CN104411897A - 遮热材料 - Google Patents

遮热材料 Download PDF

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CN104411897A
CN104411897A CN201380034111.8A CN201380034111A CN104411897A CN 104411897 A CN104411897 A CN 104411897A CN 201380034111 A CN201380034111 A CN 201380034111A CN 104411897 A CN104411897 A CN 104411897A
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magnesium hydroxide
resin
hot material
aspect ratio
plate crystal
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中村司
真锅等
工藤大辅
宫田茂男
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Kyowa Chemical Industry Co Ltd
Sea Water Chemical Institute Inc
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Sea Water Chemical Institute Inc
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Abstract

本发明的目的在于提供对为温度上升原因的红外线的反射能力优异,且对可见光透过性优异的遮热材料。本发明的遮热材料以结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下的高纵横比板状结晶氢氧化镁作为有效成分。

Description

遮热材料
技术领域
本发明涉及红外线的反射能力优异,且对可见光的透过性优异的遮热材料。
背景技术
能源价格有日渐高涨的倾向,省能源在广范围领域中已成为共通的课题。利用在屋顶涂布遮热涂料、或在窗玻璃上粘贴加入有遮热材料的树脂薄膜,从而抑制因夏季的太阳光而造成的室内温度上升的方法正急遽拓展。此外,农业领域中,为了使可见光透过,但防止温室内过度的温度上升,从而良好地保持农作物的育成,使用遮热薄膜或薄片。
此类遮热产品所使用的遮热材料为铝或银的金属薄片、氧化钛、氧化锌、珍珠颜料等。这类遮热材料会将为温度上升原因的红外线反射,在夏季时防止室内温度上升,在冬季时防止室内温度下降。但是,这类遮热材料具有透明性差、成形品表面粗糙、容易着色等缺点。因此,若粘贴于窗户便会导致视野变差。此外,农业用温室内的植物生育由于植物所需要的可见光的透过减少而有所阻碍。此外,有不易制作透明、无色的涂料等问题。
发明内容
本发明的目的在于提供:对为温度上升原因的红外线的反射能力优异,且对可见光透过性优异的遮热材料。此外,本发明的目的在于提供:含有该遮热材料的树脂组合物及成形品。
本发明者发现高纵横比板状结晶氢氧化镁的红外线反射能力优异,且对可见光的透过性优异,遂完成本发明。
即,本发明的遮热材料以结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下的板状结晶氢氧化镁作为有效成分。此外,本发明的树脂组合物含有100重量份的树脂、及1~50重量份的上述遮热材料。此外,本发明的成形品通过将上述树脂组合物成形而得到。此外,本发明的将板状结晶氢氧化镁作为红外线遮热材料使用的方法中,所述板状结晶氢氧化镁的结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下。
具体实施方式
<遮热材料>
(高纵横比板状结晶氢氧化镁)
本发明的遮热材料以结晶的横宽较大且结晶的厚度较薄的高纵横比板状结晶氢氧化镁作为有效成分。高纵横比板状结晶氢氧化镁的结晶横宽为1μm以上、优选为2μm以上、更优选为3μm以上。此外,结晶的厚度为0.2μm以下、优选为0.1μm以下、更优选为0.05μm以下。
