JP4378675B2 - Inorganic foamable composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、発泡性組成物に係り、更に詳しくは、高温下における耐火断熱性に優れた発泡体を得ることのできる発泡性組成物に関する。また、本発明は、かかる発泡性組成物を発泡硬化してなる発泡体に関する。
【０００２】
【従来の技術】
従来より、産業廃棄物として産出されるフライアッシュや高炉スラグ等の無機粉体と珪酸塩との反応系に金属（アルミニウム）及び過酸化水素を添加し、発泡硬化することにより軽量の発泡体が得られることが知られており、かかる発泡体は、例えば、発泡断熱材として建築用外壁材等の分野で用いられている。
【０００３】
例えば、（Ａ）水可溶性アルカリ珪酸塩、（Ｂ）金属系発泡剤、（Ｃ）フライアッシュまたは高炉鉱滓及び（Ｄ）水を有効成分として含む発泡性無機質組成物を用いて発泡体にすることが知られている（例えば、特許文献１参照。）。また、（Ａ）粒径が１０μｍ以下の粉体を８０重量％以上含有するフライアッシュ、粘土、メタカオリン等の反応性無機質粉体１００重量部、（Ｂ）平均粒径が０．０１〜３５μｍの粒状物であるかあるいは長尺方向の長さが１〜２５０μｍであり形状が柱状又は針状の無機質充填材２０〜８００重量部、（Ｃ）過酸化水素０．０１〜１０重量部、（Ｄ）アルカリ金属珪酸塩０．２〜４５０重量部、及び（Ｅ）水３５〜１，５００重量部からなる発泡性無機質組成物も提案されており、かかる組成物を用いることで、気泡の均一性、耐水性に優れ、高強度で低比重でありながら、熱収縮率（１００℃における）の小さい発泡体が得られるとされている（例えば、特許文献２参照。）。しかしながら、上記先行技術に記載される発泡性無機質組成物から得られる発泡体では、高温での耐火断熱性が充分とはいえなかった。
【０００４】
【特許文献１】
特開昭５７−７７０６２号公報
【特許文献２】
特開平８−７３２８３号公報
【０００５】
【発明が解決しようとする課題】
ある材質における熱の伝達としては、熱伝導、対流及び輻射が一般的に知られている。そして、材質の構造を発泡体とし、固体熱伝導部を薄膜化することにより熱伝導を小さくすることが、また、発泡体のセルを微細化・独立気泡化することで材質内の気体の対流を防ぐことが既に知られており、これらの手法は、有機発泡体及び無機発泡体において広く用いられている。
【０００６】
確かに、上記した手法は、低温から３００℃程度までの温度領域では発泡体の断熱性を改善する手法として有効であるが、３００℃以上の高温領域では輻射の効果が大きく、材質の高温断熱性を改善するためには、熱伝導及び対流に加えて、輻射による熱の伝達を低減させる必要がある。
【０００７】
また、珪酸塩と反応性無機粉体とからなる組成物においては、適当な界面活性剤を添加して発泡硬化させることにより、得られる断熱材中に微細且つ独立性を有するセルを形成させることができるが、例えば４００℃以上の高温では断熱材の収縮によりセル壁にミクロクラックが発生し、セル間における気体の対流が顕著となる結果、断熱材の断熱性が低下してしまうことも分かってきた。
【０００８】
このため、従来の無機質組成物から得られる発泡体を、耐火パネル等のような高温での耐火断熱性が求められる用途に用いる場合には、発泡体（パネル）の厚さを厚くする必要があり、経済的ではなかった。
【０００９】
【課題を解決するための手段】
本発明は、上記の点に鑑みなされたものであって、熱伝導及び対流に加え、高温熱源からの輻射熱を大幅に低減することが可能であり、高温下においても優れた耐火断熱性を有する発泡体を形成することのできる発泡体組成物の提供を目的とする。
【００１０】
すなわち、本発明は、珪酸アルミニウム系反応性無機粉体、アルカリ金属珪酸塩、発泡剤、及び赤外線不透過性粉体を含み、アルカリ金属珪酸塩、発泡剤、及び赤外線不透過性粉体の割合が、珪酸アルミニウム系反応性無機粉体１００重量部に対して、それぞれ、１０〜１００重量部、０．０５〜５重量部、及び４〜４０重量部である、発泡性組成物に関する。
【００１１】
本発明は、また、かかる発泡性組成物を発泡硬化してなる発泡体に関する。
【００１２】
【発明の実施の形態】
上述の通り、本発明の発泡性組成物は、珪酸アルミニウム系反応性無機粉体、アルカリ金属珪酸塩、発泡剤、及び赤外線不透過性粉体を必須成分として含んでおり、以下、これらの成分について説明する。
【００１３】
本発明で用いられる「珪酸アルミニウム系反応性無機粉体」とは、珪酸アルミニウム成分を含有する反応性無機粉体であって、水溶性アルカリ珪酸塩と反応硬化し得る粉体を指す。具体的には、フライアッシュ、無機化したパルプスラッジ、高炉スラグ等を挙げることができる。
【００１４】
ここで、フライアッシュとはＪＩＳ Ａ ６２０１に規定される、微粉炭燃焼ボイラーから集塵器で採取する微小な灰の粒子をいい、具体的には、シリカ４５％以上、湿分１％以下、強熱減量５％以下、比重１．９５以上、比表面積２７００ｃｍ2／ｇ以上、７５％以上の粒子が４４μｍ標準篩を通過するものを挙げることができる。本発明においては、耐熱性の点から、ＳｉＯ2：Ａｌ2Ｏ3＝４５〜６０：２０〜２８（重量比）の組成を有するフライアッシュを用いることが好ましく、また、５〜３０μｍの平均粒径を有していることが好ましい。
【００１５】
