CN1225883A - 带有压塑成型的密封/阻挡层衬垫的塑料盖 - Google Patents

带有压塑成型的密封/阻挡层衬垫的塑料盖 Download PDF

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CN1225883A
CN1225883A CN98111652A CN98111652A CN1225883A CN 1225883 A CN1225883 A CN 1225883A CN 98111652 A CN98111652 A CN 98111652A CN 98111652 A CN98111652 A CN 98111652A CN 1225883 A CN1225883 A CN 1225883A
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liner
lid
layer
matrix
barrier material
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D·B·里菲尔
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BPrex Healthcare Brookville Inc
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Owens Illinois Closure Inc
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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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • B29C43/203—Making multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/78—Moulding material on one side only of the preformed part
    • B29C70/80—Moulding sealing material into closure members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/02—Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
    • B65D41/04—Threaded or like caps or cap-like covers secured by rotation
    • B65D41/0435—Threaded or like caps or cap-like covers secured by rotation with separate sealing elements
    • B65D41/045—Discs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D53/00—Sealing or packing elements; Sealings formed by liquid or plastics material
    • B65D53/04—Discs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • B29C43/183—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles the preformed layer being a lining, e.g. shaped in the mould before compression moulding, or a preformed shell adapted to the shape of the mould
    • B29C43/184—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles the preformed layer being a lining, e.g. shaped in the mould before compression moulding, or a preformed shell adapted to the shape of the mould shaped by the compression of the material during moulding
