CN102196972B - 个人护理产品、多室材料分配系统及其制造方法 - Google Patents
个人护理产品、多室材料分配系统及其制造方法 Download PDFInfo
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- CN102196972B CN102196972B CN2009801419217A CN200980141921A CN102196972B CN 102196972 B CN102196972 B CN 102196972B CN 2009801419217 A CN2009801419217 A CN 2009801419217A CN 200980141921 A CN200980141921 A CN 200980141921A CN 102196972 B CN102196972 B CN 102196972B
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Abstract
本发明描述了材料分配系统和用于制造此类系统的方法。这些材料分配系统利用了能够收缩的容器(18),该能够收缩的容器具有至少两个不同的室(32,34)并且至少部分地由能够弹性地变形的绑带(14)围绕。当将容器(18)填充上易流动组合物时,绑带(14)会拉伸从而产生势能,该势能随后可用来替代推进剂和/或加压容器而分配所述组合物。
Description
技术领域
本发明涉及材料分配系统和用于制造所述系统的方法。本发明还公开了一种独特的阀门,所述阀门可任选地用于所述方法和/或最终的材料分配系统。本发明还涉及利用了本文所述的材料分配系统的包装和个人护理产品。
背景技术
气溶胶递送系统几十年来一直被广泛用来递送多种消费品,包括例如个人护理用品、涂料、食品和家庭护理产品。这些系统利用挥发性推进剂来将产品推出气溶胶容器。气溶胶技术因其有效性和相对廉价性而受到人们偏爱。然而,所述技术并非没有相关的缺点。传统上所用的碳氟化合物和烃类推进剂会释放到大气中,这便是一种相关的负面结果。另一个缺点是气溶胶容器被认为是压力容器,因此在其制造期间可需要具备额外的安全设备和规程。如果在贮藏、使用或废弃处理期间发生问题,加压容器也会引发对人身伤害问题的忧虑。并且与很多种气溶胶产品相伴随的高内部压力也限制了对容器的材料和几何形状的选择范围。
泵系统是气溶胶的一种供选择的替代物。泵系统一般分配定量的产品。然而,消费者可具有不同的要求,因此难以提供令所有使用者都满意的适当定量。例如,一个消费者可能需要使分配器泵送两次以分配其所期望的产品体积,并且另一个消费者可能仅要求相同的分配器泵送一次。并且如果所期望的体积是处在泵送剂量之间的某个量,则消费者可能难以成功地尝试使用泵式分配器。
已开发出了一种方法来提供类似于气溶胶的受控分配,但不会产生大部分的与气溶胶相关的负面结果。该方法包括由弹性体绑带围绕 的能够收缩的容器。将通常闭合的阀门和致动器组合件固定到容器。当容器被初始地填充有产品时,其与围绕的弹性体绑带一起膨胀。当弹性体绑带拉伸时,会产生势能。并且当操作致动器以打开阀门时,势能被转化为动能以将产品分配出容器外,直到致动器被脱离为止。这种分配系统的实例公开于美国专利4,964,540和5,232,126中。这些系统中的弹性体绑带主要在径向上进行膨胀和收缩。因此,显著量的产品可被截留在容器的闭合端中,尤其是如果容器和绑带中存在材料性能的变异以及如果涉及到粘稠产品例如凝胶的话。因此,本领域中存在改进的余地。
发明内容
本发明涉及制造材料分配系统的方法。根据一个示例性实施方案,现在提供了一种方法,所述方法包括以下步骤:(a)提供包括至少两个不同室的容器预成型件,所述容器预成型件包括聚合物预成型件和能够弹性地变形的绑带,所述绑带围绕聚合物预成型件的至少一部分;(b)加热聚合物预成型件;(c)将容器预成型件定位到模腔中;和(d)向聚合物预成型件的内部施加压力,所述压力足以导致容器预成型件向外朝模腔的壁膨胀以限定容器,在此期间能够弹性地变形的绑带被拉伸,并且产生与拉伸的能够弹性地变形的绑带相关的势能,所述势能在移除了施加的内部压力时至少部分地压缩容器。
本发明还涉及材料分配系统。所述材料分配系统一般可包括具有至少两个不同室的能够收缩的袋和围绕所述袋的至少一部分的绑带。在一个示例性实施方案中,袋所具有的长度比绑带的长度长至少约50%。在另一个示例性实施方案中,绑带是由如下材料构成,所述材料允许不可见光波透过绑带的壁,这使得在将袋预成型件吹制成最终袋构型之前,当绑带被定位在袋预成型件周围时,不可见光能够穿过绑带以加热所述预成型件。在另一个示例性实施方案中,袋包括至少一个如下部分(诸如侧壁或隔离壁),所述部分具有小于约4密耳、或小于约2密耳、甚至可低至约1密耳的壁厚。在另一个实施方案中, 袋是由注塑级聚酯制成,所述聚酯具有约0.5至约1.0、或约0.58的特性粘度值。在一个优选的实施方案中,将绑带固定到袋上,例如通过化学方法或通过除单纯摩擦之外的机械方法来固定。用以将绑带固定到袋上的合适方法的非限制性实例包括使用紧缩套管或重叠注塑由复合材料制成的扣环/扣带以将能够弹性地变形的绑带固定到所述预成形件上。借助于多室袋,所述材料分配系统可适于分配多种产品。
本发明还提供了未填充的包装和填充的包装。这些包装可包括外部容器和设置在其中的材料分配系统。外部容器可利用各种部件。在一个实施方案中,外部容器选自由下列组成的组:吹塑塑料容器、注塑容器、玻璃容器、柔性包装、纸材或纤维质包装、橡胶容器、或它们的组合或混合。例如,外部容器可呈现传统上不用于气溶胶产品的多种形状和几何形状。例如,所述容器可具有直径减小部分、具有锥形部分、或为椭圆形或正方形的。外部容器可为透明的、半透明的,或可利用窗口,所述窗口使得使用者能够看到包装中剩有多少产品(通过改变材料分配系统的外观来实现)以了解应当何时购买置换产品。对于其中可看到材料分配系统的至少一部分的实施方案来讲,材料分配系统可利用颜色和/或标记来传达其中所包含的产品的各方面信息。在一些实施方案中,外部容器可不完全包封材料分配系统。即,外部容器可仅形成用于美观和/或功能部件的外覆盖件的部分,例如材料分配系统的基座或腿部、或材料分配系统的柄部。外部容器可为刚性的或可为柔性的,或包括具有不同物理特性的多个部分。可将所述包装填充上众多不同的易流动组合物;例如个人护理组合物,包括但不限于剃刮组合物、毛发护理组合物、止汗剂/除臭剂组合物、护肤制剂、和口腔护理组合物(包括牙粉和义齿粘合剂(见例如美国专利5,073,604和6,025,411))。在本文中,本发明也可分配其他易流动产品。仅以举例的方式,本发明的系统可分配织物/毛发护理组合物、宠物护理组合物、和食物产品。
