CN100387894C - 真空隔热材料及其制造方法 - Google Patents

真空隔热材料及其制造方法 Download PDF

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CN100387894C
CN100387894C CNB2004100316320A CN200410031632A CN100387894C CN 100387894 C CN100387894 C CN 100387894C CN B2004100316320 A CNB2004100316320 A CN B2004100316320A CN 200410031632 A CN200410031632 A CN 200410031632A CN 100387894 C CN100387894 C CN 100387894C
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vacuum heat
heat insulation
insulation material
inorfil
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CN1536259A (zh
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林圣人
佐藤英人
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Asahi Fiber Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • E04B1/80—Heat insulating elements slab-shaped
    • E04B1/803—Heat insulating elements slab-shaped with vacuum spaces included in the slab
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    • B32B3/04—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • B32B2509/10—Refrigerators or refrigerating equipment
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Abstract

本发明的目的是提供一种真空隔热材料及其制造方法，所述真空隔热材料是以无机纤维作芯材的真空隔热材料，隔热性能高(热传导率低)，其隔热性能可长期维持，且表面没有大的凸凹等缺陷，而且制造周期短，成本方面有利。本发明的真空隔热材料是在将芯材(1)和气体吸附剂(2)收纳在由阻气性薄膜构成的袋体(3)中，对其内部减压、密封形成的真空隔热材料中，前述芯材(1)是①对纤维的平均直径为3～5μm的无机纤维，涂布相对于该纤维0.5～1.5重量%的粘合剂(B)，经过热压形成的成形体，或②将2枚或其以上该成形体层压复合而成的成形体。

