CN103958440B - 无定形组合物 - Google Patents
无定形组合物 Download PDFInfo
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- CN103958440B CN103958440B CN201280059269.6A CN201280059269A CN103958440B CN 103958440 B CN103958440 B CN 103958440B CN 201280059269 A CN201280059269 A CN 201280059269A CN 103958440 B CN103958440 B CN 103958440B
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Abstract
本发明提供一种糊状无定形组合物,其含有没有被包覆层包覆的以下组成的无机纤维、无机粘合剂和溶剂,还能够含有无机粉体,上述无机纤维与上述无机粉体的比例为无机纤维∶无机粉体=100∶0~10∶90,不含pH调节剂和有机纤维,在含有上述无机粉体时,上述无机粉体不含针状结晶结构。[无机纤维的组成]SiO266~82重量%、CaO10~34重量%、MgO3重量%以下、Al2O35重量%以下、SiO2、CaO、MgO、Al2O3的合计98重量%以上。
Description
技术领域
本发明涉及例如作为热处理装置、工业窑炉内或焚烧炉内的接缝材料、特别是作为填埋耐火瓷砖、绝热砖块、铁皮、灰浆耐火物等的间隙的接缝材料使用的无定形组合物,更具体而言,涉及含有特定的生物体溶解性无机纤维的无定形组合物。
背景技术
目前,无定形组合物中,作为强化纤维,含有玻璃纤维、玻璃棉、陶瓷棉、石棉、氧化铝质纤维、氧化锆质纤维、二氧化硅·氧化铝质纤维等无机纤维。不定性组合物例如通过抹子涂布、喷涂或者注入施工等,***瓷砖等的间隙,形成接缝。此时,不定性组合物中含有的无机纤维形成粉尘,在空气中飞散,作业者吸入该粉尘。由于无机纤维被人体吸入从而侵入肺时,存在损害健康的担心,现在,作为无机纤维,开发了使用生物体溶解性纤维的无定形组合物(例如,专利文献1~5)。
现有技术文献
专利文献
专利文献1:日本特开2006-306713号公报
专利文献2:日本特开2006-282404号公报
专利文献3:日本特开2005-281079号公报
专利文献4:日本特表2002-524384号公报
专利文献5:国际公开第2011/083696号小册子
发明内容
发明所要解决的课题
无定形组合物通常在制造后保存。如上所述,在炉的修补、接缝的形成等中涂布、埋入之后,进行干燥。此后,在炉中暴露于高温中。因此,保存、使用时的糊的状态时,在设备等中进行施工、干燥之后,以及在设备等的加热时,分别要求以下的实用特性。
为糊时,稠度(粘性)适当且施工性优异,具有长期稳定性(保存性优异)。干燥后,干燥收缩少,形状变化小,干燥强度高。加热时,加热收缩率小,耐热性、热传导性优异。例如,在实用上优选1100℃加热后的加热收缩率低于50%,或者外观上没有明显玻璃化、变形等。
本发明的发明人开发了耐火性、生物体溶解性优异的新型的生物体溶解性纤维(专利2011-59354)。本发明的目的之一在于提供一种含有这样的耐火性、生物体溶解性优异的生物体溶解性纤维、具有实用特性的无定形组合物。
根据本发明,提供以下的无定形组合物。
1.一种糊状无定形组合物,含有没有被包覆层包覆的以下组成的无机纤维、无机粘合剂和溶剂,
还能够含有无机粉体,
上述无机纤维与上述无机粉体的比例为无机纤维∶无机粉体=100∶0~10∶90,
不含pH调节剂和有机纤维,
在含有上述无机粉体时,上述无机粉体不含针状结晶结构,
[无机纤维的组成]
SiO266~82重量%
CaO10~34重量%
MgO3重量%以下
Al2O35重量%以下
SiO2、CaO、MgO、Al2O3的合计98重量%以上。
2.如1所述的无定形组合物,其中,含有上述无机粉体。