下文将更详细地描述本发明的这些和其他方面。
附图说明
虽然本说明书通过特别指出并清楚地要求保护被认为形成本发明的主题的权利要求作出结论,但据信阅读下列说明并结合附图可更好地理解本发明的示例性实施方案,其中:
图1A-1C为剖面图,示出了一个正在制造的示例性材料分配系统的实施方案。图1A示出了定位在吹塑模具内的容器预成型件的实施方案;图1B示出了吹塑过程中的预成型件;并且图1C示出了由拉伸的弹性绑带围绕的吹制容器/袋。
图2为示例性容器预成型件的侧视图,所述容器预成型件包括部分地由能够弹性地变形的绑带围绕的聚合物预成型件。
图3为图2所示容器预成型件的剖面图。
图4为示例性聚合物预成型件的透视图。
图5为图4所示聚合物预成型件的侧视图。
图6为包含单独且不同的室的另一个聚合物预成型件的实施方案的剖面图,当预成型件被成形为容器时所述室将被保留。
图7为另一个容器预成型件的实施方案的剖面图。
图8为包括阀门构件的容器预成型件的实施方案的局部剖面图,所述阀门构件插入到所述预成型件的开口中。
图9为根据本发明的正被填充上易流动组合物的包装的局部剖面图。
图10A和10B为在使用之前和在使用期间的填充的包装的剖面图。
图11为能够接纳本发明的材料分配系统的罐的透视图。
图12和13示出了示例性尺寸变化,所述尺寸变化可发生在将容器预成型件转变成容器/材料分配系统之后。
图14和15分别为根据本发明的包装消费品的剖面图和侧视图。
图16A和16B为各自根据本发明的至少一个实施方案的两个管的示例性侧视图。
具体实施方式
通过参考以下例证性的优选实施方案的详细描述可更容易理解本发明。应当了解,权利要求的范围并不仅限于本文所述的具体组件、方法、条件、装置或参数,并且本文所用的术语不旨在限制受权利要求书保护的本发明。此外,如在包括所附权利要求书的说明书中所用,单数形式“一个”、“一种”和“所述”还包括复数,并且对特定数值的引用包括至少那个特定值,除非上下文另外明确指定。当表示值的范围时,另一个实施方案包括从一个特定值和/或至另一个特定值。同样,当通过使用先行词基础“约”将值表示为近似值时,应当理解,所述特定值形成另一个实施方案。所有范围均包括端值在内并可合并。
根据本发明的一个方面,提供了制造材料分配系统的方法。将参照图1A-1C来描述一种示例性方法。在图1A中,示例性容器预成型件10被示出为插入到吹塑模具30的顶部中。容器预成型件10包括聚合物预成型件12、能够弹性地变形的绑带14、和阀门构件16。在一个实施方案中,聚合物预成型件是由以下材料制成:Eastman以商品名Eastar Copolyester EN058出售的注塑级PET;具有宽分子量且具有4.0的熔流指数的聚合材料;Lyondellbasell以商品名M5040出售的高密度聚乙烯、以及其他材料诸如Lyondellbasell出售的Clarify PP1903。
在一个实施方案中,能够弹性地变形的绑带包括天然橡胶材料诸如胶乳。合适的天然橡胶包括拉伸强度(psi)为最小约3500的那些。其他合适的天然橡胶可具有至少约750%的极限伸长率。此外,所述天然橡胶可具有约35+/-5的硬度(肖氏硬度A)和最大125的100%模量(psi)。合适的天然橡胶也可具有最大约0.97的比重。在一个实施方案中,能够弹性地变形的绑带包括天然橡胶,所述天然橡胶可由橡胶植物(例如,银胶菊或三叶胶树)制成。在一个实施方案中,能够弹性地变形的绑带不含或基本上不含炭黑或任何其他会过度阻碍或干扰红外光透射穿过绑带的成分。不受理论的约束,据信优选地选择能够弹性地变形的绑带而使其允许全部或至少大部分红外光波穿过能 够弹性地变形的绑带,因此红外光可到达预成型件并加热它。
在拉伸和/或吹制成容器/袋之前,对预成型件12进行加热。加热步骤可通过使光波透射穿过绑带14而到达预成型件12来进行。在一个实施方案中,将预成型件的至少一部分(优选地整个预成型件)加热至预成型件的(Tg)玻璃化转变温度以上约5至约30°F、或约10至约20°F的温度范围。在另一个实施方案中,也将绑带加热至约相同的温度。所述光波为优选的不可见光波,包括例如在红外波长范围内,例如约1.5微米左右的光波。向预成型件12的内部施加压力以塑性地膨胀预成型件12并弹性地膨胀绑带14。该压力可由加压气体(例如空气)、从动杆或其他物理构件、或这两者的组合来提供。在一个实施方案中,施加的压力介于约30psig至约130psig之间,或者为约70psig。不受理论的约束,为使预成型件快速且均匀地膨胀且对预成型件造成不可取损坏的可能性较小,据信在70psig的约±15或10psig范围内的施加的压力是优选的。如果利用物理压力,则阀门构件16可不设置在预成型件的颈部中。在一个优选的实施方案中,将阀门构件16包括在预成型件中,以便可控制气体进入预成型件的速率和气体从成形容器排出的速率。
如图1B所示,预成型件12和绑带14在轴向(纵向)和径向上膨胀。预成型件12在该膨胀期间被塑性地变形,而绑带14被弹性地变形或拉伸使得产生了与绑带14相关联的势能。在一个实施方案中,所产生的势能为约35psig或更小,或约30psig,或约20psig的流体静力学压力。在一个实施方案中,绑带被拉伸使得绑带的至少一部分具有约6密耳至约10密耳,优选约7至约8密耳,优选约8.2至约8.4密耳的壁厚范围。在一个实施方案中,聚合物预成型件的至少一部分在其被拉伸之前具有约1/16英寸至约3/8英寸、或者约1/8英寸的壁厚。图1C示出了预成型件12向外并邻近模具30的壁膨胀以限定容器或袋18。如果从容器18释放内部压力,则与绑带14相关联的势能将作用在容器18上从而至少部分地再次在轴向和径向上压缩它。