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/34—Feeding the material to the mould or the compression means
    • 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
    • B29L2031/00—Other particular articles
    • B29L2031/56—Stoppers or lids for bottles, jars, or the like, e.g. closures
    • B29L2031/565—Stoppers or lids for bottles, jars, or the like, e.g. closures for containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/02—Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
    • B65D41/04—Threaded or like caps or cap-like covers secured by rotation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/04—Non-macromolecular organic compounds
    • C09K2200/0458—Nitrogen-containing compounds
    • C09K2200/047—Amides, imides, imines, N-oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C09K2200/062—Polyethylene
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    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0622—Polyvinylalcohols, polyvinylacetates
    • 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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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • 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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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • 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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    • Y10T428/21—Circular sheet or circular blank
    • Y10T428/214—End closure
    • 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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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/21—Circular sheet or circular blank
    • Y10T428/215—Seal, gasket, or packing

Abstract

一种塑料盖包含一顶盖(22),该顶盖带有基底(30)和在外缘之上的用于将盖固定到容器上的螺纹(34),基底有一确定顶盖内部的圆周外缘(32)。衬垫(20a,20b或20C)被固定到顶盖的内部,优选通过在基底上就地压塑成型。衬垫主要由基质聚合物材料例如EVA和阻挡层材料例如 EVOH组成的交替层的多重组成,阻挡层材料是用于阻挡气体、水蒸气和/或香味透过衬垫。基质聚合物优选与亲和剂材料例如马来酸酐接枝聚合物预混,亲和剂用于将基质聚合物材料结合到阻挡层材料上。

