CN104583663A - 真空隔热材料的制造方法以及真空隔热材料 - Google Patents
真空隔热材料的制造方法以及真空隔热材料 Download PDFInfo
- Publication number
- CN104583663A CN104583663A CN201380043835.9A CN201380043835A CN104583663A CN 104583663 A CN104583663 A CN 104583663A CN 201380043835 A CN201380043835 A CN 201380043835A CN 104583663 A CN104583663 A CN 104583663A
- Authority
- CN
- China
- Prior art keywords
- vacuum heat
- heat insulation
- tackiness agent
- molding
- aerosil
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 74
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 237
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 abstract description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000004438 BET method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 101100401820 Caenorhabditis elegans alh-8 gene Proteins 0.000 description 1
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- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 238000010574 gas phase reaction Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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- F16L59/00—Thermal insulation in general
- F16L59/06—Arrangements using an air layer or vacuum
- F16L59/065—Arrangements using an air layer or vacuum using vacuum
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Abstract
本发明提供一种形状的自由度高、可稳定地得到优良的隔热性、长寿命的真空隔热材料。一种真空隔热材料(1)的制造方法,具备:对含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a的芯材(10)在1×106Pa以下的压力下进行加压,形成为成形体(12)的工序;将成形体(12)在具有气密性的外袋(14)内进行减压密封的工序。此外,真空隔热材料(1)具备具有气密性的外袋(14)、和由含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)的芯材(10)所成形的成形体(12),上述成形体(12)被减压密封在上述外袋(14)内。
Description
技术领域
本发明涉及真空隔热材料的制造方法以及真空隔热材料。
背景技术
以防止温室效应等减少对地球环境的负荷为目的,正大量进行节能推进。例如,为了通过住宅、大楼等高隔热化或汽车的门和屋檐的遮热、隔热来减少空调耗能,广泛使用隔热材料。
作为隔热材料,已知例如聚氨酯泡沫等发泡体。
但是为了以该发泡体得到足够的隔热性,发泡体的厚度需要变得较厚。为此,在可填充隔热材料的空间有限的情况下不能得到足够的隔热性。
另一方面,作为隔热材料,还已知将珍珠岩、二氧化硅等粉末材料、或玻璃纤维等纤维材料减压密封在外覆材料中的真空隔热材料(参照专利文献1~6)。
但是,在使用粉末材料的真空隔热材料中,减压密封时粉末材料容易飞散。此外,如果为了防止粉末材料的飞散,对粉末材料施加高压力进行成形来减压密封,也难以得到具有良好隔热性的真空隔热材料。