本说明书的发明背景部分曾提到过已知的材料分配系统,所述系 统包括能够收缩的袋和围绕它的弹性体绑带。这些现有系统的制造方式通常与结合图1A-1C所示和所述的方法非常不同。现有的袋一般是使用注射拉伸吹模法来制造的,其中预成型件进行注塑并接着在吹模中进行拉伸和吹制。与本发明的示例性方法不同,在吹塑过程之前和吹塑过程中,不将弹性体绑带放置在预成型件周围。相反,首先将预成型件吹制成袋,然后使其固化。从模具中取出所述袋,将其进行径向压缩,然后通过单独过程插入到绑带中。
在一个实施方案中,能够收缩的袋可由美国专利4,964,540中所公开的用于制造“可膨胀袋”的任何材料制成。因此,可用来制造袋的材料的非限制性实例包括柔性且任选地弹性的任何材料。在一个实施方案中,所述材料基本上为非弹力材料,所述材料为相对惰性的以便其不会对其内容物赋予任何味道或气味。然而,也可使用其他材料诸如聚对苯二甲酸乙二酯。例如袋可由塑性材料诸如尼龙、聚丙烯、聚酯或SARANEX制成。
在另一个实施方案中,能够收缩的袋为如美国专利5,232,126所示和所述的衬里。可构成适用作能够收缩的袋的衬里的材料的非限制性实例包括任何柔性的塑性材料,所述塑性材料可为弹性体或非弹性体,优选地为非弹性体。一种优选的材料为高密度聚乙烯(HDPE);其他合适的材料包括聚酰胺和“Barex”218,后者为一种得自BritishPetroleum的丙烯腈。如果需要,所述衬里可由两种或更多种材料通过共挤坯吹塑来形成。在将衬里从模具中取出之后,没有必要或不期望在衬里上形成任何附加层。除通向阀门中的衬里的颈部通常相当刚硬之外,衬里优选地在其整个长度上均为柔性的,但在其整个长度上足够刚硬以便自承。
衬里可具有任何合适的厚度。一个实施方案允许衬里具有如下的厚度:在基本上其整个长度上为约10至20密耳(0.010至0.020英寸)的平均侧壁厚度,优选约0.012至0.018英寸;不同的是,任选地在通向阀门的颈部处,形成颈部的衬里的部分可稍微较厚一点,所述部分在完全膨胀状态时可在阀门的1英寸以内。可容许回旋部分中的任何 给定的水平剖视平面处的厚度具有微小变化。
在另一个实施方案中,将能够收缩的袋打褶成具有峰和谷,如美国专利4,964,540和5,232,126所示和所述。也可使用其他已知的适于在加压容器中使用的能够收缩的袋或柔性袋。
参见图2和3,现在将描述示例性容器预成型件10及其组件的各方面。容器预成型件10示出于图2中,并且包括聚合物预成型件12、能够弹性地变形的绑带14、阀门构件16、以及设置在阀门构件16和预成型件12的颈部区域之间的任选的适配件/插件19。
图4和5分别示出了预成型件12的透视图和侧视图。预成型件12具有开口端20(虽然未示出实际的开口)和相对的闭合端22。在一个优选的实施方案中且如图所示,凸缘24被限定成邻近开口端20。凸缘24可有助于将预成型件保持在吹模中。凸缘24也可用于将最终形成袋接合到外部容器和/或阀门或致动器组合件的一部分上。在示例性预成型件12上利用两个附加凸缘,第一凸缘25邻近开口端20设置,并且第二凸缘26邻近闭合端22设置。一对凹槽27和28也包括在预成型件12上。附加凸缘和凹槽为任选的部件,它们可帮助定位并保持绑带14。在一个优选的实施方案中,将粘合剂放置在凹槽27和28中以将绑带14固定到预成型件12上。根据本发明,可使用的合适粘合剂的非限制性实例包括光固化粘合剂诸如: 4306TM和4307TM、非光活化粘合剂诸如 406TM和4501TM、以及它们的混合物。预成型件12可由包括例如聚酯、尼龙、聚烯烃在内的多种热塑性材料形成,并且可使用任何已知的技术诸如注塑来形成。在一个示例性实施方案中,聚合物预成型件由特性粘度值为约0.5至约1.0的注塑级聚酯材料制成。
适用于本发明的聚合物预成型件不限于所包括的各图中所示的几何形状,并且可利用与所示出和所述的那些类似的或相异的部件。图6示出了根据本发明至少一个实施方案的且具有多个室的供选择的替代型预成型件30的剖面图。预成型件30具有第一室32和第二不同的室34。其中预成型件具有两个以上不同室的其他实施方案也处于本发 明的范围内。在拉伸和/或吹制过程期间,这些单独的室得到保持,以便成形的袋也将具有至少两个诸如三个用于保持不同组合物或组合物组分的不同的室。所述不同的室由至少一个隔离壁隔开,所述隔离壁是由与聚合物预成型件的其余部分相同的材料制成。隔离壁优选地为单层壁。预成型件材料(包括任何隔离壁)自身可为多层结构,诸如通过多层注塑法诸如通过Graham Packaging′s SurShotTM多层注射技术(见例如EP 1147872、US 6787094)形成的多层结构。在一个实施方案中,预成型件包括尼龙层和夹置在PET预成型件材料中间用以改善阻隔性能的乙烯-乙烯醇(EVOH)层。所述多个不同的室从聚合物预成型件的开口端延伸至聚合物预成型件的闭合端。本领域的技术人员将会理解,可将相同或不同的组合物包含在所述室中的每个中。在一个实施方案中,可将两种化学上不相容的成分分开放入到不同的室中,使得它们在分配之前不相接触。在另一个实施方案中,可使可产生第三组合物或有益效果诸如热或泡沫的两种成分保持分开,直到进行分配时为止。技术人员将易于理解,也可利用两个以上的单独的室。
重要的是,本发明已发现,当预成型件(其至少部分地由能够弹性地变形的绑带围绕)被填充从而产生所得的能够收缩的袋时,在能够收缩的袋内会产生一定量的内部压力。已发现,如果预成型件包括多个室诸如两个或三个室,则在所述多个室内可产生相同量的压力。据信这是可能的,因为限定单独不同室的隔离壁是柔性的、能够收缩和/或可拉伸的(由与能够收缩的袋相同的材料制成),因此当不同的室释放组合物,从而减小内部压力时,隔离壁可挠曲使得所述多个室中的压力保持相同。在一个实施方案中,第一不同的室和第二不同的室之间的压力差小于约15psi,或者小于约10psi,或者小于约5psi,或者小于约1psi,或甚至为约0psi。
