CN111344144A - 玻璃和聚合物刚性制品 - Google Patents
玻璃和聚合物刚性制品 Download PDFInfo
- Publication number
- CN111344144A CN111344144A CN201780096781.0A CN201780096781A CN111344144A CN 111344144 A CN111344144 A CN 111344144A CN 201780096781 A CN201780096781 A CN 201780096781A CN 111344144 A CN111344144 A CN 111344144A
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- CN
- China
- Prior art keywords
- glass
- layer
- molded article
- thickness
- mole percent
- 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.)
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001816 cooling Methods 0.000 claims description 7
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- GCFDVEHYSAUQGL-UHFFFAOYSA-J fluoro-dioxido-oxo-$l^{5}-phosphane;tin(4+) Chemical compound [Sn+4].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O GCFDVEHYSAUQGL-UHFFFAOYSA-J 0.000 claims description 4
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- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
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- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
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Images
Classifications
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Abstract
描述了多层模制制品,这些多层模制制品包含插入在第一非玻璃层与第二非玻璃层之间的玻璃层。这些模制制品向储存的内容物提供增强的氧气和湿气阻隔保护,并且可用于医疗、药物、食品以及研究应用中作为容器和包装材料。
Description
技术领域
本发明涉及多层三维模制制品。
背景技术
人们对开发可以用于包装、储存和运输对氧气和湿气敏感的产品的高阻隔制品有着极大兴趣。玻璃制品(常用于医疗和食品储存应用)具有良好的阻隔特性,但易于破损。此外,玻璃虽然通常是非反应性的,但并不是完全惰性的材料。存在于一些玻璃配制品中的组分(比如碱金属)可能浸出到接触的产品中。此外或替代性地,与玻璃接触储存的一种或多种组分可能迁移到玻璃中。此种迁移被称为组分被玻璃“夺去(scalping)”。
这些问题已经导致了既耐久又相对惰性的聚合物制品的开发。已知聚合物注射器(例如,特别是环烯烃共聚物(COC)注射器)提供比玻璃更耐久的“洁净的”且惰性的产品接触表面。然而,聚合物制品缺乏玻璃的阻隔特性,而且许多物质(包括许多药物)是对氧气和/或湿气敏感的并且未被聚合物制品充分保护。