3.如2所述的无定形组合物,其中,上述无机粉体在大气气氛中具有1500℃以上的熔点。
4.如2所述的无定形组合物,其中,上述无机粉体包含选自二氧化硅、氧化铝、多铝红柱石、锆石、氧化锆、二氧化钛、粘土矿物、氧化钙和氧化镁中的一种或两种以上。
5.如1~4中任一项所述的无定形组合物,其中,上述无机粘合剂含有胶体。
6.如5所述的无定形组合物,其中,上述胶体为胶体二氧化硅。
7.如6所述的无定形组合物,其中,上述胶体二氧化硅的pH为9~11。
8.如1~4中任一项所述的无定形组合物,其中,上述无机粘合剂包含选自胶体二氧化硅、氧化铝溶胶、氧化锆溶胶、二氧化钛溶胶和磷酸铝水溶液中的一种或两种以上。
9.如1~8中任一项所述的无定形组合物,其中,在将上述无机纤维和上述无机粉体的合计设为100重量份时,以固态成分计含有1~30重量份的上述无机粘合剂。
10.如1~9中任一项所述的无定形组合物,其中,还含有有机粘合剂。
11.如10所述的无定形组合物,其中,上述有机粘合剂包含选自丙烯酸乳液、淀粉和增粘剂中的一种或两种以上。
12.如10或11所述的无定形组合物,其中,在将上述无机纤维和上述无机粉体的合计设为100重量份时,以固态成分计含有0.1~20重量份的上述有机粘合剂。
13.如1~12中任一项所述的无定形组合物,其中,不含不含有金属离子的螯合剂。
14.一种成型物,通过将1~13中任一项所述的无定形组合物干燥而得到。
根据本发明,能够提供一种含有耐火性、生物体溶解性优异的生物体溶解性纤维、具有实用特性的无定形组合物。
具体实施方式
本发明的无定形组合物,作为强化纤维,含有耐火性、生物体溶解性优异的特定的生物体溶解性纤维。
生物体溶解性纤维能够大致分为大量含有MgO的Mg硅酸盐纤维和大量含有CaO的Ca硅酸盐纤维。本发明中使用Ca硅酸盐纤维。由于生物体溶解性纤维容易溶于水中,因此,通常溶解在组合物所含的水中,含有成分溶出。这样,存在与组合物中的其它成分、被涂布的对象物等反应从而带来问题的担忧。因此,含有难以溶于水中的陶瓷纤维的组合物与含有生物体溶解性纤维的组合物有时显示不同的性能,另外,在生物体溶解性纤维中,含有Mg硅酸盐纤维的组合物和含有Ca硅酸盐的组合物由于溶出成分的种类和数量不同,有时显示不同的性能。
在无定形组合物中使用Mg硅酸盐纤维时,为了确保必要的强度,作为粘合剂添加有机纤维,但是Ca硅酸盐纤维不需要添加有机纤维。另外,使用Mg硅酸盐纤维时,pH调节剂(磷酸缓冲液、硼酸缓冲液等的缓冲液、乙酸等的酸)的添加是必要的。不添加pH调节剂时,存在保存中固化的担忧,干燥收缩变大。但是,Ca硅酸盐纤维不需要添加pH调节剂。并且,使用Mg硅酸盐纤维时,如果不用磷酸盐等包覆纤维的表面,在保存中就会溶解,但是Ca硅酸盐纤维不需要包覆。
本发明中使用的Ca硅酸盐纤维具有以下组成。
SiO266~82重量%(例如,能够为66~低于75重量%、68~80重量%、70~80重量%、71~低于75重量%、71~80重量%或71~76重量%)
CaO10~34重量%(例如,能够为20~30重量%或21~26重量%)
MgO3重量%以下(例如,能够为1重量%以下)
Al2O35重量%以下(例如,能够为3.5重量%以下或3重量%以下。并且,能够为1重量%以上或2重量%以上)
其它氧化物低于2重量%
SiO2为上述范围,则耐热性优异。CaO和MgO为上述范围,则加热前后的生物体溶解性优异。
Al2O3含量,例如,能够为3.4重量%以下或3.0重量%以下。并且,能够为1.1重量%以上或2.0重量%以上。优选为0~3重量%,更优选为1~3重量%。在该范围内含有Al2O3时,则强度变高。
上述的无机纤维,作为其它氧化物,可以含有碱金属氧化物(K2O、Na2O等)、Fe2O3、ZrO2、P2O5、B2O3、TiO2、MnO、R2O3(R选自Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或它们的混合物)等一种以上,或者不含有。其它氧化物可以分别为0.2重量%以下或0.1重量%以下。碱金属氧化物中,可以使各氧化物为0.2重量%以下,也可以使碱金属氧化物的合计为0.2重量%以下。