Description

带有压塑成型的密封/阻挡层衬垫的塑料盖
本发明涉及一种用于饮料、食品、浆汁、药品等类似用途的塑料容器盖，特别涉及一种生产带有密封衬垫的盖的改进方法，该衬垫具有对气体、水蒸气和/或添味剂(flavorants)(气味散失(flavor scalping))的抗透过性。
同时申请的序列号(Docketl7138)名称为“带有压塑成型的阻挡层衬垫的塑料盖”的资料已经完成，并已授权本代理人。
至此，已经建议提出一种用于容器的包含塑料顶盖的塑料盖，该顶盖带有与容器的密封表面密封接合的内部衬垫。例如，美国专利No.4,984,703公开了一种带有顶盖的塑料盖，该顶盖有一个带有圆周外缘的基底和固定顶盖到容器的螺纹，和一个在顶盖基底的内部就地压塑成型的密封衬垫。密封衬垫包含乙烯乙酸乙烯酯(EVA)和热塑性弹性体材料例如烯烃或苯乙烯-丁二烯-苯乙烯的混合物。美国专利No.5,451,360公开了一种在顶盖内部就地压塑成型衬垫的方法和装置。
然而，上述专利中所公开的盖和生产方法在当时问题的仍存在现有技术中，因此需要进一步的改进。例如，当盖被固定到容器上时，虽然柔性烯烃共聚物例如EVA有足够的弹性，从而与容器的密封表面具有良好的密封性能，但是这些材料不能够提供可令人接受的对气体透过的阻挡性，这些气体对容器内的东西有害，例如氧气和二氧化碳。至此，已经建议使用一种阻挡层材料例如乙烯乙烯醇(EVOH)作为气体透过阻挡层。然而，这些材料的特点就是昂贵并且发脆，不适合作密封材料。因此，本发明的目的是提供一种用于塑料盖的衬垫，该衬垫兼有与容器的密封表面接合的密封功能和改进的抗气体透过、气味吸收(flavor absorption)(气味散失(flavor scalping))和/或水蒸气透过的阻挡作用。本发明的另一个和更具体的目的是为了提供一种具有所述特征的衬垫，即容易加工并且制品价格不贵。本发明的又一目的是提供一种满足上述目的的衬垫，并且具有透明或半透明的结构，以便通过衬垫阅读印刷在盖上的信息。本发明的更进一步的目的是提供一种制造这样一种衬垫的方法和使用这样一种衬垫的盖。
根据本发明的一个方面的塑料盖，该盖包括塑料顶盖，该顶盖有一带有用于确定顶盖内部的圆周外缘的基底和外缘上用于将盖固定到容器上的螺纹或其它的合适的装置。衬垫被固定到基底的内部。衬垫主要由基质聚合物和用于阻挡气体透过衬垫的阻挡层材料的交替层的多层组成，该阻挡层材料平行于衬垫的表面。在本发明的优选实施例中，该衬垫在顶盖内就地被压塑成型，并包括至少9层基质聚合物和阻挡层材料的交替层，优选至少33层交替层，最优选129层交替层。
“基质聚合物”是热塑性弹性体，一种柔软的烯烃聚合物，或是上述的组合。热塑性弹性体是具有热塑性材料的加工性能和传统热固性橡胶的功能特性和性能的合成聚合物。商业上可得到的热塑性弹性体共有六个通用等级：苯乙烯嵌段，共聚物(SBC)，聚烯烃混合物(TPO)，弹性体合金，热塑性聚氨酯(TPU)，热塑性共聚酯和热塑性聚酰胺。热塑性弹性体在“Modern PlasticsEncyclopedia Handbook，”(由McGraw-Hill出版，1994)中，从64页开始被公开，其内容作为参考被引用。热塑性弹性体的例子是：由Shell Chemical生产，商标为KRATON的苯乙烯嵌段共聚物。这些合成聚合物由三段线型或A-B-A型的不连续块组成：苯乙烯。弹性体合金化聚合物是乙烯-丙烯-二烯三元共聚物(EPDM)。另一种弹性体合金化聚合物由EPDM/PP和丁基橡胶/PP的组合物组成，由Advanced Elastomer Systems生产，商品名称为SANTOPRENE和TREFSIN，在美国专利No.4,130,535，4,311,628，4,130,534和4,607,074中已经公开。通常，热塑性弹性体的特点是肖氏A级硬度为45-95，弯曲模量为30,000-100,000psi。
柔性烯烃聚合物是热塑性烯烃，均聚物和共聚物，其柔软、有弹性且肖氏A级硬度小于大约100。一般，柔性烯烃聚合物为：茂金属聚乙烯，乙烯-丙烯橡胶，乙烯共聚物和上述的混合物，乙烯共聚物例如乙烯乙酸乙烯酯，乙烯丙烯酸甲酯共聚物和离聚物及上述的混合物。柔性烯烃聚合物的例子是：由单点催化剂技术(single site catalyst technology)生产的α烯烃取代聚乙烯(在本领域中这些材料被称为茂金属聚乙烯)；乙烯乙酸乙烯酯(EVA)例如由DuPont生产，商标为ELVAX；由单一位置催化剂技术制造的聚丙烯，在本领域中被称为茂金属聚丙烯；由Fina Oil和Chemical销售的间规立构聚丙烯；由DowChemical销售的乙烯/丙烯共聚物和苯乙烯-乙烯共聚体；和离聚物例如DuPont’s SURLYN的产品系列。