已经采用产生不同聚合物层的分层技术以改善模制聚合物制品的阻隔特性。例如,在两层或三层构造中使用乙烯乙烯醇(EVOH)作为阻隔层的多层聚合物模制制品是已知的。美国专利申请公开2014/0120282描述了一种由与由基础聚合物形成的保护层相邻布置的聚合物核心层(EVOH或液晶聚合物)形成的多层共注射模制聚合物制品。然而,虽然EVOH层可以改善制品的氧气阻隔特性,但是EVOH是亲水的且对湿气敏感的。此外,已知湿气吸收损害EVOH作为气体阻隔层的有效性,导致氧气渗透性增加。参见例如Iwanimi等人,“Ethylene Vinyl Alcohol Resins for Gas-Barrier Material[用于气体阻隔材料的乙烯乙烯醇树脂],”Tappi J[Tappi杂志],1983;66:85-90。
发明内容
本发明提供多层三维模制制品,其包括玻璃层,该玻璃层插入在非玻璃材料(比如聚合物)的第一层与第二层之间。该模制制品可以被认为是复合结构,因为它包括至少三个不同的物理层。在防止玻璃组分浸出到与该制品接触的产品中的同时,分层构造提供对氧气和湿气的有效阻隔以及耐久性。模制制品可用于包装、储存、容纳、以及运输对氧气和/或湿气敏感的产品(比如食品、药品、以及医疗装置)。
与聚合物模制制品相比,玻璃层的使用赋予模制制品优越的阻隔特性,因为聚合物的阻隔特性比不上玻璃的阻隔特性。在两个聚合物层之间封装或隔离玻璃层可以增强模制制品的结构完整性,并防止玻璃层与原本与该制品接触的产品之间的直接接触。
该模制制品可以自身构成成品,或者它可以是装置或容器的子单元。该模制制品具有交替的单独的玻璃层和非玻璃材料层,并且玻璃层和非玻璃层的总数是可变的,如由具体应用的要求决定的。典型的模制制品将含有三层(例如,在第一与第二外部聚合物层之间插入一个核心玻璃层),但是在一些实施例中交替的单独的玻璃层和非玻璃材料层的总数可能大于三。
虽然本文主要参考使用一种或多种聚合物作为第一和第二非玻璃层来描述模制制品,但应理解的是,代替一个或多个聚合物层或除了一个或多个聚合物层之外,该制品可以掺入金属或其他无机材料。
如本文所用,术语“包含(comprises)”、“包含(comprising)”及其语法变型将被用于指定所述特征、整数、步骤或组分或其组的存在,但不排除存在或添加一个或多个其他特征、整数、步骤、组分或其组。
在下文中将参考附图更全面地描述多层三维模制制品,在附图中示出了本发明的一些但非全部实施例。实际上,这些发明可以以许多不同的形式体现,并且不应被解释为限于本文阐述的实施例;相反,提供这些实施例是为了使本披露将满足适用的法律要求。相同的数字始终指代相同的要素。
附图说明
本发明的其他特征和优点将从下面的详细说明、结合附图变得明显,在这些附图中:
图1是多层模制制品的实例的截面视图,该多层模制制品包括插入在第一非玻璃层与第二非玻璃层之间的核心玻璃层;
图2是说明注射器筒的纵截面视图;以及
图3是用作容器的图1的多层制品的实例的截面视图。
具体实施方式
本发明的模制制品具有至少一个单独的玻璃层(“玻璃层”)以及至少两个单独的非玻璃材料层(“第一”和“第二”非玻璃层),使得玻璃插入在第一与第二非玻璃层之间以便将玻璃隔离或封装在该模制制品内。因此,与该制品接触的产品将与该第一或第二非玻璃层接触,而不与该玻璃层接触。在该模制制品被配置为容器的实施例中,第一层可以是容器的内层,从而提供用于与容纳的物品或产品接触的容器的内表面,并且第二层可以是容器的外层,从而提供容器的外表面。玻璃的聚合物封装约束玻璃层,并且可以通过将成品零件保持在一起赋予该模制制品增强的结构完整性或刚性。
该模制制品具有作为例如且不限制于注射器、小瓶、食品容器、或其构成零件的实用性。本发明广泛地包括包含该模制制品的容器,以及包括容器和储存在该容器中的产品的组件。容纳的产品可以是固体、液体或气体。术语“液体”包括凝胶、乳液、分散体、水凝胶、乳膏、软膏、糊剂等。该模制制品特别好地适合于没有固定形状的产品的容器应用,这些产品比如液体(包括凝胶和悬浮液)和气体。液体的实例包括但不限于药剂、饮料和化学溶液。这些术语都得益于玻璃的优越的阻隔特性和聚合物的耐久性,它们被有利地组合在本发明的模制制品中。例如,在共注射模制工艺中聚合物和玻璃的共注射可以用于形成被配置为注射器筒的多层成品零件。在预填充注射器应用中,药剂与筒的内表面上的化学惰性的聚合物层接触,并且在外表面上的聚合物层保护免遭破损,同时封装的玻璃层增强该模制制品的阻隔特性而不浸出到筒的内容物中和/或减少夺去药剂。预填充注射器和小瓶可以被用于胃肠外药物的给予。除了其许多医疗应用之外,刚性玻璃/聚合物共注射也可以扩展到食品包装,从而产生可以代替金属罐和玻璃罐使用的耐久的刚性容器。区别于柔性的平面(二维)膜,这些模制制品是具有固定形状的三维制品,并且很好地适合于在医疗、工业、食品以及研究应用中用作容器和其他包装工具。