另外,生物体溶解性纤维中,可以使SiO2、CaO、MgO、Al2O3的合计超过98重量%或超过99重量%。
生物体溶解性无机纤维例如是40℃时的生理盐水溶解率为1%以上的无机纤维。
生理盐水溶解率,例如可以如下操作来测定。即,首先,在三角烧瓶(容积300mL)中加入将无机纤维粉碎为200目以下制备得到的试样1g和生理盐水150mL,放置于40℃的恒温箱中。接着,对三角烧瓶持续施加每分钟120转的水平振动50小时。此后,利用ICP发光分析装置测定在过滤得到的滤液中所含有的各元素的浓度(mg/L)。接着,基于测得的各元素的浓度和溶解前无机纤维中各元素的含量(重量%),算出生理盐水溶解率(%)。即,例如,测定元素为硅(Si)、镁(Mg)、钙(Ca)和铝(Al)时,利用以下的式子,算出生理盐水溶解率C(%):C(%)=[滤液量(L)×(a1+a2+a3+a4)×100]/[溶解前的无机纤维的重量(mg)×(b1+b2+b3+b4)/100]。该式子中,a1、a2、a3和a4分别为测得的硅、镁、钙和铝的浓度(mg/L),b1、b2、b3和b4分别为溶解前的无机纤维中的硅、镁、钙和铝的含量(重量%)。
另外,本发明中使用的纤维,可以用表面活性剂、分散剂进行前处理。若进行前处理,表面变得光滑,与其它成分混合制造组合物时,难以折断,以长的状态包含于组合物中。其结果,施工性提高,强度提高,收缩变少。另外,耐湿性改善,保存稳定性变好。
从强度的观点出发,无机纤维的平均纤维直径通常为1~50μm,优选为2~10μm,特别优选为2~5μm,平均纤维长通常为1~200mm,优选为2~50mm。
另外,也可以使无机纤维中所含的粒径45μm以上的颗粒的量超过10重量%。减少颗粒的量的处理中,存在纤维长度过度变短,对加热收缩、强度等产生影响的担心。
本发明的无定形组合物中所含的无机纤维的表面不需要用包覆层包覆。作为在无机纤维的表面形成包覆层的物质,可以列举磷酸盐、钼化合物、聚脒化合物、吖丙啶化合物等。作为磷酸盐,可以列举三聚磷酸铝、三聚磷酸二氢铝、偏磷酸铝、磷酸锌、磷酸钙等。作为钼化合物,可以列举钼酸锌、钼酸铝、钼酸钙、磷钼酸钙、磷钼酸铝等。作为聚脒化合物,可以列举丙烯酰胺、丙烯腈、N-乙烯基丙烯脒盐酸盐、N-乙烯基丙烯酰胺、乙烯胺盐酸盐、N-乙烯基甲酰胺共聚物等。作为吖丙啶化合物,可以列举氮丙环、二亚甲基亚胺等。这些形成包覆层的物质,能够单独使用一种或者组合两种以上使用。
本发明的无定形组合物含有上述无机纤维,并且适当还含有包含Si、Al和/或Ca的无机粉体、无机粘合剂等。无机粉体可以添加、也可以不添加,添加时,为了提高耐火性,希望无机粉体的耐热性高于无机纤维。
无机粉体没有特别限制,优选在1100℃以上、更优选1300℃以上、更加优选1500℃以上的大气气氛中具有熔点。
具体而言,例如,使用包含二氧化硅、氧化铝、多铝红柱石(二氧化硅20~30重量%、氧化铝70~80重量%)、锆石、氧化锆、高岭土、二氧化钛等的粘土矿物、氧化钙和氧化镁中的一种或两种以上(混合物)的无机粉体。优选二氧化硅、氧化铝。
本发明中,能够使用不含针状结晶结构的无机粉体。作为具有针状结晶结构的无机粉体,可以列举选自硅灰石粉末、海泡石粉末、绿坡缕石粉末等中的一种以上。
作为无机粘合剂,可以列举胶体二氧化硅、氧化铝溶胶、氧化锆溶胶、二氧化钛溶胶、磷酸铝水溶液等。
无机粘合剂可以为胶体二氧化硅、氧化铝溶胶、氧化锆溶胶、二氧化钛溶胶、或这些成分复合化得到的胶体等的胶体,优选为胶体二氧化硅。胶体二氧化硅优选pH为8以上,更优选为9~11。若低于8,则存在无法形成具有适度的粘度的糊的担心。若含有胶体二氧化硅,则加热后的组合物的强度提高。如果过多,则存在无定形组合物固化的担心。
在将无机纤维和无机粉体的合计重量设为100重量份时,以固态成分含量计,能够含有1~30重量份(优选1~25重量份、更优选1~20重量份、更加优选1~15重量份、更加优选1~12重量份、特别优选2~10重量份)的无机粘合剂。无机纤维和无机粉体配合为所期望的耐热性、密度等。无机纤维多、无机粉体少,则容易得到轻质的无定形组合物。