在一个实施方案中,第一不同的室包含第一组合物,并且第二不同的室包含第二组合物。在一个实施方案中,第一组合物与第二组合物不相同。当第一组合物和第二组合物不相同时,可使用的合适组合物的实例包括如下任何合适的组合物:当彼此接触时,它们可为不相 容的。此外,被分开放入到第一室和第二室中的组合物还可形成自热组合物,所述自热组合物可适用于各种美容护理应用,包括但不限于剃刮预备。合适的自热组合物的一个非限制性实例包括当存在水时会产生热的组合物。在一个实施方案中,第一组合物包括还原性组分诸如无水成分。合适的无水成分的一个实例包括沸石和/或无机盐。当还原性组分为无水成分时,氧化性组分包括水源。因而无水成分和水之间的接触将产生热。本领域的技术人员将会理解,当还原性组分接触氧化性组分时,将会产生热。
在一个实施方案中,在第二组合物中提供氧化性组分。如果在第二组合物中提供氧化性组分,则当使用者从第一室和第二室分配组合物并且使组合物彼此接触并最终混合时,可产生热。氧化性组分的一个实例为水源。还原性组分和氧化性组分的合适组合的一个实例为U.S.PG Pub.2004/0166085、2006/0029566和2006/0029565中所述的那些。在这种实施方案中,氧化剂组分包括第一剃刮泡沫基料和氧化剂,并且还原剂组分包括第二剃刮泡沫基料和还原剂。剃刮泡沫基料各自独立地包括水包油乳液,所述乳液包括水、在21℃下具有约40psig或更大蒸气压力的挥发性发泡剂、和包含非离子表面活性剂的水分散性表面活性剂。选择氧化剂和还原剂的量和比例以在使用剃刮泡沫产品期间在混合氧化剂组分和还原剂组分时提供具有所期望的热特征图的放热反应。优选地,所述剃刮泡沫基料中的至少一种或更优选地两种均基本上不含皂和离子表面活性剂(例如,阴离子表面活性剂)。所谓“基本上不含”是指剃刮泡沫基料包含小于约2%的皂和离子表面活性剂,优选小于约1.5%的皂和离子表面活性剂,更优选小于约1%的皂和离子表面活性剂,并且最优选0%的皂和离子表面活性剂。
所述非离子的、基本上无皂的制剂与用来产生温热感觉的活性剂相容,并且在存在所述活性剂的情况下是稳定的。非离子剃刮泡沫基料还可提供其他优点,诸如减轻与皂基产品相关联的问题。非离子表面活性剂可包括两种表面活性剂的共混物,所述表面活性剂中的一种比另一种更具疏水性。通常,表面活性剂共混物可包括具有相对较长 和较短聚环氧乙烷链(聚氧乙烯链)的脂肪醇乙氧基化物。例如,所述共混物可包括具有2至20个乙氧基团的脂肪醇乙氧基化物和具有21至100个乙氧基团的脂肪醇乙氧基化物,所述两种脂肪醇乙氧基化物以约2.5∶1至约1∶2.5范围内的比率提供。
优选地,第一剃刮泡沫基料和第二剃刮泡沫基料基本上相同,所述相同是指每种剃刮泡沫基料具有至少三种、优选地至少四种、更优选地至少五种与另一种剃刮泡沫基料中的成分相同的成分,并且最优选地,此类成分以与另一种剃刮泡沫基料中的比例大约相同的比例存在。
一些具体实施可表现出下列一个或更多个优点。剃刮泡沫产品具有相对长的架藏稳定性,优选地为约一年至约三年。在一些实施方案中,剃刮泡沫产品不需要通过摇动来产生剃刮泡沫。在一些具体实施中,在贮藏在容器中期间,剃刮泡沫产品的发泡剂和其他成分保持乳化和稳定,而不是相分离成异质混合物。这可消除在使用之前摇动剃刮泡沫产品的必要性,所述摇动在两组分容器中可为不利的。在剃刮之前和剃刮期间,剃刮泡沫产品与泡沫的美观性能联合向使用者提供悦人的温热感。剃刮泡沫的加热效应帮助水合使用者的毛发(例如胡须)并且使毛发预备好以便剃刮,从而改善使用者的舒适感。剃刮泡沫产品是架藏稳定的(例如,它们的内容物在它们的容器中不发生相分离),并且以吸引人的美观形式从容器中分配出来。在分配之后,当将剃刮泡沫铺展到皮肤上时,剃刮泡沫迅速起泡成柔软的、奶油状的、稳定的泡沫。在施用到使用者的皮肤(例如,使用者的面部)上之后,所起的泡沫在剃刮期间保持在皮肤上(例如,所述泡沫不滑脱面部),甚至当泡沫因放热反应而受到加热时也是如此。所起的泡沫在剃刮期间帮助软化毛发(例如,胡须)并且保护皮肤。当剃刮泡沫组合物受到加热时,所起的泡沫保持奶油状且保持稳定。剃刮泡沫提供所期望的性能特性诸如润滑性和皮肤友好性,这些特性在加热期间和加热之后保持不变。用来加热剃刮泡沫的加热系统的化学性质用在皮肤上时是安全的并且不会刺激皮肤。在剃刮之后,所起的泡沫可相对容易地 从皮肤上除去。
除了前述成分以外,一种更优选的剃刮泡沫基料还包括以下任选的成分中的一种或多种(或在一个最优选的实施方案中,包括全部):水溶性聚合物、脂肪醇、两性表面活性剂、润肤剂(例如,油)、和增稠剂。剃刮泡沫基料通常呈水包油乳液的形式。选择水分散性表面活性剂(其优选地为表面活性剂的共混物)以提供若干种功能。其用作乳化剂、增溶剂、洗涤剂、和铺展剂或分散剂。水分散性表面活性剂包括非离子表面活性剂,更优选地包括两种或更多种非离子表面活性剂的共混物。由于它们在存在弱酸和弱碱的情况下是稳定的,因此非离子表面活性剂可提供制剂灵活性,而在使用皂时一般不可能实现所述制剂灵活性。优选的非离子表面活性剂包括聚乙氧基化脂肪醇醚。
用于氧化性组分的合适氧化剂的实例包括过氧化物诸如过氧化氢(通常作为35%的溶液加入)、过氧苯甲酰、过氧单磺酸、过氧化硫酸氢盐、过氧化脲、叔丁基过氧化物、以及它们的混合物。在一些实施方案中,剃刮泡沫组合物的氧化剂组分可包括约2%至约10%的氧化剂。在某些实施方案中,氧化剂组分可包括约12%至约16%的氧化剂,诸如过氧化氢(35%)(其对应于约4%至约6%的H2O2活性物质)。
用于还原性组分的合适还原剂的实例为如下的还原剂:当将制剂的所述两种组分混合时,所述还原剂将与氧化剂起反应以产生明显的放热反应。合适的还原剂按制剂中所用的量用在人的皮肤上时也应当是安全的。还原剂可包括例如硫代硫酸盐和亚硫酸盐化合物,诸如亚硫酸钠、硫代硫酸纳(例如,五水合硫代硫酸纳)、硫代硫酸铵/硫代硫酸钾、硫脲、以及它们的混合物。其他合适的还原剂包括具有硫脲主链的化合物诸如1,5-二乙基-2-硫代巴比妥酸或其衍生物、或抗坏血酸。也可使用上述还原剂和其他合适还原剂的混合物。在一些实施方案中,剃刮泡沫组合物的还原剂组分可包括约2%至约10%、优选地约3%至约8%的还原剂。
基于将要发生的氧化还原反应,一般按大约化学计量比例来包括氧化剂和还原剂。过氧化氢与硫代硫酸纳的主要氧化还原反应如下:
2S2O3 2-+H2O2→S4O6 2-+2OH-