图1示出了被配置为容器100的多层模制制品的实例的截面,该容器具有内表面105和外表面115。容器100包含具有厚度TG的核心玻璃层30,其插入在具有厚度T1的内部非玻璃第一层10与具有厚度T2的外部非玻璃第二层20之间。
图2示出了被配置为注射器筒200的模制制品的实例。注射器筒200的主体240包含该模制制品,该模制制品由内部和外部非玻璃层以及插入在内部与外部非玻璃层之间的核心玻璃层形成。存在于筒腔220内的液体与该内部非玻璃层的内表面210接触。
图3示出了作为组件用来容纳液体300的如图1中的容器100。容器100容纳的液体300与非玻璃第一层10接触,但不与玻璃层30或非玻璃第二层20相触。
与常规的模制包装材料相比,这些模制制品展现出优越的气体和水阻隔特征,在一些实施例中,这些模制制品在23℃和0%相对湿度下的氧气透过率在从0至1cm3/m2/24h的范围内。在一些实施例中,这些模制制品在38℃和90%相对湿度下的水蒸气透过率在从0至1g/m2/24h的范围内。使用渗透测量设备可以测定氧气和水蒸气的渗透。可以在23℃和0%相对湿度下测定氧气渗透,并在38℃和90%相对湿度下测定水蒸气渗透。本领域技术人员将认识到氧气透过率在从0至1cm3/m2/24h范围内和/或水蒸气透过率在从0至1g/m2/24h范围内的制品表明无缺陷的高阻隔材料。
该模制制品的玻璃(核心)层由具有低玻璃化转变温度(Tg)的玻璃形成。例如,该模制制品的玻璃层的玻璃可以具有约500℃或更低、约300℃或更低、或者约200℃或更低的玻璃化转变温度Tg。例如,玻璃化转变温度可以低于500℃、低于400℃、低于350℃、低于300℃、低于250℃、低于200℃、或低于150℃。在一些实施例中,该玻璃的Tg低于350℃。在一些实施例中,该玻璃是碱性磷酸盐玻璃。在一些实施例中,该玻璃是氟磷酸锡玻璃(有时称为“SnF-玻璃”)。此类玻璃可以通过比如但不限于BaF2、SnF2、ZnF2、P2O5、Sn(PO4)2、SnO、Sn2P2O7、SnCl2、NH4H2PO4、NH4F以及NH4PF6等无机材料的分批熔融而制成,并且可以在不超过600℃(典型地在400℃至500℃范围内)的温度下熔融,以提供具有良好品质和相对高化学耐久性的均质玻璃。其他示例性玻璃包括但不限于氧化铜玻璃、氧化锡玻璃、氧化硅玻璃、磷酸锡玻璃、氯磷酸盐玻璃、硫属化物玻璃、亚碲酸盐玻璃、硼酸盐玻璃、氧化铋玻璃、及其组合。
在一些实施例中,该模制制品的玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比为至少7.4、至少12.0、或至少15.4、并且至多17.1或至多30.0的锡。
在一些实施例中,该模制制品的玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比为至少4.9、至少11.2、或至少19.6、并且至多24.3或至多47.2的氟。
在一些实施例中,该模制制品的玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比为至少6.7、至少12.1、或至少14.2、并且至多16.6、至多19.6、或至多23.1的磷。
在一些实施例中,该模制制品的玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比为至少20.8、或至少43.3、并且至多56、至多61.1、或至多61.5的氧。
