CN114981509A - 耐火隔热板及耐火隔热结构体 - Google Patents
耐火隔热板及耐火隔热结构体 Download PDFInfo
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- CN114981509A CN114981509A CN202180009020.3A CN202180009020A CN114981509A CN 114981509 A CN114981509 A CN 114981509A CN 202180009020 A CN202180009020 A CN 202180009020A CN 114981509 A CN114981509 A CN 114981509A
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- heat
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- refractory
- heat insulating
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Images
Classifications
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- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
- E04B1/941—Building elements specially adapted therefor
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- B32B5/02—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 structural features of a fibrous or filamentary layer
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Abstract
耐火隔热板,其由在具有连续孔隙的发泡树脂成型体中填充浆料而构成,填充的浆料在填充后通过水合反应生成含有50kg/m3以上的结晶水的水合物,用选自由玄武岩纤维及陶瓷纤维组成的组中的一种以上的无机纤维对表面的至少一部分进行增强。
Description
技术领域
本发明涉及用于构筑建筑物的耐火隔热结构的耐火隔热板及耐火隔热结构体。
背景技术
建筑物中使用各种各样的隔热材料、耐火材料,作为隔热材料,使用作为隔热效果高、轻量且操作性良好的树脂发泡体的聚氨酯泡沫体、聚苯乙烯泡沫体及酚醛泡沫体等,另外还可使用成本低廉的玻璃棉、石棉等无机系的纤维集合体。
树脂发泡体由于为有机物,因此在发生火灾时会燃烧,时常成为延烧导致的损害扩大的原因,故而期望其对策。
一方面,玻璃棉、石棉等无机系的纤维集合体以不可燃的原材料为主体而构成,但有下述问题:有与树脂发泡体相比热导率高的倾向,在隔热性这一点上差,此外,由于为纤维状,因而会感受到穿刺感,操作性差。此外,以往施工时采用设为将纤维集合体收纳于塑料制的袋中的包装式样,并将其嵌入住宅的柱子与外壁之间的方法,但存在会产生间隙、或者年久脱落的课题。
另一方面,对树脂发泡体赋予了不燃性的隔热材料已有市售。例如可举出,有以作为不燃材料的铝箔、氢氧化铝纸、石膏系板材等对酚醛泡沫体的板的单面或双面进行层叠而成的结构的不燃隔热板。然而,这种以往的不燃隔热板无法解决下述课题:火灾时尽管直面火焰的表面不会燃烧,但内部的酚醛泡沫体会因其热量而熔化并产生空洞,板自身脱落进而延烧,无法成为满足建筑基准法所规定的耐火结构规格的材料。