此外,使用纤维材料的真空隔热材料为了得到足够的隔热性,与使用粉末材料的情况相比,需要将纤维材料在高真空(10Pa以下)下进行减压密封。为此,如果由于经时劣化而导致真空隔热材料的真空度下降,则隔热性急剧下降,存在寿命短的问题。此外,使用纤维材料的真空隔热材料无法制造板状的隔热材料,隔热材料的形状的自由度低。
现有技术文献
专利文献
专利文献1:日本专利特开平8-28776号公报
专利文献2:日本专利特开2002-310383号公报
专利文献3:日本专利特开2003-74786号公报
专利文献4:日本专利第3482399号公报
专利文献5:日本专利第3558980号公报
专利文献6:日本专利特开2008-215492号公报
发明内容
发明所要解决的技术问题
本发明能够提供一种可制造隔热材料的形状的自由度高、可稳定地得到优良的隔热性、长寿命的真空隔热材料的真空隔热材料的制造方法。此外,本发明提供一种隔热材料的形状的自由度高、可稳定地得到优良的隔热性、长寿命的真空隔热材料。
解决技术问题所采用的技术方案
本发明的真空隔热材料的制造方法是具备下述工序(I)以及工序(II)的方法。
(I)对含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)的芯材在1×106Pa以下的压力下进行加压,形成为成形体的工序。
(II)将所述成形体在具有气密性的外袋内进行减压密封的工序。
本发明的真空隔热材料的制造方法中,可在所述工序(I)中将所述芯材以收纳在具有通气性的内袋内的状态进行加压,形成所述成形体;在所述工序(II)中将所述成形体以收纳在所述内袋内的状态减压密封在所述外袋内。
上述芯材优选含有多孔质二氧化硅(B)。
上述气相二氧化硅(A)和上述多孔质二氧化硅(B)的质量比A/B优选20/80~90/10。
上述芯材可含有选自石墨、炭黑、氧化钛以及钛酸钾的至少1种添加材料(C)。
上述粘合剂优选无机粘合剂。
本发明的真空隔热材料包括具有气密性的外袋、和由含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)的芯材所成形的成形体,上述成形体被减压密封在上述外袋内。
另外,本发明的真空隔热材料优选具备具有通气性的内袋,上述成形体以收纳在上述内袋内的状态被减压密封在上述外袋内。
发明的效果
如果采用本发明的真空隔热材料的制造方法,则可制造隔热材料的形状的自由度高、可稳定地得到优良的隔热性、长寿命的真空隔热材料。
本发明的真空隔热材料,其隔热材料的形状的自由度高、可稳定地得到优良的隔热性、寿命长。
附图说明
图1是通过本发明的真空隔热材料的制造方法的一个工序而得的成形体的剖面图。
图2是示出本发明的真空隔热材料的一例的剖面图。
图3是本发明的真空隔热材料中的成形体的扩大剖面图。
图4是本发明的真空隔热材料中的成形体的扩大剖面图。
图5是通过本发明的真空隔热材料的制造方法而得的成形体的剖面图。
图6是示出本发明的真空隔热材料的另一例的剖面图。
具体实施方式
<真空隔热材料的制造方法>
作为本发明的真空隔热材料的制造方法,根据内袋使用的有无,可例举下述方法(α)以及(β)的2种方法。
(α)对芯材以其原有状态进行加压而形成成形体,将该成形体直接在外袋内进行减压密封的方法。
(β)对芯材以收纳在内袋内的状态进行加而压形成成形体,将该成形体以收纳在上述内袋内的状态在外袋内进行减压密封的方法。
[方法(α)]
在方法(α)中,不使用内袋。方法(α)按顺序具有下述工序(I-1)以及工序(II-1)。
(I-1)如图1所示,对含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a的芯材10,直接在1×106Pa以下的压力下进行加压,形成为成形体12的工序。
(II-1)如图2所示,对成形体12直接在外袋14内进行减压密封,得到真空隔热材料1的工序。
(工序(I-1))
芯材10含有气相二氧化硅(A)的表面赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a。
芯材10可以如图3所示,仅由带粘合剂气相二氧化硅(A’)10a构成,也可以如图4所示,由带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的混合物构成。芯材10从可得到更优良的隔热性的方面考虑,优选含有带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b。
