CN102667298A - 真空隔热材料用膜和真空隔热材料 - Google Patents
真空隔热材料用膜和真空隔热材料 Download PDFInfo
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Abstract
本发明提供:与以往的真空隔热材料用膜相比,隔气性优异,且弯折或变形加工后仍可保持优异的隔气性的真空隔热材料用膜;以及使用该真空隔热材料用膜将芯材密封包装得到的真空隔热材料。该真空隔热材料用膜的特征在于:具有保护层、隔气层和热熔接层,其中,所述保护层含有将尼龙系树脂和乙烯-乙烯基醇共聚物和尼龙系树脂依次层叠得到的共挤出拉伸膜。
Description
技术领域
本发明涉及真空隔热材料用膜和真空隔热材料。
背景技术
近年来,从保护地球环境、特别是节省能源的观点考虑,人们需求具有优异的隔热性能的材料,在这方面,真空隔热材料具有特别优异的隔热性能,因此在冰箱用隔热材料或住宅隔热墙用的隔热板等中广泛应用。该真空隔热材料含有芯材、包被该芯材的真空隔热材料用膜。
作为真空隔热材料用膜,为了防止外部气体(空气)的侵入、保持长时间的真空状态而需求优异的隔气性。因此,真空隔热材料用膜使用含有保护层和隔气层和热熔接层的层叠膜,其中,所述保护层含有将拉伸聚酯膜、拉伸尼龙膜、拉伸聚丙烯膜单独或用适当的粘合剂层叠而得到的复合膜(专利文献1),或者将双轴拉伸尼龙膜和双轴拉伸乙烯-乙烯基醇共聚物膜用粘合剂层叠而得到的复合膜(专利文献2)等;所述隔气层含有形成了金属·金属氧化物薄膜层的聚对苯二甲酸乙二醇酯膜或金属箔等;所述热熔接层含有低密度聚乙烯或高密度聚乙烯等。
此外,近年来,由于真空隔热材料周围的翅片部(ヒレ部,经热熔接的位置)与含有芯材的部分相比隔热性能低,因此将翅片部弯折以保持全体的隔热性能,或者将真空隔热材料本身变形为符合容纳空间的结构的形状,以在复杂的形状(例如圆弧形状或直角形状)的场所使用。基于以上情况,对于真空隔热材料用膜进行弯折或变形加工时,也要求隔气性不会降低。
但是,在保护层中层叠以往的膜所得到的上述真空隔热材料用膜具有在进行弯折或变形加工后隔气性降低的问题。
现有技术文献
专利文献
专利文献1:日本特开昭62-28242号公报
专利文献2:日本特开2006-17209号公报。
发明内容
发明要解决的课题
本发明的目的在于提供:与使用以往的保护层的真空隔热材料用膜相比,隔气性优异,且在弯折或变形加工后仍可保持优异的隔气性的真空隔热材料用膜、以及使用该真空隔热材料用膜将芯材密封包装得到的真空隔热材料。
解决课题的手段
本发明人为解决上述课题进行了深入的研究,结果发现:通过在保护层中使用将尼龙系树脂和乙烯-乙烯基醇共聚物和尼龙系树脂依次层叠而成的共挤出拉伸膜,可以实现上述目的,从而完成了本发明。
即,本发明的主要内容如下:
(1) 真空隔热材料用膜,其特征在于:该真空隔热材料用膜具有保护层、隔气层和热熔接层,其中,所述保护层含有将尼龙系树脂和乙烯-乙烯基醇共聚物和尼龙系树脂依次层叠得到的共挤出拉伸膜。
(2) 权利要求1的真空隔热材料用膜,其特征在于:上述隔气层具有铝箔。
(3) 真空隔热材料,其特征在于:该真空隔热材料由(1)或(2)的真空隔热材料用膜将芯材密封包装而成。
发明的效果
本发明的真空隔热材料用膜与使用以往的保护层的真空隔热材料用膜相比,隔气性优异,且在弯折或变形加工后仍可保持优异的隔气性,因此,使用该真空隔热材料用膜的真空隔热材料即使长时间使用,仍可以以高的可靠度保持真空,具有隔热性能不降低的效果。
附图简述
图1是本发明的真空隔热材料用膜的截面图。
发明的实施方式
以下详细说明本发明。
本发明中,真空隔热材料用膜的保护层使用将尼龙系树脂和乙烯-乙烯基醇共聚物和尼龙系树脂依次层叠而成的共挤出拉伸膜(以下称为共挤出拉伸膜)。该共挤出拉伸膜不使用粘合剂,而是通过共挤出,在具有隔气性的乙烯-乙烯基醇共聚物的两侧层叠具有柔软性的尼龙系树脂,从而赋予其柔软性和隔气性的特征。