在一些实施例中,该模制制品的玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比在7.4至30范围内的锡、摩尔百分比在从4.9至47.2范围内的氟、摩尔百分比在从6.7至23.1范围内的磷、以及摩尔百分比在从20.8至61.5范围内的氧。在一些实施例中,该玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比在从12至17.1范围内的锡、摩尔百分比在从11.2至24.3范围内的氟、摩尔百分比在从12.1至19.6范围内的磷、以及摩尔百分比在从43.3至61.1范围内的氧。在一些实施例中,该玻璃可以具有在元素的基础上包含以下的组成:摩尔百分比在从15.4至17.1范围内的锡、摩尔百分比在从19.6至24.3范围内的氟、摩尔百分比在从14.2至16.6范围内的磷、以及摩尔百分比在从43.3至56范围内的氧。在一些实施例中,玻璃组成中存在附加的元素,例如包括钨或铌。
多层模制制品的玻璃组成的元素组分的定性和定量测定可以通过能量色散x射线(EDX)光谱分析来测定。无机组成的EDX光谱分析技术是熟知的,并且可以由本领域的技术人员容易地进行而无需过度实验。
如所指出的,该模制制品具有至少两个非玻璃层,使得玻璃层被插入在第一与第二非玻璃层之间。第一和第二非玻璃层可以由相同材料或不同材料构成。任何聚合物、金属或无机材料可以用于该模制制品的非玻璃层。在一些实施例中,第一非玻璃层和第二非玻璃层都是聚合物层。如进一步所指出的,本文主要参考使用一种或多种聚合物作为第一和第二非玻璃层来描述该模制制品;然而,代替一个或多个聚合物层或除了一个或多个聚合物层之外,该制品可以掺入金属或其他无机材料。在掺入金属或其他无机材料作为第一和/或第二非玻璃层的实施例中,优选低熔点金属和/或低熔点无机材料。
在其中第一和第二非玻璃层由相同材料(例如,聚合物A)制成的实施例中,该制品的结构可以具有A/B/A型截面构造。当存在于该模制制品的外表面上时,第一和第二聚合物层A可以与产品和/或与外部环境接触。玻璃层B被插入在两个聚合物层A之间。说明性模制制品具有呈A/B/A构造的三个层,其中,A是聚合物并且B是低Tg玻璃。
玻璃层和非玻璃层的厚度可以根据该模制制品的预期用途进行调整,在该模制制品的一些实施例中,玻璃层的厚度可以是约50微米(μm)或更小;在一些实施例中,玻璃层的厚度可以是约20μm或更小;在一些实施例中,玻璃层的厚度可以是约10μm或更小。在该模制制品的一些实施例中,玻璃层的厚度与第一层的厚度的比率为1:3或更小。在一些实施例中,玻璃层的厚度与第二层的厚度的比率为1:3或更小。例如,玻璃层的厚度与第一层的厚度的比率可以在从约1:3至约1:200的范围内,和/或玻璃层的厚度与第二层的厚度的比率可以在从约1:3至约1:200的范围内。玻璃层可以,例如,小于总制品厚度(即,所有玻璃层和非玻璃层的合并厚度)的30%、小于总制品厚度的25%、小于总制品厚度的20%、小于总制品厚度的15%、小于总制品厚度的10%、小于总制品厚度的5%、小于总制品厚度的1%、或小于总制品厚度的0.5%,第一和第二非玻璃层的厚度(分别为T1和T2)可以是相同的或基本上相同的,或者它们可以是不同的。例如,当该模制制品用于容器应用时,与容纳的产品接触的非玻璃材料的内层可以比与外部环境接触的非玻璃材料的外层更厚、或者可以更薄。
用于该模制制品的非玻璃层的聚合物的实例是烯烃聚合物,比如环烯烃聚合物(COP)或环烯烃共聚物(COC)。可商购的环烯烃共聚物的实例包括但不限于从日本东京的宝理塑料株式会社(塞拉尼斯-泰科纳)(Polyplastics(Celanese-Ticona),Tokyo,Japan)可获得的系列树脂。其他有用的聚合物包括但不限于聚丙烯(PP)和聚碳酸酯(PC),以及聚烯烃比如聚乙烯、乙烯α-烯烃共聚物、聚丙烯共聚物、乙烯乙酸乙烯酯共聚物、离聚物、以及其共混物。
