CN113966430B - 真空隔热玻璃 - Google Patents

真空隔热玻璃 Download PDF

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CN113966430B
CN113966430B CN202080043927.7A CN202080043927A CN113966430B CN 113966430 B CN113966430 B CN 113966430B CN 202080043927 A CN202080043927 A CN 202080043927A CN 113966430 B CN113966430 B CN 113966430B
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vacuum insulating
insulating glass
glass
vig
glass according
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CN113966430A (zh
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卡洛杰罗·夏夏
奥马尔·萨翁切拉
斯特凡诺·热布基尼
费德里科·加利诺
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    • EFIXED CONSTRUCTIONS
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    • E06B3/66Units comprising two or more parallel glass or like panes permanently secured together
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Abstract

本发明涉及能够为建筑物的幕墙***的透明组件以及为家用或商用制冷机的柜体提供优异隔热的真空隔热窗用玻璃(VIG),以及用于该真空隔热窗用玻璃的制造的方法。

Description

真空隔热玻璃
产生本申请的项目已根据第723868号拨款协议获得来自欧盟地平线(EuropeanUnion’s Horizon)2020研究和创新计划的资助。
技术领域
本发明涉及新的真空隔热玻璃(Vacuum Insulating Glazing,VIG)***以及用于制造所述VIG的方法,所述真空隔热玻璃(VIG)***为多种应用(从建筑物的幕墙***到家用和商用制冷机的柜体)中的透明组件提供优异的隔热。
现有技术
常规的真空隔热玻璃(VIG)包括两个平行的玻璃平板并且包括由设置在两个玻璃板之间的间隔件形成的窄的抽空空间,所述两个平行的玻璃平板通过***的间隔件保持分离并沿边缘密封在一起。已知能够吸收真空管中的残留气体或杂质的吸气剂也已公开用于包含在VIG装置中,以吸收或结合可能在密封(即除气过程)之后残留在玻璃板之间的抽空空间中或可能从外部环境渗透到内部(即渗透过程)的残留杂质和气体。
1913年在专利文献中首次描述了VIG装置,但是,尽管概念简单并且从那以后进行了数十年的研究,但是第一个VIG装置实际上在1989年才制造出来,而市场上出现的第一个商业版本不早于1996年。VIG装置代表着想法比其实际实现出现得早得多的典型实例,因为许多技术方面阻碍了实际工作装置的实现。在VIG装置成功的关键因素中,可以提及间隔件的材料、形状和定位,以及边缘密封剂的材料和加工;玻璃及其涂层的品质(通常提供低发射率和抗反射特性);以及用于VIG抽空的接口、管和方法。
另一方面,在家用建筑和商业建筑二者中,愈来愈感觉到需要通过用越来越大的玻璃同时改善外部墙的隔热和透明度来提高建筑物的能源效率。因此,建筑行业正在努力提供用于建筑物的更有效的VIG装置。