作为提高树脂发泡体的耐燃烧性的技术,已知有以下的技术。例如,作为提高聚氨酯泡沫体的耐燃烧性的技术,已知有:涉及用碱金属碳酸盐、异氰酸酯类、水及反应催化剂形成发泡体的隔热材料的技术(专利文献1);主要涉及隧道的地基改良用的注入材料的技术,其中,使用含有选自由金属的氢氧化物、氧化物、碳酸盐类、硫酸盐、硝酸盐、铝酸盐、硼酸盐、及磷酸盐类组成的组中的一种或两种以上的无机化合物、水及异氰酸酯类的固化性组合物,所述金属选自由锂、钠、钾、硼及铝组成的组(专利文献2)。然而,专利文献2的现有技术是用于地基改良而开发的,并非以获得隔热性能为目的。另外,特别是如专利文献1所示,认为使碱金属碳酸盐的30%以上的水溶液与异氰酸酯类反应的现有方法中,由于使用大量水,故而会残留大量未反应的水,因此用作隔热材料时需要进行干燥,而且所得到的发泡体的气泡尺寸变大,因此隔热性能不好。
作为包覆合成树脂发泡体以提高耐燃烧性的技术,公开了下述技术:涉及对形成包含海泡石和以水溶性树脂为主要成分的水性有机粘结剂的包覆而实施了表面处理的合成树脂的发泡体粒子,进一步包覆含有无机粉体和包含以碱金属硅酸盐为主要成分的水玻璃的水性无机粘结剂的涂布材料,使其干燥固化而得到隔热性包覆粒体的技术(专利文献3);涉及在合成树脂发泡体的至少一部分的表面的气泡结构内,填充由硅酸钙、硅酸镁、硅酸铝、铝硅酸盐中的一种或两种以上的混合物形成的二氧化硅系无机物,得到含无机物的合成树脂发泡体的技术(专利文献4)。然而,上述使用硅酸盐类的现有技术中,因燃烧而导致树脂发泡体熔化,填充的硅酸盐自身的键合力丧失而发生粉化,因此认为难以保持作为隔热板的形状。
作为用纤维增强耐火隔热材料表面的技术,公开了涉及层叠物的技术,该层叠物具有:吸热材料,其具备包括由含硅酸钙粉体的已吸水的无机多孔质成型体形成的多孔质成型体、磷酸镁水合物及粘结剂的粒子;纤维隔热材料,其由1100℃24小时的收缩率为5%以下的无机纤维形成(专利文献5)。然而,专利文献5为通过层叠隔热性高的材料从而防止电缆的延烧的技术,其性能主要是基于隔热性,并不能直接应用于建筑物。专利文献5中记载的耐火结构不含有结晶水。
已知有下述技术:涉及在由珠粒法聚苯乙烯泡沫体形成的发泡树脂中,在形成于发泡珠粒间的连通孔隙中填充含有氧指数大于21的有机系物质的填充材料而得到发泡树脂复合结构体的技术(专利文献6);涉及在具有连通的孔隙且孔隙率为5~60%的热塑性树脂发泡粒子成型体的孔隙中,填充含有蒙脱石的水泥或石膏的固化物而得到复合成型体的技术(专利文献7)。然而,专利文献6中,将作为有机系物质的填充材料填充于连通孔隙中,因此无法期待不燃等级的耐燃烧性的提高。另外,专利文献6中,以具有发泡体的孔隙率为3%左右的非常密实的孔隙的发泡聚苯乙烯泡沫体为对象,很难说能够有效地利用该孔隙。专利文献7中,优选作为水泥,在其固化物中含有钙矾石,并以产品名例示了含有钙矾石的水泥,但并没有针对使用的增强纤维的记载。
专利文献8中记载了,含有CaO含量为40质量%以上的铝酸钙、石膏、平均粒径为20~60μm的具有中空结构的无机粉末、平均粒径为20~130μm的废玻璃发泡体粉末的组合物,还记载了能够将无纺布、纤维片等增强材料配置于不燃隔热材料的成型体的单面或双面,但并未限定增强材料等的种类。专利文献9中记载的材料是以包覆钢架表面免受火灾侵害的目的而使用的,认为不具有大的隔热性能。
已知耐火包覆用组合物,其特征在于,含有钙矾石作为主要成分,且含有于100~1000℃会释放不燃性气体的无机化合物粉粒体、氧化钛粉粒体(专利文献10)。
已知有涉及含有耐热性骨料、轻量骨料、氧化铝系结合材料、碳化硅及增强纤维的非烧成耐火隔热材料的技术(专利文献11)。专利文献11中记载了作为轻量骨料的白砂中空球(Shirasu balloons)、作为氧化铝系结合材料的铝酸钙。
现有技术文献
专利文献
专利文献1:日本特开平10-067576号公报
专利文献2:日本特开平08-092555号公报
专利文献3:日本特开2001-329629号公报
专利文献4:日本特开2012-102305号公报