从耐热性的观点出发,在以下例示无机纤维∶无机粉体的合适的配比。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择氧化铝时,能够为无机纤维∶无机粉体=100∶0~10∶90的比例。优选无机纤维∶无机粉体=100∶0~95∶5和80∶20~10∶90,更优选无机纤维∶无机粉体=100∶0~95∶5和75∶25~10∶90,更加优选100∶0和70∶30~10∶90,更加优选无机纤维∶无机粉体=100∶0和65∶35~10∶90,最优选无机纤维∶无机粉体=100∶0和40∶60~10∶90。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择多铝红柱石时,能够为无机纤维∶无机粉体=100∶0~10∶90的比例。优选100∶0~90∶10和70∶30~10∶90,更优选100∶0~90∶10和65∶35~10∶90,更加优选无机纤维∶无机粉体=100∶0~95∶5和60∶40~10∶90。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择高岭土时,能够为无机纤维∶无机粉体=100∶0~10∶90的比例。优选无机纤维∶无机粉体=100∶0~80∶20和60∶40~10∶90,更优选100∶0~80∶10和50∶50~10∶90,更加优选无机纤维∶无机粉体=100∶0~85∶15和50∶50~10∶90,更加优选100∶0~90∶10和40∶60~10∶90。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择二氧化硅时,为无机纤维∶无机粉体=100∶0~10∶90。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择锆石、氧化锆、二氧化钛中的一种以上时,为无机纤维∶无机粉体=100∶0~10∶90。
含有无机粉体时,作为无机粘合剂选择胶体二氧化硅、作为无机粉体选择氧化钙、氧化镁中的一种以上时,能够为无机纤维∶无机粉体=100∶0~10∶90的比例。优选为70∶30~10∶90、更优选为60∶40~10∶90。
组合物中的SiO2、CaO、Al2O3的重量比,例如,可以调整无机纤维、无机粉体、无机粘合剂的量,使得成为在所期望的使用温度范围中不熔融的范围。
本发明的无定形耐火物,适当组合无机纤维、无机粉体、无机粘合剂,使得所得到的成型体优选在1100℃加热后不熔融或收缩率低于50%。更优选选择为在1200℃加热后不熔融或收缩率低于50%、更加优选选择为在1300℃加热后不熔融或收缩率低于50%。收缩率优选为30%以下,更优选为20%以下,更加优选为10%以下,特别优选为5%以下。
本发明的组合物中使用的无机粉体的平均粒径,通常为0.1~100μm、优选为0.2~50μm、特别优选为0.2~10μm。如果平均粒径低于0.1μm,则变得容易分离。另外,如果平均粒径超过100μm,则变得难以均匀分散。
本发明的无定形组合物还含有溶剂。
作为溶剂,没有特别限制,可以列举水和极性有机溶剂,作为极性有机溶剂,可以列举乙醇、丙醇等一元醇类、乙二醇等二元醇类。这些之中,从作业环境不恶化、对环境没有负担的方面考虑,优选水。作为悬浊液、分散液等配合成分时,也包括其溶剂。并且,作为悬浊液、分散液等配合固体时,其配合量为固态成分的配合量。
溶剂的含量,在将无机纤维和无机粉体的合剂含量设为100重量份时,通常为100~600重量份(优选为20~400重量份)。通过含有溶剂,能够调节流动性,提高接缝的机械强度,特别是提高弯曲强度。如果含量过多,则存在由于无定形组合物的稠度提高、在施工时组合物滴流,并且,由于干燥导致的接缝收缩变大的担心。
本发明的无定形组合物中,除了上述无机纤维、无机粉体、无机粘合剂、溶剂以外,还能够含有有机粘合剂、添加剂等。没有必要含有“不含有金属离子的螯合剂”。