在存在足够量的有效催化剂的情况下,所述反应如下:
Na2S2O3+4H2O2→Na2SO4+3H2O+H2SO4
优选地,在所述反应期间剃刮泡沫所获得的最高温度为约30℃至约60℃,并且该温度是在所述两种组分混合之后约10秒至约45秒达到的(这是当剃刮泡沫的氧化剂组分和还原剂组分在烧杯中以化学计量的量混合时,剃刮泡沫所达到的温度,所述量提供总重量为10克的剃刮泡沫;当将约5克至约8克典型量的剃刮泡沫施用到皮肤上时,皮肤上的实际温度通常为约28℃至约45℃)。当使用上述氧化剂和还原剂时,剃刮泡沫组合物一般包括按大约化学计量比例计约2%至约10%的氧化剂和约2%至约10%的还原剂。
为了获得上述的热特征图,可有利地在剃刮泡沫组合物中包括催化剂。将催化剂选择成催化放热反应,而不会对皮肤或剃刮泡沫的特性产生有害影响。催化剂一般包括在剃刮泡沫组合物的还原剂组分中。用于上述放热反应的合适的催化剂包括钼酸钠(例如,二水合钼酸钠)、钼酸钾、钼酸氨、钨酸钠、钨酸钾、以及它们的混合物。所述组合物一般包括0.1%至约1.5%、优选地约0.2%至约1.0%的催化剂。
如果放热反应生成酸,如上述氧化剂和还原剂的反应一般将会生成的那样,则优选地使所述组合物(例如,还原剂组分)也包括中和剂(中和剂)。选择并以充足量提供中和剂以中和足够的酸,以便使放热反应完成并且剃刮泡沫组合物将不会刺激使用者的皮肤。优选地,基本上全部的酸均被中和。合适的中和剂包括例如三乙醇胺、氧化物(例如,金属氧化物)、氢氧化物(例如,金属氢氧化物)、和金属碳酸盐诸如碱性金属(例如,钠、钾)、碱土金属(例如,镁、钡)、或过渡金属(例如,锌)的碳酸盐。例如,中和剂可包括氧化钙、氢氧 化钾、氢氧化钠、碳酸氢钾、碳酸氢钠或碱式碳酸铝。在一些实施方案中,剃刮泡沫组合物(优选地剃刮泡沫组合物的还原剂组分)可包括约0.5%至约10%的这种中和剂。例如,还原剂组分可包括约1%的氧化钙或约7%的三乙醇胺。
在另一个实施方案中,不在第二隔室中提供氧化性组分,例如氧化性组分可为水源诸如由使用者提供的水-例如源自水龙头的水。其中氧化性组分不包括在材料分配系统内所包含的任何组合物中的一个实例为如下实例:其中第一组合物包括丁二醇中的沸石,并且第二组合物包括聚乙二醇(诸如PEG 8)。
在另一个实施方案中,第二室也包括还原性组分,所述还原性组分可相同于或不同于第一组合物中的还原性组分。
自热组合物的其他实例包括美国专利3,772,203、4,439,416中所公开的那些。
不受理论的约束,已发现,所述至少两个不同的室所包含的每种相应组合物的量不是由室的尺寸或所述室内的相对压力控制,而是由阀门内所形成的相应孔口的尺寸控制,所述孔口背离所述室通向能够收缩的袋之外。在一个实施方案中,阀门包括与不同室的数目一样多的孔口,其中每个室通向其自己的孔口。在一个实施方案中,这些孔口具有相同的横截面积。在另一个实施方案中,这些孔口具有不同的横截面积,其中较大面积相对于较小面积允许具有较高的分配速率。
分配系统中所包含的组合物也可包括口腔护理或美容护理组合物。在一个实施方案中,第一组合物或第二组合物包含铝盐,并且另一种组合物包含氟化物诸如U.S.4,425,322中所公开的氟化物。在另一个实施方案中,第一室具有包含过氧化钙的组合物,并且第二室具有包含碳酸氢钠的组合物,如U.S.5,599,525中所公开。在另一个实施方案中,第一室具有包含雕刻相(包括凝胶形成基质、硬化树脂、改性剂、溶剂或载体、以及任选地至少一种防粘剂、光亮剂或上光剂)的组合物,并且第二室具有包含光亮相(包括凝胶形成基质、成膜剂或改性剂、溶剂或载体、以及至少一个种防粘剂、光亮剂或上光剂)的 组合物,如U.S.5,059,414中所公开(见权利要求2)。在另一个实施方案中,第一室中的组合物可包括阴离子表面活性剂诸如洗涤剂、或皂诸如洗发剂,并且第二室中的组合物可包括阳离子表面活性剂诸如软化剂、或调理剂诸如毛发调理剂。
在另一个实施方案中,第一室和第二室中所包含的组合物具有不同的颜色,或其中一种组合物为着色的,并且另一种为非着色的(透明的或白色的)。在另一个实施方案中,所述一种组合物为透明或半透明的,并且另一种组合物为不透明的。这些实施方案可能是某些消费者所尤其期望的,因为它们可提供组合物(当它们被分配时)之间的明显的视觉对比,从而使得使用者能够理解每种组合物中均存在着提供不同有益效果的不同成分。
再参见图2和3,绑带14是由能够弹性地变形(即,基本上非永久地变形)的材料或材料的共混物制成,在所述变形期间会产生势能。绑带14优选地由弹性体材料例如橡胶材料或热塑性弹性体(TPE)制成。所述橡胶材料可为天然橡胶、合成橡胶、或它们的混合物。在一个示例性实施方案中,能够弹性地变形的绑带是由天然橡胶制成,所述天然橡胶为非不透明的且具有750%以上的弹性。技术人员应当理解,也可利用具有较小弹性度的橡胶材料。如上所述,聚合物预成型件在被膨胀成容器/袋之前受到加热。可在加热预成型件之前、期间或之后将围绕的绑带放置到预成型件上。如果在加热之前将绑带设置在预成型件周围,则优选地利用如下的绑带材料,所述绑带材料使得光波能够从其中透过以便可通过热源充分地加热预成型件,所述热源定位在预成型件/绑带组合件的外部上。允许红外光透过的绑带材料为一种优选的材料类别。不受理论的约束,据信当透过能够弹性地变形的绑带加热聚合物预成型件时,不透明的橡胶材料可造成困难。因此,优选使能够弹性地变形的绑带具有所期望的弹性性能,但仍然允许透过绑带加热聚合物预成型件。
