的METHOCEL A和METHOCEL B的性能要优于矿物油。
Claims (19)
1.一种通过吹膜挤出法制备热塑性膜的方法，包括：将熔融的热塑性聚合物从管形模头挤出以形成一种熔融聚合物管；当熔融聚合物管脱离模头时将所述管的内壁与一种水溶性多糖醚的水溶液相接触；将熔融聚合物管进行充气膨胀以形成一吹制的圆筒形薄膜，而后将这个圆筒形的薄膜消气成平膜。
2.根据权利要求1方法，其中热塑性聚合物为偏二氯乙烯聚合物，氯乙烯聚合物，聚对苯二甲酸乙二醇酯，聚丙烯，聚苯乙烯，聚碳酸酯，聚酰胺或乙烯-乙烯醇共聚物。
3.根据权利要求1的方法，其中热塑性聚合物为偏二氯乙烯聚合物，包含有主要含量的偏二氯乙烯和少量的一种或多种能与偏二氯乙烯单体共聚合的单烯键式不饱和单体。
4.根据权利要求1的方法，其中热塑性聚合物为氯乙烯聚合物，包含有主要含量的氯乙烯和少量的一种或多种能与氯乙烯单体共聚合的单烯键式不饱和单体。
5.根据权利要求1的方法，其中多糖是一种水溶性的非离子型或离子型纤维素醚或其水溶性盐。
6.根据权利要求5的方法，其中水溶性的非离子型纤维素醚为甲基纤维素、乙基纤维素、羟丙基纤维素或羟丙基甲基纤维素。
7.根据权利要求6的方法，其中水溶性的非离子型纤维素醚为甲基纤维素。
8.根据权利要求5的方法，其中水溶性的离子型纤维素醚为羧甲基纤维素、羧甲基乙基纤维素或羧甲基羟乙基纤维素。
9.根据权利要求1的方法，其中水溶性多糖醚水溶液包含1份纤维素醚和5-30份水。
10.一种带有水溶性多糖醚涂层的热塑性膜。
11.根据权利要求10中的热塑性薄膜，包括偏二氯乙烯聚合物、氯乙烯聚合物、聚对苯二甲酸乙二醇酯、聚丙烯、聚苯乙烯、聚碳酸酯、聚酰胺或乙烯-乙烯醇共聚物。
12.根据权利要求11的热塑性薄膜，偏二氯乙烯聚合物包括主要含量的偏二氯乙烯和少量的一种或多种能偏二氯乙烯单体共聚合的单烯键式不饱和单体。
13.根据权利要求10中的热塑性薄膜，氯乙烯聚合物包括主要含量的氯乙烯和少量的一种或多种能氯乙烯单体共聚合的单烯键式不饱和单体。
14.根据权利要求10中的热塑性薄膜，其中水溶性的多糖醚为水溶性的非离子型或离子型纤维素醚或其水溶性盐。
15.根据权利要求14的热塑性薄膜，其中水溶性非离子型纤维素醚为甲基纤维素、乙基纤维素、羟丙基纤维素或羟丙基甲基纤维素。
16.根据权利要求15热塑性薄膜，其中水溶性非离子型纤维素醚为甲基纤维素。
17.根据权利要求14的热塑性薄膜，其中水溶性离子型纤维素醚为羧甲基纤维素、羧甲基乙基纤维素或羧甲基羟乙基纤维素。
18.根据权利要求10中的热塑性薄膜，包含在其两个主表面的一个表面上具有水溶性多糖醚涂层的单层膜。
19.根据权利要求10中的热塑性薄膜，包含在相邻的两个膜层之间具有水溶性多糖醚涂层的双层膜。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/281,837 | 1999-03-31 | ||
| US09/281,837 US20020014717A1 (en) | 1999-03-31 | 1999-03-31 | Process for producing thermoplastic films by blown film extrusion and films produced thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1348407A true CN1348407A (zh) | 2002-05-08 |
Family
ID=23078987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00806661A Pending CN1348407A (zh) | 1999-03-31 | 2000-03-07 | 通过吹膜挤出法制备热塑性膜的方法及由此制得的薄膜 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20020014717A1 (zh) |
| EP (1) | EP1171276A1 (zh) |
| JP (1) | JP2002539986A (zh) |
| KR (1) | KR20020004986A (zh) |
| CN (1) | CN1348407A (zh) |
| AR (1) | AR023218A1 (zh) |
| AU (1) | AU3728900A (zh) |
| CA (1) | CA2366452A1 (zh) |
| MX (1) | MXPA01009844A (zh) |
| NZ (1) | NZ514309A (zh) |
| WO (1) | WO2000058070A1 (zh) |
| ZA (1) | ZA200107823B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149367A (zh) * | 2014-06-30 | 2014-11-19 | 苏州博云塑业有限公司 | 一种肠衣薄膜的制备方法 |
| CN104829966A (zh) * | 2015-04-29 | 2015-08-12 | 桐城市福润包装材料有限公司 | 一种高分子药品包装材料的制备方法 |
| CN110625908A (zh) * | 2019-09-27 | 2019-12-31 | 河南双汇投资发展股份有限公司 | 一种pvdc保鲜膜的制备方法 |
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| IT1314223B1 (it) * | 1999-11-16 | 2002-12-06 | Tecno Coating Eng Srl | Metodo ed impianto per la biorientazione di materiali termoplasticimultistrato. |
| US20050012235A1 (en) * | 2001-11-30 | 2005-01-20 | Schregenberger Sandra D | Oxygen tailoring of polyethylene resins |
| ITMI20020386A1 (it) * | 2002-02-27 | 2003-08-27 | Ledysan S P A | Procedimento per realizzare una pellicola biodegradabile per articoliassorbenti igienici-sanitari e pannolini che la contengono |
| US20060038315A1 (en) * | 2004-08-19 | 2006-02-23 | Tunnell Herbert R Iii | Oxygen tailoring of polyethylene resins |
| US7892466B2 (en) | 2004-08-19 | 2011-02-22 | Univation Technologies, Llc | Oxygen tailoring of polyethylene resins |
| US8202940B2 (en) * | 2004-08-19 | 2012-06-19 | Univation Technologies, Llc | Bimodal polyethylene compositions for blow molding applications |