为了保持VIG装置的隔热,必须保持高真空水平(10-3托或更低):从外部环境渗透到装置的密封空间中的大气气体越少,内部抽空空间内的压力将越低。玻璃和金属是具有可忽略的渗透率的材料,因此乍一看它们可以被认为是完美的屏障,但对于在不同程度上易于气体渗透的聚合物材料而言并非如此。从这个意义上来说,使用玻璃料(glass frit)或焊接金属条提供了密封的边缘密封剂,并且VIG装置中的压力演变仅来自除气过程。这允许较低的吸气剂量,通常是一个或两个非蒸散型吸气剂(NEG)烧结丸,或几平方厘米的蒸散型钡。相反,聚合物根据定义是半渗透材料,并且由于除气过程和渗透过程二者,使用所述聚合物作为VIG边缘密封剂需要处理更大的气体量,产生超出任何吸气剂方案的最大可接受尺寸的风险。从这个意义上来说,通常认为聚合物无法满足VIG应用的严格的气体渗透率要求,如也被Collins教授(其被认为是现代VIG之父)在2017年的陈述所证实的:“目前所有可用聚合物材料对于该应用而言渗透性太强。在作者看来,这不太可能改变。”[参见Conference Proceedings of Glass Performance Days GPD 2017,第264至267页]。因此,在VIG装置中使用常规的聚合物材料作为密封剂似乎不可行。
在一定程度上,已知吸气剂体系可以通过吸收N2、O2、CO2、CO和H2O而用于处理大气气体;但是对于吸气剂而言大的气体渗透率是不能承受的并且可能导致不可行的负载。此外,由于惰性气体不能被吸除并且Ar占总大气组成的≈1%体积/体积,因此对于VIG应用的阻挡特性目标由密封剂Ar渗透率限定,足够低以保证在整个VIG使用寿命内VIG内部的Ar压力演变不超过10-3托。根据VIG尺寸和密封边缘宽度,该目标Ar渗透率可以估计在10-2÷10- 3barrer的范围内。迄今为止,用作隔热玻璃的二次密封剂的商用聚合物的Ar渗透率比VIG的目标高一至两个数量级。因此,需要更有效的解决方案以提供能够通过基于聚合物的密封剂实现的VIG装置。
欧洲专利申请公开第2576950号公开了VIG装置,其建议使用有机粘合剂密封剂,但设置有无机涂层。该文献指出“没有已知的粘合剂或环氧树脂是足够不可渗透以防止在VIG装置使用寿命期间大气气体进入其腔体”。事实上,该申请要求保护“设置在粘合剂层上的高度密封的涂层,其中所述涂层为无机层”。
美国专利申请公开第US2007178256号也要求保护有机气体密封剂,但其仅提及使用低热导率气体填充以提供隔热的隔热而非抽空的玻璃。使用填充气体的隔热玻璃(IG)在市场上普及推广,但它们与VIG是完全不同类别的装置,具有与VIG相比差得多的热性能和简单得多的生产工艺。
据申请人所知,描述了在VIG装置的边缘密封中使用有机材料的仅有的专利文献是专利号CN107285650和EP1794404。具体地,欧洲专利第EP1794404描述了使用环氧材料、丙烯酸酯材料、丁基材料、聚氨酯材料、多硫化物材料、丙烯酸类材料及其混合物作为用于密封剂的有机材料。EP1794404中没有提供关于所得VIG装置的气体渗透率的进一步信息或建议,但在同类最佳材料(即环氧复合材料)的文献中,报告了Ar的渗透率在0.1Barrer至0.6Barrer的范围内。报告了其他提及的密封剂系列例如丁基橡胶表现出0.85至1.1的范围内的Ar的渗透率,而对于多硫化物材料为0.8至1.5,丙烯酸酯和聚氨酯通常根据渗透性[L.K.Massey,Permeability properties of plastics and elastomers:a guide topackaging and barrier materials,William Andrew,2003]。对于其他大气气体的情况甚至更严重:O2和N2通常具有与Ar相同量级的渗透率,但它们的丰度高一至两个数量级,因此它们的渗透相应地更高。甚至最糟糕的情况是,水蒸气相对于其他永久气体通常显示出更大的渗透率(通常表示为水蒸气透过率(WVTR)),随之而来的结果是腔体内的压力升高以及热性能丧失。