作为有机粘合剂,可以列举有机纤维、丙烯酸乳液、淀粉、增粘剂等。
在将无机纤维和无机粉体的合计设为100重量份时,例如,能够以固态成分含量计,含有0.1~20重量份(优选0.5~10重量份、优选0.5~8重量份、更优选1~5重量份)的有机粘合剂。
有机纤维作为无机纤维的保护膜发挥作用,本发明的组合物不需要含有有机纤维。作为有机纤维,没有特别限制,可以是天然纤维或疏水处理过的合成纤维中的任意种,作为天然纤维,可以列举纸浆、棉、麻等,作为合成纤维,可以列举维尼纶、人造丝、聚丙烯、聚乙烯等。
作为增粘剂,可以列举羟乙基纤维素、丙烯酸钠聚合物、聚醚多元醇、丙烯酸类高分子聚酯胺、环氧乙烷、羧甲基纤维素(CMC)等。
在将上述无机纤维和无机粉体的合计设为100重量份时,无机粘合剂和有机粘合剂的合计固态成分含量优选为1~50重量份、更优选为1~30重量份、更加优选为1~20重量份。
从将无机纤维投入水中时不急剧沉降,以某种程度的时间浮游,相互之间或者与其它混合材料的混合性变好的观点出发,优选无机纤维具有某种程度的疏水性。疏水处理是指提高纤维的疏水性的处理,作为疏水处理的方法,例如,可以列举将纤维的周围用疏水性的药剂涂敷的方法。
作为添加剂,可以列举分散剂、防腐剂、pH调节剂等。
作为防腐剂,没有特别限制,例如,可以列举具有氮原子或硫原子的无机化合物或有机化合物等,防腐剂的含量,没有特别限制,相对于无机纤维和无机粉体的合计含量100重量份,优选为0.1~5重量份。
另外,本发明的组合物不需要含有pH调节剂。作为pH调节剂,例如,可以列举缓冲溶液或酸。作为缓冲溶液,可以列举作为pH4标准溶液的邻苯二甲酸盐标准溶液(瑟连森缓冲液)、作为pH7标准溶液的中性磷酸盐标准溶液,作为酸,可以列举乙酸、甲酸等。pH优选4~8.5左右。
作为分散剂,没有特别限制,能够使用公知的物质。具体而言,可以列举羧酸类、多元醇、胺类等,分散剂的含量没有特别限制,相对于无机纤维和无机粉体的合计固态成分含量100重量份,优选为1~5重量份。
作为增粘剂,没有特别限制,能够使用公知的物质。具体而言,可以列举羟乙基纤维素、丙烯酸钠聚合物、聚醚多元醇、丙烯酸类聚合高分子聚酯胺、环氧乙烷、羧甲基纤维素(CMC)等。增粘剂的含量没有特别限制,相对于无机纤维和无机粉体的合计固态成分含量100重量份,优选固态成分含量为0.1~20重量份。
本发明所涉及的无定形组合物,能够将各成分混合搅拌来制造。本发明所涉及的成型体,能够将无定形组合物成型并干燥/加热而得到。由于本发明的组合物为糊状(灰浆),能够用抹子涂布、用手加固、用压力枪散布。
由本发明的无定形组合物得到的成型体的耐热性优异,优选在1100℃、更优选在1300℃、更加优选在1500℃不熔融。具体而言,成型体可以根据JISR2553,将无定形组合物成形为长160×宽40×高40mm,在100℃加热干燥24小时来得到。优选将该成型体在炉中以规定温度加热24小时时不熔融。“熔融”是指用实施例的方法测定的加热收缩率为50%以上,或者外观上明显玻璃化、变形。
本发明的无定形组合物干燥之后的密度,通常为0.1~1.5g/cm3。
本发明的无定形组合物,从长期稳定性、弯曲强度、加热收缩率的方面考虑,具有良好的实用特性。
特别是使用了Ca硅酸盐纤维的本发明的无定形组合物,与使用了陶瓷纤维(含有二氧化硅40~60重量%、氧化铝60~40重量%)、Mg硅酸盐纤维的无定形组合物相比,加热收缩率小。加热收缩率优选10%以下,更优选5%以下,特别优选3%以下。
实施例
实施例1
[无定形组合物的制造]
制造表1所示的组成的无定形组合物1~4。
无机纤维A含有SiO273重量%、CaO24重量%、MgO0.3重量%、Al2O32重量%。
作为无机粘合剂,使用了胶体二氧化硅(SNOWTEX30,日产化学工业社制,pH9~10,固态成分为30%的悬浊液)。
作为有机粘合剂使用了增粘剂和丙烯酸乳液。
表1中,无机纤维A和无机粉末的量为将无机纤维A和无机粉末的合计设为100重量%时的重量%。