用于带粘合剂气相二氧化硅(A’)10a的气相二氧化硅(A)为由非晶且球状、没有细孔的一次粒子构成的二氧化硅微粒子。气相二氧化硅(A)例如可通过将四氯化硅气化、在高温的氢焰中进行气相反应的方法而得。
由于气相二氧化硅(A)是极其微细的粉末,因此作为表示颗粒大小的指标,通常使用比表面积。
气相二氧化硅(A)的比表面积优选50~400m2/g,更优选100~350m2/g,特别优选200~300m2/g。如果气相二氧化硅(A)的比表面积在下限值以上,则容易得到优良的隔热性。如果气相二氧化硅(A)的比表面积在上限值以下,则粘合剂容易附着在粒子的表面,在工序(II-1)的减压密封时容易抑制带粘合剂气相二氧化硅(A’)飞散。
本发明中的比表面积通过氮气吸附法(BET法)测定。
作为气相二氧化硅(A)的具体例,例如可例举AEROSIL 200(一次平均粒径:12nm,比表面积:200m2/g,日本阿尔洛希尔株式会社(日本アエロジル社)制),AEROSIL 300(一次平均粒径:7nm,比表面积:300m2/g,日本阿尔洛希尔株式会社制)等。
气相二氧化硅(A)可只使用1种,也可将2种以上组合使用。
作为粘合剂,可以是有机粘合剂,也可以是无机粘合剂。其中,作为粘合剂,从热传导性低、容易得到优良的隔热性的方面考虑,优选无机粘合剂。
作为无机粘合剂,例如可优选例举选自硅酸钠、磷酸铝、硫酸镁、以及氯化镁等的1种。其中,从容易得到优良的隔热性的方面考虑,特别优选硅酸钠。
粘合剂可以只使用1种,也可将2种以上组合使用。
对制造带粘合剂气相二氧化硅(A’)10a的方法没有特别的限制,例如可例举对气相二氧化硅(A)涂布粘合液的方法等。对气相二氧化硅(A)涂布粘合液后,可通过混合器等进行混合。
作为粘合液的涂布方法,例如可例举喷涂等。
涂布气相二氧化硅(A)的粘合液的溶剂可在成形前使其挥发。藉此,可良好地体现存在于带粘合剂气相二氧化硅(A’)10a的表面的粘合剂的粘接力。溶剂的挥发可通过加热进行。
作为粘合液所使用的溶剂,没有特别的限定,例如可例举水、乙醇等。
粘合液中的粘合剂的比例优选3~30质量%,更优选4~20质量%。如果上述粘合剂的比例在上述范围内,则容易向气相二氧化硅(A)赋予粘合剂。作为粘合液,特别优选作为硅酸钠的水溶液的水玻璃。
芯材根据后文所说明的理由,优选在气相二氧化硅(A)中含有多孔质二氧化硅(B)的芯材,但在含有多孔质二氧化硅(B)的情况下,作为粘合液,特别优选作为硅酸钠的水溶液的水玻璃。
带粘合剂气相二氧化硅(A’)10a中的粘合剂的比例在将带粘合剂气相二氧化硅(A’)作为100质量%时,优选1~30质量%,更优选2~20质量%,特别优选3~15质量%。此外,带粘合剂气相二氧化硅(A’)10a中的粘合剂的比例在将气相二氧化硅(A)、多孔质二氧化硅(B)和粘合剂的总计作为100质量%时,优选1~30质量%,更优选2~20质量%,特别优选3~15质量%。如果上述粘合剂的比例在下限值以上,则由于可以更低的压力成形成形体,因此可降低成形体中的带粘合剂气相二氧化硅(A’)的密度,可得到优良的隔热性。如果上述粘合剂的比例在上限值以下,则可防止粘合剂过度增加而导致的隔热性下降。
带粘合剂气相二氧化硅(A’)10a可只使用1种,也可将2种以上组合使用。
多孔质二氧化硅(B)10b的比表面积优选100~800m2/g,更优选200~750m2/g,特别优选300~700m2/g。如果多孔质二氧化硅(B)10b的比表面积在下限值以上,则容易得到优良的隔热性。如果多孔质二氧化硅(B)10b的比表面积在上限值以下,则由于可减少多孔质二氧化硅(B)10b吸收的粘合剂量,因此即使添加的粘合剂量减少也能够以更低的压力成形成形体。藉此,可降低成形体的密度,可得到优良的隔热性。
多孔质二氧化硅(B)10b的气孔率优选60~90%,更优选65~85%,特别优选70~80%。如果多孔质二氧化硅(B)10b的气孔率在下限值以上,则由于可使固体的热传导变少,因此容易得到优良的隔热性。如果多孔质二氧化硅(B)10b的气孔率在上限值以下,则由于在施加压力时多孔质二氧化硅粒子难以压碎、可维持多孔性而容易得到优良的隔热性。
上述气孔率通过氮气吸附法(BET法)测定。
多孔质二氧化硅(B)10b的平均粒径优选1~20μm,更优选2~15μm,特别优选3~10μm。如果多孔质二氧化硅(B)10b的平均粒径在下限值以上,则容易得到具有高气孔率的多孔质二氧化硅,容易得到优良的隔热性。如果多孔质二氧化硅(B)10b的平均粒径在上限值以下,则由于与带粘合剂气相二氧化硅(A’)10a混合而得的成形体的密度不会变得过高,因此容易得到优良的隔热性。