| RU2397183C2 (ru) * | 2004-10-12 | 2010-08-20 | Дау Глобал Текнолоджиз Инк. | Пластификатор для полимера алкилакрилата-винилиденхлорида |
| US7451600B2 (en) * | 2005-07-06 | 2008-11-18 | Pratt & Whitney Canada Corp. | Gas turbine engine combustor with improved cooling |
| JPWO2007018204A1 (ja) * | 2005-08-10 | 2009-02-19 | 旭化成ケミカルズ株式会社 | ポリ塩化ビニリデン系樹脂ラップフィルム及びその製造方法 |
| EP2123428B1 (en) | 2007-03-12 | 2011-11-02 | Asahi Kasei Chemicals Corporation | Polyvinylidene chloride resin wrap film and process for producing the same |
| KR101951290B1 (ko) * | 2012-04-18 | 2019-02-22 | 롯데정밀화학 주식회사 | 필름 및 그의 제조방법 |
| JP5907829B2 (ja) * | 2012-07-10 | 2016-04-26 | 旭化成ケミカルズ株式会社 | 塩化ビニリデン系樹脂ラップフィルム及びその製造方法 |
| JP6100034B2 (ja) * | 2013-03-11 | 2017-03-22 | 旭化成株式会社 | 塩化ビニリデン系樹脂ラップフィルム及びその製造方法 |
| JP6175363B2 (ja) * | 2013-12-13 | 2017-08-02 | 旭化成株式会社 | スキンケアフィルム |
| US10293585B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10293584B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10195826B2 (en) | 2016-03-11 | 2019-02-05 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10293583B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10293582B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10293579B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
| US10293580B2 (en) | 2016-03-11 | 2019-05-21 | Solutia Inc. | Cellulose ester multilayer interlayers |
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1999
- 1999-03-31 US US09/281,837 patent/US20020014717A1/en not_active Abandoned
-
2000
- 2000-03-07 CA CA002366452A patent/CA2366452A1/en not_active Abandoned
- 2000-03-07 AU AU37289/00A patent/AU3728900A/en not_active Abandoned
- 2000-03-07 NZ NZ514309A patent/NZ514309A/xx not_active Application Discontinuation
- 2000-03-07 EP EP00916138A patent/EP1171276A1/en not_active Withdrawn
- 2000-03-07 CN CN00806661A patent/CN1348407A/zh active Pending
- 2000-03-07 JP JP2000607806A patent/JP2002539986A/ja active Pending
- 2000-03-07 KR KR1020017012417A patent/KR20020004986A/ko not_active Application Discontinuation
- 2000-03-07 WO PCT/US2000/005938 patent/WO2000058070A1/en not_active Application Discontinuation
- 2000-03-07 MX MXPA01009844A patent/MXPA01009844A/es not_active Application Discontinuation
- 2000-03-30 AR ARP000101438A patent/AR023218A1/es unknown
-
2001
- 2001-09-21 ZA ZA200107823A patent/ZA200107823B/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149367A (zh) * | 2014-06-30 | 2014-11-19 | 苏州博云塑业有限公司 | 一种肠衣薄膜的制备方法 |
| CN104829966A (zh) * | 2015-04-29 | 2015-08-12 | 桐城市福润包装材料有限公司 | 一种高分子药品包装材料的制备方法 |
| CN110625908A (zh) * | 2019-09-27 | 2019-12-31 | 河南双汇投资发展股份有限公司 | 一种pvdc保鲜膜的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3728900A (en) | 2000-10-16 |
| MXPA01009844A (es) | 2002-05-06 |
| WO2000058070A1 (en) | 2000-10-05 |
| AR023218A1 (es) | 2002-09-04 |
| NZ514309A (en) | 2002-09-27 |
| ZA200107823B (en) | 2002-09-23 |
| EP1171276A1 (en) | 2002-01-16 |
| US20020014717A1 (en) | 2002-02-07 |
| CA2366452A1 (en) | 2000-10-05 |
| KR20020004986A (ko) | 2002-01-16 |
| JP2002539986A (ja) | 2002-11-26 |
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