即使是表现非常出色的环氧树脂密封剂制剂,例如在国际专利申请公开号WO 95/26997中描述的那些,也不能承受VIG应用。特别地,这种制剂被公开为能够降低例如二氧化碳和/或氧气的气体通过包装材料的渗透率,而没有提及用于密封抽空室或密封VIG装置。事实上,根据所声称的渗透值,树脂本身不应能够使气体到VIG中的渗透保持足够低。如上所述,在VIG应用中使用聚合物和有机材料的问题之一是它们通常具有超过1%重量/重量的水含量并且它们产生除气产物,主要是水分子,如果不清除,则将导致真空压力升高到高于玻璃板之间的空间的工作压力。
类似的考虑可以适用于CN107285650,其公开了用于气密封钢化玻璃的密封剂组合物,所述密封剂组合物包含有机硅树脂密封剂、催化剂和石墨烯微粒。事实上,例如在“The behaviour of water in poly(dimethylsiloxane)”J.M.Watson,M.G.Baron,Journal of Membrane Science 110(1996)47-57中已知有机硅树脂对非常透气,比如公开的上述环氧树脂差几个数量级。
因此,以上现有技术中公开的已知材料中均无法达到为VIG器件提供能量高效的密封剂的目标,因此仍是迫切需要的。机械特性是另一个至关重要的密封剂特征。事实上,密封剂必须提供玻璃粘附强度和高于由玻璃升温可能产生的最大剪切应力的屈服应力(例如,对于2.5m乘1.5m玻璃板,估计的最大应力:7MPa)。此外,密封剂必须具有足够的刚性以避免可能导致柱移动的玻璃板之间的明显滑动。
因此,本发明的主题是这样的真空隔热玻璃(VIG):其解决了以上强调的对于已知VIG装置的技术问题,由于优异的边缘阻挡特性和机械强度而分别提供了优异的隔热性能和结构可靠性。
本发明的另一个主题是包括以上所述的真空隔热玻璃的窗户或立面,所述窗户或立面潜在地也用作建筑物或温室农业中的门和/或天窗元件和/或用作用于车辆(例如汽车、高速铁路和飞行器)的平坦窗户。
本发明的又一个主题是包括以上所述的真空隔热玻璃的家用和/或商用制冷机的柜体(例如冰柜、酒柜、展示柜)。
本发明的又一个主题是用于制造以上所述的真空隔热玻璃的方法,该方法可以至少部分地自动化并且允许获得具有合适密封边缘的VIG装置。后者意味着均匀沉积,没有空隙或气泡,并且轮廓笔直而没有随着在升高温度下的密封剂粘度降低而在热固化过程中可能出现的扩展问题。
这些主题和另外的主题通过根据本发明的真空隔热玻璃装置及用于其制造的方法来实现,其基本特征在本文所附的独立权利要求中限定。根据本发明的主题的另外重要特征在从属权利要求中限定。
附图说明
根据本发明的真空隔热玻璃及用于其制造的方法的特征和优点将在其实施方案并且参照附图的以下示例性且非限制性描述中得到清楚说明,其中:
-图1示意性地示出了本真空隔热玻璃及其主要组件的一个优选的实施方案;
-图2是具有四个条和相等密封边缘宽度的吸气剂全框的VIG优先设计的简图;
-图3a、3b和3c示出了仅具有两个吸气剂条和不同的密封边缘宽度的替代VIG设计。
具体实施方式
如上所述,本发明的目的是首先从隔热和能量效率的角度,提供一种改善的真空隔热玻璃(本文中也表示为“VIG”)。
现在,本申请人已开发了基于真空隔热玻璃技术(Vacuum Insulating Glasstechnology)的新装置,该新装置由于涉及使用吸气剂和特殊的密封剂组合物二者的创新***,因此能够提供优异的隔热和对气体渗透性的阻挡。
具体参照图1,示出了根据本发明的真空隔热玻璃1的一个优选的实施方案,其中彼此面对的两个玻璃板2和2’由复数个柱3、3’、3”……彼此间隔开以在其间形成空隙体积4。柱3、3’、3”……必须放置在玻璃板2和2’之间以使玻璃板2和2’保持在由柱的高度施加的预定距离。优选地,柱平均分布在整个玻璃表面上;它们的数量可以根据表面的大小而变化,并且可以由本领域任何普通技术人员容易地确定。