本领域都知道，基质聚合物一般由抗氧化剂、润滑剂和其它的稳定剂组成。
“亲和剂”是将两种不同的热塑性材料通过反应(共价或偶极-偶极)键或不反应(链缠结)方式联结在一起的热塑性材料。例子包括：马来酸酐接枝聚合物或乙烯乙酸乙烯酯接枝聚合物例如Quantum Chemical’PLEXAR(商标)，Mitsui Petrochemical’s ADMER(商标)和DuPont’s BYNEL(商标)产品系列，乙烯丙烯酸甲酯，和离聚物。
“阻挡层材料”是热塑性材料，具有低气体和/或水蒸气透过速率并对香料和主要油类具有高阻挡性。如下材料的气体透过速率低于工业标准衬垫材料EVA：EVOH(乙烯乙烯醇)例如Nippon Goshei’SOARNOL(商标)产品系列和Evalca’s EVAL(商标)产品系列，尼龙例如DuPont’s SELAR(商标)PA，EMS’sG21和Mitsubishi Gas’MXD6产品系列，British Petroleum’s BAREX(商标)丙烯腈产品系列，EVOH和不定形尼龙的混合物，EVOH和离聚物例如SURLYN(DuPont)的混合物，及例如由Ticona销售的环烯烃共聚物。其它合适的阻挡层材料是混合物如美国专利Nos.4,977,004和5,064,716所公开，和EVOH或尼龙与粘土的毫微复合材料(nanocomposites)如美国专利Nos.4,472,538和5,552,469所公开，其内容作为参考被引用。
一般优选，衬垫还包括一种用于降低衬垫与容器的密封表面之间摩擦系数的添加剂。降低摩擦的添加剂包括金属硬脂酸盐，微晶蜡，聚乙二醇，脂肪酸酯和酰胺，这些在本领域中其被称为“润滑剂”。优选的润滑剂是低分子量脂肪酸酰胺材料，该材料由于从熔融态冷却而在聚合物材料的暴露表面起霜，因此降低了衬垫和容器密封表面之间的摩擦系数。例子是：化学通式为R-CO-NH2的伯酰胺，其中R是烷基基团；化学通式为R-CO-NH-R’的仲酰胺，其中R，R’是烷基基团；化学通式为R-CO-NH-A-NH-CO-R的仲二-酰胺，其中R，R’是烷基基团，A是亚烷基基团；和上述的混合物如美国专利No.5,306,542所公开的。润滑剂优选包括衬垫成份总重量的大约0.5％-1.5％，最优选为大约0.5％重量。该润滑剂优选被原料生产者混合到基质聚合物材料中(与其它任何所需的着色剂一起)。润滑剂和/或着色剂的数量不包括在本发明的组分计算中。
衬垫中的阻挡层材料和基质聚合物都各自在大约2％-50％的重量百分比范围内。衬垫中阻挡层材料最优选的数量范围是6％-35％的重量百分比，亲和剂优选范围是6％-20％的重量百分比，余量的由基质聚合物组成。
根据本发明的第二个方面，用于塑料盖的衬垫的生产方法包括以下步骤：挤出颗粒，该颗粒由基质聚合物和阻挡气体透过的阻挡层材料的交替层的多重组成，以及压塑成型该颗粒，使之成为衬垫圆盘，其中交替层主要在平行于圆盘的平面的方向被定向。颗粒中的层优选由阻挡层材料、基质聚合物和亲和剂的进料被共挤出。这些原料可以被分别挤出，或者在挤出前亲和剂与阻挡层材料、基质聚合物或两者混合。在本发明的优选实施方案中，颗粒中的层由包含基质聚合物和亲和剂材料的混合物的第二进料被共挤出，亲和剂是用来增加原料层之间的粘合性。压塑成型衬垫的步骤优选实施在盖的顶盖内就地压塑成型衬垫。
因此，根据本发明的第三个方面，提供一种用于塑料盖的密封衬垫，该衬垫包括一圆盘，该圆盘主要由基质聚合物材料和用于阻挡氧气和二氧化碳通过层的阻挡层材料的交替层的多重组成。密封衬垫优选在塑料盖内就地由压塑成型装模料或颗粒压塑成型，其中交替层是被共挤出的。
附图说明
本发明与其目的、特征和优点一起将在以下的说明、权利要求和附图中被很好的理解：
图1是根据本发明的优选实施例现在生产压塑成型装模料颗粒的流程的功能框图；
图2是根据本发明的优选实施例说明压塑成型装模料颗粒成为阻挡层衬垫的示意简图；
图3是根据图1、图2所示的本发明的优选方法，比例放大的塑料盖的截面正视图；
图4A和4B是申请中所述的装模料颗粒在盖顶盖中测试定向的示意图；
图5A是所指出盖上的点被拍成显微像片(图5C-5G)的示意图；
图5B-5G是根据本发明的优选方案得到的测试结果的显微像片；
图6和7与图3相似，但所示的是改进的衬垫几何结构；及
图8是与图1相似的图，但所示的是改进的方法。