無機化したパルプスラッジとは、製紙工程において副産される廃物を焼却無機化したもので、具体的には、シリカ４０％以上、湿分１％以下、強熱減量１％以下、比重１．８０以上、比表面積２５００ｃｍ2／ｇ以上、７５％以上の粒子が４４μｍ標準篩を通過するものである。本発明においては、耐熱性の面から、ＳｉＯ2：Ａｌ2Ｏ3＝３０〜５０：２５〜３５（重量比）の組成のものを用いることが好ましく、また、５〜３０μｍの平均粒径を有していることが好ましい。。
【００１６】
高炉スラグとは、ＪＩＳ Ａ５０１１−１に規定される鉄鉱石から鉄を精錬採取する際に副産される無機系の粉体であり、具体的には、酸化カルシウム４５％以下、硫黄分２．０％以下、比重２．５０以上のもの等が挙げられる。本発明においては、７０％以上の粒子が４４μｍ標準篩を通過するものが好ましく、好ましい平均粒子径は５〜３０μｍである。
【００１７】
本発明においては、上記した以外にも、化学組成としてＳｉＯ2を１０〜８０重量％、Ａｌ2Ｏ3を９０〜１０重量％を含有する無機粉体を、珪酸アルミニウム系反応性無機粉体として使用することも可能である。このような粉体としては、メタカオリンなどのカオリン鉱物、雲母粘土鉱物、ワラストナイト、タルクなどが挙げられる。ただし、組成粒度等が適当であり、高温での寸法安定性に優れたものであれば、これらに限定されるものではない。
【００１８】
次に、本発明で用いられるアルカリ金属珪酸塩は、Ｍ2Ｏ・ｎＳｉＯ2（Ｍ＝Ｋ、Ｎａ、Ｌｉから選ばれる１種以上の金属）として表すことができる。ここで、ｎは０．５〜４の範囲が好ましく、更に好ましくは１．０〜２．５である。ｎの値がこれより小さくなると反応が速すぎて発泡体のセルが連続気泡となり、断熱性能が低下する。逆に、ｎの値が大きくなり過ぎると反応が進みにくくなる。なお、アルカリ金属珪酸塩は水溶液として配合することが好ましい。水溶液の濃度については特に限定されないが、薄くなると反応性粉末との反応性が低下する。また、濃くなるとアルカリ金属珪酸塩が析出しやすくなるので、１０〜６０重量％とすることが好ましい。また、上記アルカリ金属珪酸塩水溶液は、アルカリ金属珪酸塩をそのまま加圧、加熱下で水に溶解させて調製してもよいが、まず、アルカリ金属珪酸塩に、珪砂、珪石粉などのＳｉＯ2成分を加えてｎを所定の値とした後に、加圧、加熱下で溶解させ、アルカリ金属珪酸塩水溶液としてもよい。
【００１９】
本発明で用いられる発泡剤としては、過酸化物および金属系発泡剤が主なものとして挙げられる。過酸化物としては、具体的には、過酸化水素、ｔ-ブチルハイドロパーオキサイド、過酸化カリウム、過酸化ナトリウム、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウムなどが用いられる。これらの過酸化物は水溶液として通常用いられ、例えば、濃度が５〜４０重量％の過酸化水素水、６０〜７０重量％のｔ−ブチルハイドロパーオキサイド水溶液が好ましい。金属系発泡剤としては、具体的には、金属元素、金属合金、金属間化合物などが用いられる。金属元素としては、アルミニウム、珪素、カルシウム、バリウム、鉄、ニッケル、ガリウムなどの周期律表第３〜５周期に属するものが好ましく、また、金属合金および金属間化合物としては、アルミニウム−珪素、アルミニウム−チタン、アルミニウム−マンガン、アルミニウム−銅、アルミニウム−銅−珪素などが好ましい。これらのなかでも特にアルミニウム、珪素などが好ましい。これらの金属系発泡剤は、通常、平均粒径が０．１〜２００μｍ、好ましくは１〜５０μｍの粉体として用いるのが好ましい。
【００２０】
続いて、本発明で使用される「赤外線不透過性粉体」とは、赤外線の透過に不透明で輻射熱を散乱させ遮断する材料を意味する。本発明においては、赤外線不透過性粉体として、酸化ジルコニウム及び酸化チタンからなる群から選ばれる少なくとも１種のものを用いることが好ましい。
【００２１】
酸化ジルコニウムとしては、熱反射性及び高温での断熱性という点から、平均粒径が１〜８０μｍのものを用いることが好ましく、より好ましくは１〜５０μｍである。平均粒径の大きな酸化ジルコニウムを使用すると（＞８０μｍ）、組成物中における酸化ジルコニウムの存在が疎となるため、輻射防止による断熱性改善効果が充分に発揮されず、また、平均粒径が１μｍ以下では赤外線の波長より小さくなるため赤外線が通過してしまい反射効果が小さくなってしまう。また、本発明においては、ジルコンサンドのような安価な珪砂化合物を用いることもできる。
【００２２】
酸化チタンとしては、熱反射性という点から、赤外波長（０．７６μｍ）以上の粒径を有するものを用いることが好ましいが、酸化チタンは非常に細かい粉体であり、一般的に、その平均一次粒子径の上限は０．２〜０．３μｍ程度である。このため、本発明においては、平均粒径が０．１μｍ以上である酸化チタンを使用することが好ましく、より好ましくは０．２μｍ以上である。０．１μｍより小さい粒径の酸化チタンを添加しても赤外線が通過してしまい、目的とする熱反射性効果が得られない。
【００２３】
なお、酸化チタンは高い屈折率を有するため、反射材として公知であり、表面層を酸化チタンコート層とした断熱材も存在するが、高温領域における断熱性に関し顕著な結果は得られなかった。しかし、薄膜（セル壁）よりなる無機発泡硬化断熱材に配合することにより、薄膜全てが反射層となり、断熱効果の高い断熱材となりうる。
【００２４】
また、本発明においては、より良好な断熱性を得るという点から、赤外線不透過性粉体として、酸化ジルコニウムと酸化チタンとを併用することが好ましい。
【００２５】