可以使用热塑性塑料来形成该模制制品的第一和/或第二层。热塑性塑料在本文中称为在暴露于热时软化并在冷却至室温时恢复其初始状态的任何聚合物或聚合物混合物。在一些实施例中,聚合物可以包括结晶或半结晶的热塑性塑料、无定形热塑性塑料、以及其共混物,包括但不限于脂肪族和芳香族聚酰胺、聚醚、聚酰亚胺、离聚物、脂肪族和芳香族聚酯(比如,聚对苯二甲酸乙二醇酯、二醇改性的聚对苯二甲酸乙二醇酯、聚间苯二甲酸乙二醇酯、和聚萘二甲酸乙二醇酯)、环烯烃共聚物、聚烯烃均聚物和共聚物(比如,聚乙烯、高密度聚乙烯、马来酸酐改性的聚乙烯、乙烯乙烯醇共聚物、乙烯乙酸乙烯酯共聚物、乙烯丙烯酸、乙烯甲基丙烯酸、乙烯丙烯酸烷基酯和聚丙烯)、聚酰胺酰亚胺、聚碳酸酯、聚醚醚酮、聚醚酰亚胺、聚醚砜、聚甲基丙烯酸甲酯、聚甲醛、聚苯硫醚、聚苯乙烯(包括高抗冲聚苯乙烯)、未增塑聚氯乙烯、热塑性聚氨酯、以及其共混物。
在一些实施例中,用于该模制制品的玻璃和非玻璃材料展现出相似的粘度-剪切速率曲线,这有利于共挤出。
在一些其他实施例中,用于该模制制品的玻璃和非玻璃材料可以展现出不相似的粘度-剪切速率曲线。
本发明的制品可以使用任何多材料刚性零件工艺来制成,该工艺能够形成多层模制制品,其中玻璃层被插入在第一与第二非玻璃层之间以便将玻璃隔离或封装在该模制制品内。实例包括共注射模制、嵌入模制以及包覆模制。用于制造多层模制制品的方法的一个实施例包括加热玻璃和至少一种非玻璃材料(比如聚合物),将经加热的玻璃和非玻璃材料引入模具中以形成布置在第一与第二非玻璃层之间的玻璃层,以及冷却经加热的玻璃和非玻璃材料以形成多层模制制品。
在一个实施例中,共挤出玻璃和聚合物层以形成多层模制制品。例如,聚合物和玻璃层的共挤出可以使用多组分模制工艺比如共注射模制或者双注射模制来实现。可以用于制造本发明的三维模制制品的用于多层注射模制的装置和一般方法的实例在美国专利公开2014/0120282 A1(多层共注射模制制品)中找到。
在传统的注射模制工艺中,以单层制造注射模制零件,该单层可以是纯的聚合物或者聚合物的共混物;在共注射模制中,通过单独的流道系统将两种材料引入单个模具内。共注射模制寻求产生离散的层,这些层可以包括纯的或者共混的聚合物。可以在一些单杯咖啡粉囊包中找到实例,其中共注射制品是聚丙烯和乙烯乙烯醇共聚物(EVOH)的三层复合物。两个最外层是聚丙烯,并且核心层是EVOH。
使用共注射模制,可以通过将玻璃和非玻璃材料(比如聚合物)共注射到模具内以产生其中核心玻璃层被插入在第一与第二非玻璃层之间的多层模制制品来制成模制制品。这种三层构造有效地将玻璃隔离或封装在该模制制品内,使得玻璃层不构成该制品的表面。将经加热的聚合物和玻璃共注射到三维模具内。将聚合物材料引入到一个螺杆中,并且将玻璃引入到另一个螺杆中。该模制制品可以通过将玻璃和聚合物层一起共挤出以及冷却挤出物以形成零件来形成。如果需要,可以调整层的厚度,使得第一聚合物层的厚度与第二聚合物层不同。冷却可以通过任何方便的方法来完成,包括但不限于使制品经受低于环境温度,例如,通过冷藏或扇风,或者通过使制品在环境温度下或在一个或一系列高于环境温度的预设温度下随着时间的推移冷却。
玻璃和非玻璃(例如,聚合物)材料的共注射可以是同时的或顺序的。对于同时共注射,外部(即,聚合物)材料从第一注射单元(通常通过歧管,比如上述那些)注射并进入模腔。随着将来自第二来源或筒的内部或核心(玻璃)材料连同外部材料一起注射入模具内(通常通过共注射歧管),外部材料向模具内的流动然后可以减慢。换句话说,外部(聚合物)和核心(玻璃)混合物可以并行地或同时地流入到模腔内。这使核心材料得以注射在外部材料里面。随后,外部和核心材料流动可以基本上同时终止,或替代性地,核心材料的流动可以停止,而外部材料继续流动来完成零件。替代性地,同时注射可以包括:将来自第一来源的外部(聚合物)材料注射入模腔内,然后将核心(玻璃)材料注射入模腔内,使得核心材料和外部材料同时进入模腔,终止外部材料的流动,而使核心材料继续流动,终止核心材料的流动,并且使外部材料的流动重新开始并且随后终止以便完成零件的生产。
当使用顺序共注射时,首先将来自第一来源的外部材料注射入歧管内以产生进入模具和模腔内的外部材料的流动。然后停止进入模腔内的外部材料的流动。外部材料可以填充模腔的大约30%-50%。随后,使用来自第二来源的外部材料填充模腔的剩余部分并完成零件,或者替代性地,将外部材料注射入模腔内并且接近塑料注射的最末端,可以停止外部材料的流动并且使外部材料的注射重新开始以向最终产品提供更好的装饰外观。