上述平均粒径通过激光衍射散射法、电子显微镜(SEM)观察等测定。
多孔质二氧化硅(B)10b可以只使用1种,也可将2种以上组合使用。
在芯材10含有带粘合剂气相二氧化硅(A’)10a以外的成分的情况下,芯材(100质量%)中的带粘合剂气相二氧化硅(A’)10a的含量优选16~89质量%,更优选24~79质量%,特别优选32~69质量%。如果上述含量在上述范围内,则可得到优良的隔热性。
在使用混合了带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的芯材10的情况下,带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的质量比以带粘合剂前的气相二氧化硅(A)和多孔质二氧化硅(B)的质量比A/B计,优选20/80~90/10,更优选30/70~80/20,特别优选40/60~70/30。如果上述质量比A/B在上述范围,则即使以低压力成形成形体也由于粘合剂的效果而不会损害处理性,可得到低密度的成形体,因此可得到优良的隔热性。
此外,芯材10可含有选自石墨、炭黑、氧化钛以及钛酸钾的至少1种添加材料(C)。藉此,可得到具有更优良的隔热性的真空隔热材料。
在芯材10含有添加材料(C)的情况下,芯材10(100质量%)中的带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b总计的含量优选80~99质量%,更优选85~98质量%,特别优选90~95质量%。如果上述含量在上述范围内,则可得到优良的隔热性。
在芯材10含有添加材料(C)的情况下,芯材10(100质量%)中的添加材料(C)的含量优选1~20质量%,更优选2~15质量%,特别优选5~10质量%。如果上述含量在上述范围内,则可容易地得到优良的隔热性。
在芯材10含有添加材料(C)的情况下,相对于芯材10中的带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的总计量,添加材料(C)的质量比C/(A’+B)优选0.01~0.25,更优选0.02~0.18,特别优选0.05~0.11。如果上述质量比C/(A’+B)在上述范围内,则可容易地得到优良的隔热性。
作为混合带粘合剂气相二氧化硅(A’)10a、和根据需要使用的多孔质二氧化硅(B)10b以及添加材料(C)的方法,例如可例举使用V型混合机、带有搅拌机的混合器等的方法。其中,为了分散性良好地进行混合,混合方法优选使用带有搅拌机的混合器这样的高速搅拌装置的方法。
多孔质二氧化硅(B)10b的混合可以在对气相二氧化硅(A)的表面赋予粘合剂之前进行,优选在对气相二氧化硅(A)的表面赋予粘合剂而得到带粘合剂气相二氧化硅(A’)10a之后进行。藉此,可使多孔质二氧化硅(B)10b吸收粘合剂,抑制粘合剂的浪费。此外,还可抑制多孔质二氧化硅(B)10b的多孔性的下降。
添加材料(C)的混合可在对气相二氧化硅(A)的表面赋予粘合剂、得到带粘合剂气相二氧化硅(A’)10a之后进行,也可以在对气相二氧化硅(A)赋予粘合剂之前进行。
作为成形芯材10的方法,没有特别的限定,例如可例举使用模具的方法。具体而言,可例举不将芯材10收纳在内袋内而是直接投入模具进行成形的方法等。
成形芯材10时加压的压力设为1×106Pa以下。工序(I-1)中,由于芯材10通过存在于带粘合剂气相二氧化硅(A’)10a的表面的粘合剂的粘接力相互接合,因此即使为1×106Pa以下的加压也可得到具有足够强度的成形体12。此外,通过以1×106Pa以下的加压进行成形,可抑制形成的成形体12中的芯材10的密度过高。其结果是,介由芯材10的热传导减少,可得到优良的隔热性。
加压成形芯材10时的压力的下限值从可得到强度高、形状难以崩坏的成形体、减压密封时芯材难以飞散的方面考虑,优选0.5×105Pa。
加压成形芯材10得到成形体12后,优选对成形体12进行干燥。通过在成形后进行干燥,可通过存在于带粘合剂气相二氧化硅(A’)10a的表面的粘合剂将芯材10之间更好地接合。作为干燥成形体12的方法,例如可例举以定温干燥机、电炉等进行加热的方法等。
干燥温度优选80~150℃,更优选100~120℃。
干燥时间根据干燥温度而不同,优选12~120小时,更优选24~60小时。
与使用内袋的方法(β)不用,在不将成形体收纳于内袋内的方法(α)中,可在成形后将成形体12在200~600℃的温度下进行1~24小时左右的加热。藉此可更可靠地减少多孔质二氧化硅(B)10b的气孔内残存的水分。