上記した特定の成分を含む本発明の発泡性組成物は、発泡硬化することで、微細且つ独立気泡化したセルを有する発泡体となる。ここで、「独立気泡」とは、発泡体を構成している気泡構成単位であるセルが、隣接するセルとつながっておらず、セルを形成している壁（セル壁）によって完全に囲まれている構造を指す。このような微細且つ独立気泡化したセルを有する発泡体は、輻射による熱の伝達を低減させることができ、高温下においても優れた断熱性を有するため、断熱材として好適に用いられる。なお、本発明の発泡性組成物を用いた場合、発泡の進行過程において、赤外線不透過性粉体が発泡体セル壁面に沿って配向しながらセル壁面全体に広がっていく（セル壁面全体を覆う）と考えられる。このように、本発明の発泡体は赤外線不透過性粉体がセル壁面に沿って存在したものとなり、発泡体の高温での耐火断熱性をより効果的に高めることができる。
【００２６】
また、発泡体温度が４００℃以上になると、発泡体の収縮よりセル壁にミクロクラックが発生する場合があるため、かかる場合には、本発明の発泡性組成物に、更に耐熱性繊維を配合することが好ましい。なお、このミクロクラックの発生は、セル間同士が連なった連通体構造の原因となり、結果的にセル内部の気体の対流を増加させ、発泡体の断熱性を低下させることになる。耐熱性繊維を配合することにより、高温下においても発泡体が収縮し難くなり、ミクロクラックの発生を防止することが可能となる。配合可能な耐熱性繊維としては無機繊維が好ましく、更に、無機繊維として、チタン酸カリウム繊維、ボロン繊維及びシリカ繊維からなる群から選ばれる少なくとも１種を用いることが特に好ましい。
【００２７】
なお、ビニロン繊維、ポリプロ繊維、アラミド繊維などの有機繊維は高温領域で炭化燃焼してしまうおそれがあり、また、Ｅガラスよりなるガラス繊維も耐熱性が低く、高温領域で溶融軟化してしまうため、これらの繊維を本発明の組成物に添加することは、必ずしも適当でない。しかし、これらは従来から知られている補強繊維であり、成型体の強度を向上させ、且つ保形性をも向上させるために、これらの繊維を反応性無機粉体１００重量部に対して２重量部より少ない範囲で添加することは問題ない。２重量部より多くなると、粘度上昇により組成物の混練性、発泡性が悪化する。
【００２８】
かかる耐熱性繊維の繊維長及び繊維径に関しては、繊維長と繊維径との比、いわゆるアスペクト比を２０〜２０００の範囲内にすることが好ましく、より好ましくは５０〜１０００である。アスペクト比が２０より小さくなると、目的とする補強効果が得られず、一方、２０００より大きくなると、本発明で用いられる各成分からなる原料液の粘度が高くなりすぎて、耐熱性繊維を所定量添加した場合、原料液の攪拌が均一に実施できなくなるおそれがある。ただし、繊維長と繊維径との比率、すなわち、アスペクト比が上記範囲内であっても、繊維径１５μｍ以上の繊維を添加した場合、発泡体のセル壁に対して耐熱性繊維の存在が疎となるため、高温時のセル壁のクラック防止効果が得られなくなる。
【００２９】
なお、本発明の組成物には、必要に応じて発泡助材を添加してもよい。発泡助材としては、発泡する泡を微細なまま安定にするものであれば特に限定されない。例として、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸アルミニウム、マレイン酸亜鉛、マレイン酸カルシウムなどの脂肪酸金属塩、ひまし油系の界面活性剤、カゼインなど動物系たん白質などが挙げられる。これらは単独で用いても良いし、２種類以上を用いても構わない。
【００３０】
続いて、本発明の発泡性組成物を構成する各成分の量について説明する。まず、アルカリ金属珪酸塩の量は、珪酸アルミニウム系反応性無機粉体１００重量部に対して１０〜１００重量部とすることが好ましく、より好ましくは２０〜６０重量％である。アルカリ金属珪酸塩の量がこれより多いと、成型体が脆くなりやすく、一方、アルカリ金属珪酸塩の量が少ないと、珪酸アルミニウム系反応性無機粉体との硬化反応が遅くなる。なお、上述の通り、アルカリ金属珪酸塩は水溶液の状態で配合することが好ましく、例えば、アルカリ金属珪酸塩の５０％水溶液を用いた場合には、珪酸アルミニウム系反応性無機粉体１００重量部に対して２０〜２００重量部を加えることが好ましい。
【００３１】
また、発泡剤の量は、珪酸アルミニウム系反応性無機粉体１００重量部に対して０．０５〜５重量部とすることが好ましい。発泡剤が過酸化物の場合には、０．２〜３重量％が好ましく、より好ましくは０．５〜２重量％である。例えば、過酸化物として過酸化水素を用いる場合、過酸化水素の量がこれより多いと、異常発泡により破泡が進み、発泡体のセルが連続気泡となり断熱性能が低下する。また、適切な密度よりも小さな密度となるため、充分な強度を有する成型体が得られない。一方、過酸化水素の量が少ないと、発泡が小さいため成型体の密度が高くなり、強度と独立気泡は確保できるものの、軽量性が損なわれ断熱性能が劣る。なお、本発明においては、作業者の安全を考え、過酸化水素も水溶液、つまり過酸化水素水として配合することが好ましく、例えば、市販品の３５％水溶液を適度に水で希釈して用いることが好ましい。濃度１０％の過酸化水素水を用いた場合には、珪酸アルミニウム系反応性無機粉体１００重量部に対して２〜３０重量部を加えることが好ましい。発泡剤が金属系発泡剤の場合には、０．０５〜５重量部が好ましく、特に、０．１〜３重量部が好ましい。０．０５重量未満では、得られる発泡体の密度が高くなり過ぎ断熱性能が劣化するので好ましくない。また、５重量部を超えると、発泡過剰となり正常な発泡セルを形成できず、密度が低くなり過ぎ、成形体がもろくなり過ぎるとともに、良好な断熱性能が得られないので、好ましくない。
【００３２】