尼龙系树脂可举出:6-尼龙、6,6-尼龙、6,10-尼龙、6,12-尼龙、11-尼龙、12-尼龙以及2种以上这些树脂的混合物等。只要不脱离本发明宗旨,尼龙系树脂中可以配合各种稳定剂、染料、颜料、润滑剂、防粘连剂等添加剂。
乙烯-烯基醇共聚物(以下称为EVOH),特别优选在EVOH中乙烯含有率为20-65%摩尔,进一步优选29-44%摩尔,皂化度适当地为95%摩尔以上,优选98%摩尔以上。乙烯含有率低于20%摩尔,则熔融挤出时的熔融挤出性差,还容易着色,因此不优选。乙烯含有率超过65%摩尔,则有隔气性降低的倾向,不优选。另外,EVOH的皂化度低于95%摩尔,则隔气性或耐湿性差,因此不优选。
保护层所使用的共挤出拉伸膜可按照以往公知的方法,例如通过共挤出得到尼龙系树脂和EVOH和尼龙系树脂依次层叠而成的膜,然后将该膜拉伸,并为了对膜赋予尺寸稳定性等而实施热处理,获得共挤出拉伸膜。拉伸方法只要是不脱离本发明的宗旨即可,可以采用拉幅机式逐次双轴拉伸、拉幅机式同时双轴拉伸、管式同时双轴拉伸等以往公知的拉伸方法。
上述共挤出拉伸膜的总厚度为10-30μm,进一步优选15-25μm。总厚度低于10μm,则在拉伸中容易断裂,生产稳定性上有问题,而超过30μm,则柔软性不足,操作性变差,不实用。另外,本发明的共挤出拉伸膜的EVOH厚度为2-10μm,进一步优选3-10μm。EVOH的厚度低于2μm,则隔气性可能受损,而超过10μm,则不仅共挤出拉伸膜的柔软性受损,并且共挤出拉伸膜的材料成本升高,因此不优选。进而,配置于本发明的共挤出拉伸膜表里的尼龙系树脂的各层厚度优选为3-10μm的范围。
本发明的真空隔热材料用膜中使用的保护层可以只由上述共挤出拉伸膜构成,只要不脱离本发明的宗旨,还可以根据需要设置其它所需的层。
本发明的真空隔热材料用膜中使用的隔气层可以使用金属箔,或者形成了金属或金属氧化物的薄膜层的塑料膜,或将它们多种组合而成的材料。
从隔气性或经济性等各种角度考虑,金属箔可以特别理想地使用以往公知的铝箔。铝箔的厚度优选5-50μm,进一步优选5-30μm。通常铝箔变薄则针孔容易增加,变厚则热漏泄增大,因此隔热性能变差,不优选。
形成了金属或金属氧化物的薄膜层的塑料膜例如是在聚对苯二甲酸乙二醇酯膜或EVOH膜上,形成含有铝等金属或者二氧化硅、氧化铝等金属氧化物(单独或者它们的混合物)的单层或多层的薄膜层。
与形成了金属或金属氧化物的薄膜层的塑料膜相比,本发明的隔气层优选使用金属箔,特别是铝箔。
构成本发明的真空隔热材料用膜的热熔接层是在真空隔热材料用膜中透气率最大的部分,热熔接层的性质对于真空隔热材料的长期隔热性能有很大影响。考虑到减压密封工序中密封品质的稳定性、或抑制由热熔接部端面侵入气体的问题,热熔接层的厚度优选10-100μm。热熔接层的厚度低于10μm时,难以充分获得热熔接带来的粘合力,而超过100μm,则成本升高或气体由热熔接层的端部侵入,使真空度降低,因此不优选。热熔接层的材料可使用以往公知的材料,例如可使用含有以下中的一种至多种的树脂:低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直链状低密度聚乙烯、环状聚烯烃、聚丙烯、乙烯-乙酸乙烯基酯共聚物、离聚物树脂、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-丙烯共聚物;或者将聚乙烯或聚丙烯等聚烯烃系树脂用丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸、其它等不饱和羧酸改性所得的酸改性聚烯烃系树脂;聚酯系树脂、聚苯乙烯系树脂、其它树脂。尚需说明,本发明中,可以使用上述树脂使热熔接层为多层,例如可以制成下述层构成的热熔接层:在隔气层的一侧使用与金属箔和其它树脂的粘合性良好的酸改性聚烯烃系树脂,使最内层为聚烯烃系树脂。