图1所示是根据本发明的一个优选实施方案的系统10，该系统包括一对挤出机12，14，每一个挤出机都有一个与之相联的混合料斗13，15。挤出机12，14把作为第一第二进料的挤出物对准层形成装置16。层形成装置16将各自的进料变成一般是不连续的、平行的层，并将平行层送到层合装置18。层合装置18的出料是挤出棒，将其切割成离散的装模料颗粒20。颗粒20有主要平行的不连续交替层，每一层都由一种从挤出机12，14送到层形成装置16的进料组成。在颗粒20中平行层的数量是层合装置18中的级数和每一级的结构的函数。在本发明的一个优选实施方案中，层形成装置16和层合装置18如美国专利Nos.5,094,793和5,628,950中所公开，这里作为参考被引用。可以使用其它的传统的层形成方法。
图8是改进的系统10a，其中阻挡层、基质聚合物和亲和剂由相关联的、分开的挤出机12，14a，14b被送进传统的共挤出装置16a中。最终的颗粒20d具有多层平铺的、螺旋的或共轴的层。如图8所示的三进料系统配置中，亲和剂的层是薄薄的并排列在阻挡层材料和基质聚合物每一顺次的层之间。合适的传统共挤出装置已被公开，例如，美国专利Nos.4,522,775和美国专利No.5,628,950的背景技术中所公开。这些材料的内容作为参考被引用。图1实施例的另一改进，阻挡层材料可以被添加到基质聚合物和亲和剂的挤出机14的进料中。例如到挤出机14的进料可以由10％的EVOH、10％的亲和剂和80％的EVA组成，都指重量百分比。挤出机12a以较低的速率工作，使得全部组成保持在上述讨论的范围之内。在热塑性弹性体之中加入阻挡层材料可以进一步加强材料的阻挡性能。
根据本发明的优选方案，为了生产塑料盖阻挡层衬垫，挤出机12或12a在料斗13的进料优选主要由一种或多种阻挡层聚合物组成，而挤出机14在料斗15的进料优选主要由一种或多种基质聚合物(TPE或柔性烯烃)和亲和剂材料组成。基质聚合物优选与润滑剂和任何所需的着色剂一起预混。这些原料在料斗15中被完全搅拌混合。挤出机12的阻挡层聚合物进料优选是一种或多种高气体阻挡性塑料树脂，选自以下组成：EVOH，尼龙，丙烯腈共聚物例如苯乙烯丙烯腈和丙烯腈丙烯酸甲酯，EVOH和不定形尼龙的混合物，EVOH或尼龙和粘土的毫微复合材料(nanocomposites)，EVOH和离聚物的混合物，丙烯腈，环烯烃共聚物，及上述的混合物。挤出机14的基质聚合物进料优选选自以下组成：EVA，乙烯/丙烯共聚物，苯乙烯嵌段共聚物，三元共聚物，离聚物，热塑性橡胶，苯乙烯/乙烯/丁二烯/苯乙烯嵌段共聚物，苯乙烯/乙烯/丁二烯/苯乙烯组合物，苯乙烯/丁二烯/苯乙烯嵌段共聚物，EPDM，金属茂线型低聚乙烯，茂金属间规立构聚丙烯，合成一弹性体合金，橡胶例如丁基橡胶，苯乙烯共聚物例如苯乙烯/乙烯和三元共聚物例如苯乙烯/乙烯/丁烯，聚丙烯/丁基橡胶，和上述的混合物。挤出机14的亲和剂进料优选选自以下组成：马来酸酐接枝聚合物，乙烯乙酸乙烯酯接枝聚合物，乙烯丙烯酸甲酯，离聚物和上述的混合物。如上所述，选自以下组成的润滑剂优选与基质聚合物预混：脂肪酸酯，乙二醇，蜡，伯酰胺，仲酰胺，仲-二酰胺和上述的混合物。
阻挡层聚合物、基质聚合物和亲和剂材料的相对百分含量根据在步骤16、18中成型的各个层的厚度而定，相对百分含量还依次根据挤出机12，14的挤出流动速率而定。挤出机14的混合物进料和挤出的相对速率优选成这样：使最终衬垫中的阻挡层材料和基质聚合物的数量各自在2％-50％的重量百分比范围内。最优选的是，最终出料20中的阻挡层聚合物的数量优选在6％-35％的重量百分比范围内，亲和剂材料的优选范围是6％-20％的重量百分比，余量由基质聚合物组成。增加阻挡层材料的百分含量就增加了最终衬垫的成本。确实，本发明的关键优点在于这样一个事实：例如，与EVA/EVOH的混合物相比，衬垫的层结构增加了衬垫的阻挡性能，因此使用的阻挡层材料的数量较由聚合物混合组成的衬垫中的阻挡层材料的数量少。选择粘合剂/亲和剂材料的数量来实现所需的层与层之间的接合数量，并且调整与亲和剂混合的基质聚合物的粘度。这方面应该引起注意，即挤出前亲和剂与基质聚合物的混合省去了第三挤出机，该挤出机在其他情况下也许是必需的，并且允许使用亲和剂来调整基质聚合物的粘度。如下情形也被认为是所需的，即供到层形成步骤16的挤出物的流动速率尽可能地一致。原料流动速率已被原料生产者公开，并可以在选择合适的原料时使用。通过将EVA和马来酸酐亲和剂混合，亲和剂的粘度降低得与EVOH的粘度更加一致。分开的喂料流的粘度必须充分的一致以提供合适的层成型。如美国专利No.5,628,950所教导，其内容作为参考被引用，为了提供合适的层成型，不同层材料之间的熔化粘度差异应该不大于指数5。
应该知道，相对百分含量随着用途的变化而变化，除了其它因素外，还随着硬度和因此的密封性、和所需的可移动转矩的变化而变化。至于硬度，发现衬垫硬度高于大约94或95肖氏(A)级时，用来与容器进行合适的密封显得太硬。当使用相对硬的基质聚合物时，例如EVA，阻挡层材料的上限可以相对低一些。然而当使用相对硬度低的基质聚合物时，例如聚丙烯/丁基橡胶，阻挡层材料的上限可以更加高一些。