无机粘合剂、有机粘合剂、水的量为将无机纤维A和无机粉末的合计设为100重量份时的重量份。表中的无机粘合剂、有机粘合剂的值为固态成分量。
100℃干燥24小时后的密度,分别为0.26g/cm3、0.44g/cm3、0.75g/cm3、1.07g/cm3,没有干燥收缩。密度根据JISA1116,测量尺寸体积和重量来算出。
[表1]
比较例1
[无定形组合物的制造]
制造表2所示的组成的无定形组合物1′~4′。具体而言,将无定形组合物1~4的无机纤维A改变为陶瓷纤维(二氧化硅52重量%、氧化铝48重量%),不使用无机粉末二氧化硅,制造无定形组合物1′~4′。
作为参考,在表7中表示组合物中的SiO2、CaO、Al2O3的重量比。
[表2]
无定形组合物 | 1’ | 2’ | 3’ | 4’ |
陶瓷纤维 | 78 | 65 | 33 | 26 |
氧化铝 | 22 | 35 | 67 | 74 |
无机粘合剂 | 3 | 5 | 4 | 3 |
有机粘合剂 | 4 | 3 | 2 | 1 |
水 | 360 | 180 | 90 | 45 |
评价例1
对实施例1和比较例1中所得到的无定形组合物1~4、1′~4′,进行以下的评价。
(1)长期稳定性
对在刚制造后、保存3个月后、保存6个月后的无定形组合物,用以下的方法,测定稠度、弯曲强度、加热收缩率。在表3中表示结果。实施例1中所得到的无定形组合物1~4在保存6个月之后也没有发现物性降低。
(i)稠度
根据JISK2220,使用稠度计进行测定。金属杯使用内径100mm、内高50mm的金属杯,圆锥使用圆锥A。
(ii)弯曲强度
将无定形组合物成型为长160×宽40×高40mm,在100℃加热干燥24小时,得到绝热材料。
将该绝热材料在1100℃加热24小时,求出加热后的绝热材料的弯曲强度。弯曲强度使用三点弯曲强度试验机(万能拉力机),测定破裂负荷,根据下式算出。
弯曲强度(MPa)={3×最大负荷(N)×支撑辊的中心距离(mm)}/{2×绝热材料的宽度(mm)×(绝热材料的厚度(mm))2}
(iii)加热收缩率
根据JISR2553,将无定形组合物成型为长160×宽40×高40mm,在100℃加热干燥24小时,得到绝热材料。
将该绝热材料在电炉中以1300℃加热24小时,测定加热后的绝热材料的长度。加热收缩率以加热前的绝热材料的长度为Xmm、加热后的长度为Ymm,根据下式求出。
加热收缩率(%)={(X-Y)/X}×100
[表3]
(2)加热收缩率
对于刚制造后的无定形组合物,与上述(1)(iii)同样地测定在1100℃、1200℃和1300℃加热24小时之后的收缩率(%)。在表4中表示5次测定的平均值。可知,无定形组合物1~4的收缩率小于无定形组合物1′~4′的收缩率。
[表4]
(3)弯曲强度
对于刚制造后的无定形组合物,与上述(1)(ii)同样地测定在1100℃、1200℃和1300℃加热24小时之后的弯曲强度(MPa)。在表5中表示5次测定的平均值。无定形组合物1~4的弯曲强度与无定形组合物1′~4′大致相同。
[表5]
实施例2
[无定形组合物的制造]
除了为表6的组成以外,与实施例1同样操作,得到无定形组合物10~20。作为参考,在表7中表示组合物中的SiO2、CaO、Al2O3的重量比。
评价例2
[无定形组合物的评价]
对实施例2中得到的无定形组合物10~20,与评价例1同样操作,测定在1100℃、1200℃、1300℃、1400℃、1500℃加热24小时时的加热收缩率(%)。并且,在加热收缩率为50%以上,或者外观上明显玻璃化、变形时,记为“熔融”。在表6中表示结果。
实施例3
[无定形组合物的制造]
除了为表8、9的组成以外,与实施例1同样操作,得到无定形组合物21~30。
评价例3
[无定形组合物的评价]
对实施例3中得到的无定形组合物21~30,与评价例1同样操作,测定在1300℃加热24小时时的加热收缩率(%)。在表8、9中表示结果。
[表8]
[表9]
工业上的可利用性