在这些层的共注射之后,将制品典型地暴露于“压紧并保持”步骤。在压紧并保持期间,减小压力并且还逐渐降低温度。随着层冷却,它们开始收缩。因此,仍保持减小的压力,并且如果需要,可以将一些附加的聚合物引入模具内。在“压紧并保持”之后,进一步减小压力,并且当制品仍然在模腔中时冷却零件。最后,打开模具并移除成品制品以完成周期。
术语“共注射模制”意指涵盖共注射方法,通过这些方法,在单个周期期间将来自不同来源的两种材料基本上同时地或顺序地注射入单个模具内。共注射模制,在另一方面,并不意味着是指形成零件、将其冷却、并且然后在模具外部在冷却的零件上使材料成层。共注射模制也与以下不同:用来自一个筒的一种材料填充双腔模具的一个腔,并且然后用来自第二个筒的不同材料填充另一个腔。其也不意味着是指使用气体作为核心材料并且然后使气体消散在大气中(气体辅助)的工艺。最后,共注射模制不包括提供预先制成的零件并且然后部分或完全在其上模制表面,换句话说,共注射模制与嵌入模制或包覆模制不同。
实例
实例1.低温玻璃/聚合物共注射制品
共注射是在由赫斯基公司(Husky)生产的型号H120RS28/22共注射模制机上进行的。将环烯烃共聚物(COC)引入22mm 25:1L/D单螺杆柱塞式挤出机中,该环烯烃共聚物以商品名TOPAS(系列树脂,宝理塑料株式会社,塞拉尼斯-泰科纳,东京,日本)等级5013L10(Tg 130℃,熔体流动速率43dg/min,1.02g/cm3)可获得。将来自Mo-Sci公司的氟磷酸锡玻璃等级1648L(Tg130℃)引入在250℃熔体温度下具有14mm螺杆25:1L/D的单螺杆挤出机中,该单螺杆挤出机为活塞柱塞式挤出机供应熔融玻璃。
通过加热至250℃的热流道系统进料两个熔体流,并且同时在78巴的压力下注射到模具内。将熔体在设置为60℃的模具中冷却,其中有效冷却时间为8秒。每个共注射零件的总周期时间是13秒。
将共注射零件横切开,并用带有背散射电子探测器的Jeol 6010 SEM检查。调整对比度来突出两种材料之间电子密度的差异,使得能够测量玻璃及总复合物的厚度。
测定玻璃层的厚度(T玻璃或TG)为约8μm,而测定共注射零件的总厚度(T总)为约936μm,T玻璃与T总的比率为约0.009(0.9%)。
氧气的透过率为0.01cm3/m2/24h,并且水蒸气的透过率为0.01g/m2/24h。
替代性地,玻璃组合物可以内部制备。例如,可以通过以下方式制备摩尔组成为20%SnO+50%SnF2+30%NH4H2PO4的氟磷酸锡玻璃的批料:在500℃的碳坩埚中在空气中于电炉中熔融15分钟,将熔融的组合物浇铸到铝上并冷却至室温。将冷却的烧结的玻璃组合物研磨至大约3mm的粒度。
以上描述和实例说明本发明的某些实施例,而不应解释为限制性的。对特定实施例、其组合的选择,对各种实施例的修改和改编,本领域通常遇到的条件和参数对于本领域技术人员而言将是显而易见的,并且被认为是在本发明的精神和范围内。
Claims (20)
1.一种多层三维模制制品,其包括:
第一层;
第二层;以及
在该第一层与该第二层之间的玻璃层,其中该玻璃层包含玻璃化转变温度(Tg)为约500℃或更低的玻璃。
2.根据权利要求1所述的模制制品,其中,该玻璃包含碱性磷酸盐玻璃。
3.根据权利要求1所述的模制制品,其中,该玻璃包含氟磷酸锡玻璃。
4.根据权利要求1所述的模制制品,其中,该玻璃在元素的基础上包含摩尔百分比在从7.4至30范围内的锡、摩尔百分比在从4.9至47.2范围内的氟、摩尔百分比在从6.7至23.1范围内的磷、以及摩尔百分比在从20.8至61.5范围内的氧。
5.根据权利要求1所述的模制制品,其中,该玻璃在元素的基础上包含摩尔百分比在从12至17.1范围内的锡、摩尔百分比在从11.2至24.3范围内的氟、摩尔百分比在从12.1至19.6范围内的磷、以及摩尔百分比在从43.3至61.1范围内的氧。
6.根据权利要求1所述的模制制品,其中,该玻璃在元素的基础上包含摩尔百分比在从15.4至17.1范围内的锡、摩尔百分比在从19.6至24.3范围内的氟、摩尔百分比在从14.2至16.6范围内的磷、以及摩尔百分比在从43.3至56范围内的氧。