根据本发明的一个特定的实施方案,本VIG装置中的玻璃板2和2’为钢化玻璃,其中至少一个表面被面向VIG的内部体积4的低发射层覆盖。玻璃板2和2’的横向尺寸通常为0.25m至3m,以及柱3、3’、3”……的厚度范围为0.1mm至0.6mm。
为了封闭空隙体积4,在本VIG装置中,基于聚合物的密封剂6沉积在玻璃板的边缘上以限定玻璃板2和2’之间的内部闭合空间。在固化之后,考虑到本VIG的典型尺寸细节,沿VIG周边的密封边缘的相应优选宽度为5mm至35mm。
本VIG装置中的密封边缘6通过密封剂组合物的沉积和固化获得,所述密封剂组合物包含:
(a)可固化热固性非卤化聚环氧化物树脂,所述可固化热固性非卤化聚环氧化物树脂每分子平均包含至少两个环氧基;
(b)芳族二胺固化剂,所述芳族二胺固化剂的量足以提供环氧树脂中每当量环氧基0.5当量至2.0当量,优选0.5当量至1.0当量的胺N-H;和
(c)无机干燥剂,所述无机干燥剂的量相对于所述密封剂组合物的总重量为5重量%至25重量%。
根据本发明的一个优选的实施方案,本密封剂组合物中的非卤化聚环氧化物树脂为酚醛树脂或多酚二缩水甘油醚(也称为Novolac树脂),并且更优选地,其具有以下式(I):
Figure BDA0003412048240000061
其中n为0至8范围内的整数。
作为固化剂,本密封剂组合物中的芳族二胺优选包含磺化基团和/或酚基,并且更优选为4,4’-二氨基-二苯砜。
如上所述的本密封剂组合物的如根据ISO 11357-2:2013通过差示扫描量热法(DSC)测量确定的玻璃化转变温度优选高于100℃,并且更优选高于150℃。
如由欧洲专利申请公开第2576950号所公开的,本密封剂组合物可以与适合于进一步降低渗透气体负荷的其他密封剂成分组合使用,这主要是在几何因素上起作用:可以在外部VIG边缘上或其至少一部分上添加与本密封剂组合物胶合的***不可渗透框架(例如金属的或玻璃的或陶瓷的U形型材夹紧组合件)。在这样的配置中,渗透可以降低,甚至当出于美学或技术原因应显著降低密封剂的宽度时,渗透也可以降低。
根据本发明,图1中表示为5和5’的非蒸散型吸气剂体系放置在玻璃板2和2’之间形成的空隙体积4内。
在本发明的一个特定的实施方案中,非蒸散型吸气剂为在室温下通过ASTM吸收测试测量的N2吸收能力≥1cctorr/g的Zr合金。作为可能用于本发明的吸气剂中的Zr合金,选自ZrTiV、ZrTiVAl、ZrVAl、ZrVFe和ZrVFeMn-RE的合金,其中RE为一种或更多种稀土元素,任选为以包含Zr粉末的混合物的烧结态的。尽管可以有用地选择和使用丸剂,例如像TiVFeAlSi的吸气剂合金,但根据本发明优选的是层合在金属条上或涂覆在金属带上的粉末吸气剂,吸气剂沉积在金属载体的一侧上或两侧上。通常,用于吸气剂的金属载体为5mm至20mm大以及0.05mm至0.3mm厚,其中负载在载体上的活性吸气剂材料的量例如为10mg/cm至30mg/cm。
图1还示出了在至少一个玻璃板2或2”中存在抽空孔7,抽空孔7是VIG装置最常见的制造工艺所需要的。
图2中报告了根据本发明的最简单的VIG配置,其中具有最大量的吸气剂并包括定位在全第二框架中靠近密封剂的四个吸气剂条。
在图3a至3c中,示出了根据本发明的VIG的替代设计,其中相对于图2的设计其中包括较少数量的吸气剂条。这些替代设计在两个不同的边缘上具有两个条以简化活化过程。通过减少条的数量,我们失去了对称性,这可能导致不对称的总边缘宽度(图3a)或不对称的密封剂宽度(图3b和3c)。图3b和3c的设计是等效的,并且它们的区别是吸气剂条的位置:对于图3b的设计在短边上以及对于图3c的设计在长边上。
在不对称密封剂宽度的情况下,沉积过程可以通过选择与窄密封剂沉积物等效的密封剂边料(sealant curb)并通过利用该边料的倍数来产生宽密封剂沉积物来进行。
本密封剂组合物中的无机干燥剂可以选自不可逆干燥剂,例如CaO、其他氧化物、高氯酸盐干燥剂和吸湿性盐,或者选自可逆干燥剂,例如沸石或活性炭或其混合物。