赤外線不透過性粉体の量は、珪酸アルミニウム系反応性無機粉体１００重量部に対して４〜４０重量部とすることが好ましく、より好ましくは１０〜３０重量部である。４重量部未満では、輻射による熱の伝達を充分に抑制することが出来ず、逆に、４０重量部より多くなると、得られる発泡体の強度が弱くなり高温時に割れを生じる可能性がある。なお、本発明においては、赤外線不透過性粉体として、１種類のものを単独で使用した場合でも、２種類以上のものを組み合わせて用いた場合でも、配合量の上限は４０重量部である。
【００３３】
本発明の発泡性組成物に、更に耐熱性繊維（無機繊維）を加える場合には、反応性粉体１００重量部に対して０．３〜５重量部の量の耐熱性繊維を加えることが好ましい。耐熱性繊維の量が少なすぎると高温下におけるミクロクラック発生防止効果が得られず、多すぎると混練がうまく行えなくなる。また、発泡性組成物に耐熱性繊維（無機繊維）を配合する場合も、赤外線不透過性粉体の量は、反応性粉体１００重量部に対して４〜４０重量部とすることが好ましい。
【００３４】
本発明の発泡性組成物は、上記した成分に加え、シラスバルーン、セラミックバルーンなどの無機耐熱中空粒子を本発明の目的を損なわない範囲で配合することもできる。
【００３５】
本発明の発泡性組成物の特性は、ＩＳＯ ８３４の耐火試験に従い、以下の方法により確認することができる。すなわち、ＩＳＯ ８３４加熱温度曲線に準じる昇温条件で、発泡性組成物から得られた発泡体の片面を所定時間加熱した際に、その反対側の面、すなわち発泡体の非加熱面の平均温度と室温との差が１４０℃以下となり、且つ発泡体非加熱面の最高温度と室温との差が１８０℃以下となる場合、高温下での耐火断熱性に優れた発泡体が得られていると評価することができる。なお、本発明の発泡性組成物から得られる発泡体の加熱には、耐火試験炉または耐火試験炉を再現しうる装置を用いることができる。
【００３６】
ここで、一般的に耐火構造体に発泡体を使用する場合、密度が高いと発泡体中の空隙率が低く、熱伝導率が高くなり好ましくない。また、密度が低い場合には、発泡体中のセルサイズが大きくなり、セル中で対流が大きくなり熱伝導率が高くなる。本発明では、発泡体中に赤外線不透過性粉体を添加せしめることにより、低密度から高密度までの幅広い範囲において優れた断熱性を有する発泡体を得ることができ、具体的には、密度１００〜７００ｋｇ／ｍ3の発泡体とすることも可能である。
【００３７】
本発明は、上述の通り、発泡体中に赤外線不透過性粉体を添加せしめ輻射による伝熱を低減し、更に必要に応じて高温でも安定な耐熱性繊維を補強材として添加することにより、ミクロクラック発生を防止し、対流による伝熱を低減するものである。したがって、本発明の発泡体は、土木建築用耐火断熱材、耐火充填材、吸音材、産業資材用耐熱性断熱材として好適に用いられる。
【００３８】
本発明の発泡性組成物から発泡体を得るには、例えば、アルカリ金属珪酸塩の水溶液、珪酸アルミニウム系反応性無機粉体及び赤外線不透過性粉体、更に必要に応じて無機繊維及び発泡助剤を混合してスラリーとし、これに発泡剤である過酸化物の水溶液を加えて混合し、通常の方法により、所定の形状物に充填し、発泡硬化させる方法が採用できる。あるいは、例えば、珪酸アルミニウム系反応性無機粉体、金属系発泡剤及び赤外線不透過性粉体、更に必要に応じて無機繊維及び発泡助剤を混合して均一な粉体とし、これにアルカリ金属珪酸塩の水溶液を加えて混合してスラリーとし、通常の方法により、所定の形状物に充填し、発泡硬化させる方法が採用できる。
【００３９】
【実施例】
以下、本発明についてより詳細に説明するが、本発明はこれらの例に限定される訳ではない。なお、以下において、「部」及び「％」とあるのは、特に断りのない限り、それぞれ「重量部」及び「重量％」を意味する。
【００４０】
耐火試験炉実験
以下の実施例及び比較例で得られた発泡体を、５０℃乾燥機で２４時間充分乾燥した。乾燥後、１０００×１０００×４０ｍｍの試験体に切り出し、ＪＩＳ Ｋ７２２２に準じて試験体の密度を計り取った後、１ｍ耐火炉に試験体を据え付けた。試験体の加熱温度はＩＳＯ８３４（建築構造・部材の耐火試験方法)加熱温度曲線に準じる昇温条件となるようにプログラムした。図１に示すように、試験体の非加熱面（裏面）の所定の位置（●で示される４箇所）に、それぞれ０．３２ｍｍのクロメルアルメル熱電対を固定して、１分おきに各熱電対位置における試験体の非加熱面の温度を測定し、加熱終了時間までにおける試験体非加熱面の最高平均温度と最高温度を求めた。加熱時間は７２分とした。発泡体非加熱面の最高平均温度と室温との差が１４０℃以下であり、且つ発泡体非加熱面の最高温度と室温との差が１８０℃以下である場合を「良」とし、それ以外の場合を「不可」と評価した。
【００４１】
実施例１〜３、比較例１〜２
表１に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液（組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％）、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム（和光純薬社製、平均粒子径３０μｍ）をハンドミキサーで混合して得られたスラリーに、過酸化水素水（濃度１０％）を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。実施例１〜３の発泡体においては、赤外線不透過性粉体がセル壁面に沿って存在することが確認された。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表１に示す。