本发明的无机纤维为糊状,能够作为接缝材料、修补材料、绝热材料使用。
以上对本发明的实施方式和/或实施例进行详细地说明,但是,本领域技术人员能够容易地在实质上不脱离本发明的新型教导和效果的情况下,对这些作为例示的实施方式和/或实施例进行大量的变更。因此,这些大量的变更也包括在本发明的范围内。
在这里全部援引该说明书中记载的文献和作为本申请的巴黎优先基础的日本申请说明书的内容。
Claims (13)
1.一种接缝材料,其特征在于:
所述接缝材料为糊状无定形组合物,含有没有被包覆层包覆的以下组成的无机纤维、无机粘合剂和溶剂,
还能够含有无机粉体,
所述无机纤维与所述无机粉体的比例为无机纤维∶无机粉体=100∶0~10∶90,
不含pH调节剂和有机纤维,
在含有所述无机粉体时,所述无机粉体不含针状结晶结构,
[无机纤维的组成]
SiO266~82重量%
CaO10~34重量%
MgO3重量%以下
Al2O35重量%以下
SiO2、CaO、MgO、Al2O3的合计98重量%以上。
2.如权利要求1所述的接缝材料,其特征在于:
含有所述无机粉体。
3.如权利要求2所述的接缝材料,其特征在于:
所述无机粉体在大气气氛中具有1500℃以上的熔点。
4.如权利要求2所述的接缝材料,其特征在于:
所述无机粉体包含选自二氧化硅、氧化铝、多铝红柱石、锆石、氧化锆、二氧化钛、粘土矿物、氧化钙和氧化镁中的一种或两种以上。
5.如权利要求1~4中任一项所述的接缝材料,其特征在于:
所述无机粘合剂含有胶体。
6.如权利要求5所述的接缝材料,其特征在于:
所述胶体为胶体二氧化硅。
7.如权利要求6所述的接缝材料,其特征在于:
所述胶体二氧化硅的pH为9~11。
8.如权利要求1~4中任一项所述的接缝材料,其特征在于:
所述无机粘合剂包含选自胶体二氧化硅、氧化铝溶胶、氧化锆溶胶、二氧化钛溶胶和磷酸铝水溶液中的一种或两种以上。
9.如权利要求1~4中任一项所述的接缝材料,其特征在于:
在将所述无机纤维和所述无机粉体的合计设为100重量份时,以固态成分计含有1~30重量份的所述无机粘合剂。
10.如权利要求1~4中任一项所述的接缝材料,其特征在于:
还含有有机粘合剂。
11.如权利要求10所述的接缝材料,其特征在于:
所述有机粘合剂包含选自丙烯酸乳液、淀粉和增粘剂中的一种或两种以上。
12.如权利要求10所述的接缝材料,其特征在于:
在将所述无机纤维和所述无机粉体的合计设为100重量份时,以固态成分计含有0.1~20重量份的所述有机粘合剂。
13.如权利要求1~4中任一项所述的接缝材料,其特征在于:
不含不含有金属离子的螯合剂。
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- 2012-11-09 CN CN201280059269.6A patent/CN103958440B/zh active Active
- 2012-11-09 EP EP20120853336 patent/EP2786976A4/en not_active Withdrawn
- 2012-11-09 WO PCT/JP2012/007209 patent/WO2013080455A1/ja active Application Filing
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JP5022512B1 (ja) | 2012-09-12 |
CN103958440A (zh) | 2014-07-30 |
JP2013112600A (ja) | 2013-06-10 |
US20140378596A1 (en) | 2014-12-25 |
EP2786976A1 (en) | 2014-10-08 |
EP2786976A4 (en) | 2014-12-10 |
WO2013080455A1 (ja) | 2013-06-06 |
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