专利文献5:日本特开2016-065360号公报
专利文献6:日本专利第4983967号公报
专利文献7:日本特开2015-199945号公报
专利文献8:日本特开2017-077994号公报
专利文献9:日本特开平07-048153号公报
专利文献10:日本特开平07-061841号公报
专利文献11:日本特开昭62-041774号公报
发明内容
发明所要解决的课题
然而,上述的专利文献10及11中记载的现有技术是以用于炼铁、炼钢中使用的高温区域的耐火隔热材料为前提的,无论是通常环境下的隔热性能还是火灾时的耐火性均不充分。因此,谋求能够兼顾隔热性和耐火性的方法。
用于解决课题的手段
本申请发明人反复进行了各种研究,结果发现,通过使用特定的组成可解决前述的课题,得到能够兼顾高的隔热性能和耐火性能的耐火隔热板,从而完成了本发明。
即,能够提供以下的本发明的实施方式。
(1)耐火隔热板,其由在具有连续孔隙的发泡树脂成型体中填充浆料而构成,填充的浆料在填充后通过水合反应生成含有50kg/m3以上结晶水的水合物,用选自由玄武岩纤维及陶瓷纤维组成的组中的一种以上的无机纤维对表面的至少一部分进行增强。
(2)如(1)所述的耐火隔热板,其中,前述水合物含有50质量%以上的选自由二水石膏及钙矾石组成的组中的一种以上。
(3)如(1)或(2)所述的耐火隔热板,发泡树脂成型体包含选自由发泡聚氨酯树脂、发泡聚苯乙烯树脂、发泡聚烯烃树脂及发泡酚醛树脂组成的组中的一种以上。
(4)如(1)~(3)中任一项所述的耐火隔热板,其中,前述发泡树脂成型体的连续孔隙率为25~70体积%。
(5)如(1)~(4)中任一项所述的耐火隔热板,其中,密度为250~800kg/m3。
(6)耐火隔热结构体,其包含(1)~(5)中任一项所述的耐火隔热板。
发明效果
本发明所涉及的耐火隔热板发挥同时具有耐火性和隔热性的效果。通过使用该耐火隔热板构筑壁、柱子等的耐火隔热结构体,即使遭受火焰也能够维持形状,不会塌陷、变形,因此还发挥阻止火灾时的延烧的效果。
附图说明
[图1]为示出耐火试验的侧视图。
[图2]为示出耐火试验的俯视图。
具体实施方式
以下,对本发明详细地进行说明。需要说明的是,除非特别说明,本说明书中的份、%以质量基准表示。除非另有规定,本说明书中的数值范围包括其上限值及下限值。
本发明的实施方式所涉及的耐火隔热板的特征在于,含有水合物。作为这样的水合物,例如可以含有钙矾石(3CaO·Al2O3·3CaSO4·32H2O)、二水石膏、或其混合物。在优选的实施方式中,水合物优选含有50质量%以上、进一步优选含有60质量%以上、80质量%以上、90质量%以上、或也可含有100质量%的钙矾石或二水石膏、或其混合物。
水合物优选含有50kg/m3以上、更优选含有70kg/m3以上的结晶水。水合物优选含有400kg/m3以下、更优选含有300kg/m3以下的结晶水。
此外,从耐火性提高的观点考虑,优选该水合物通过向具有连续孔隙的发泡树脂成型体(以下,也简写为树脂成型体)的孔隙中填充原材料之后进行水合反应而形成。作为这样的原材料,没有特别限定。作为生成钙矾石的原材料,可举出蓝方石贝利特水泥与石膏的混合物、铝酸钙与石膏的混合物等。另一方面,作为生成二水石膏的原材料,可举出α型半水石膏、β型半水石膏等。原材料之中,优选生成钙矾石的原材料。生成钙矾石的原材料之中,优选铝酸钙与石膏的混合物。
该铝酸钙是指,将氧化钙原料与氧化铝原料等混合,在窑中进行烧成或者在电炉中熔融并冷却而得到的以CaO和Al2O3为主要成分的具有水合活性的物质的总称。铝酸钙没有特别限定,从固化后的初始强度显现性的方面考虑,优选为在熔融后进行急冷而得的非晶质铝酸钙。从反应活性的方面考虑,铝酸钙的CaO含量优选为30质量%以上,更优选为34质量%以上,最优选为40质量%以上。CaO含量为34质量%以上时,则呈现耐火性。铝酸钙的CaO含量优选为50质量%以下。