【００４２】
実施例４〜６、比較例３〜４
表２に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。密度調整のため、過酸化水素を除く各成分の配合量は、比較例１〜２実施例１〜３の３倍とした。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表２に示す。
【００４４】
実施例７〜９、比較例５〜６
表３に示す配合に従い、高炉スラグ（組成ＳｉＯ2：Ａｌ2Ｏ3＝２：１（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表３に示す。
【００４６】
実施例１０〜１２、比較例７
表４に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化チタン(テイカ（株）社製、平均粒子径０．３μｍ)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表４に示す。
【００４８】
実施例１３〜１５、比較例８
表５に示す配合に従い、高炉スラグ（組成ＳｉＯ2：Ａｌ2Ｏ3＝２：１（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化チタン(テイカ（株）社製、平均粒子径０．３μｍ)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表５に示す。
【００５０】
実施例１６〜１７、比較例９
表６に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)を及び酸化チタン(テイカ（株）社製、平均粒子径０．３μｍ)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表６に示す。
【００５２】
実施例１８〜１９、比較例１０〜１１
表７に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)を及びチタン酸カリウム繊維(商品名：ＴＩＳＭＯ−Ｄ、大塚化学社製、平均繊維長と繊維径の平均比７０)をハンドミキサーで混合した得られたスラリーに、過酸化水素水(濃度１０％)を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表７に示す。
【００５４】
実施例２０〜２２、比較例１２〜１３
表８に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液（組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％）、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム（和光純薬社製、平均粒子径３０μｍ）をハンドミキサーで混合して得られたスラリーに、１２．０〜１４．０μｍのアルミニウム粉体を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。実施例２０〜２２の発泡体においては、赤外線不透過性粉体がセル壁面に沿って存在することが確認された。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表８に示す。
【００５６】
実施例２３〜２５、比較例１４〜１５
表９に示す配合に従い、フライアッシュ（組成ＳｉＯ2：Ａｌ2Ｏ3＝１１：５（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)をハンドミキサーで混合した得られたスラリーに、１２．０〜１４．０μｍのアルミニウム粉体を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。密度調整のため、アルミニウム粉体を除く各成分の配合量は、実施例２０〜２２及び比較例１２〜１３の３倍とした。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表９に示す。
【００５８】
実施例２６〜２８、比較例１６〜１７
表１０に示す配合に従い、高炉スラグ（組成ＳｉＯ2：Ａｌ2Ｏ3＝２：１（重量比）、平均粒径１０μｍ）、珪酸ナトリウム水溶液(組成ＳｉＯ2／Ｎａ2Ｏ＝１．５、濃度５５％)、ステアリン酸亜鉛（和光純薬社製）、及び酸化ジルコニウム(和光純薬社製、平均粒子径３０μｍ)をハンドミキサーで混合した得られたスラリーに、９．０〜１１．０μｍのアルミニウム粉体を添加して、更に混合した後に、１１００×１１００×４０ｍｍの型に流し込み発泡硬化させ、無機発泡体を得た。得られた発泡体を用い、上記方法に従い物性を評価した。結果を表１０に示す。
【００６０】
【発明の効果】
本発明の発泡性組成物を用いることにより、高温下でも優れた耐火断熱性を有する発泡体を得ることが可能となる。
【図面の簡単な説明】
【図１】耐火試験体の非加熱面上に設置する熱電対の位置（●の４箇所）を表わす概略図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a foamable composition, and more particularly, to a foamable composition capable of obtaining a foam excellent in fire resistance and heat insulation at high temperatures. The present invention also relates to a foam obtained by foaming and curing such a foamable composition.
