CN103108749A - 真空绝热材料用复合芯材及其制备方法、以及利用该复合芯材的真空绝热材料 - Google Patents

真空绝热材料用复合芯材及其制备方法、以及利用该复合芯材的真空绝热材料 Download PDF

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CN103108749A
CN103108749A CN2011800398174A CN201180039817A CN103108749A CN 103108749 A CN103108749 A CN 103108749A CN 2011800398174 A CN2011800398174 A CN 2011800398174A CN 201180039817 A CN201180039817 A CN 201180039817A CN 103108749 A CN103108749 A CN 103108749A
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heat insulation
vacuum heat
insulation materials
mentioned
core
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CN103108749B (zh
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韩程弼
黄承锡
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Ace Global Ltd.
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LG Chemical Co Ltd
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Abstract

本发明公开一种初期绝热性能和长期耐久性能优秀的真空绝热材料用复合芯材及其制备方法、以及利用该复合芯材的真空绝热材料。本发明的真空绝热材料，其特征在于，包含：芯材，其由玻璃纤维棉和玻璃纤维板复合而成的复合体形成；以及外皮材料，其对上述芯材进行真空包装，该外皮材料自外而内具有表面保护层、金属阻隔层及粘合层的层压结构。

Description

真空绝热材料用复合芯材及其制备方法、以及利用该复合芯材的真空绝热材料
技术领域
本发明涉及一种真空绝热材料，更详细地涉及一种通过由玻璃纤维棉(wool)及玻璃纤维板的2种以上的复合材质形成芯材来确保优秀的初期绝热性能及长期耐久性的真空绝热材料。
背景技术
真空绝热材料(Vacuum Insulation Panel)通常如下制造：在由气体阻隔性优异的复合塑料层压膜形成的袋体内，收纳连续气泡硬质塑料发泡体或无机物等作为芯材，并对内部进行减压之后，对周围边缘的气体阻隔性膜之间的层压部分进行热封。
此时，用于真空绝热材料的芯材适用热传导率低、产生少量气体的无机化合物。特别是，众所周知，使用玻璃纤维的层压体作为芯材的真空绝热材料具有优秀的绝热性能。
在以往的真空绝热材料中，单独使用玻璃纤维棉作为芯材或单独使用玻璃纤维板作为芯材。玻璃纤维棉通过对体积大的(bulky)的玻璃纤维进行集棉之后，利用热压接工序来制备，并将其用作芯材，从而在制备真空绝热材料时能够确保0.0025Kcal/mhr℃以下水准的热传导率。
但是，在将玻璃纤维棉用作真空绝热材料芯材的情况下，虽能够确保优秀的初期绝热性能，但在长时间使用时，由通过外皮材料膜透过的气体导致热传导率上升，因而存在长期耐久性降低的问题。