图2所示是置于预制塑料盖顶盖22之内的装模料颗粒20，该顶盖在压塑模26中的阴模24中。阳模部分28紧紧地靠在颗粒20、顶盖22、和模24上，以便压塑成型颗粒20变成与顶盖基底的内表面融合或粘合的衬垫。即，参考图3，装模料颗粒在顶盖22的基底30上就地被压塑成型而形成衬垫20a。这可以用手工完成，或更优选用如上述美国专利No.5,451,360所公开的机械装置。顶盖22还包括一个从基底30的圆周延伸的外缘32，其内螺纹34用于将顶盖22固定到容器上。可选择地，颗粒20可以被分开压塑成型为衬垫20a，然后将其粘合固定到顶盖22内的基底30上。这样一种操作需要额外的步骤和费用，因此不是优选的。作为第二选择，衬垫可以如美国专利Nos.3,674,393，3,702,148，3,877,497,和4,518,336中所公开的在盖内成型。图6所示是另一种具有一平坦几何形状的衬垫20b，与图3所示的具有加厚圆周的衬垫20a正相反。图7所示是用于容纳增加的阻挡层材料的具有平坦圆周和加厚的中间部位的衬垫20c。
本发明实施方案中的样品已经被制造出来并进行了测试。在这些样品中，基质聚合物是由DuPont销售的、商标为ELVAC650的EVA。阻挡层材料或者是由Evalca销售的、商品名称为E105B的EVOH，或者是由DuPont销售的商标为SELAR PA的尼龙。亲和剂是马来酸酐基质聚合物，由Mitsui Petrochemical销售，商品名称为ADMER QF551。
样品的第一系列是由压塑成型的衬垫膜(即，未配置在顶盖22内)制造的。这些测试样品是在熔化温度380-440°F，由图1的挤出系统以所需的比例由所挤出的材料制成的。挤出物有129层。该挤出物仍处在熔化温度时，被两个Teflon-coated金属板夹在中间，这些层或者是平行或者是垂直于板的平面。该组合件然后被置于Carver压力机中，在大约450psi下压塑大约30秒，形成一个厚度为25-30密耳的薄膜。将薄垫片置于两板的中间来测定最后的厚度。然后将该组合件(板和压塑膜)从压力机中移走，置于室温的水浴中15秒。压塑膜从板中被移走然后干燥。在100％的相对湿度和75°F下，根据ASTM D3985来测量氧气渗透率。平面的方向被定向，如图4B所示。第五测试样品由10％的尼龙、80％的EVA和10％的亲和剂组成，其中膜层的定向如图4A所示，及第六测试样品由10％的尼龙、80％的EVA和10％的亲和剂组成，其中膜层的定向如图4B所示。所有膜均为相同的厚度，即25-30密耳。表1所示是测试结果：
                                         表1
测试样品       氧气渗透率(cc*mil/d*atm*100sq.in.)在75°F和100％RH 硬度计(Shore A Scale)
    (1)100％EVA对照          790         92
(2)25％EVOH，10％c，65％EVA(混合物)          110         93
(3)10％EVOH，10％c，80％EVA(图4A)          16         94
(4)10％EVOH，10％c，80％EVA(图4B)          20         94
(5)10％尼龙，10％c，80％EVA(图4A)          25         94
(6)10％尼龙，10％c，80％EVA(图4B)          31         94
应该注意的是，与100％的EVA对照样品1和混合物对照样品2相比，根据本发明的测试例3-6在氧气渗透率方面都显示出明显的降低。确实，与混合物样品2相比，根据本发明的甚至带有明显较少量EVOH的测试样品在氧气渗透率方面都显示出明显的降低。在较少量EVOH的情形下，渗透率的降低是由于在膜中的层合和在压塑成型过程中膜中层的重新定向。在这方面应该注意，即虽然样品3和5的测试结果，其中膜中的层如图4A所示被定向于平行于膜平面的方向，较如图4B所示的层被定向在垂直于膜平面方向的测试结果稍好一些，但结果的差别是不明显的。这被认为是由于以下的事实造成：压塑成型作业中产生的热量和压力导致层压材料表面上径向向外的流动，以便重新配置颗粒的层的结构，甚至于在膜中的层合和在压塑成型过程中膜中层的重新定向。在这方面应该注意，即虽然样品3和5的测试结果，其中膜中的层如图4A所示被定向于平行于膜平面的方向，较如图4B所示的层被定向在垂直于膜平面方向的测试结果稍好一些，但结果的差别是不明显的。这被认为是由于以下的事实造成：压塑成型作业中产生的热量和压力导致层压材料表面上径向向外的流动，以便重新配置颗粒的层的结构，甚至当层起初垂直于最终膜平面时。也如图5A-5G所示。图5A是顶盖和衬垫的平面示意图，指出了样品的五个被切割和染色的位置，并把此处拍成显微像片图5C-5G。图5B所示是最初的颗粒层构型，其中装模料颗粒中的层主要在垂直于顶盖基底平面的方向被定向。EVOH层已经被着色，在图5B-5G中是黑色的。图5B是放大10X图形，图5C-5G是放大100X的图形。也应该注意，表1中样品的硬度基本保持稳定，这表示所有的样品均适用于作为密封衬垫使用。