构成本发明的真空隔热材料用膜的保护层、隔气层和热熔接层各层的层叠方法可以采用以往公知的方法,例如可采用:使用双液固化型氨基甲酸酯系粘合剂等的干式层压、挤出涂布、热层压等的方法。还可以根据需要,在任意的层上施加结合层(anchor coat)或印刷·着色层、底涂层、外涂层等。
本发明的真空隔热材料用膜的特征在于:在以往通过粘合剂将单层膜或多层膜层叠而成的保护层中,不使用粘合剂,而是通过使用具有柔软性和隔气性的、将尼龙系树脂和EVOH和尼龙系树脂依次层叠而成的共挤出拉伸膜,使得隔气性优异,并且在弯折或变形加工后,优异的隔气性仍不会降低。
使用本发明的真空隔热材料用膜得到的真空隔热材料的制造方法可以采用以往公知的方法,例如将真空隔热材料用膜的热熔接层之间热熔接,制作成袋,填充芯材,然后将袋中的空气排出,形成真空状态,将开口部热熔接,由此可得到真空隔热材料。制作填充芯材的袋时,可以将两片膜组合,在任意的三边将热熔接层之间进行热熔接,也可以将一片膜折叠,在任意的两边将热熔接层之间热熔接。
芯材可以使用以往公知的材料,例如优选选自玻璃棉、玻璃纤维、氧化铝纤维、氧化硅-氧化铝纤维、二氧化硅纤维、碳化硅纤维、石棉、粉状聚氨酯、二氧化硅、聚苯乙烯、硅酸钙或聚氨酯发泡体中的至少一种。
另外,在进一步提高真空隔热材料的初期隔热性能和长期隔热性能时,也可以使用气体吸附剂或水分吸附剂等吸气剂物质。
实施例
以下根据实施例进一步详细说明本发明,但本发明的真空隔热材料用膜并不限于实施例。
尚需说明,本发明的真空隔热材料用膜的评价如下进行。
将200 mm×300 mm的试验片的两端贴合,围成圆筒状,将制成筒状的试验片的两端用固定头和驱动头支撑住,一边施加440度的扭曲一边将固定头和驱动头的间隔由7英寸缩小到3.5英寸,进一步在施加扭曲的状态下使头的间隔缩小至1英寸,然后将头的间隔扩大到3.5英寸,再一边将扭曲返回一边使头的间隔扩大到7英寸,以40次/分钟的速度将这样的往复运动进行50次,进行弯曲疲劳试验,按照JIS K7126 (等压法)测定弯曲疲劳试验前后的试验片的透氧率(隔气性)。
(实施例1)
保护层是由尼龙系树脂(6μm)/EVOH (3μm)/尼龙系树脂(6μm)构成的厚度15μm的共挤出拉伸膜,隔气层是厚度6.5μm的铝箔,热熔接层是厚度50μm的直链状低密度聚乙烯膜,使用氨基甲酸酯系粘合剂将它们依次层叠并粘合,得到真空隔热材料用膜。
(比较例1)
保护层使用厚度15μm的拉伸尼龙膜,以此代替实施例1的共挤出拉伸膜,除此之外与实施例1同样进行,得到真空隔热材料用膜。
(比较例2)
保护层使用厚度12μm的拉伸聚对苯二甲酸乙二醇酯膜,以此代替实施例1的共挤出拉伸膜,除此之外与实施例1同样进行,得到真空隔热材料用膜。
(比较例3)
保护层使用自铝箔一侧将厚度15μm的拉伸尼龙膜和厚度12μm的拉伸聚对苯二甲酸乙二醇酯膜用氨基甲酸酯系粘合层叠得到的复合膜,以此代替实施例1的共挤出拉伸膜,除此之外与实施例1同样进行,得到真空隔热材料用膜。
(比较例4)
代替比较例3的铝箔,隔气层使用蒸镀了铝的、厚度12μm的拉伸聚对苯二甲酸乙二醇酯膜和铝箔,在铝箔一侧施加蒸镀层并进行层叠使得铝箔在热熔接层一侧,除此之外与比较例3同样进行,得到真空隔热材料用膜。
(比较例5)
与专利文献2具有类似的构成,保护层是厚度12μm的拉伸聚对苯二甲酸乙二醇酯膜和厚度10μm的双轴拉伸EVOH膜的层叠膜,隔气层是厚度7μm的铝箔,热熔接层是厚度50μm的直链状低密度聚乙烯膜,将它们用氨基甲酸酯系粘合剂依次层叠,得到真空隔热材料用膜。
对实施例1和比较例1-5所得到的真空隔热材料用膜进行评价,结果如表1所示。
尚需说明,弯曲疲劳试验前是指在进行上述弯曲疲劳试验之前测定的透氧率的值,弯曲疲劳试验后是指进行了弯曲疲劳试验后测定的透氧率的值。
[表1]
如上述表1所示,本发明的实施例1的真空隔热材料用膜的弯曲疲劳试验前的透氧率比比较例1-5的真空隔热材料用膜良好。并且,弯曲疲劳试验后,实施例1的真空隔热材料用膜的透氧率比比较例1-5的真空隔热材料用膜良好,耐弯曲性优异。