作为该铝酸钙,也可使用铝酸钙的CaO、Al2O3的一部分被置换为碱金属氧化物、碱土类金属氧化物、氧化硅、氧化钛、氧化铁、碱金属卤化物、碱土类金属卤化物、碱金属硫酸盐、及碱土类金属硫酸盐等的化合物,或者也可使用在以CaO和Al2O3为主要成分的铝酸钙中少量固溶有上述物质的化合物。
铝酸钙的玻璃化率优选为8%以上,优选为50%以上,最优选为90%以上。铝酸钙的玻璃化率能够用以下的方法算出。针对加热前的样品,利用粉末X射线衍射法预先测定晶体矿物的主峰面积S,然后于1000℃加热2小时后,以1~10℃/分钟的冷却速度逐渐冷却,求出基于粉末X射线衍射法的加热后的晶体矿物的主峰面积S0,进一步地,使用这些S0及S的值,使用下式算出玻璃化率χ。
玻璃化率χ(%)=100×(1-S/S0)
从初始强度显现性的方面考虑,铝酸钙的粒度以布莱恩比表面积值计优选为3000cm2/g以上,更优选为5000cm2/g以上。若该粒度为3000cm2/g以上,则初始强度显现性得以提高,故而优选。此处,布莱恩比表面积值是指依照JIS R5201:2015(水泥的物理试验方法)进行测定的值。
作为本组合物所包含的石膏,也可使用无水石膏、半水石膏、二水石膏中的任一者,并没有特别限定。无水石膏为无水硫酸钙,是以CaSO4这一分子式表示的化合物的总称,半水石膏为以CaSO4·1/2H2O这一分子式表示的化合物的总称,二水石膏为以CaSO4·2H2O这一分子式表示的化合物的总称。
对于石膏的粒度而言,从可得到不燃性、初始强度显现性及适当的操作时间的方面考虑,平均粒径优选为1~30μm,更优选为5~25μm。此处,平均粒径是指使用测定激光衍射式粒度分布计,在使用超声波装置使其分散的状态下测定的值。
对于石膏的粒度而言,从可得到不燃性、初始强度显现性及适当的操作时间的方面考虑,以布莱恩比表面积值计优选为3000cm2/g以上,更优选为4000cm2/g以上。
使石膏浸渍于水中时的pH优选呈现弱碱性至酸性的值,更优选为pH8以下。若为pH8以下,则石膏成分的溶解度小,提高不燃性、初始强度显现性,故而优选。此处所说的pH为使用离子交换电极等对在石膏/离子交换水=1g/100g的20℃的条件下的稀释浆料的pH进行了测定的值。
相对于铝酸钙100质量份而言,本组合物中的石膏的使用量优选为70~250质量份,更优选为100~200质量份。若石膏为70质量份以上或300质量份以下,则可赋予充分的耐火性,故而优选。
本发明的实施方式中,通过向该发泡树脂成型体的孔隙中填充原材料之后进行水合反应而形成水合物时,将用于生成该水合物的原材料与水(自来水等)混合,制备用于生成水合物的浆料。作为这样的原材料,优选为粉体(将作为粉体的原材料也称作“粉体原料”)。制备该浆料时的水的使用量没有特别限定,相对于原材料100质量份而言,优选为40~300质量份,更优选为80~250质量份。若水的使用量为40质量份以上,则向孔隙中的填充不会发生不均,不会损害耐火性。若水的使用量为300质量份以下,则孔隙内的固化物中的水合物含量不会减少,不会损害耐火性。
某一实施方式中,制备该浆料时,能够进一步在不对性能造成影响的范围内使用一种以上的所有各种的添加剂。作为这种添加剂,没有特别限定,例如可举出以下添加剂。调节浆料的流动性的各种表面活性剂。导入气泡的引气剂。糖类等碳化促进剂。磷化合物、溴化合物、硼化合物、氮化合物、氢氧化镁、碳酸氢钠等阻燃性赋予剂。热膨胀石墨等防延燃剂。滑石、沸石等无机物。消石灰、各种碳酸盐等水合促进剂。羟基羧酸、酒石酸等缓凝剂。以往的防锈剂、防冻剂、减缩剂。膨润土、海泡石等粘土矿物。水滑石等阴离子交换剂。