Description

真空隔热材料及其制造方法
技术领域
本发明涉及芯材使用无机纤维的真空隔热材料及其制造方法。
背景技术
作为将芯材收纳在由阻气性薄膜构成的袋体中对其内部减压、密封的真空隔热材料的芯材，已知以往以来是使用聚氨酯泡沫、无机纤维、无机粉末等材料，但其中即便使用无机纤维作芯材时，也能达到0.0025W/mk左右的低热传导率(高隔热性能)。
但是，在对无机纤维不做前处理原样插入袋体进行减压脱气的场合，存在作业性能差、必须提高密度以保持真空隔热材料表面的平滑性的问题。另外，无机纤维的一部分容易附在袋体开口部的密封封口部，这种场合，还存在减压密封后的密封不充分，造成制品无法达到规定性能的问题。
因此，为了解决上述问题，在收入袋体之前，需要将无机纤维加固成片状，但仅使用有机粘合剂制成片状成形芯材时，会随时间变化从芯材产生逸出气体，产生隔热性能随着时间流逝而恶化的另外的问题。另外，虽然可以使用无机粘合剂代替有机粘合剂制成片状成形芯材，但这会造成失去弹性，减压排气时发生裂痕，或由无机粘合剂形成膜，减压排气花费时间等问题。
若用具体事例说明上述问题点的话，在专利文献1中，记载有真空隔热壁的制造方法，即，将由含有有机粘合剂、且被压缩固化到与隔热壁的隔热空间大致相等厚度的无机纤维构成的隔热垫，插入隔热空间内后，在空气存在下加热直到有机粘合剂的分解温度，使有机粘合剂成分气化清除，然后对隔热空间内进行真空排气的法。另外，在专利文献2中记载有，将多张酸性抄浆纸与无机质纤维层压复合，无机质纤维相互间通过由这些纤维洗提的成分在各交点粘结的真空隔热材料。再有，在专利文献3中记载有，使无机质纤维集棉，经过酸性水溶液附着处理后，使其脱水、干燥，使无机质纤维的洗提成分聚集在无机质纤维的交点使其固化，无机质纤维相互之间通过由这些纤维洗提的成分在各交点粘结的真空隔热材料。其次，在专利文献4中记载有，由在微细无机纤维构成的无机纤维集合体的至少一面层压了增强材料的芯材，和具有阻气性外被覆材料构成的真空隔热材料，在上述无机纤维集合体中不含有为使纤维材料固形化的粘结剂的真空隔热材料。
但是，如专利文献1那样，即使进行了有机粘合剂的热分解，也难以全部将其清除，而且还有非常费时和成本方面的问题。另外，如专利文献2、3那样，进行酸性处理，必须要有包括酸性处理后的中和、干燥处理，需要大型的设备，进而，由于熔融部分的热传导，就有可能降低隔热性能。其次，如专利文献4那样使用增强材料时，由于无机纤维集合体和增强材料的强度不同发生翘曲，进而严重影响增强材料的隔热性能，就可能大大损害无机纤维单体的隔热性能。
【专利文献1】
特开平5-87292号公报
【专利文献2】
特开平7-139691号公报
【专利文献3】
特开平7-167376号公报
【专利文献4】
特开2002-310384号公报
发明内容
本发明鉴于在以往芯材中使用无机纤维的真空隔热材料等存在如上述问题点，以此为课题，对以无机纤维为芯材的真空隔热材料，提供一种隔热性能高(热传导率低)，且能长期维持其隔热性能，表面没有大凸凹等缺陷，而且制造周期短，在成本方面有利的真空隔热材料及其制造方法。
以解决上述课题为目的而实施的本发明的真空隔热材料的构成的特征是，在将芯材和气体吸附剂收纳在由阻气性薄膜构成的袋体中、并对其内部进行减压、密封的真空隔热材料中，前述芯材是对平均纤维径3～5μm的无机纤维，涂布相对于该纤维为0.5～1.5重量％的粘合剂，进行热压形成的成形体，或是将2张或其以上该成形体进行层压而成的成形体。
本发明在上述构成中，无机纤维可以使用选自玻璃纤维、陶瓷纤维、石毛、硅酸铝绒的任一种或两种或其以上，另外，粘合剂可以使用选自酚醛树脂、NBR橡胶改性高邻酚醛树脂、NBR橡胶改性酚醛树脂、蜜胺树脂、环氧树脂、NBR、丁腈橡胶、丙烯酸类橡胶、硅酸铝等的任一种或两种或其以上。
另外，以解决上述课题为目的而实施的本发明的真空隔热材料的制造方法的构成为，其特征在于，将对平均纤维径3～5μm的无机纤维涂布相对于该纤维为0.5～1.5重量％的粘合剂后边加热边加压成形的芯材、或将2张或其以上该芯材层压而成的芯材，与气体吸附剂一起收纳在由阻气性薄膜构成的袋体内，对其内部减压后，密封开口部。另外，开口部还可以实施双重热封来进行密封。
本发明者们为了完成上述目的，经过锐意研究的结果得知，通过将极微量的粘合剂(树脂)涂布于无机纤维，经过热压而成形的产品作为芯材，或将2枚或其以上该成形体层压的产物作为芯材，可解决上述问题，并完成了本发明。
本发明，如以上所述，本发明的真空隔热材料，由于以对无机纤维涂布极微量的粘合剂，并经过热压成形的产物作为芯材，所以能得到隔热性能高、其隔热性能可长期维持、且表面没有大的凸凹等缺陷的效果。而且制造周期短，制造成本也能降低。
另外，本发明的真空隔热材料，由于如上所述隔热性能高(热传导率低)，所以可取得可广泛使用于笔记本型电脑或电烤箱、电热水器、冷冻·冷藏机器、冷冻库、冷冻车、冷冻贮存器、冷冻箱等各种用途的效果。
附图说明
图1是本发明一例的真空隔热材料的剖面图。
图2是本发明另一例的真空隔热材料的剖面图。
图3是按时间顺序表示图1的真空隔热材料的制造方法一例的概念图。
符号的说明
1芯材
2气体吸附剂
3袋体
3a开口部
S无机纤维
N喷嘴
B粘合剂
具体实施方式
以下，根据附图说明本发明的实施形态例。图1是本发明一例的真空隔热材料的剖面图，图2是本发明另一例的真空隔热材料的剖面图，图3是按时间顺序表示图1的隔热材料的制造方法一例的概念图。
本发明的真空隔热材料，如图1所示，将通过对无机纤维实施规定成形而成形的芯材1，和气体吸附剂2一起收纳在由阻气性薄膜构成的袋体3中，对其内部进行减压，密封开口部3a而成的材料，或者如图2所示，将由2枚通过对无机纤维实施规定成形而成形的成形体1′进行层压复合构成的芯材11，和气体吸附剂2一起收纳在由阻气性薄膜构成的袋体3中，对其内部减压，密封开口部3a而成的材料。另外，也可将3枚或其以上的成形体1′层压而成的成形体作为芯材。在这里，作为无机纤维，可列举：玻璃纤维、陶瓷纤维、石毛、硅酸铝绒等，这些既可以单独，也可以适当组合不同种类的物质使用。