特别是,若将实施例1的真空隔热材料用膜与比较例5的真空隔热材料用膜比较,虽然保护层同样具有EVOH层,但实施例1的真空隔热材料用膜在弯曲疲劳试验后的透氧率是比较例5的真空隔热材料用膜的一半以下,显示优异的隔气性。这是由于,并不只是在保护层中配置EVOH层,而是将尼龙系树脂与乙烯-乙烯基醇共聚物和尼龙系树脂依次不用粘合剂、通过共挤出而层叠,使用这样得到的共挤出拉伸膜而可见的效果。
产业实用性
使用本发明的真空隔热材料用膜的真空隔热材料可作为冰箱、电热水瓶、电饭煲、自动销售机等机器,热水器、浴缸、整体浴室、马桶座等住宅设备,地暖、天然冷却剂热泵热水器、低温辐射板等住宅系统,外墙用隔热板等住宅建材,低温箱、瓶套等生活用品等的隔热材料有效使用。
符号说明
1 真空隔热材料用膜
2 保护层(共挤出拉伸膜)
2-1 尼龙系树脂
2-2 乙烯-乙烯基醇共聚物
3 隔气层
4 热熔接层。
Claims (3)
1. 真空隔热材料用膜,其特征在于:该真空隔热材料用膜具有保护层、隔气层和热熔接层,其中,所述保护层含有将尼龙系树脂和乙烯-乙烯基醇共聚物和尼龙系树脂依次层叠得到的共挤出拉伸膜。
2. 权利要求1的真空隔热材料用膜,其特征在于:上述隔气层具有铝箔。
3. 真空隔热材料,其特征在于:该真空隔热材料由权利要求1或2的真空隔热材料用膜将芯材密封包装而成。
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CN104816517B (zh) * | 2013-11-20 | 2017-11-14 | 三亚铝业株式会社 | 用于真空隔热件的增强复合阻燃性外包装件、其制造方法及包含该外包装件的真空隔热件 |
CN104746825A (zh) * | 2013-12-27 | 2015-07-01 | 常州山由帝武节能新材料制造有限公司 | 适于保温的超薄型石材装饰板及其安装方法 |
CN104742445A (zh) * | 2013-12-27 | 2015-07-01 | 常州山由帝武节能新材料制造有限公司 | 一种真空绝热板用封装膜及真空绝热板 |
CN104742445B (zh) * | 2013-12-27 | 2017-02-15 | 江苏山由帝奥节能新材股份有限公司 | 一种真空绝热板用封装膜及真空绝热板 |
CN104746825B (zh) * | 2013-12-27 | 2017-05-03 | 江苏山由帝奥节能新材股份有限公司 | 适于保温的超薄型石材装饰板及其安装方法 |
CN105729961A (zh) * | 2014-12-26 | 2016-07-06 | 三星电子株式会社 | 层叠结构体和包括层叠结构体的真空绝热材料 |
CN110603403A (zh) * | 2017-05-09 | 2019-12-20 | 大日本印刷株式会社 | 真空绝热材料用外包材料、真空绝热材料和带真空绝热材料的物品 |
CN110603403B (zh) * | 2017-05-09 | 2021-02-19 | 大日本印刷株式会社 | 真空绝热材料用外包材料、真空绝热材料和带真空绝热材料的物品 |
Also Published As
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EP2508785A1 (en) | 2012-10-10 |
KR20120123263A (ko) | 2012-11-08 |
JPWO2011068148A1 (ja) | 2013-04-18 |
US20120237716A1 (en) | 2012-09-20 |
WO2011068148A1 (ja) | 2011-06-09 |
EP2508785A4 (en) | 2014-01-15 |
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