7.根据前述权利要求中任一项所述的模制制品,其中,该玻璃具有约300℃或更低的Tg。
8.根据前述权利要求中任一项所述的模制制品,其中,该玻璃具有约200℃或更低的Tg。
9.根据前述权利要求中任一项所述的模制制品,其中,该第一层包含聚合物,并且该第二层包含聚合物。
10.根据权利要求9所述的模制制品,其中,该第一层和第二层包含相同的聚合物。
11.根据权利要求10所述的模制制品,其中,该第一层和第二层包含环烯烃共聚物(COC)。
12.根据前述权利要求中任一项所述的模制制品,其中,该玻璃层的厚度与该第一层的厚度的比率为1:3或更小,并且其中,该玻璃层的厚度与该第二层的厚度的比率为1:3或更小。
13.根据前述权利要求中任一项所述的模制制品,其中,该玻璃层的厚度与该第一层的厚度的比率在从约1:3至约1:200的范围内,其中该玻璃层的厚度与该第二层的厚度的比率在从约1:3至约1:200的范围内。
14.根据前述权利要求中任一项所述的模制制品,其中,该玻璃层具有约50微米或更小的厚度。
15.根据前述权利要求中任一项所述的模制制品,其中,该玻璃层具有约20微米或更小的厚度。
16.根据前述权利要求中任一项所述的模制制品,其中,该第一层和第二层的厚度是基本上相同的。
17.一种容器,其包含根据前述权利要求中任一项所述的模制制品。
18.一种组件,其包括:
根据权利要求17所述的容器;以及
储存在该容器内的药剂。
19.根据权利要求18所述的组件,其中,该容器形成注射器的至少一个零件。
20.一种用于形成根据权利要求1至16中任一项所述的模制制品的方法,该方法包括:
加热该玻璃和至少一种非玻璃材料;
将经加热的玻璃和非玻璃材料引入模具中以形成布置在第一非玻璃层与第二非玻璃层之间的玻璃层;以及
冷却经加热的玻璃和非玻璃材料以形成该制品。
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Application Number | Priority Date | Filing Date | Title |
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PCT/US2017/051060 WO2019054982A1 (en) | 2017-09-12 | 2017-09-12 | RIGID GLASS AND POLYMERIC ARTICLES |
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CN111344144A true CN111344144A (zh) | 2020-06-26 |
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CN201780096781.0A Pending CN111344144A (zh) | 2017-09-12 | 2017-09-12 | 玻璃和聚合物刚性制品 |
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US (1) | US20200269538A1 (zh) |
EP (1) | EP3681712A4 (zh) |
CN (1) | CN111344144A (zh) |
BR (1) | BR112020004885A2 (zh) |
WO (1) | WO2019054982A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3502010A1 (en) * | 2017-12-19 | 2019-06-26 | Clariant Healthcare Packaging (France) SAS | Flow-limiting device and cap for a container including same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE758410A (fr) * | 1969-11-06 | 1971-05-03 | Kalle Ag | Complexe, compose de verre et de matiere plastique |