上述板状结晶氢氧化镁在树脂中的取向性优异、光反射率高。结果,能将为温度上升原因的红外线良好地反射,从而使其透过率降低。纵横比定义为结晶的横宽/厚度之比。
高纵横比板状结晶氢氧化镁的结晶的横宽越大,则取向性(成形面与结晶的横向呈平行)越好,越接近镜面反射,遮热效果提升。另一方面,结晶的厚度越薄,则越提升可见光的透过率,透明性良好。现有的氢氧化镁结晶的横宽约为1μm以下,且厚度约为0.5μm以上。因此,结晶的取向性不良且厚度较厚,故透明性差、遮热效果小。
为提升与树脂的相溶性、分散性,高纵横比板状结晶氢氧化镁可经表面处理后使用。作为表面处理剂使用:高级脂肪酸或其碱金属盐、磷酸酯、阴离子类表面活性剂;硅烷、铝、钛酸酯等偶联剂等等。表面处理可通过相对于高纵横比板状结晶氢氧化镁的重量,使0.1~10重量%的表面处理剂溶解于水或醇等有机溶剂中,在水等液状介质中施行搅拌下添加高纵横比板状结晶氢氧化镁的湿式法实施。或者,亦可通过将板状结晶氢氧化镁粉末利用诸如亨舍尔搅拌机等搅拌机施行搅拌下,添加上述表面处理剂的所谓干式法实施。
为提升其体积比重从而使其与树脂进行混练时的加工性良好,板状结晶氢氧化镁亦可经成形为例如直径0.5~5mm的粒状后使用。成形可使用挤出造粒、滚动造粒等以往公知手段实施。
(高纵横比板状结晶氢氧化镁的制造)
在微结晶氢氧化镁与单羧酸/或其金属盐的共存下,于100℃以上、优选150~250℃施行搅拌下,优选施行2~10小时的水热处理便可制造高纵横比板状结晶氢氧化镁。
亦可在利用于水溶性镁盐水溶液中添加当量以上的NaOH等碱,优选在0~40℃进行反应的共沉淀法制造氢氧化镁的阶段,在共沉淀反应前将单羧酸添加至镁的卤化物、硝酸盐、单羧酸盐等水溶性镁盐,利用氢氧化钠等碱进行共沉淀后,施行水热处理。单羧酸相对于氢氧化镁,依摩尔比添加优选0.01以上、更优选0.1~1.0。
作为水溶性镁盐,优选可列举如:氯化镁、硝酸镁、醋酸镁。作为单羧酸优选可列举如:醋酸、丙酸、丁酸、羟基乙酸、乳酸。
<树脂组合物>
再者,本发明的树脂组合物含有100重量份的树脂及1~50重量份的上述遮热材料。
作为树脂,优选为从热塑性树脂、热固性树脂及橡胶所构成组中选择的至少一种树脂。作为树脂,可例示:聚乙烯,乙烯与α-烯烃的共聚物,乙烯与醋酸乙烯酯、丙烯酸乙酯或丙烯酸甲酯的共聚物,聚丙烯,丙烯与其他α-烯烃的共聚物,聚丁烯-1,聚4-甲基戊烯-1,聚苯乙烯,苯乙烯与丙烯腈、乙烯-丙烯-二烯橡胶或丁二烯的共聚物,聚醋酸乙烯酯,聚乙烯醇,聚丙烯酸酯,聚甲基丙烯酸酯,聚氨酯,聚酯,聚醚,聚酰胺,ABS,聚碳酸酯,聚苯硫醚等热塑性树脂;酚树脂、三聚氰胺树脂、环氧树脂、不饱和聚酯树脂、醇酸树脂等热固性树脂;EPDM、SBR、NBR、乙烯与其他α-烯烃(例如丙烯、辛烯等)的共聚橡胶、丁基橡胶、氯丁橡胶、异戊二烯橡胶、氯磺化橡胶、硅橡胶、氟橡胶、氯化丁基橡胶、溴化丁基橡胶、表氯醇橡胶、氯化聚乙烯橡胶等。
作为树脂组合物可列举遮热涂料。在这种情况中,作为树脂,可含有例如:酚树脂涂料、醇酸树脂涂料、氨基醇酸树脂涂料、氯乙烯树脂涂料、丙烯酸类树脂涂料、环氧树脂涂料、硅树脂涂料、聚氨酯树脂涂料、氟树脂涂料、油性涂料等。
相对于100重量份的树脂,遮热材料在树脂组合物中的含量为0.1~100重量份、优选1~50重量份。
在将树脂与上述遮热材料进行混合后,利用以往公知的混练手段便可制造树脂组合物。例如,将树脂与遮热材料利用双螺杆挤出机施行加热熔融混合后,予以颗粒化便可制造。
<成形品>
将树脂组合物利用挤出成形、射出成形、真空成形、充气成形、狭缝成形等惯用成形机、手段,予以成形为薄膜、薄片、厚壁成形品等便可获得成形品。作为成形品,可列举:粘贴于窗户玻璃上的遮热薄膜、屋顶等处所使用的遮热涂料、用以调节温室内温度的农业用遮热薄膜或薄片、户外使用的树脂成形品等。
<作为遮热材料使用的方法>
本发明包含将结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下的高纵横比板状结晶氢氧化镁用作红外线遮热材料的方法。
实施例
以下,利用实施例说明本发明,但是本发明并不仅局限于这类实施例。
实施例1
(氢氧化镁的调制)