(工序(II-1))
将工序(I-1)所得的成形体12以不收纳在内袋内的状态直接收纳在外袋14内,通过对外袋14的内部进行减压并密封来减压密封成形体12,得到真空隔热材料1。
作为对外袋14内进行减压的方法,可使用真空隔热材料的制造中通常使用的方法。例如可例举将收纳在预先3边密封的外袋14内的成形体在带有热密封功能的真空腔内进行减压,在腔内减压到规定的压力后,对外袋14的开放的1边进行热密封来真空密封的方法等。
外袋14内的真空度从可得到优良的隔热性、且真空隔热材料1的寿命变长的方面考虑,优选1×103Pa以下,更优选1×102Pa以下。外袋14内的真空度从容易对外袋内进行减压的方面考虑,优选1Pa以上。
外袋14只要具有气密性、可对成形体12进行减压密封即可。作为外袋14,例如可例举由阻气膜构成的袋等。阻气膜可使用用于真空隔热材料的公知的阻气膜,没有限制。
对外袋14的大小以及形状没有特别限定,只要根据作为目的物的真空隔热材料1的大小以及形状适当决定即可。
[方法(β)]
在方法(β)中,使用内袋。方法(β)按顺序具有下述工序(I-2)以及工序(II-2)。
(I-2)如图5所示,对含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a的芯材10,以收纳在具有通气性的内袋16中的状态在1×106Pa以下的压力下进行加压,形成为成形体12的工序。
(II-2)如图6所示,对成形体12以收纳在内袋16中的状态在外袋14内进行减压密封,得到真空隔热材料2的工序。
对图5以及图6中的与图1以及图2相同部分添加相同符号,省略其说明。
(工序(I-2))
工序(I-2)除了使用内袋16以外可与方法(α)的工序(I-1)以相同的方式进行,优选的实施方式也相同。在成形为较薄的成形体、或曲面形状的成形体等的情况下,由于芯材收纳在内袋中而有对成形体的操作变得容易的优点。
例如,可将含有带粘合剂气相二氧化硅(A’)10a的芯材10收纳在内袋16内之后,通过将收纳了该芯材10的内袋16投入模具中,以将芯材10收纳在内袋16内的状态进行加压,形成成形体12。
作为内袋16,只要是具有通气性、在将形成成形体12的芯材进行减压密封时可不漏出的内袋即可,例如可例举由纸材、无纺布等构成的袋等。
对内袋16的大小以及形状没有特别限定,只要根据作为目的物的真空隔热材料2的大小以及形状适当决定即可。
方法(β)中,成形芯材10时加压的压力设为1×106Pa以下。由于芯材10通过存在于带粘合剂气相二氧化硅(A’)10a的表面的粘合剂的粘接力相互接合,因此即使为1×106Pa以下的加压也可得到具有足够强度的成形体12。通过以1×106Pa以下的加压进行成形,可抑制形成的成形体12中的芯材10的密度过高,其结果是,介由芯材10的热传导减少,可得到优良的隔热性。
加压成形芯材10时的压力的下限值从可得到强度高、形状难以崩坏的成形体、减压密封时芯材难以飞散的方面考虑,优选0.5×105Pa。
(工序(II-2))
将工序(I-2)所得的收纳在内袋16内的状态的成形体12以收纳在内袋16内的状态直接在外袋14内进行减压密封,得到真空隔热材料2。
对外袋14内进行减压的方法可例举与方法(α)的工序(II-1)所例举的方法相同的方法。
外袋14内的真空度的优选例与方法(α)的工序(II-1)的情况相同。
(作用效果)
本发明的真空隔热材料的制造方法中,通过存在于带粘合剂气相二氧化硅(A’)的表面的粘合剂的粘接力,即使以1×106Pa以下的压力进行加压成形,也可形成形状难以崩坏、具有充分的强度、处理容易的成形体,且在减压密封时充分抑制芯材飞散。为此,可以成形体的密度保持在低水平、成形体充分减压的状态将成形体密封在外袋内,其结果是,可得到介由芯材的热传导进一步减少、显示出更优良的隔热性的真空隔热材料。
此外,本发明的真空隔热材料的制造方法中,通过将带粘合剂气相二氧化硅(A’)和多孔质二氧化硅(B)作为芯材并用,与单独使用带粘合剂气相二氧化硅(A’)的情况下相比,可得到显示出更加优良的隔热性的真空隔热材料。这认为是由于多孔质二氧化硅(B)为多孔质,残存在其孔内的空气难以移动的缘故。
<真空隔热材料>
作为本发明的真空隔热材料,可例举不具有内袋的真空隔热材料、和具有内袋的真空隔热材料。
作为不具有内袋的真空隔热材料,例如可例举图2所例示的真空隔热材料1。真空隔热材料1具备具有气密性的外袋14、和由含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a的芯材所成形的成形体12。真空隔热材料1是将成形体12在外袋14内进行了减压密封而得的隔热材料。