[0002]
[Prior art]
Conventionally, lightweight foam has been obtained by adding metal (aluminum) and hydrogen peroxide to the reaction system of inorganic powder such as fly ash and blast furnace slag produced as industrial waste and silicate, and then foaming and curing. It is known that it can be obtained, and such a foam is used, for example, in the field of a building outer wall material as a foam heat insulating material.
[0003]
For example, using (A) water-soluble alkali silicate, (B) metal-based foaming agent, (C) fly ash or blast furnace slag and (D) a foamable inorganic composition containing water as active ingredients to form a foam. Is known (for example, see Patent Document 1). (A) 100 parts by weight of a reactive inorganic powder such as fly ash, clay, metakaolin, etc. containing 80% by weight or more of a powder having a particle size of 10 μm or less, (B) an average particle size of 0.01 to 35 μm 20 to 800 parts by weight of an inorganic filler that is granular or has a length in the longitudinal direction of 1 to 250 μm and a columnar or needle shape, (C) 0.01 to 10 parts by weight of hydrogen peroxide, (D There is also proposed a foamable inorganic composition comprising 0.2 to 450 parts by weight of an alkali metal silicate and (E) 35 to 1,500 parts by weight of water. By using such a composition, the uniformity of bubbles is proposed. It is said that a foam having a low heat shrinkage (at 100 ° C.) can be obtained while having excellent water resistance, high strength and low specific gravity (see, for example, Patent Document 2). However, the foam obtained from the foamable inorganic composition described in the above prior art cannot be said to have sufficient fire resistance at high temperatures.
[0004]
[Patent Document 1]
JP-A-57-77062
[Patent Document 2]
JP-A-8-73283
[0005]
[Problems to be solved by the invention]
As heat transfer in a certain material, heat conduction, convection and radiation are generally known. The material structure is made of foam, and the heat conduction is reduced by thinning the solid heat conduction part. Also, the convection of the gas in the material is achieved by making the foam cells finer and closed cells. It is already known to prevent this, and these techniques are widely used in organic foams and inorganic foams.