US4314031A (en) * | 1980-06-17 | 1982-02-02 | Corning Glass Works | Tin-phosphorus oxyfluoride glasses |
US5089446A (en) * | 1990-10-09 | 1992-02-18 | Corning Incorporated | Sealing materials and glasses |
KR20040044551A (ko) * | 2001-10-12 | 2004-05-28 | 코닌클리케 필립스 일렉트로닉스 엔.브이. | 배리어 및 그 제조 방법 |
DE102007054437A1 (de) * | 2007-11-13 | 2009-05-20 | Tesa Ag | Verfahren zur Herstellung eines schichtförmigen oder geschichteten anorganisch/organischen Verbundmaterials |
US8563113B2 (en) * | 2010-04-20 | 2013-10-22 | Corning Incorporated | Multi-laminate hermetic barriers and related structures and methods of hermetic sealing |
US20140120315A1 (en) * | 2012-10-25 | 2014-05-01 | Bruce Gardiner Aitken | Flexible multilayer hermetic laminate |
JP6443940B2 (ja) * | 2013-02-26 | 2018-12-26 | コーニング インコーポレイテッド | 形状保持性フレキシブルガラス−ポリマーラミネートの成形方法 |
WO2015123254A1 (en) * | 2014-02-13 | 2015-08-20 | Corning Incorporated | Ultra low melting glass frit and fibers |
-
2017
- 2017-09-12 WO PCT/US2017/051060 patent/WO2019054982A1/en unknown
- 2017-09-12 EP EP17925087.3A patent/EP3681712A4/en not_active Withdrawn
- 2017-09-12 CN CN201780096781.0A patent/CN111344144A/zh active Pending
- 2017-09-12 BR BR112020004885-2A patent/BR112020004885A2/pt not_active Application Discontinuation
- 2017-09-12 US US16/646,954 patent/US20200269538A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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EP3681712A1 (en) | 2020-07-22 |
BR112020004885A2 (pt) | 2020-09-15 |
EP3681712A4 (en) | 2021-04-21 |
US20200269538A1 (en) | 2020-08-27 |
WO2019054982A1 (en) | 2019-03-21 |
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