绑带14可永久地或可拆卸地在邻近预成型件开口端20和闭合端22的点位固定到预成型件12上。在一个实施方案中,绑带的一部分 永久地固定到预成型件上。任选的凹槽27和28被适宜地构造成用于接纳粘合剂;然而,应当指出的是,在缺乏任何具体的接纳部件诸如任选的凹槽27和28的情况下,也可将粘合剂简单地沉积在预成型件的外部上。合适的粘合剂可包括环氧树脂、氨基甲酸酯、丙烯酸盐(酯),并且可使用其他的可使橡胶或其他能够弹性地变形的材料与塑性材料粘结的粘合剂。氰丙烯酸酯是一种优选的粘合剂材料。所述粘合剂通常为空气固化的、光(可见光/非可见光)固化的、和/或通过化学交联固化的。在一个示例性实施方案中,绑带14并不在显著地与端20和闭合端22间隔开的点固定到预成型件12上,以便聚合物预成型件的壁可尽可能有效且高效地流动并膨胀至吹模边界而不受到绑带14的束缚。也可利用机械方法将绑带14固定到预成型件12上。绑带可被构造成使得没有必要将绑带的远端部分固定到预成型件上。例如且如图7所示,绑带114可具有远端115,所述远端封闭在聚合物预成型件112的闭合端122上,从而当预成型件在吹塑期间纵向膨胀时,绑带114可相应地纵向拉伸。封闭的远端可例如通过以粘合方式将内壁部分粘附到彼此上而制成。也可在远端的外部周围放置限制构件(例如,夹具)以保持远端封闭。虽然远端115被示出为完全封闭的,但其也可为部分地封闭的或被制造成具有比其相对侧小的开口,以使预成型件和由预成型件吹制的袋不会挤过绑带的远端。
如上所述,在将预成型件吹塑/拉伸成最终袋期间,优选地将阀门构件16包括在预成型件中。然而,在本文所提供的制造方法中,该优选的布置不排除缺乏阀门。阀门可帮助调节空气压力和/或提供阻尼效应以减缓当空气进入预成型件中时空气压力的突然增加。可将这种气流控制思想重新应用于常规的吹塑法,以获得在关键轮廓区域具有4密耳或更小(甚至低至约1至约2密耳)壁厚的成形瓶/袋。这种气流控制思想可通过将预吹和/或终吹气流速率编程到预成型件中或通过连结阀门来执行,所述阀门将执行与吹塑供气喷嘴类似的功能。阀门也可完全阻止气流离开吹制的容器和/或在由预成型件吹制成袋之后帮助减小内部压力的泄放速率。在袋的形成期间,绑带产生显著量的 势能,如果不存在对内部压力泄放的调节,则所述势能可非常快速地压缩最近形成的袋。申请人已发现,内部空气压力的快速泄放可潜在地在袋中产生缺陷或弱化预成型件上的锚定了粘合剂的固定点(当它们存在于外部绑带和袋之间时),因为紧接在吹塑过程之后或在袋材料充分地固化或冷却之前,所述快速泄放会导致外部绑带收缩,所述收缩会快速地压缩内部袋。也可利用包括不与袋/绑带组合件相关联的阀门的周边制造设备来帮助调节内部压力的泄放和袋压缩速率。插入的阀门也可在模制了袋之后保持内部空气压力,以便在模制和填充上可分配产品之间可进行渗漏测试。在吹塑过程中插入到预成型件中的阀门可与最终产品中所用的阀门相同或不同。如果使用单一阀门,则其可用来帮助模制过程、用于将袋填充上可分配产品、并且让最终使用者来控制分配。
阀门构件16代表了可用于本发明的产品、系统和方法的一个示例性实施方案。参见图8,示例性阀门构件16包括与插件19协作的能够弹性地变形的主体40。插件/适配件不是必要的组件-在所述示例性阀门的操作中,预成型件的内壁或成品袋颈部可起到与插件19相同的作用。插件19(或者吹制的袋/容器的颈部区域)用作套管以将阀门16密封在其通常闭合的位置。能够弹性地变形的主体可由弹性体材料例如橡胶材料制成。也可利用技术人员已知的其他材料。阀门主体40包括开口端42、相对的闭合端43、和邻近开口端42设置的凸缘44。盲孔45从开口端42延伸并终止于盲孔底部46。盲孔45限定阀门主体的侧壁47。通孔48延伸穿过侧壁47并定位在开口端42和盲孔的底部46之间。当极小的应力至没有应力施加到阀门主体40上时,主体外部和通孔48两者或仅通孔48以下的主体外部贴紧外部套管密封,所述外部套管可由插件/适配件(例如,插件19)、预成型件/袋颈部区域、或它们的其他组件或部分限定。因此,外部套管通常由刚性材料例如塑料、金属、硬弹性体、玻璃和纸板或其他基于纤维素的材料制成。施加足够水平的轴向应力将导致能够弹性地变形的主体40在轴向上伸长,从而导致主体40的直径减小。当主体40伸长因而直径减小 时,在主体40的外表面和围绕的套管之间产生流体流槽。所述槽一旦产生就与预成型件或袋的内部、通孔48、和盲孔45及其开口端42保持流体连通。因此流体槽使得易流动的材料能够行进到预成型件或由预成型件形成的袋/容器的内部中并从其中退出。在吹塑过程中,轴向应力来自被导入到盲孔45中的加压空气。轴向应力也可在填充过程中通过将加压产品加料到成形袋的内部中来产生(见例如图9)。并且轴向应力可通过向下位移插入到盲孔45中的管来产生,所述盲孔构成阀门和致动器系统的一部分(见例如图10A和10B)。
再参见图1A-1C,将聚合物预成型件和能够弹性地变形的绑带加热并放置到吹模中,其中预成型件塑性地膨胀成能够收缩的容器/袋,并且绑带由于在吹塑过程中所产生的内部压力而弹性地膨胀。当绑带弹性地膨胀时会产生势能。并且当内部压力排出时,该势能可压缩能够收缩的袋。现在,使压缩的袋和围绕的绑带尺寸得当,并且被构造成用于插入到如图11所示的示例性罐100或瓶或其他外包装容器的顶部开口90中。袋的顶部可利用有利于连结到外包装容器上的部件。可将易流动产品加料到压缩的袋中。在这种填充过程中,袋在径向和轴向上膨胀,这继而导致能够弹性地变形的绑带相应地在径向和轴向上膨胀。当能够弹性地变形的绑带膨胀时,势能再次产生。通常闭合的阀门与填充的袋和绑带组合件流体连接。闭合的阀门防止绑带势能作用在填充的袋上以将内容物挤过阀门。阀门可例如通过启动致动器来打开。
已知的利用能够收缩的袋和弹性绑带系统的材料分配系统使能够收缩的袋达到其最终长度,然后将处于压缩状态的袋插入到弹性绑带中。处于其未拉伸状态的弹性绑带通常具有如下长度,该长度覆盖袋的最终长度的大部分,从而导致绑带主要在径向上进行膨胀和收缩。当袋在使用期间收缩时,该方法可导致显著量的产品被截留在袋的底部中。相比之下,本发明提供了在径向和轴向(或纵向)上膨胀和收缩显著量的系统。在一些优选的实施方案中,绑带因此在轴向或纵向上拉伸其初始未拉伸长度的至少约50%、100%、150%或200%。图 12和13以举例的方式示出了处于未应变/未拉伸状态的绑带14与拉伸状态相比的尺寸差别。类似地,在使用期间,从首次使用时的初始分配到最终完全分配(其中在打开通常闭合的阀门时,不再有产品流出材料分配系统),绑带在轴向上紧缩或收缩至少约50%、100%、150%或200%。并且由于这种显著的轴向膨胀和收缩,能够收缩的袋的长度可显著地大于能量绑带在其未应变/未拉伸状态时的长度。例如,能够收缩的袋可为相关联且未应变的能量绑带的长度的至少约100%、150%、200%或300%。