作为不具有内袋的真空隔热材料的制造方法,优选上述的方法(α)。
真空隔热材料1的成形体12中的芯材10可以如图3所示,仅由带粘合剂气相二氧化硅(A’)10a构成,也可以如图4所示,由带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的混合物构成。
作为成形体12,从可得到更优良的隔热性的方面考虑,优选将含有带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的芯材10进行成形而得的成形体。
通过带粘合剂气相二氧化硅(A’)10a的粘合剂将芯材10相互接合,形成真空隔热材料1的成形体12。
如图3所示,在芯材10仅由带粘合剂气相二氧化硅(A’)10a构成的情况下,通过对气相二氧化硅(A)的表面赋予的粘合剂,将带粘合剂气相二氧化硅(A’)10a同士相互接合。如图4所示,在芯材10含有带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的情况下,带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b通过存在于带粘合剂气相二氧化硅(A’)10a的表面的粘合剂相互接合。
即使对多孔质二氧化硅(B)赋予粘合剂,也由于粘合剂被多孔质二氧化硅(B)吸收殆尽,而难以仅由多孔质二氧化硅(B)而相互接合形成成形体。如图4所示,通过在其间存在带粘合剂气相二氧化硅(A’)10a,多孔质二氧化硅(B)10b相互接合。
带粘合剂气相二氧化硅(A’)10a以及多孔质二氧化硅(B)10b的优选例与上述方法(α)所说明的优选例相同。
芯材10中的带粘合剂气相二氧化硅(A’)10a的含量、以及带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的质量比的优选例与上述方法(α)所说明的优选例相同。
真空隔热材料1的成形体12中的芯材10可含有上述添加材料(C)。
在芯材10含有添加材料(C)的情况下的添加材料(C)的含量、以及芯材10中的相对于带粘合剂气相二氧化硅(A’)10a和多孔质二氧化硅(B)10b的总计量的添加材料(C)的质量比C/(A’+B)的优选例与上述方法(α)所说明的优选例相同。
成形体12的密度优选0.1~0.5g/cm3,更优选0.1~0.4g/cm3,进一步优选0.15~0.3g/cm3。如果成形体12的密度在下限值以上,则成形体的处理容易、且减压密封时形成成形体的芯材难以飞散。如果成形体12的密度在上限值以下,则可容易地得到优良的隔热性。
真空隔热材料1中的外袋14内的真空度从可得到优良的隔热性、且真空隔热材料1的寿命变长的方面考虑,优选1×103Pa以下,更优选1×102Pa以下。外袋14内的真空度从容易进行外袋内的减压的方面考虑,优选1Pa以上。
作为具有内袋的真空隔热材料,例如可例举图6所例示的真空隔热材料2。
真空隔热材料2具备具有气密性的外袋14、具有通气性的内袋16、和由含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)10a的芯材所成形的成形体12。真空隔热材料2是将成形体12以收纳在内袋16内的状态在外袋14内进行了减压密封的隔热材料。
真空隔热材料2除了将成形体12以收纳在内袋16内的状态在外袋14内进行了减压密封之外,与真空隔热材料1相同。
作为具有内袋的真空隔热材料的制造方法,优选上述的方法(β)。
(作用效果)
本发明的真空隔热材料由于使用含有带粘合剂气相二氧化硅(A’)的芯材,因此可稳定得到优良的隔热性,寿命长。可得到这些效果的主要原因如下所示。
气相二氧化硅(A)与其他粉末材料相比,制成成形体时粒子之间的接触点少,具有热导率变低的性质。因此,通过将气相二氧化硅(A)用于芯材,可得到优良的隔热性。此外,含有带粘合剂气相二氧化硅(A’)的芯材体现了存在于带粘合剂气相二氧化硅(A’)的表面的粘合剂的粘接力。因此,即使以1×106Pa以下的压力进行加压成形,也不仅可形成形状难以崩坏、具有充分强度、容易处理的成形体,还可在减压密封时充分抑制芯材飞散。藉此,可以以成形体的密度保持在低水平、成形体充分减压的状态将成形体密封在外袋内。其结果是,介由芯材的热传导进一步减少,可稳定得到更优良的隔热性。
此外,本发明的真空隔热材料通过将带粘合剂气相二氧化硅(A’)和多孔质二氧化硅(B)作为芯材并用,与单独使用带粘合剂气相二氧化硅(A’)的情况相比,可得到更加优良的隔热性。