对于无机纤维，可以使用涂布树脂(粘合剂B)成熟成形的物质。作为这种粘合剂B的树脂，可列举：酚醛树脂、NBR橡胶改性高正酚树脂、NBR橡胶改性酚醛树脂、蜜胺树脂、环氧树脂、NBR、丁腈橡胶、丙烯酸类橡胶、硅酸铝等，优选酚醛树脂，更优选未添加尿素的酚醛树脂单体型。
上述粘合剂B的涂布量，相对于无机纤维为0.5～1.5重量％，优选0.75～1.25重量％。如果在该涂布量范围，便能降低加压成形时常常变硬的无机纤维表面层的树脂量，减少成为减压费时原因的固体层，可减薄规定量的无机纤维的厚度，容易操作，可达到本发明的目的。
作为压缩后的无机纤维(芯材1)的密度，优选为150kg/m3～250kg/m3。如果在该密度范围内，则可保持高隔热性能的状态。另外，作为芯材1的成形厚度，设定值为10～50mm，优选为10～15mm，由此复原，优选厚度为30～50mm。如在该范围内，则操作性没有问题。
其次，作为构成袋体3的阻气性薄膜，可使用金属箔和塑料薄膜的层压复合薄膜(金属箔薄膜)、或层压了代替金属箔的蒸镀膜和塑料薄膜的复合薄膜(蒸镀膜薄膜)等。
作为金属箔，可使用铝箔或不锈钢箔等金属箔；蒸镀膜薄膜的蒸镀层可使用铝、不锈钢等。作为塑料薄膜，可使用聚对苯二甲酸乙二酯、尼龙、低密度聚乙烯、高密度聚乙烯、聚丙烯等。
作为阻气性薄膜的一例，可列举：聚对苯二甲酸乙二酯薄膜/尼龙薄膜/铝箔/聚乙烯薄膜的四层结构的层压复合薄膜，或聚对苯二甲酸乙二酯薄膜/铝箔/高密度聚乙烯薄膜的3层结构的层压复合薄膜。
在使这些薄膜形成袋体3时，聚乙烯薄膜要构成为袋体内侧。用蒸镀膜代替上述层压复合薄膜的铝箔的蒸镀膜薄膜，当然也可使用。而且，也可以使用以热熔性粘合剂在蒸镀膜薄膜表面粘接了金属箔薄膜的复合薄膜。
作为和芯材1一起收纳在袋体3中的物质，还有气体吸附剂2。气体吸附剂2是为了吸收随时间变化从芯材1产生的逸出气体的吸附剂。具体说来，可使用氧化钙、活性碳、硅胶、分子筛、沸石等，这些可单独使用，或者使用2种或其以上的组合物。
以下根据图3，就本发明的真空隔热材料的制造方法进行说明。首先，向芯材1成形前的无机纤维S涂布粘合剂B。作为涂布方法，有在无机纤维制造时从周围通过喷雾涂布的方法、含浸法等。其中优选喷雾涂布。N是喷雾的喷嘴，从该喷嘴N向无机纤维S表面均匀涂布粘合剂B。涂布量，相对于无机纤维S为0.5～1.5重量％，优选为0.75～1.25重量％。涂布时，粘合剂B要用溶剂稀释使用。作为稀释溶剂，可适当使用水、稀释剂等。
热压机(图中未示)可使用通常加压作业所用的一般用品。用该压机，以压力10～10000g/cm2、温度100～300℃的条件，按设定值厚度10～50mm，对经过上述处理的无机纤维S进行成形。成形时间，只要无机纤维复原后成为厚度30～50mm、且操作便利，可任意进行，但从成形性、作业性的平衡的观点，优选1～5分钟。
将如上述成形的芯材1，与气体吸附剂2一起收纳在由阻气性薄膜构成的袋体3中，对其内部减压后，密封开口部3a，制造真空隔热材料。另外，开口部3a的密封，一般用热熔密封，但在本发明中，考虑到袋体的密封度，优选进行双重热封。L1，L2表示在开口部3a实施的双重热封线。在即使单重也能将袋体充分密封的场合，单重热封也可以。
如图2所示，在芯材11为成形体1′、1′的层压复合型的场合，通过热压机对形成成形体1′的无机纤维S的压力，在规定温度条件下的设定值厚度，要综合制造的真空隔热材料的使用条件，适当设定。
实施例
以下是图1所示的以单张成形体做芯材的本发明的真空隔热材料，无机纤维使用玻璃纤维、粘合剂使用不添加尿素的酚醛树脂单体、袋体的阻气性薄膜使用铝箔和塑料薄膜的复合薄膜制造的真空隔热材料，进行了有关以下(1)～(5)点的性能试验。
(1)热传导率
改变对构成芯材的无机纤维涂布的粘合剂的涂布量，制造真空隔热材料，进行了这些材料的高温老化试验。真空隔热材料的规格是10×300×300(mm)。热传导率如下述表1所示。
【表1】
真空隔热材料的高温老化试验
Figure C20041003163200091
老化温度：70℃
气体吸附剂：COMBO-E 1个(サエス·ゲツタ一ズ制)
从上述表1明显可知，在本发明的粘合剂涂布量范围(0.5～1.5wt％)内的涂布量(0.5，1.0，1.5wt％)的真空隔热材料，显示出与完全不涂粘合剂的真空隔热材料相同程度的低热传导率，并能经过长时期维持该低热传导率。与此相反，粘合剂涂布量为3.0，10.0wt％的真空隔热材料，热传导率高，特别是粘合剂涂布量为10.0wt％的真空隔热材料，长时期使用时，其热传导率显著劣化。
另外，在本发明中，由于对以前成形玻璃纤维通常使用的酚醛树脂粘合剂，从添加尿素型改变为不添加的酚醛树脂单体型，可以说减少了多余的逸出气体的发生，降低了热传导率。
顺便说明，本发明由于减少了粘合剂的涂布量，即使加压成形，无机纤维的表面层也没有变硬。另外，在抽真空时，可以减少成为其阻力的固体层。
以下，就上述真空隔热材料，包括其制造阶段，进行了下述评价。
(2)表面性
◎；平整。
○；略微有凸凹。
×；凸凹严重。
(3)芯材的操作性
◎；可用单手容易操作。
○；用单手或两手操作。
×；需用夹具操作。
(4)放入包装袋的难易度
◎；容易放入包装袋。
○；虽难放入包装袋，但不需夹具。
×；使用夹具也难放入。
(5)热传导率(隔热性能)
◎；不足0.0023w/m·K
○；0.0023或其以上，不足0.0028。
△；0.0028或其以上，不足0.0033。
×；0.0033或其以上。
下述表2表示评价结果
【表2】
Figure C20041003163200101
从上述表2明显可知，在本发明粘合剂涂布量范围(0.5～15wt％)内的涂布量(0.5，1.0，1.5wt％)的真空隔热材料，在上述的点(2)～(5)中，隔热性能(热传导率)与完全不涂布粘合剂的真空隔热材料大致相同，在真空隔热材料的表面性、芯材的操作性、放入包装袋的难易程度等方面具有优势。而且，本发明的真空隔热材料，对于使用粘合剂涂布量3.0，10.0wt％的真空隔热材料和连通PUF(聚氨酯泡沫)，表面性、芯材的操作性、放入包装袋的难易度相同，在隔热性能方面有利。