一种提供能量绑带的显著的轴向膨胀和收缩的方法是,制造图1A-1C所示且结合所述图所述的能够收缩的袋和能量绑带组合件。即,将能量绑带放置在注塑预成型件周围并且使用吹塑法形成袋,其中当袋形成时,能量绑带显著地纵向膨胀和拉伸。另一种可用来提供增加的轴向膨胀(在填充期间)和收缩(在分配产品时)的制造技术包括:将预成型的袋操纵至比其完全延伸长度短的长度,然后将操纵过的袋插入到能量绑带中,所述能量绑带比所述袋的完全延伸长度短至少约50%或100%。能量绑带可固定到袋的底部上或被构造成防止袋简单地伸出绑带的端部,以便当袋在填充期间膨胀时其在纵向上拉伸绑带。因此,在一个实施方案中,制造本发明的材料分配系统的方法还包括操纵聚合物预成型件以使其呈现短于轴向延伸长度的长度的步骤,所述步骤选自由下列组成的组:将聚合物预成型件的底部固定到能够弹性地变形的绑带的底端上;至少部分地密封能够弹性地变形的绑带的底端,使得聚合物预成型件不延伸越过能够弹性地变形的绑带的至少部分地密封的端部;以及它们的组合。可用各种方法来操纵袋,包括例如通过朝袋的开口端折叠袋的闭合端或通过倒置袋的闭合端来操纵。
图1A-1C示出了用于制造材料分配系统的示例性方法。可将所得系统放置到单独制造的外部容器(诸如上文的发明内容中所述的外部容器)中,合适的外部容器的非限制性实例包括瓶或罐。然而,根据本发明所提供的另一种示例性方法,外部容器可与材料分配系统同时 制造。在该方法中,在吹塑过程中使用包装预成型件,所述包装预成型件具有内容器预成型件、外部容器预成型件、以及设置在所述两个预成型件之间的能够弹性地变形的构件。通过使用加压空气和/或推杆,所有三个结构均膨胀至模腔的壁。在一个其中将推杆用于注射应力吹塑(ISBM)过程的实施方案中,阀门是在所述ISBM过程之后安装。在所述ISBM方法之后安装阀门允许推杆挤过预成型件的开口端20。在排出内部压力时,能够弹性地变形的构件收缩,因而压缩由相应的预成型件形成的内容器,而在用以中断负压的外部容器和能够弹性地变形的构件之间的开口或间隙的帮助下,由相应的预成型件形成的外部容器基本上保持由吹模腔体所限定的几何形状。内容器预成型件和外部容器预成型件可由相同的聚合材料或不同的材料(例如,具有不同的热转变温度诸如熔融温度或玻璃化转变温度)制成。
一种示例性个人护理产品200示出于图14和15中。所述产品包括由成型容器212和上盖214限定的外包装210。材料分配系统216设置在容器212内,所述系统包括填充有易流动组合物219的袋218和围绕袋218的拉伸的绑带220。致动器222定位在容器212上,并且包括部分地由管226限定的流动通道224。管226连接到能够弹性地变形的阀门构件228上。管226的向下位移充分地伸长阀门构件228以允许某个体积的组合物219行进到阀门构件的通孔229中,所述通孔与管226中的通孔或端部开口的狭槽(图16A示出了管226上的通孔66,并且图16B示出了另一个管226上的端部开口的狭槽266)对齐,使得组合物继续沿管226和流动通道224向上行进以退出包装210。在一个示例性实施方案中,管226可在阀门构件228内旋转,使得管的通孔在一个位置中与通孔229对齐而在另一个位置中不与通孔229对齐。该特征提供了锁定方式以防止或限制组合物219的排放(如果致动器意外地受到碰撞或按压的话)。
不应将本文所公开的量纲和值理解为严格限于所引用的精确值。相反,除非另外指明,每个这样的量纲旨在表示所引用的值和围绕该值功能上等同的范围。例如,所公开的量纲“40mm”旨在表示“约 40mm”。
发明详述中引用的所有文件都在相关部分中以引用方式并入本文;对任何文献的引用均不应解释为承认其是关于本发明的现有技术。当本文件中术语的任何含义或定义与以引用方式并入的文件中同一术语的任何含义或定义矛盾时,应当服从在本文件中赋予该术语的含义或定义。
尽管举例说明和描述了本发明的具体实施方案,但是对本领域的技术人员显而易见的是,在不背离本发明的实质和范围的情况下可作出许多其他的改变和变型。因此,所附权利要求中旨在涵盖处于本发明范围内的所有这些改变和变型。
Claims (15)
1.一种材料分配系统,所述材料分配系统包括:
(a)能够收缩的袋,所述袋包括至少两个不同的隔室;和
(b)能够弹性地变形的绑带,所述绑带围绕所述袋的至少一部分,
其中所述能够弹性地变形的绑带能够沿着径向方向和轴向方向两个方向弹性地变形,由此产生轴向地和径向地作用在能够收缩的袋上的势能。
2.如权利要求1所述的材料分配系统,其中所述至少两个不同的隔室由隔离壁隔开,所述隔离壁由与所述能够收缩的袋的其余部分相同的材料制成。
3.如权利要求1或2所述的材料分配系统,其中所述隔离壁具有一个以上的层。
4.如权利要求1所述的材料分配系统,其中所述能够收缩的袋包括至少一个具有小于4密耳壁厚的部分。
5.如权利要求1所述的材料分配系统,其中所述能够收缩的袋包括注塑级聚酯,所述聚酯具有0.5至1.0的特性粘度值。
6.如权利要求1所述的材料分配系统,其中所述能够收缩的袋具有开口端和与所述开口端相对的闭合端,并且所述能够弹性地变形的绑带包括邻近所述袋的开口端的第一端部和邻近所述袋的闭合端的第二端部。
7.如权利要求1所述的材料分配系统,其中所述能够弹性地变形的绑带通过化学粘合剂、除单纯摩擦之外的机械方法或它们的组合中的至少一种固定到所述能够收缩的袋。
8.如权利要求1所述的材料分配系统,其中所述能够弹性地变形的绑带包括允许不可见的光波和/或红外光波通过所述能够弹性地变形的绑带的壁的材料。
9.如权利要求1所述的材料分配系统,所述系统还包括外部容器,其中所述材料分配系统设置在所述外部容器中,并且其中所述外部容器包括聚合材料,任选地为吹塑塑料容器,并且其中所述外部容器包括开口端、相对的闭合端、以及设置在所述开口端和所述闭合端之间的直径减小区域。
10.如权利要求1所述的材料分配系统,其中所述第一室包括还原性组分,所述还原性组分任选地包括无水成分、硫代硫酸盐、亚硫酸盐化合物以及它们的混合物中的至少一种。
11.如权利要求1所述的材料分配系统,其中所述第二室包括氧化性组分,所述氧化性组分任选地包括水源、过氧化物以及它们的混合物中的至少一种。
12.如权利要求1所述的材料分配系统,所述材料分配系统还包括连接到所述能够收缩的袋的阀门,所述阀门形成连接到第一不同室上的第一孔口和连接到第二不同室的第二孔口。