测试样品的第二第三系列已被制造，这次是以衬垫压塑成型在盖内的形式。在熔化温度440°F，按照所需重量比例的产量，由图1的系统挤出测试材料。颗粒20(图2)从挤出物被手工切割并置于盖外壳22内。当颗粒20仍处在或接近熔化温度时，盖和颗粒被置于图2的压塑模中，启动压塑模具来压塑该颗粒。所有颗粒中的膜层都如图4B的垂直定向。压塑力约为800psi，并持续大约15秒。每一带有衬垫的测试盖然后被拧到PET瓶口螺纹上，以工业标准应用的转矩(25-30英寸-磅，对于43mm的盖)。螺纹从瓶子上被切割并用环氧树脂粘合到环绕孔的金属板上，该孔与清洗管相连。然后带有盖的板被置于MoconOXYTRAN氧气透过率试验机中。盖外面的氧气保持在1大气压，75°F和100％的相对湿度，用氮气来清洗盖内的空间以便测量氧气的浓度，和氧气透过盖的透过率。当氧气的透过率达到一稳定的状态时，记录该数值。
如图4B所示，由20％的EVOH，16％的亲和剂和64％的EVA组成的样品的第二组是以颗粒层定向构造的。这些样品就地被压塑成型到聚丙烯顶盖中，测试两月之后，与渗透率为0.012cc/天、带有100％EVA衬垫的相同顶盖相比，测得氧气透过率为0.001cc/天。所有的测试中所有的衬垫均为0.025英寸厚且直径为1.509英寸。测试样品的第三组由压塑成型在43mm塑料顶盖22里的衬垫组成。所有的衬垫都厚0.025英寸，直径为1.509英寸。下表是说明测试结果的：
                               表2
      样品                                     氧气透过率
                                                (cc/天)
      1.100％EVA衬垫                             0.012
      2.34％EVOH，1％亲和剂，                    0.006
      65％EVA(混合物)
      3.层合的20％EVOH，80％EVA/亲和剂           0.0015
因此可以看出，有点令人惊讶的是，在测试样品中氧气的渗透率并不根据成型前颗粒层的定向而定。上面讨论的所有测试样品中，颗粒都包含129层基质聚合物(EVA)和阻挡层聚合物(EVOH或尼龙)的交替层，并带有与基质聚合物预混的亲和剂。其它的测试由在挤出的颗粒中只含有9层的相似材料进行。当最初颗粒中的层在平行于衬垫最终平面的方向定向时-即如图4A所示平行于盖基底-氧气透过率为0.0017cc/天。当层最初垂直定向时如图4B所示，氧气渗透率在相同的测试条件下为0.0029cc/天。可以认为，只要在挤出的颗粒和最终衬垫中有足够的层数量，无需考虑成型前层的定向，衬垫的阻挡性能就可以实现。
优选多重层的每一层基本上都具有均匀的厚度，虽然由于层的多重性这不是关键性的。还优选每一层都是均匀的组成。预计在某种应用中可以使用显示所需性能的其它材料添加层。
已经公开了一种阻挡层衬垫、带有衬垫的盖及其加工方法，完全满足了前面所提出的目的和任务。使用其它传统的技术和装置，由其它的传统材料可以很容易地生产衬垫。就使用的阻挡层材料的数量与气体的渗透率和透过率的比较而言，该衬垫具有改进的效果，这些气体例如氧气和二氧化碳，水蒸气和主要的油类气味(气味散失)。专门的基质/阻挡层组合已被公开。对于不同用途预见的其它组合物，根据在此讨论的原理和特性将向人们或本领域的普通技术人员推荐。
以上所提到的所有专利和或出版物在此作为参考被引用。

Claims (30)

1.一种用于塑料盖的密封衬垫，该衬垫包括一个圆盘(20a，20b或20c)，该圆盘主要由基质聚合物材料和阻挡层材料的交替层的多重组成，阻挡层材料是用于阻挡气体、水蒸气和/或香味透过所述衬垫。
2.如权利要求1所述的衬垫，其中所述的衬垫包括一种增加层与层之间粘合性的亲和剂材料。
3.一种塑料盖，包括：