根据本发明的一个特定的实施方案,本密封剂组合物还包含一种或更多种惰性填料,所述惰性填料可以为有机填料或无机填料,例如聚(乙烯醇)(PVOH)、聚酰亚胺、SiO2、TiO2、玻璃珠、玻璃纤维(其可以为短切的或呈变形形式的)、金属带或玻璃带、以及金属丝或玻璃丝。
在下表1中,描述了本密封剂组合物中组分的示例性重量百分比。
Figure BDA0003412048240000071
表1:基于聚合物的密封剂的示例性组成
此外,本发明的主题是用于制造真空隔热玻璃的方法,包括以下步骤:
i)提供顶部玻璃板和底部玻璃板,并通过以下步骤a至c以任意顺序(不一定按照以下报告的顺序)来准备所述底部玻璃板:
a.布置柱;
b.将非蒸散型吸气剂体系布置在玻璃表面(例如在吸气剂条的情况下)上或专用空间(例如用于吸气剂丸的钻孔)中,以及任选地将吸气剂胶合以避免其在摞合(对应布置)操作期间移动;
c.沉积如上所述的密封剂组合物;
ii)将顶部玻璃板摞合在底部玻璃板上;
iii)优选通过加热以及任选地也通过UV固化使密封剂固化;
iv)优先在烘烤下将VIG室抽空以改善真空条件;
v)优先通过在300℃至600℃的温度范围内的射频(RF)加热使吸气剂活化。
vi)将抽空孔密封。
密封剂沉积可以通过常规的沉积技术进行,例如通过沉积来自预填充注射器的密封剂组合物的针分配(needle dispensing),或通过布置密封剂组合物的预成型层合条。
根据本发明的一个方面,固化步骤iii)在约200℃下进行1小时。
在本发明的另一个方面中,固化步骤iii)在约170℃下进行1小时。
在本制造方法的一个特定的实施方案中,以上步骤i)和ii)可以在装下整个VIG的大抽空室中进行,而无需随后的抽空。
本发明的优点与由于具有吸气剂和上述密封边缘二者的本真空隔热玻璃而获得的高能量效率和隔热有关。由于包含在密封剂组合物中的干燥剂的存在而不是在VIG装置的内部体积4中将干燥剂与密封剂组合物分离,本VIG装置也显示出对大气气体和水分的高阻挡特性。本密封剂组合物已如以下实验部分所示进行了测试,并且发现其能够在任何所测试的老化方案下产生真空等级,而比较组合物失效,特别是对于较长时间的老化的情况。
此外,密封剂制剂中干燥剂的存在允许用较少量的吸气剂或者根据由VIG生产过程施加的温度限制以甚至在未完全活化的吸气剂的条件下使用而达到相同的高效率。
本VIG装置的另外的优点也在于其机械特性:本VIG装置特别是其密封边缘实际上能够适应由于内部体积4与外部大气之间的压力差而引起的大的应力。其还能够适应内部玻璃板和外部玻璃板之间不同的热膨胀,以及能够在制造过程结束时在高于100℃但低于密封剂Tg的温度下维持除气过程以除去来自VIG装置的内部体积的气体和水分。与包含不同密封剂组合物的装置相比,在搭接剪切测试之后的以下实验部分中示出本装置的玻璃表面上的高屈服应力和粘附强度(>7MPa)。
此外,关于用于制造真空隔热玻璃的本方法,通过本密封剂边缘显示出的优点尤其在于其固化温度低于250℃且玻璃化转变温度高于100℃。此外,观察到在聚合期间没有释放气体物质。
最后,本发明的另一个重要优点在于,用于制造本VIG装置的方法是简单且成本有效的。
实验部分
在最终影响热特性的压力演变方面对经受了不同的老化方案(参见表2)的一些代表性VIG样品进行测试。
老化方案 时间(天) 温度(℃)/相对湿度(%)
A 1 25°/90%
B 15 25°/90%
C 30 25°/90%
表1.老化方案。
选择密封边缘宽度为1Gm且真空间隙为0.25mm的300mm×300mm的VIG尺寸。
表2中报告了具有本发明的制剂的密封剂样品A、B和C。比较密封剂组合物1、2、3、4和5,其中为了比较已经考虑使用其他树脂作为密封剂;它们也列于下面的同一表3中。所有这些基于聚合物的密封剂在以上报告的老化方案之后进行了测试,并且结果报告在表3中。所有测试均用如下形式的完全活化的吸气剂进行:ZrVAl合金层合在0.1mm厚镀镍铁的8mm宽的条的两侧上。对于每个VIG样品,使用如图2中所示的四个吸气剂条。