13.如权利要求12所述的材料分配系统,其中所述第一孔口不具有与所述第二孔口相同的横截面积。
14.一种个人护理产品,所述产品包括:
(a)外部容器;
(b)设置在所述外部容器中的材料分配系统,所述材料分配系统包括:
i)包括至少两个不同的室的能够收缩的袋,所述能够收缩的袋包括袋开口端和袋闭合端;
ii)设置在所述袋开口端中的阀门;和
iii)弹性构件,所述弹性构件在未拉伸构型中具有小于2英寸的长度,所述弹性构件围绕所述袋的至少一部分并且以化学方式或通过除单纯摩擦之外的机械方法固定到所述袋闭合端;以及
(c)个人护理组合物,所述个人护理组合物包括第一组合物和第二组合物,每种组合物均被包含在所述至少两个不同的室中的一个内,所述个人护理组合物设置在所述能够收缩的袋内,使得所述弹性构件在轴向和径向上被拉伸,由此产生与被拉伸相关的势能;
此后打开所述阀门,允许所述个人护理组合物通过施加到所述袋上的源自所述弹性构件的势能而从能够收缩的袋中流出,并且其中当所述势能消耗时,所述弹性构件在轴向和径向上朝其未拉伸构型紧缩。
15.一种制造材料分配系统的方法,所述方法包括以下步骤:
(a)提供容器预成型件,所述容器预成型件包括至少两个不同的室,所述容器预成型件包括聚合物预成型件和围绕所述聚合物预成型件的至少一部分的能够弹性地变形的绑带;
(b)加热所述聚合物预成型件;
(c)将所述容器预成型件定位到模腔中;并且
(d)向所述聚合物预成型件的内部施加压力,所述压力足以导致所述容器预成型件向外朝所述模腔的壁膨胀以限定容器,在此期间所述能够弹性地变形的绑带被轴向地且径向地拉伸,并且产生与拉伸的所述能够弹性地变形的绑带相关联的势能,所述势能在移除了所述施加的内部压力时至少部分地在轴向方向和径向方向两个方向上压缩所述容器。
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US10790508P | 2008-10-23 | 2008-10-23 | |
US61/107,905 | 2008-10-23 | ||
PCT/US2009/061860 WO2010048518A2 (en) | 2008-10-23 | 2009-10-23 | Multi-chamber material dispensing system and method for making same |
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CN102196972B true CN102196972B (zh) | 2013-05-29 |
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CN200980141904.3A Expired - Fee Related CN102196890B (zh) | 2008-10-23 | 2009-10-23 | 用于制造材料分配系统的方法 |
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EP (2) | EP2349869A2 (zh) |
JP (2) | JP5260749B2 (zh) |
CN (2) | CN102196972B (zh) |
AU (2) | AU2009308259A1 (zh) |
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MX (2) | MX2011004271A (zh) |
PL (1) | PL2361175T3 (zh) |
WO (2) | WO2010048518A2 (zh) |
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CA2741394A1 (en) | 2010-04-29 |
WO2010048501A3 (en) | 2010-09-16 |
CA2741556A1 (en) | 2010-04-29 |
MX2011004271A (es) | 2011-05-24 |
JP2012506793A (ja) | 2012-03-22 |
EP2361175A2 (en) | 2011-08-31 |
US20100133295A1 (en) | 2010-06-03 |
WO2010048518A3 (en) | 2010-07-22 |
CA2741394C (en) | 2014-03-18 |
WO2010048501A2 (en) | 2010-04-29 |
US20100133294A1 (en) | 2010-06-03 |
WO2010048518A2 (en) | 2010-04-29 |
WO2010048501A4 (en) | 2010-11-11 |
PL2361175T3 (pl) | 2017-05-31 |
CN102196890A (zh) | 2011-09-21 |
US8631970B2 (en) | 2014-01-21 |
EP2361175B1 (en) | 2016-11-30 |
MX2011004273A (es) | 2011-05-24 |
AU2009308276A1 (en) | 2010-04-29 |
CN102196972A (zh) | 2011-09-21 |
JP2012506350A (ja) | 2012-03-15 |
CA2741556C (en) | 2014-01-14 |
EP2349869A2 (en) | 2011-08-03 |
CN102196890B (zh) | 2015-05-06 |
JP5260749B2 (ja) | 2013-08-14 |
AU2009308259A1 (en) | 2010-04-29 |
US8454882B2 (en) | 2013-06-04 |
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