相反，在将玻璃纤维板用作真空绝热材料用芯材的情况下，即使长时间使用，也能够在气体透过时，基于玻璃纤维板的小气孔直径将气体的热传递最小化，从而具有长期耐久性优秀的优点，但是，存在初期热传导率为0.0035Kcal/mhr℃以下水准而高于玻璃纤维棉的缺点。
结果，在现有的真空绝热材料中，使用玻璃纤维棉作为芯材的情况下，因长期耐久性能降低而具有较短的寿命，因而，不管应用于需要10年以上的寿命的建筑领域时，还是应用于家用电器领域时，都存在可靠性问题。
并且，在使用玻璃纤维板作为芯材的情况下，因初期绝热性能降低而存在应用于绝热材料时受限制的问题。
发明内容
技术问题
本发明的一个目的在于，提供一种利用由复合玻璃纤维棉和玻璃纤维板复合而成的复合体形成的真空绝热材料用芯材来实现初期绝热性能和长期耐久性能均优秀的芯材。
本发明的另一个目的在于提供一种包含芯材的真空绝热材料的制备方法，其中，上述芯材通过使用层压法、热压接法、无机粘结剂粘合法及针刺(needling)加工法中的方法对玻璃纤维棉和玻璃纤维板进行复合而成。
本发明的再另一个目的在于，提供一种通过使如上所述的所有因素最佳化而能够具备至少10年以上的长期耐久性能的真空绝热材料。
解决问题的手段
用于达成上述一个目的的本发明一实施例的真空绝热材料用复合芯材，其特征在于，该真空绝热材料用复合芯材具有由平均直径为4μm～6μm的玻璃纤维形成的玻璃纤维棉和1μm～4μm的玻璃纤维板的复合层压结构，并且包含烘制二氧化硅粉、二氧化硅粉、珍珠岩粉以及气凝胶粉中的一种以上。
用于达成上述另一个目的的本发明一实施例的真空绝热材料用复合芯材的制备方法，其特征在于，由通过对玻璃纤维棉和玻璃纤维板进行复合而成的复合体形成真空绝热材料用复合芯材，此时，玻璃纤维棉和玻璃纤维的复合利用层压法、热压接法、无机粘结剂粘合法及针刺加工法中的方法。
用于达成上述再另一个目的的本发明一实施例的真空绝热材料，其特征在于，包含：芯材，其由玻璃纤维棉和玻璃纤维板复合而成的复合体形成；以及外皮材料，其对上述芯材进行真空包装。
有益效果
如上所述，本发明的真空绝热材料用芯材通过复合应用初期绝热性能优秀的玻璃纤维棉和长期耐久性能优秀的玻璃纤维板，从而具有初期绝热性能及长期耐久性能均优秀的优点。
进而，根据如上所述的芯材及其他多种材料的特性，本发明的真空绝热材料具有至少能够维持10年以上的长期耐久性能且绝热性能优秀的优点。
附图说明
图1至图4表示本发明的多个实施例的真空绝热材料用芯材的截面图。
图5是表示本发明的实施例的真空绝热材料所包含的吸气(getter)材料的截面图。
图6及图7是表示本发明的实施例的真空绝热材料所包含的外皮材料的截面图。
图8及图9是表示本发明的实施例的真空绝热材料的截面图。
图10是表示对实施例的真空绝热材料及比较例的真空绝热材料的绝热性能进行比较并评价的曲线图。
具体实施方式
参照附图以及以下详细说明的实施例，就能够明确本发明的优点和特征，以及达成该优点和特征的方法。但是本发明并不限于在下面公开的一些实施例，而能够通过互相不同的各种方式来实现，本实施例只是使本发明的公开更完整，并为了向本发明所属于技术领域的普通技术人员完全告知发明的范畴而提供的，本发明仅由权利要求书来定义。在说明书全文中相同的附图标记是指相同的结构部件。
下面，参照附图对本发明的优选实施例的真空绝热材料用复合芯材及其制备方法以及利用该复合芯材的真空绝热材料进行说明如下。
首先，对本发明的芯材及其制备方法进行说明如下。
图1至图4表示本发明的多个实施例的真空绝热材料用芯材的截面图。
参照图1，准备大致具有所要形成的芯材100的形态的玻璃纤维棉120。