Figure BDA0003412048240000101
表2.试验例中研究的密封剂样品的组成
对上述样品的测量是通过经由旋转转子计(spinning rotor gauge,SRG)监测总压力演变来进行的。尽管SRG被认为是高真空压力测量的高精度传输标准,但其需要气体相关的校准因子,由于渗透混合物未知该校准因子目前尚不知晓[参见例如,NIST SpecialPublication 250-93,Robert F.Berg和James A.Fedchak的“NIST Calibration Servicesfor Spinning Rotor Gauge Calibrations”以及来自https://www.mksinst.com/f/srg-3-spinning-rotor-vacuum-gauge-system的MKS的手册]。由于这个原因,结果以真空等级品质的比较方面报告于下表4中:
+意指高真空,即压力≤10-3毫巴;
≈意指中等压力,即在5·10-3毫巴至10-3毫巴的范围内,以及
–意指低真空范围,即压力≥5·10-3毫巴。
Figure BDA0003412048240000111
表3.对于经历不同老化方案的不同的基于聚合物的密封剂的真空等级结果。
获得的结果表明本密封剂组合物胜过比较密封剂组合物的优异性,后者不能在所有测试的老化条件下达到高真空等级,尤其是对于较长时间的情况(老化方案C)。相反,本发明的密封剂组合物能够保持高真空等级或中等真空等级甚至持续更长时间。特别地,包含一种或更多种氧化物干燥剂的本组合物中的那些在任何老化方案下都显示出高真空等级。
所有样品和比较样品都通过搭接剪切试验测试了它们的机械特性。结果汇总在下表中。
数据根据ISO 4587:2013“粘合剂——刚性与刚性粘接组合件的拉伸搭接剪切强度的测定(Adhesives-Determination of tensile lap-shear strength of rigid-to-rigid bonded assemblies)”收集。
密封剂 粘合强度(MPa)
样品A >7
样品B >7
样品C >7
比较1 ≈2.4
比较2 ≈4
比较3 ≈1.2
比较4 ≈1.5
比较5 ≈2
表5.对于不同的基于聚合物的密封剂组合物的搭接剪切试验。
这些结果确定了玻璃表面上的高屈服应力和粘合强度(>7MPa),表明本密封剂组合物满足VIG应用的机械要求。
*****
以上已经参考本发明的优选实施方案描述了本发明,但是可以存在另外的实施方案,所有这些实施方案都包括在如由所附权利要求的范围限定的相同的发明核心中。

Claims (27)

1.一种真空隔热玻璃(1),包括:
-两个玻璃板(2、2’),所述两个玻璃板(2、2’)彼此面对并由一个或更多个柱(3、3’、3”)彼此间隔开以在其间形成空隙体积(4),
-非蒸散型吸气剂体系(5、5’),所述非蒸散型吸气剂体系(5、5’)放置在所述体积(4)内,
-基于聚合物的密封边缘(6),所述密封边缘(6)封闭所述体积(4)以限定所述玻璃板(2、2’)之间的闭合空间,
-所述真空隔热玻璃的特征在于,所述密封边缘(6)通过使密封剂组合物固化而获得,所述密封剂组合物包含:
(a)可固化热固性非卤化聚环氧化物树脂,所述可固化热固性非卤化聚环氧化物树脂按平均计每分子包含至少两个环氧基;
(b)芳族二胺固化剂,所述芳族二胺固化剂的量足以提供环氧树脂中每当量环氧基0.5当量至2.0当量的胺N-H;和
(c)无机干燥剂,所述无机干燥剂的量相对于有机组合物的总重量为5重量%至25重量%。
2.根据权利要求1所述的真空隔热玻璃,其中所述芳族二胺固化剂的量提供所述环氧树脂中每当量环氧基0.5当量至1.0当量的胺N-H。
3.根据权利要求1所述的真空隔热玻璃,其中所述无机干燥剂选自氧化物,吸湿性盐和可逆干燥剂。
4.根据权利要求3所述的真空隔热玻璃,其中所述氧化物为CaO。
5.根据权利要求3所述的真空隔热玻璃,其中所述吸湿性盐为高氯酸盐干燥剂。