[0006]
Certainly, the above-mentioned method is effective as a method for improving the heat insulating property of the foam in the temperature range from low temperature to about 300 ° C., but the radiation effect is large in the high temperature region above 300 ° C. In order to improve performance, it is necessary to reduce heat transfer by radiation in addition to heat conduction and convection.
[0007]
In addition, in a composition composed of a silicate and a reactive inorganic powder, an appropriate surfactant is added and foam-cured to form fine and independent cells in the obtained heat insulating material. However, at high temperatures of 400 ° C. or higher, for example, microcracks occur in the cell walls due to shrinkage of the heat insulating material, and gas convection between the cells becomes significant, and as a result, the heat insulating property of the heat insulating material decreases. I came.
[0008]
For this reason, when using the foam obtained from the conventional inorganic composition for the use as which a fireproof thermal insulation property at high temperature like a fireproof panel etc. is calculated | required, it is necessary to thicken the thickness of a foam (panel). Yes, it wasn't economical.
[0009]
[Means for Solving the Problems]
The present invention has been made in view of the above points, and in addition to heat conduction and convection, it is possible to significantly reduce radiant heat from a high-temperature heat source, and has excellent fire and heat insulation even at high temperatures. An object of the present invention is to provide a foam composition capable of forming a foam.
[0010]
That is, the present invention includes an aluminum silicate-based reactive inorganic powder, an alkali metal silicate, a foaming agent, and an infrared opaque powder, and a ratio of the alkali metal silicate, the foaming agent, and the infrared opaque powder. However, it is related with the foamable composition which is 10-100 weight part, 0.05-5 weight part, and 4-40 weight part, respectively with respect to 100 weight part of aluminum silicate type | system | group reactive inorganic powder.
[0011]
The present invention also relates to a foam obtained by foam-curing such a foamable composition.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the foamable composition of the present invention contains aluminum silicate-based reactive inorganic powder, alkali metal silicate, foaming agent, and infrared opaque powder as essential components. Will be described.
[0013]
The “aluminum silicate-based reactive inorganic powder” used in the present invention refers to a reactive inorganic powder containing an aluminum silicate component, which can be reacted and cured with a water-soluble alkali silicate. Specific examples include fly ash, mineralized pulp sludge, blast furnace slag, and the like.
[0014]
Here, fly ash refers to fine ash particles collected by a dust collector from a pulverized coal combustion boiler as defined in JIS A 6201. Specifically, silica 45% or more, moisture 1% or less, Ignition loss 5% or less, specific gravity 1.95 or more, specific surface area 2700cm 2 / G or more and 75% or more of the particles can pass through a 44 μm standard sieve. In the present invention, from the viewpoint of heat resistance, SiO 2 : Al 2 O Three = Fly ash having a composition of 45 to 60:20 to 28 (weight ratio) is preferably used, and it is preferable to have an average particle diameter of 5 to 30 μm.
[0015]
Mineralized pulp sludge is obtained by incineration mineralization of waste produced as a by-product in the papermaking process. Specifically, silica 40% or more, moisture 1% or less, ignition loss 1% or less, specific gravity 1. 80 or more, specific surface area 2500cm 2 / G or more, 75% or more of the particles pass through the 44 μm standard sieve. In the present invention, from the viewpoint of heat resistance, SiO 2 : Al 2 O Three = 30-50: 25-35 (weight ratio) is preferable, and it is preferable to have an average particle diameter of 5-30 μm. .
[0016]
Blast furnace slag is an inorganic powder produced as a by-product when iron is refined from iron ore specified in JIS A5011-1. Specifically, calcium oxide is 45% or less, sulfur content is 2. Examples thereof include 0% or less and a specific gravity of 2.50 or more. In the present invention, it is preferable that 70% or more of the particles pass through a 44 μm standard sieve, and a preferable average particle diameter is 5 to 30 μm.
[0017]
In the present invention, in addition to the above, the chemical composition is SiO. 2 10 to 80% by weight, Al 2 O Three It is also possible to use an inorganic powder containing 90 to 10% by weight as an aluminum silicate-based reactive inorganic powder. Examples of such powders include kaolin minerals such as metakaolin, mica clay minerals, wollastonite, and talc. However, it is not limited to these as long as the composition particle size is appropriate and the dimensional stability at high temperature is excellent.