此外,相对于在使用玻璃纤维等纤维材料的真空隔热材料中为了得到充分的隔热性需要1Pa以下的高真空条件,本发明的真空隔热材料即使在1×103Pa左右的真空度下也可得到同等的隔热性。因此,如果将本发明的真空隔热材料中的真空度设为与使用纤维材料的真空隔热材料的真空度同等的1Pa以下,则即使经时劣化导致真空度下降,到1×103Pa为止隔热性也几乎不变化,寿命长。
此外,本发明的真空隔热材料与使用纤维材料的真空隔热材料相比,隔热材料的形状的自由度也高。
实施例
以下通过实施例对本发明进行详细说明,但本发明不受以下记载的限定。例1~7是实施例,例8是比较例。
[热导率测定]
各例所得的真空隔热材料的热导率通过热导率测定装置HC-110(英弘精机株式会社(英弘精機株式会社)制)进行测定。
[例1(方法(α))]
对气相二氧化硅(A)(商品名“AEROSIL 200”,一次平均粒径:12nm,比表面积:200m2/g,日本阿尔洛希尔株式会社制)40g喷涂粘合液后,通过混合机进行混合得到带粘合剂气相二氧化硅(A’);所述粘合液是将作为无机粘合剂的3号水玻璃6.9g用30g的离子交换水稀释而得。
将得到的带粘合剂气相二氧化硅(A’)75g投入纵125mm×横125mm的模具中,施加0.8×105Pa的压力成形为厚度13mm的板状后,在120℃下加热48小时形成成形体。由该成形体的尺寸和质量求出该成形体的密度,结果为0.3g/cm3。
将上述成形体收纳在由市售的真空包装用尼龙高分子袋“NHP-3245”构成的外袋内,通过将该外袋的内部减压至1×102Pa后进行密封来减压密封,得到真空隔热材料。
[例2(方法(α))]
对气相二氧化硅(A)(商品名“AEROSIL 300”,一次平均粒径:7nm,比表面积:300m2/g,日本阿尔洛希尔株式会社制)150g喷涂粘合液后,通过混合机进行混合得到带粘合剂气相二氧化硅(A’);所述粘合液是将作为无机粘合剂的3号水玻璃15.5g用75g的离子交换水稀释而得。
将得到的带粘合剂气相二氧化硅(A’)26g投入纵125mm×横125mm的模具中,施加4.3×105Pa的压力成形为厚度5mm的板状后,在120℃下加热48小时形成成形体。由该成形体的尺寸和质量求出该成形体的密度,结果为0.2g/cm3。
与例1相同,将上述成形体收纳在上述外袋内,通过将该外袋的内部减压至1×102Pa后进行密封来减压密封,得到真空隔热材料。
[例3(方法(β))]
将以与例1相同的方式得到的带粘合剂气相二氧化硅(A’)75g收纳在由聚对苯二甲酸乙二醇酯制的无纺布构成的内袋内,整理形状,通过冲压模具施加0.8×105Pa的压力进行成形后,在120℃下加热48小时,形成纵110mm×横110mm×厚度17mm的板状的成形体。由该成形体的尺寸和质量求出该成形体的密度,结果为0.3g/cm3。
除了使用收纳在上述内袋内的上述成形体之外,以与例1相同的方式得到真空隔热材料。即、将收纳在上述内袋内的上述成形体收纳在上述外袋内,通过将该外袋的内部减压至1×102Pa后进行密封来减压密封,得到真空隔热材料。
[例4(方法(β))]
除了将成形时的压力设为0.6×105Pa之外,以与例3相同的方式,以收纳在内袋内的状态形成成形体。由得到的成形体的尺寸和质量求出该成形体的密度,结果为0.25g/cm3。
除了使用收纳在内袋内的上述成形体之外,以与例1相同的方式得到真空隔热材料。
[例5(方法(β))]
对例1所使用的气相二氧化硅(A)30g喷涂粘合液,得到带粘合剂气相二氧化硅(A’);所述粘合液是将作为无机粘合剂的3号水玻璃6.9g用30g的离子交换水稀释而得。之后,利用混合机混合多孔质二氧化硅(B)(商品名“sunsphere H-53”,平均粒径:5μm,气孔率:80%,比表面积:700m2/g,AGC硅技术株式会社(AGCエスアイテック株式会社)制)30g,得到由二氧化硅的混合粉末构成的芯材(该混合粉末构成的芯材中的气相二氧化硅(A)和多孔质二氧化硅(B)的质量比A/B为50/50。)。
使用上述混合粉末,以与例3相同的方式得到收纳在内袋内的板状的成形体。
除了使用所述收纳在内袋内的成形体之外,以与例1相同的方式得到真空隔热材料。
[例6(方法(β))]
使用混合了对例1所使用的气相二氧化硅(A)30g喷涂粘合液而得的带粘合剂气相二氧化硅(A’)、和例5所使用的多孔质二氧化硅(B)13g的混合粉末(该混合粉末构成的芯材中的气相二氧化硅(A)和多孔质二氧化硅(B)的质量比A/B为70/30。),以与例2相同的方式,得到收纳在内袋内的板状的成形体;所述粘合液是将作为无机粘合剂的3号水玻璃