6.根据权利要求5所述的真空隔热玻璃,其中所述高氯酸盐干燥剂为Mg(ClO4)2
7.根据权利要求3所述的真空隔热玻璃,其中所述可逆干燥剂选自沸石和活性炭,或其混合物。
8.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述密封剂组合物还包含一种或更多种惰性填料。
9.根据权利要求8所述的真空隔热玻璃,其中所述惰性填料选自聚乙烯醇、聚酰亚胺、SiO2、TiO2、玻璃珠、玻璃纤维、金属带或玻璃带、以及金属丝或玻璃丝。
10.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述非卤化聚环氧化物树脂为酚醛树脂。
11.根据权利要求10所述的真空隔热玻璃,其中所述酚醛树脂具有以下式(I):
Figure FDA0003681494440000021
其中n为0至8的整数。
12.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述芳族二胺固化剂包含磺化基团和/或酚基。
13.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述芳族二胺固化剂为4,4’-二氨基-二苯砜。
14.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述密封剂组合物根据依据ISO 11357-2:2013通过差示扫描量热法(DSC)测量确定的玻璃化转变温度Tg高于100℃。
15.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述非蒸散型吸气剂体系包括Zr合金,所述Zr合金在室温下通过ASTM吸收测试的N2吸收能力≥1cctorr/g。
16.根据权利要求15所述的真空隔热玻璃,其中所述Zr合金选自ZrTiV、ZrTiVAl、ZrVAl、ZrVFe和ZrVFeMn-RE合金,其中RE为一种或更多种稀土元素。
17.根据权利要求16所述的真空隔热玻璃,其中所述RE呈进一步包含Zr粉末的混合物的烧结态。
18.根据权利要求1至7中任一项所述的真空隔热玻璃,其中所述吸气剂体系包括分布在金属条的至少一侧上的粉末吸气剂。
19.一种包括根据权利要求1至18中任一项所限定的真空隔热玻璃的窗户或立面。
20.一种包括根据权利要求1至18中任一项所限定的真空隔热玻璃的家用或商用制冷机的柜体。
21.一种用于制造根据权利要求1至18中任一项所述的真空隔热玻璃的方法,包括以下步骤:
i)提供顶部玻璃板和底部玻璃板,并通过任意顺序的以下步骤a至c准备所述底部玻璃板:
a.布置柱;
b.将非蒸散型吸气剂体系布置在玻璃表面上或专用空间中;
c.沉积所述密封剂组合物;
ii)将所述顶部玻璃板摞合在所述底部玻璃板上;
iii)使所述密封剂组合物固化,由此形成VIG室;
iv)将所述VIG室抽空;
v)使所述吸气剂活化;以及
vi)将抽空孔密封。
22.根据权利要求21所述的方法,其中步骤i)b.还包括将所述非蒸散型吸气剂体系胶合。
23.根据权利要求21所述的方法,其中所述步骤i)c.通过布置所述密封剂组合物的预成型层合条或通过沉积来自预填充注射器的所述密封剂组合物来进行。
24.根据权利要求21至23中任一项所述的方法,其中所述密封剂组合物的所述固化步骤iii)通过加热来进行。
25.根据权利要求24所述的方法,其中所述密封剂组合物的所述固化步骤iii)还通过UV固化来进行。
26.根据权利要求21至23中任一项所述的方法,其中所述吸气剂活化步骤v)通过在300℃至600℃的温度范围内的射频(RF)加热来进行。
27.根据权利要求21至23中任一项所述的方法,其中将所述玻璃板摞合和使所述密封剂组合物固化的所述步骤ii)和iii)在装下整个VIG的大抽空室中进行。
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