Claims (5)

1.一种真空隔热材料，其特征在于，在将芯材(1或11)和气体吸附剂(2)收纳在由阻气性薄膜制成的袋体(3)内，对该袋体(3)内部减压、密封而形成的真空隔热材料中，前述芯材是
①芯材(1)，即对纤维的平均直径为3～5μm的无机纤维，涂布相对于该纤维0.5～1.5重量％的有机粘合剂，经过热压形成的成形体，或者
②芯材(11)，即将2枚或其以上的上述成形体层压复合而成的成形体，
该芯材(1或11)被收纳在上述袋体(3)内。
2.如权利要求1所述的真空隔热材料，无机纤维是选自玻璃纤维、陶瓷纤维、石毛、硅酸铝绒的任一种或两种或其以上。
3.如权利要求1或2所述的真空隔热材料，有机粘合剂是选自酚醛树脂、NBR改性高正酚醛树脂、NBR改性酚醛树脂、蜜胺树脂、环氧树脂、NBR、丙烯酸类橡胶的任一种或两种或其以上。
4.一种真空隔热材料的制造方法，其特征在于，将对纤维的平均直径为3～5μm的无机纤维，涂布相对于该纤维0.5～1.5重量％的有机粘合剂(B)，边加热边加压成形的芯材(1)，或将两张或其以上该芯材层压复合而成的芯材(11)，与气体吸附剂(2)一起收纳在由阻气性薄膜构成的袋体(3)内，对其内部减压后，密封开口部(3a)。
5.如权利要求4的真空隔热材料的制造方法，开口部(3a)的密封实施双重热封。
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