使用由上述玻璃纤维棉120和上述玻璃纤维板110复合而成的复合体形成的芯材100作为真空绝热材料用芯材。上述复合可形成为在上述玻璃纤维棉120的单面或者双面层压玻璃纤维板110的形态。
图2至图4是表示其他实施例的真空绝热材料用芯材的截面图。
上述玻璃纤维棉及玻璃纤维板的复合可分别由单层层压，根据需要也可由多层层压。由上述多层层压的多个实施例见图2至图4。
图2中示出在玻璃纤维棉140的上部依次层压玻璃纤维板110和玻璃纤维棉120的形态的芯材。
图3中示出在玻璃纤维棉120的上部依次层压两层玻璃纤维板130、110的形态的芯材。
图4中示出在玻璃纤维棉140的上部依次层压玻璃纤维板130、玻璃纤维棉120及玻璃纤维板110的形态的芯材。
除了在上述图1至图4中示出的芯材以外，可通过改变层压顺序或层数来以多种形态使用。
玻璃纤维棉120具有对玻璃纤维进行集棉的形态的结构，可根据热压接工序来制备玻璃纤维棉120。热压接工序可包括进行10分钟的加压及加热的工序。
玻璃纤维棉120的玻璃纤维的平均直径优选为4μm～6μm。如果玻璃纤维的直径小于4μm，则对于通过对纤维进行集棉来形成的玻璃纤维棉120来说，由于气孔率变小，因而在用作真空绝热材料的芯材的情况下导致初期绝热性能降低；如果玻璃纤维的直径大于6μm，则由于气孔大小变大，因而存在长期耐久性能降低的问题。
可提出如下玻璃纤维棉120，其由55％～70％的氧化硅、0.5％～5.0％的氧化铝、2.5％～4.0％的氧化镁、4.5％～12％的氧化钙以及0.1％～0.5％的氧化钾等形成。此外，可利用具有多种结构的玻璃纤维棉。
玻璃纤维棉120可根据真空绝热材料的形状，将玻璃棉面料裁剪成四边形、圆形等形态来使用。
然后，准备大致具备芯材100的形态的玻璃纤维板110。
玻璃纤维板110可使用平均纤维直径为1μm～4μm的玻璃纤维。如果玻璃纤维的直径小于1μm，对于以湿式制备法形成的玻璃纤维板110来说，由于气孔率变得过小而绝热性能降低，因而不适合用作真空绝热材料的芯材，如果玻璃纤维的直径大于4μm，则由于气孔大小变大，因而为了改善长期耐久性能而复合形成玻璃纤维板的效果变小。
玻璃纤维板的制备可通过湿式制备法来制备，该湿式制备法为将玻璃纤维分散到无机粘结剂(可溶性硅酸钠、氧化铝溶胶、硅溶胶、磷酸氧化铝中的一种以上)中来制成板的方法。特别是，可溶性硅酸钠包含水、二氧化硅粉及氢氧化钠。
可提出如下玻璃纤维板110，其由55％～70％的氧化硅、0.5％～5.0％的氧化铝、2.5％～4.0％的氧化镁、4.5％～12％的氧化钙以及0.1％～0.5％的氧化钾等形成。此外，可利用具有多种结构的玻璃纤维板。
玻璃纤维板110中包含有可确保优秀的长期耐久性的材料，并可使用玻璃纤维板、薄片或者纸产品形态。另外，作为提高长期耐久性的材料，可包含烘制二氧化硅粉、二氧化硅粉、珍珠岩粉及气凝胶粉中的一种以上。
本发明的真空绝热材料用芯材100的制备方法包括由玻璃纤维棉120和玻璃纤维板110复合而形成复合体的步骤，上述复合可通过层压法、热压接法、无机粘结剂粘合法及针刺(needling)加工法中的至少一种方法进行。
在实现复合结构的上述方法中的层压法为层压2种以上的材料的方法。
热压接法为在高温条件下进行热压接的方法，可使用板压(plate press)、带压(belt press)等方法。热压接优选在400℃～1000℃的温度下执行。如果在低于400℃的温度下执行热压接，则由于不能顺利实现构成棉及板的玻璃纤维组织的变形，因而不能有效地进行压接，如果热压接温度高于1000℃，则存在需要过多的制备费用的问题。
无机粘结剂粘合法为利用无机粘结剂来将玻璃纤维棉120和玻璃纤维板110粘合的方法，可使用氧化铝溶胶、硅溶胶、磷酸氧化铝或可溶性硅酸钠等作为无机粘结剂，并且可根据情况，包含其中的两种或者两种以上。