本发明的实施方式所涉及的发泡树脂成型体为具有连续孔隙的树脂,是指具有能够填充浆料等水合物的孔隙的成型体。作为树脂的种类,例如可举出发泡聚乙烯醇树脂、发泡聚氨酯树脂、发泡聚苯乙烯树脂、发泡聚烯烃树脂、发泡酚醛树脂等。上述之中,优选为选自由发泡聚氨酯树脂、发泡聚苯乙烯树脂、发泡聚烯烃树脂及发泡酚醛树脂组成的组中的一种以上。将由这些树脂形成的、具有独立气泡的直径数mm的粒状发泡体装填于模具中并进行加热加压成型,以在粒状发泡体间产生连续孔隙的方式进行成型,由此得到该树脂成型体。树脂成型体的连续孔隙率可通过制造时的加压的程度来调节。针对聚苯乙烯树脂,能够依照珠粒法聚苯乙烯泡沫体的制造方法来制造具有连续孔隙的树脂成型体。上述之中,从通用性的观点考虑,优选使用发泡聚苯乙烯树脂成型体。若发泡树脂成型体的连续孔隙率为25体积%以上,则能够对得到的板赋予充分的耐火性,故而优选。另外,若发泡树脂成型体的连续孔隙率为70体积%以下,则板密度变小,热导率小,隔热性得以提高,故而优选。
向树脂成型体中的浆料等水合物的填充方法没有特别限定,可举出:通过基于压缩空气的压入进行填充、用真空泵进行减压而通过抽吸进行填充的方法;将树脂成型体设置于振动台,边施加30~60赫兹的振动边填充于孔隙内的方法。其中,从品质稳定性的面考虑,优选边施加振动边填充于孔隙内的方法。
在耐火隔热板暴露于高温状态的情况下,该耐火隔热板所包含的至少选自由玄武岩纤维及陶瓷纤维中的一种以上的无机纤维(以下,也简称为“无机纤维”)可抑制该耐火隔热板的变形、收缩,进而抑制水合物的结晶水的蒸发速度,从而发挥提高耐火性的效果。
玄武岩纤维是指通过将高密度的玄武岩进行粉碎,在1500℃以上的高温下熔融并对其进行纺纱而得到的纤维。陶瓷纤维是指以氧化铝(Al2O3)和二氧化硅(SiO2)为主要成分的人造矿物纤维的总称。陶瓷纤维可分类为非晶质的氧化铝二氧化硅纤维(RCF:Refractory Ceramic Fiber(耐火陶瓷纤维))、含有氧化铝含量为60%以上的氧化铝与二氧化硅的结晶质的纤维(AF:Alumina Fiber(氧化铝纤维)),均可使用。
该无机纤维的使用形态没有特别限定,能够使用将纤维的束以交叉状进行编织加工而成的无机纤维、裁切成长度为1~50mm或1~30mm左右并加工成短纤维状的无机纤维、将短纤维状的纤维与有机溶剂等混合并利用抄造法加工成厚为0.1mm~3mm左右的片状的无机纤维等。上述之中,从操作容易的方面考虑,优选以交叉状进行加工而成的无机纤维。优选这种无机纤维适用于耐火隔热板的表面的至少一部分、更优选适用于整个表面以增强该板。另外,也可以以将无机纤维包含在耐火隔热板的内部的方式设置。需要说明的是,此处所说的“耐火隔热板的表面”优选是指具有以大于厚度的纵横所确定的面积的面,也可包括与厚度方向平行的面。
该无机纤维的使用量没有特别限定,优选为30~350g/m2,更优选为50~200g/m2。若无机纤维为30g/m2以上,则可得到充分的收缩抑制效果,若为350g/m2以下,则效果的增强被认为达到可期待的上限,是经济的。
将耐火隔热组合物浆料填充于孔隙中后的耐火隔热板的养护方法没有特别限定,填充后,可以在常温下进行空气养护、或者用塑料膜覆盖耐火隔热板表面在常温下进行空气养护,进一步,为了缩短养护时间,也可以在30~50℃的温度下进行养护。
某一实施方式中,也可进一步用无纺布包覆整个耐火隔热板,或者将不燃纸、铝牛皮纸等贴附于耐火隔热板表面。
本发明的实施方式所涉及的耐火隔热板的形状没有特别限定,优选为纵500~1000mm、横1000~2000mm、厚10~100mm的范围。若尺寸在该范围,则不会变得过重,设置时的操作性良好。
本发明的实施方式所涉及的耐火隔热板的密度能够在不损害耐火性及隔热性的范围进行调节,例如优选为250~800kg/m3,更优选为300~600kg/m3。若密度为250kg/m3以上,则能够确保充分的耐火性,故而优选。若密度为800kg/m3以下,则可得到充分的隔热性能,故而优选。
某一实施方式中,也使用上述的耐火隔热板,提供可用于建筑物的耐火结构体。作为这种耐火结构体,例如可举出以下结构:从外壁侧的层构成来看,由壁板、透湿防水片、耐火隔热板、结构用合板、耐火隔热板的顺序的层形成,结构用合板与耐火隔热板之间用壁骨设置了100mm左右的空间(收纳玻璃棉等隔热材料的空间)。也可在壁板与透湿防水片之间设置横撑(参见图2)。