在一级试剂氯化镁与醋酸钠的混合水溶液(Mg=2摩尔/L、醋酸钠=1.2摩尔/L、30℃)20L中,于搅拌下,添加8摩尔/L的一级试剂氢氧化钠水溶液(30℃)8L,使其进行共沉淀反应。将该反应物装入容量50L高压釜中,于170℃施行8小时水热处理。取出水热处理物,经减压过滤、水洗后,利用搅拌机使滤饼分散于水中。加热至约80℃后,于搅拌下添加将40g硬脂酸(纯度90%)利用氢氧化钠中和并加热溶解而成的水溶液1L,施行表面处理。然后,将施行加压过滤、水洗所获得的滤饼利用造粒用双螺杆挤出机造粒成直径约2mm,利用烘箱于约120℃干燥。
采取表面处理前的一部分试料,施行利用X射线衍射、SEM、及液态氮吸附法的BET比表面积测定。
X射线衍射的结果,鉴定为氢氧化镁。SEM测定的结果,各个结晶为接近六角形的板状结晶外形,厚度为0.07μm、横宽为3.2μm。因此,纵横比为50。BET比表面积为12m2/g。
(薄片的成形)
相对于LLDPE(直链低密度聚乙烯)100重量份,将造粒物10重量份、抗氧化剂(イルガノックス1010)0.1重量份进行混合后,使用布拉本德(Brabender)施行熔融混练。将混练物使用压制成形机成形为厚度1mm、长134mm、宽99mm的薄片。针对该薄片使用分光光度计,测定可见光(380~780nm)透过率与近红外线(780~2500nm)反射率。结果示于表1。
将该薄片装设于仅1方向设有40mm见方的窗口且经利用绝热剂覆盖的纸制箱体的窗部分,距离10.5cm照射红外线灯(185W),测定箱体内的温度及薄片温度。结果示于表1。结果可知,调配有本发明遮热材料的树脂薄片透明性良好(因为可见光线透过率高),且可抑制室内温度上升。
实施例2
(氢氧化镁的调制)
在实施例1中,依高纵横比板状结晶氢氧化镁的制造条件,除使用丙酸钠1.6摩尔代替醋酸钠之外,其余均与实施例1同样地实施而制造氢氧化镁。表面处理前的该物质经X射线衍射的结果鉴定为氢氧化镁。SEM测定的结果,各个结晶为接近六角形的板状结晶外形,厚度为0.05μm、横宽为4.5μm。因此,纵横比为90。BET比表面积为8.2m2/g。
(薄片的成形)
将所获得的造粒物依照与实施例1同样的方式成形为薄片并施行遮热试验。结果示于表1。可知实施例2亦呈现与实施例1同样的倾向。
比较例1
将市售氢氧化镁(厚度0.3μm、横宽0.9μm、BET比表面积6m2/g、纵横比3)依照与实施例1同样的方式利用硬脂酸钠施行表面处理后,与实施例1同样地施行遮热试验,结果示于表1。由表1可知,市售氢氧化镁的透明性差,近红外线反射率、遮热性均劣于本发明的遮热材料。
比较例2
使用在横宽约15μm云母的表面上形成有氧化钛的珍珠颜料类市售遮热材料,依照与实施例1同样的方式制成LLDPE的薄片。其评估结果示于表1。由表1可知,市售遮热材料的透明性差。
表1
(发明效果)
本发明的遮热材料红外线反射能力优异,且可见光透过性优异。此外,本发明的树脂组合物及成形品具有呈现透明性优异、表面光泽优异的高级感的外观。
(产业上的可利用性)
本发明的遮热材料可应用于以遮热为目的的任何用途。可列举如:粘贴于住家、汽车等的窗玻璃上的遮热薄膜、屋顶等处所使用的遮热涂料、用以调节温室内温度的农业用遮热薄膜或薄片、户外使用的家具等树脂成形品等等。

Claims (8)

1.一种遮热材料,其以结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下的高纵横比板状结晶氢氧化镁作为有效成分。
2.根据权利要求1所述的遮热材料,其中,高纵横比板状结晶氢氧化镁的横宽为2μm以上,且厚度为0.1μm以下。
3.根据权利要求1所述的遮热材料,其中,高纵横比板状结晶氢氧化镁的横宽为3μm以上,且厚度为0.1μm以下。
4.根据权利要求1所述的遮热材料,其中,高纵横比板状结晶氢氧化镁的横宽为3μm以上,且厚度为0.05μm以下。
5.一种树脂组合物,其含有100重量份的树脂、及1~50重量份的根据权利要求1所述的遮热材料。
6.一种成形品,其通过将根据权利要求1所述的树脂组合物成形而得到。
7.根据权利要求6所述的成形品,其为薄膜。
8.一种将高纵横比板状结晶氢氧化镁作为红外线遮热材料使用的方法,该高纵横比板状结晶氢氧化镁的结晶的横宽为1μm以上,且结晶的厚度为0.2μm以下。
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