针刺加工法为对玻璃纤维棉和玻璃纤维板进行层压之后、利用针来针刺加工的方法。
本发明的真空绝热材料包含：芯材，其由复合玻璃纤维棉和玻璃纤维板的复合体形成；以及外皮材料，其对上述芯材进行真空包装，上述真空绝热材料还可包含附着或插入到上述芯材的吸气材料。
图5是表示实施例的真空绝热材料所包含的吸气材料的截面图。
根据外部的温度变化，有可能在外皮材料的内部产生气体及水分，近来，为了防止此现象，而使用吸气材料，对本发明的吸气材料进行说明如下。
参照图5，可看到装在袋子210中的生石灰(CaO)200。本发明中使用纯度为95％以上的生石灰粉，而且由皱纹纸及聚丙烯(PP)浸渍无纺布来形成袋子210，以确保25％以上的吸湿性能。此时，考虑到绝热衬垫的总厚度，吸气材料的厚度优选为2mm以下。
图6及图7是表示实施例的真空绝热材料所包含的外皮材料的截面图。
形成外皮材料300、400，其成为包裹本发明的真空绝热材料用芯材的袋体。下面，对其具体形状及制备方法进行说明如下。
就外皮材料300、400而言，首先，在粘合层330、440的上部，依次形成金属阻隔层320、430及表面保护层310。此时，粘合层330、440可定义为形成于袋体内部的层，表面保护层310可定义为暴露在最外围的层。
并且，粘合层330、440作为借助热封方式相互热熔化粘合的层，能够起到维持真空状态的作用。因此，粘合层330、440由容易进行热熔化粘合的热塑性塑料膜形成，该热塑性塑料膜包含选自高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、流延聚丙烯(CPP)、定向聚丙烯(OPP)、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、乙烯-醋酸乙烯共聚物(EVA)及乙烯-乙烯醇共聚物(EVOH)中的一种以上，粘合层330、440的厚度优选为1μm～100μm，以提供充分的密封特性。
然后，在粘合层330、440的上部形成厚度为6μm～7μm的金属膜作为用于阻隔气体并保护芯材的阻隔层320、430。此时，通常使用最多的是铝箔(Foil)金属阻隔层320、430，由于还未明确出现具有相比铝箔更优秀的特性的膜，因而，本发明中也使用铝箔。此时，由于铝是金属材料，因而，在折叠时存在产生裂纹(Crack)等的问题，为了防止这种现象，在金属阻隔层320、430的上部形成表面保护层310。
优选地，本发明的外皮材料的表面保护层由厚度为10μm～14μm的聚对苯二甲酸乙二醇酯(PET)膜410及厚度为20μm～30μm的尼龙(Nylon)膜420的层压结构形成。
在这种情况下，如果在金属阻隔层430产生的裂纹程度严重，则也会对聚对苯二甲酸乙二醇酯膜410/尼龙膜420造成损伤，本发明中，为了防止这种现象，在聚对苯二甲酸乙二醇酯层的上部涂敷乙烯基系树脂层。
上述乙烯基系树脂层优选使用乙烯基系树脂，该乙烯基系树脂由选自聚氯乙烯(PVC)、聚乙酸乙烯酯(PVA)、聚乙烯醇(PVAL)、聚乙烯醇缩丁醛(PVB)以及聚偏二氯乙烯(PVDC)中的一种以上形成。
并且，为了进一步提高外皮材料的气密特性，上述表面保护层310、金属阻隔层320、430及粘合层330、440分别优选利用聚氨酯(PU)系树脂来进行粘合。
通过这样形成外皮材料300、400，使本发明的真空绝热材料能够具有最佳的气密性和长期耐久性能。
图8及图9是表示实施例的真空绝热材料的截面图。
图8示出在使吸气材料510附着于芯材500的表面的状态下、利用外皮材料520来进行密封的状态的真空绝热材料，图9示出在将吸气材料插入芯材600的内部的状态下、密封外皮材料620的状态的真空绝热材料。