构筑耐火结构体时,根据需要的耐火规格,可以重叠并贴附多片耐火隔热板,或者也可并用耐火隔热板与增强石膏板、硅酸钙板等。
实施例
以下,列举实施例、比较例进一步详细地对内容进行说明,但本发明并不限于此。
“实验例1”
将表1所示的无机纤维适用于具有连续孔隙的发泡树脂成型体(尺寸:纵20cm×横20cm×厚5cm)的整个下表面,进行增强,进一步自其之上重叠聚乙烯制无纺布。将其设置于振动含浸装置,在该树脂成型体的上表面,浇注后述方式制备的浆料(生成水合物的浆料),给予1分钟60赫兹的振动,使浆料含浸于孔隙内,制造耐火隔热板。浆料为混合了粉体原料和水的、填充后生成水合物的浆料。浆料填充后,从装置中取出耐火隔热板,在常温下养护7天,对水合物所具有的结晶水的含量、耐火性、形状保持性、形状保持率及热导率进行评价。将结果示于表1。
(使用材料)
发泡树脂成型体A2:将市售的聚苯乙烯树脂发泡珠粒(直径1~5mm)填充于成型机(Daisen Co.,Ltd.制:VS-500),利用蒸汽进行加热,以发泡粒子间具有孔隙的状态使发泡粒子彼此熔合,由此制造具有连续气泡的发泡树脂成型体。连续孔隙率可通过调节加压程度来控制。填充后述的浆料前的发泡树脂成型体的连续孔隙率为36.8体积%、发泡树脂成型体的密度为10.5kg/m3、热导率为0.033W/(m·K)。需要说明的是,发泡树脂成型体的密度可通过求出发泡树脂成型体的质量与外形尺寸,用该质量除以由该外形尺寸得到的表观体积而求得。
浆料原料粉体1(RM1):铝酸钙(CA1)100质量份与石膏(CS1)120质量份的混合物;生成水合物:钙矾石100%。需要说明的是,钙矾石的生成率利用X射线衍射法而求得。
铝酸钙(CA1):以成为CaO:43质量%、Al2O3:53质量%的方式进行制备,在电炉中熔融·急冷的非晶质铝酸钙,布莱恩比表面积值6100cm2/g、玻璃化率:95%
石膏(CS1):天然无水石膏粉碎品,布莱恩比表面积值4600cm2/g、pH8以下
无机纤维1(IF1):GBF Basalt Fiber公司制玄武岩纤维布,产品名:BCGM120,纤维使用量:100g/m2
无机纤维2(IF2):GBF Basalt Fiber公司制玄武岩短纤维,产品名:KV13,平均纤维长度:5mm,纤维使用量:150g/m2
无机纤维3(IF3):Zircar Ceramics公司制氧化铝纸,产品名:Alumina TypeAL25/1700,产品厚度:1mm,纤维使用量:40g/m2无机纤维4(IF4):NITIVY CO.,LTD.制氧化铝短切纤维,产品名:NITIVY ALF,平均纤维长度:5mm,纤维使用量:100g/m2玻璃纤维1(G1):Nippon Electric Glass Co.,Ltd.制玻璃纤维布,产品名:ARG TG10x10,纤维使用量:150g/m2
(浆料的制备与加样量)
加入粉体(浆料原料粉体1)100质量份和水(自来水)100质量份,搅拌5分钟,制备生成水合物的浆料。将制备的浆料以成为810cm3(相对于树脂成型体孔隙量为1.1倍)的方式浇注于发泡树脂成型体上表面。
(测定方法)
连续孔隙率:求出发泡树脂成型体的连续孔隙率。从在温度23℃、相对湿度50%的环境下放置24小时以上的发泡树脂成型体中切取样品,由该样品的外形尺寸(纵10cm×横10cm×厚5cm)求出表观体积(Va),使用金属丝网将该样品沉入装有温度23℃的乙醇的量筒中,施加轻微振动等,由此对成型体中的孔隙中存在的空气进行脱气。通过以轻微的力度叩击量筒来赋予轻微振动。持续进行轻微振动直至该样品的体积达到恒定。然后,考虑金属丝网的体积,读取水位上升量,测定该样品的真实体积(Vb)。由求得的样品的表观体积(Va)和真实体积(Vb),利用下式求出连续孔隙率(V)。
连续孔隙率V(%)=〔(Va-Vb)/Va〕×100