6.9g用30g的离子交换水稀释而得。
除了使用所述收纳在内袋内的成形体之外,以与例1相同的方式得到真空隔热材料。
[例7(方法(β))]
使用混合了对例1所使用的气相二氧化硅(A)20g喷涂粘合液而得的带粘合剂气相二氧化硅(A’)、和例5所使用的多孔质二氧化硅(B)30g的混合粉末(该混合粉末构成的芯材中的气相二氧化硅(A)和多孔质二氧化硅(B)的质量比A/B为40/60。),以与例3相同的方式,得到收纳在内袋内的板状的成形体;所述粘合液是将作为无机粘合剂的3号水玻璃6.9g用30g的离子交换水稀释而得。
除了使用所述收纳在内袋内的成形体之外,以与例1相同的方式得到真空隔热材料。
[例8(方法(β))]
除了使用例5所使用的多孔质二氧化硅(B)40g,不使用带粘合剂气相二氧化硅(A’),并且使用市售的纸材(复印用纸)制作的内袋来代替由无纺布构成的内袋以外,以与例3相同的方式制作成形体。另外,使用由纸材构成的内袋的理由是:由于未使用带粘合剂气相二氧化硅(A’),如果将多孔质二氧化硅(B)收纳在与例3相同的采用无纺布的内袋内,则在减压密封时粉末穿过无纺布而飞散。
将收纳在上述内袋内的成形体收纳在由市售的阻气膜(真空包装用铝规格袋ALH-8)构成的外袋内,通过将该外袋的内部减压至1×102Pa后进行密封来减压密封,得到真空隔热材料。
各例所得的真空隔热材料的热导率的测定结果示于表1。
[表1]
如表1所示,使用了带粘合剂气相二氧化硅(A’)的例1~7的真空隔热材料的热导率低,具有优良的隔热性。例1的不使用内袋的情况和例2的使用内袋的情况下可得到几乎同等的隔热性。此外,成形时的压力低、成形体中的带粘合剂气相二氧化硅(A’)的密度低的例4的真空隔热材料与例3的真空隔热材料相比,热导率更低,具有优良的隔热性。此外,并用带粘合剂气相二氧化硅(A’)和多孔质二氧化硅(B)的例5~例7的真空隔热材料与例3相比具有更优良的隔热性。
另一方面,仅使用多孔质二氧化硅(B)的例8不能得到充分的隔热性。
产业上利用的可能性
如果采用本发明的真空隔热材料的制造方法,则可制造隔热材料的形状的自由度高、可稳定地得到优良的隔热性、长寿命的真空隔热材料。这样的真空隔热材料可用作为住宅用、大楼用、汽车用等的隔热材料。
这里引用2012年8月23日提出申请的日本专利申请2012-184412号的说明书、权利要求书、附图和摘要的全部内容作为本发明的说明书的揭示。
符号说明
1,2···真空隔热材料,10···芯材,12···成形体,14···外袋,16···内袋。
Claims (8)
1.一种真空隔热材料的制造方法,其特征在于,具有下述工序(I)以及工序(II):
(I)对含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)的芯材在1×106Pa以下的压力下进行加压,形成为成形体的工序;
(II)将所述成形体在具有气密性的外袋内进行减压密封的工序。
2.如权利要求1所述的真空隔热材料的制造方法,其特征在于,在所述工序(I)中将所述芯材以收纳在具有通气性的内袋内的状态进行加压,形成所述成形体;在所述工序(II)中将所述成形体以收纳在所述内袋内的状态减压密封在所述外袋内。
3.如权利要求1或2所述的真空隔热材料的制造方法,其特征在于,所述芯材含有多孔质二氧化硅(B)。
4.如权利要求3所述的真空隔热材料的制造方法,其特征在于,所述气相二氧化硅(A)和所述多孔质二氧化硅(B)的质量比A/B为20/80~90/10。
5.如权利要求1~4中任一项所述的真空隔热材料的制造方法,其特征在于,所述芯材含有选自石墨、炭黑、氧化钛以及钛酸钾的至少1种添加材料(C)。
6.如权利要求1~5中任一项所述的真空隔热材料的制造方法,其特征在于,所述粘合剂为无机粘合剂。
7.一种真空隔热材料,其特征在于,包括:
具有气密性的外袋,和
由含有气相二氧化硅(A)的表面上赋予了粘合剂的带粘合剂气相二氧化硅(A’)的芯材所成形的成形体;
所述成形体被减压密封在所述外袋内。
8.如权利要求7所述的真空隔热材料,其特征在于,还具备具有通气性的内袋,所述成形体以收纳在所述内袋内的状态被减压密封在所述外袋内。
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US20150147514A1 (en) | 2015-05-28 |
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