这样制备的真空绝热材料均发挥出了优秀的绝热性能和长期耐久性能，对其具体实施例进行说明如下。
实施例
下面，通过本发明的优选实施例对本发明的结构及作用进行更加详细地说明。但这些实施例只作为本发明的优选示例而提出的，无论在什么情况下也不能解释为本发明局限于此。
真空绝热材料的制备
实施例1
首先，将上述图1中说明的由利用层压法分别将玻璃纤维棉和玻璃纤维板层压单层而成的复合体形成的芯材制备成8mm×190mm×250mm(厚度×宽度×长度)的大小之后用作真空绝热材料用芯材。
其次，形成外皮材料，该外皮材料由12μm的聚偏二氯乙烯(PVDC)/聚对苯二甲酸乙二醇酯(PET)膜、25μm的尼龙(Nylon)膜、7μm的铝箔以及50μm的线性低密度聚乙烯(LLDPE)膜的结构形成。
再其次，如图9所示，将2个吸气材料插入到芯材的表面，其中，所述吸气材料通过将25g的纯度为95％的生石灰(CaO)装入袋子而制成。
然后，将芯材插入到袋体之后，在10Pa的真空度状态下进行密封，制备出本发明的真空绝热材料。
实施例2
按照与上述实施例1相同的条件制备真空绝热材料，但芯材由通过层压法来将一层玻璃纤维板层压在两层玻璃纤维棉的上部而成的复合体形成，并且，芯材制成8mm×190mm×250mm(厚度×宽度×长度)的大小。
比较例1
制备与上述实施例1的所有条件相同的真空绝热材料，但芯材仅由玻璃纤维板形成，并且，该芯材制成8mm×190mm×250mm(厚度×宽度×长度)大小。
比较例2
制备与上述实施例1的所有条件相同的真空绝热材料，但芯材通过利用层压法将两层玻璃纤维板层压的方式来形成，并且，该芯材制成8mm×190mm×250mm(厚度×宽度×长度)大小。
比较例3
制备与上述实施例1的所有条件相同的真空绝热材料，但芯材仅由玻璃纤维棉形成，并且，该芯材制成8mm×190mm×250mm(厚度×宽度×长度)大小。
比较例4
制备与上述实施例1的所有条件相同的真空绝热材料，芯材通过利用层压法将两层玻璃纤维棉层压的方式来形成，并且，该芯材制成8mm×190mm×250mm(厚度×宽度×长度)大小。
性能试验及评价
将上述实施例1、2、及比较例1、2、3、4的真空绝热材料分别放入85℃的恒温室，并维持3个月左右，同时与未进行整体加热的真空绝热材料进行热传导率比较。此时，在测定热传导率时，使用HC-074-200(EKO公司制)热传导测定器。然后，应用加速因子来预测0年～10年的热传导率，其结果如图10所示。
图10是表示对实施例的真空绝热材料的绝热性能及比较例的真空绝热材料的绝热性能进行比较并评价的曲线图。
参照上述图10可知，在实施例1、2的情况下，由于初期热传导率低、根据时间的热传导率的增加量较低，因而，由复合芯材形成的真空绝热材料的初期绝热性能和长期耐久性能均优秀。
相反，在比较例1、比较例2的情况下，由于根据时间的热传导率的增加量低，因而长期耐久性能优秀，但因初期的热传导率高而初期绝热性能不良。此外，在比较例3、比较例4的情况下，初期热传导率几乎与实施例1、2相同，初期性能优秀，但是，由于根据时间的热传导率的增加量高，因而，根据时间的长期耐久性能不良。
因此，如上所述的本发明的真空绝热材料提供一种能够使初期绝热性能最大化的结构，并提供能够使长期耐久性能增加到至少10年以上的效果。
以上，参照附图对本发明的实施例进行了说明，但本发明不局限于上述实施例，可制成相互不同的各种形态，对于本发明所属技术领域的普通技术人员来说，应当理解，在不变更本发明技术思想和必要特征的情况下，能够实施其他具体方式，因此，如上所述的实施例在各方面上都是示例性的，而不是限制性的。

Claims (23)

1.一种真空绝热材料用芯材，其特征在于，上述真空绝热材料用芯材由玻璃纤维棉和玻璃纤维板复合而成的复合体形成。