结晶水的含量(结晶水量):从耐火隔热板中取样20g,用丙酮溶解固化物中的自由水和发泡体,过滤后,用丙酮彻底清洗残渣物,在25℃的环境下、于干燥器中进行48小时真空干燥。用热分析装置(升温速度:10℃/分钟,空气中)测定对于经干燥的固化物的50~200℃的范围的质量减少量,由此算出结晶水量。需要说明的是,此处所说的结晶水是指,除利用丙酮等进行干燥能够去除的自由水之外、该耐火隔热板中所含的化学或物理键合的水。
耐火性:使用小型气体燃烧器和热电偶,如图1~2所示,对耐火性简单地进行评价。使用纵10cm×横10cm×厚5cm的试验品,以使试验品的表面温度成为900℃的方式调节气体燃烧器的距离,通过热电偶测定背面的温度,计测直至到达100℃的时间。即,到达100℃的时间越长,耐火性越优异。
热导率:使用由耐火隔热板得到的纵10cm×横5cm×厚5cm的试验品,利用快速热导仪(箱式探针法)测定热导率。
形状保持性:将耐火性试验后的试验品中没有龟裂、裂纹、塌陷、缺陷的情况记作Good(良好);将确认到龟裂、裂纹、塌陷、缺陷的情况记作NG(不适合)。
形状保持率:将试验品放入电炉中加热至900℃,测定经过1小时后的试验品的体积,与加热前的试验品的体积进行比较,算出形状保持率。
[表1]
根据表1可知,通过使用满足规定条件的无机纤维来增强耐火隔热板,耐火性和形状保持性得以大幅提高。
“实验例2”
使用表2所示的种类与量的无机纤维制作板,除此以外,与实验例1同样地进行操作。将结果示于表2。
[表2]
可知利用表2所示的使用量的无机纤维,耐火隔热板的耐火性与形状保持性得以大幅提高。
“实验例3”
使用以下的表3所示的种类的浆料原料粉体制作板,除此以外,与实验例1同样地进行操作。将结果示于表3。
(使用材料)
浆料原料粉体2(RM2):铝酸钙(CA2)100部与石膏(CS1)100部的混合物生成水合物:钙矾石82%、氢氧化铝:8%、其他:10%
铝酸钙(CA2):CaO:34质量%,布莱恩比表面积值4500cm2/g、玻璃化率15%
浆料原料粉体3(RM3):蓝方石贝利特水泥(BUZZI公司制,产品名:BUZZI NEXTBASE)生成水合物:钙矾石90%、其他:10%
浆料原料粉体4(RM4):β型半水石膏(Noritake Co.,Ltd.制、产品名:FT-2、平均粒径15μm)生成水合物:二水石膏100%
合成钙矾石1(ET1):将消石灰与硫酸铝及石膏作为起始原料,将水热合成的产物进行过滤、干燥而得的钙矾石粉末,结晶水率:46%
[表3]
根据表3可知,通过使用填充后通过水合反应生成水合物的原料粉体,可呈现优异的耐火性、形状保持性、隔热性。另一方面,对于使用了合成钙矾石的比较例即实验编号3-4而言,尽管结晶水量比实验编号3-3多,但是并未呈现优异的性能。其原因在于,制备浆料时加入的水没有在水合反应中被消耗,而是作为自由水存在,因此当经时干燥、受到加热时,该自由水容易流失,会丧失试验品的致密性。
“实验例4”
相对于粉体(浆料原料粉体1)100质量份而言,以表4所示的方式加入水,制作浆料,除此以外,与实验例1同样地进行操作。将结果示于表4。
[表4]
水为相对于粉体100质量份而言的质量份。
根据表4可知,通过以适宜的水的使用量制备耐火隔热组合物浆料,呈现优异的耐火性、形状保持性、及隔热性。
“实验例5”
使用无机纤维1(IF1)作为无机纤维,使用浆料原料粉体1作为浆料原料粉体,使用表5所示的发泡树脂成型体作为发泡树脂成型体,除此以外,与实验例1同样地进行操作。将结果示于表5。此处,测定得到的耐火隔热板的密度,作为板密度。
(使用材料)
发泡树脂成型体A(A1~A4):将市售的发泡聚苯乙烯树脂珠(粒径1~5mm)填充于成型机(Daisen Co.,Ltd.制:VS-500),利用蒸汽进行加热,以发泡粒子间具有孔隙的状态使发泡粒子彼此熔合,由此制造具有连续气泡的发泡树脂成型体。连续气泡率可通过调节加压程度来控制。未填充不燃材料浆料的发泡树脂成型体的热导率为0.033W/(m·K)