一带有基底(30)和用于将盖固定到容器上的在外缘之上装置(34)的顶盖(22)，该基底有一确定顶盖内部的圆周外缘(32)，和
如权利要求1或2所述被固定到基底内部的衬垫(20a，20b或20c)。
4.如权利要求3所述的发明，其中所述的衬垫是在该顶盖内就地被压塑成型。
5.前述任一权利要求中的盖，其中所述的阻挡层材料在衬垫中的重量百分比范围为大约6％-35％，亲和剂在大约6％-20％的重量百分比范围内，余量由基质聚合物材料组成。
6.如权利要求5所述的盖，其中所述的基质聚合物选自以下组成：热塑性弹性体，柔性烯烃聚合物和上述的混合物。
7.如权利要求6所述的盖，其中所述的基质聚合物是热塑性弹性体，其肖氏A级硬度为45-95，弯曲模量为30,000-100,000psi。
8.如权利要求6所述的盖，其中所述的基质聚合物是热塑性弹性体，选自以下组成：苯乙烯嵌段共聚物和弹性体合金。
9.如权利要求6所说的盖，其中所述的基质聚合物是一种烯烃聚合物，该聚合物的肖氏A级硬度小于100。
10.如权利要求9所述的盖，其中所述的烯烃聚合物是选自以下组成：茂金属聚乙烯，乙烯-丙烯橡胶，乙烯共聚物及上述的混合物。
11.如权利要求5所述的盖，其中所述的阻挡层材料选自以下组成：EVOH，尼龙，丙烯腈共聚物，EVOH和不定形尼龙的混合物，EVOH或尼龙和粘土的毫微复合材料组成，EVOH和一种离聚物的混合物，丙烯腈，环烯烃共聚物及上述的混合物。
12.如权利要求5所述的盖，其中所述的亲和剂选自以下组成：马来酸酐接枝聚合物，乙烯乙酸乙烯酯接枝聚合物，乙烯丙烯酸甲酯，离聚物和上述的混合物。
13.如权利要求5所述的盖，其中所述的阻挡层材料包含EVOH或尼龙，所述的基质聚合物包含EVA。
14.如权利要求4所述的盖，其中所述的基质聚合物材料主要由一种或多种基质聚合物和所述的亲和剂材料形成的混合物组成。
15.如前述任一权利要求中的盖，其中所述的衬垫至少由9层基质聚合物和阻挡层材料的交替层组成。
16.如权利要求15所述的盖，其中所述的衬垫由至少33层交替层组成。
17.如权利要求16所述的盖，其中所述的衬垫由129层交替层组成。
18.如前述任一权利要求中的盖，其中所述的衬垫的肖氏A级硬度不大于94。
19.如前述任一权利要求中的盖，其中所述的衬垫包含的润滑剂的重量百分比为约0.5％-1.5％。
20.如权利要求19所述的盖，其中所述的润滑剂的数量为约0.5％的重量百分比。
21.如权利要求19所述的盖，其中所述的润滑剂选自以下组成：脂肪酸酰胺，脂肪酸酯，微晶蜡，聚乙二醇，伯酰胺，仲酰胺，仲-二酰胺和上述的混合物。
22.一种用于如前述任一权利要求的塑料盖的衬垫生产方法，包括以下步骤：
(a)挤出颗粒(20)，该颗粒主要由基质聚合物材料和用于阻挡气体透过的阻挡层材料的交替层的多重组成，和
(b)压塑成型该颗粒，使之成为一衬垫圆盘(20a，20b或20c)，其中交替材料层一般平行于圆盘被定向。
23.如权利要求22所述的方法，其中所述的基质聚合物材料主要由一种或多种基质聚合物和一种亲和剂材料形成的混合物组成。
24.如权利要求23所述的方法，其中所述的基质聚合物和亲和剂材料的混合物的熔化粘度与阻挡层材料的差别不大于指数5。
25.如权利要求22所述的方法，其中所述的步骤(a)包括挤出带有基质聚合物和阻挡层材料的亲和剂材料的步骤。
26.如权利要求25所述的方法，其中所述的亲和剂材料在挤出前与基质聚合物和阻挡层材料中的其一或二者混合。
27.如权利要求25所述的方法，其中所述的基质聚合物材料，阻挡层材料和亲和剂材料是作为分开的层被挤出的。
28.如权利要求27所述的方法，其中所述的阻挡层材料和基质聚合物材料的层彼此交替，亲和剂材料层排列在每一阻挡层材料层和每一基质聚合物材料层之间。
29.权利要求22-28中任一项所述的方法，还包括以下附加步骤：
(c)提供一带有基底(30)和确定顶盖内部的圆周外缘(32)和外缘之上的用于将顶盖固定到容器上的装置(34)的顶盖(22)，和
(d)将所述的衬垫圆盘固定到基底的内部。
30.如权利要求29所述的方法，其中所述的步骤(b)和(d)是通过在所述的基底的内部就地压塑成型所述的颗粒同步进行。
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US6677016B2 (en) 2004-01-13
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US20020104818A1 (en) 2002-08-08
PT926078E (pt) 2004-07-30
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