2.根据权利要求1所述的真空绝热材料用芯材，其特征在于，上述玻璃纤维板形成于上述玻璃纤维棉的单面或者上述玻璃纤维棉的双面。
3.根据权利要求1所述的真空绝热材料用芯材，其特征在于，在上述真空绝热材料用芯材分别层压有一层以上的玻璃纤维棉和一层以上的上述玻璃纤维板。
4.根据权利要求1所述的真空绝热材料用芯材，其特征在于，在上述玻璃纤维棉中玻璃纤维的平均直径为4μm～6μm。
5.根据权利要求1所述的真空绝热材料用芯材，其特征在于，在上述玻璃纤维板中玻璃纤维的平均直径为1μm～4μm。
6.根据权利要求1所述的真空绝热材料用芯材，其特征在于，上述玻璃纤维板包含烘制二氧化硅粉、二氧化硅粉、珍珠岩粉及气凝胶粉中的一种以上。
7.一种真空绝热材料用芯材的制备方法，其特征在于，由通过对玻璃纤维棉和玻璃纤维板进行复合而成的复合体形成真空绝热材料用芯材。
8.根据权利要求7所述的真空绝热材料用芯材的制备方法，其特征在于，上述玻璃纤维棉和上述玻璃纤维板的复合利用层压法、热压接法、无机粘结剂粘合法及针刺加工法中的一种以上的方法来实施。
9.根据权利要求8所述的真空绝热材料用芯材的制备方法，其特征在于，
上述热压接法在400℃以上的温度下实施。
10.根据权利要求8所述的真空绝热材料用芯材的制备方法，其特征在于，
上述热压接法利用板压法或带压法。
11.根据权利要求8所述的真空绝热材料用芯材的制备方法，其特征在于，
利用于上述无机粘结剂粘合法的无机粘结剂包含氧化铝溶胶、硅溶胶、磷酸氧化铝及可溶性硅酸钠中的一种以上。
12.一种真空绝热材料，其特征在于，包含：
芯材，其由玻璃纤维棉和玻璃纤维板复合而成的复合体形成；以及
外皮材料，其对上述芯材进行真空包装。
13.根据权利要求12所述的真空绝热材料，其特征在于，还包含吸气材料，该吸气材料附着或插入到上述芯材。
14.根据权利要求13所述的真空绝热材料，其特征在于，上述吸气材料通过在袋子中包装纯度为95％以上的生石灰CaO粉而成。
15.根据权利要求14所述的真空绝热材料，其特征在于，上述袋子由皱纹纸及聚丙烯PP浸渍无纺布形成。
16.根据权利要求13所述的真空绝热材料，其特征在于，上述吸气材料的吸湿率为25％以上。
17.根据权利要求12所述的真空绝热材料，其特征在于，上述外皮材料自外而内具有表面保护层、金属阻隔层及粘合层的层压结构。
18.根据权利要求17所述的真空绝热材料，其特征在于，上述表面保护层具有聚对苯二甲酸乙二醇酯PET膜及尼龙膜的层压结构。
19.根据权利要求18所述的真空绝热材料，其特征在于，在上述聚对苯二甲酸乙二醇酯膜PET膜的上部涂敷有乙烯基系树脂。
20.根据权利要求19所述的真空绝热材料，其特征在于，上述乙烯基系树脂为选自聚氯乙烯PVC树脂、聚乙酸乙烯酯PVA树脂、聚乙烯醇PVAL树脂、聚乙烯醇缩丁醛PVB树脂及聚偏二氯乙烯PVDC树脂中的一种以上。
21.根据权利要求17所述的真空绝热材料，其特征在于，上述金属阻隔层由铝箔形成。
22.根据权利要求17所述的真空绝热材料，其特征在于，上述粘合层包含选自高密度聚乙烯HDPE、低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、流延聚丙烯CPP、定向聚丙烯OPP、聚偏二氯乙烯PVDC、聚氯乙烯PVC、乙烯-醋酸乙烯共聚物EVA及乙烯-乙烯醇共聚物EVOH中的一种以上。
23.根据权利要求17所述的真空绝热材料，其特征在于，上述表面保护层和金属阻隔层之间的粘合以及金属阻隔层和粘合层之间的粘合分别利用聚氨酯PU系树脂进行粘合。
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