发泡树脂成型体B(B1~B4):将市售的发泡硬质聚氨酯树脂成型体粉碎,调节成粒径为1~5mm的粒状物。将得到的粒状物填充于成型机(Daisen Co.,Ltd.制:VS-500),利用蒸汽进行加热,以发泡粒子间具有孔隙的状态使发泡粒子彼此熔合,由此制造具有连续气泡的发泡树脂成型体。连续气泡率可通过调节加压程度来控制。未填充不燃材料浆料的发泡树脂成型体的热导率为0.027W/(m·K)
发泡树脂成型体C(C1~C4):将市售的聚乙烯泡沫塑料粉碎,调节成粒径为1~5mm的粒状物。将得到的粒状物填充于成型机(Daisen Co.,Ltd.制:VS-500),利用蒸汽进行加热,以发泡粒子间具有孔隙的状态使发泡粒子彼此熔合,由此制造具有连续气泡的发泡树脂成型体。连续气泡率可通过调节加压程度来控制。未填充不燃材料浆料的发泡树脂成型体的热导率为0.030W/(m·K)
发泡树脂成型体D(D1~D4):将市售的酚醛树脂泡沫塑料粉碎,调节成粒径为1~5mm的粒状物。将得到的粒状物填充于成型机(Daisen Co.,Ltd.制:VS-500),利用蒸汽进行加热,以发泡粒子间具有孔隙的状态使发泡粒子彼此熔合,由此制造具有连续气泡的发泡树脂成型体。连续气泡率可通过调节加压程度来控制。未填充不燃材料浆料的发泡树脂成型体的热导率为0.022W/(m·K)
[表5]
根据表5可知,通过使用具有适宜的连续孔隙的发泡树脂成型体,呈现优异的不燃性、形状保持性、及隔热性。
“实验例6”
用实验编号1-1、1-2、2-5及5-2的耐火隔热组合物制作耐火隔热板(纵1000mm×横1000mm×厚25mm),以成为图1~2中示出的耐火结构体的结构的方式进行组装,设置于耐火炉。耐火结构体的尺寸设为横2200mm×纵1200mm。试验中,改变耐火隔热板的耐火隔热组合物的种类与厚度,确认试验结束后的耐火结构体的燃烧状态。需要说明的是,改变厚度设置板时,通过改变设置片数来进行。将结果示于表6。
(耐火试验方法)
如图1的侧视图及图2的俯视图所示,将耐火结构体设置于耐火炉,加热在模拟内壁的内部装饰侧进行,由气体燃烧器(共计5台)喷火,以依据ISO 834的标准加热曲线对耐火结构体进行1小时加热。然后,停止加热,维持设置于耐火炉的状态3小时。从耐火炉中取出结构体,剥下耐火隔热板并确认柱子的燃烧状态。
[表6]
根据表6可知,用本发明的实施例所涉及的耐火隔热板制作耐火结构体时,耐火性得以提高。特别是,通过重叠贴附2片耐火隔热板,木材部分完全没有燃烧,呈现优异的耐火性。
产业上的可利用性
通过使用本实施方式所涉及的耐火隔热组合物及其浆料,能够得到具有耐火性和隔热性的耐火隔热板。通过使用本实施方式所涉及的耐火隔热板构筑壁、柱子等结构体,即使遭受火焰也能够维持形状,因此具有阻止火灾时的延烧的效果。可见,本实施方式的耐火隔热结构体能够有助于防火安全性高的建筑物、车辆、航空器、船舶、冷冻设备、及冷藏设备的建造。
Claims (6)
1.耐火隔热板,其由在具有连续孔隙的发泡树脂成型体中填充浆料而构成,填充的所述浆料在填充后通过水合反应生成含有50kg/m3以上的结晶水的水合物,用选自由玄武岩纤维及陶瓷纤维组成的组中的一种以上的无机纤维对表面的至少一部分进行增强。
2.如权利要求1所述的耐火隔热板,其中,所述水合物含有50质量%以上的选自由二水石膏及钙矾石组成的组中的一种以上。
3.如权利要求1或2所述的耐火隔热板,其中,所述发泡树脂成型体包含选自由发泡聚氨酯树脂、发泡聚苯乙烯树脂、发泡聚烯烃树脂及发泡酚醛树脂组成的组中的一种以上。
4.如权利要求1~3中任一项所述的耐火隔热板,其中,所述发泡树脂成型体的连续孔隙率为25~70体积%。
5.如权利要求1~4中任一项所述的耐火隔热板,其中,密度为250~800kg/m3。
6.耐火隔热结构体,其包含权利要求1~5中任一项所述的耐火隔热板。
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