[0018]
Next, the alkali metal silicate used in the present invention is M. 2 O · nSiO 2 (M = one or more metals selected from K, Na, and Li). Here, n is preferably in the range of 0.5 to 4, more preferably 1.0 to 2.5. If the value of n is smaller than this, the reaction is too fast, and the foam cell becomes open-celled and the heat insulation performance decreases. Conversely, if the value of n becomes too large, the reaction becomes difficult to proceed. In addition, it is preferable to mix | blend alkali metal silicate as aqueous solution. The concentration of the aqueous solution is not particularly limited, but the reactivity with the reactive powder decreases as the thickness decreases. Moreover, since it will become easy to precipitate an alkali metal silicate when it becomes thick, it is preferable to set it as 10 to 60 weight%. Further, the alkali metal silicate aqueous solution may be prepared by dissolving the alkali metal silicate as it is in water under pressure and heating, but first, the alkali metal silicate is mixed with SiO such as silica sand and silica powder. 2 The components may be added to make n a predetermined value, and then dissolved under pressure and heating to obtain an alkali metal silicate aqueous solution.
[0019]
As the foaming agent used in the present invention, a peroxide and a metal-based foaming agent are mainly exemplified. Specific examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, potassium peroxide, sodium peroxide, ammonium persulfate, sodium persulfate, and potassium persulfate. These peroxides are usually used as an aqueous solution. For example, a hydrogen peroxide solution having a concentration of 5 to 40% by weight and a t-butyl hydroperoxide aqueous solution having a concentration of 60 to 70% by weight are preferable. Specifically, metal elements, metal alloys, intermetallic compounds, and the like are used as the metal foaming agent. As the metal element, those belonging to the third to fifth periods of the periodic table such as aluminum, silicon, calcium, barium, iron, nickel, gallium, etc. are preferable, and as the metal alloy and intermetallic compound, aluminum-silicon, aluminum -Titanium, aluminum-manganese, aluminum-copper, aluminum-copper-silicon and the like are preferable. Of these, aluminum, silicon and the like are particularly preferable. These metal foaming agents are usually preferably used as a powder having an average particle size of 0.1 to 200 μm, preferably 1 to 50 μm.
[0020]
Subsequently, “infrared impervious powder” used in the present invention means a material that is opaque to infrared transmission and scatters and blocks radiant heat. In the present invention, it is preferable to use at least one selected from the group consisting of zirconium oxide and titanium oxide as the infrared opaque powder.
[0021]
Zirconium oxide preferably has an average particle diameter of 1 to 80 μm, more preferably 1 to 50 μm, from the viewpoints of heat reflectivity and heat insulation at high temperatures. When zirconium oxide having a large average particle size is used (> 80 μm), the presence of zirconium oxide in the composition becomes sparse, so that the effect of improving heat insulation by preventing radiation is not sufficiently exhibited, and the average particle size is 1 μm. Below, since it becomes smaller than the wavelength of infrared rays, infrared rays pass through and the reflection effect becomes small. In the present invention, an inexpensive silica sand compound such as zircon sand can also be used.
[0022]
As titanium oxide, it is preferable to use a titanium oxide having a particle diameter of infrared wavelength (0.76 μm) or more from the viewpoint of heat reflectivity, but titanium oxide is a very fine powder, The upper limit of the average primary particle diameter is about 0.2 to 0.3 μm. For this reason, in this invention, it is preferable to use the titanium oxide whose average particle diameter is 0.1 micrometer or more, More preferably, it is 0.2 micrometer or more. Even if titanium oxide having a particle size of less than 0.1 μm is added, infrared rays pass through, and the desired heat reflecting effect cannot be obtained.
[0023]
In addition, since titanium oxide has a high refractive index, it is known as a reflective material, and there is a heat insulating material in which the surface layer is a titanium oxide coating layer, but a remarkable result was not obtained regarding the heat insulating property in a high temperature region. However, by blending with an inorganic foam-cured heat insulating material made of a thin film (cell wall), the entire thin film becomes a reflective layer and can be a heat insulating material with a high heat insulating effect.
[0024]
Moreover, in this invention, it is preferable to use together a zirconium oxide and a titanium oxide as infrared impervious powder from the point of obtaining a more favorable heat insulation.
[0025]
The foamable composition of the present invention containing the above-described specific component becomes a foam having fine and closed cells by foaming and curing. Here, the “closed cell” means that a cell which is a bubble constituent unit constituting a foam is not connected to an adjacent cell and is completely surrounded by a wall (cell wall) forming the cell. Refers to the structure that is. A foam having such fine and closed-cells can be suitably used as a heat insulating material because it can reduce heat transfer due to radiation and has excellent heat insulating properties even at high temperatures. When the foamable composition of the present invention is used, in the process of foaming, the infrared-impermeable powder spreads over the entire cell wall surface while being oriented along the foam cell wall surface (covering the entire cell wall surface). )it is conceivable that. As described above, the foam of the present invention has the infrared-impermeable powder along the cell wall surface, and can effectively improve the fire-resistance and heat-resistance at a high temperature of the foam.
[0026]
In addition, when the foam temperature is 400 ° C. or higher, micro cracks may occur in the cell wall due to the shrinkage of the foam. In such a case, a heat-resistant fiber is further added to the foamable composition of the present invention. It is preferable to do. In addition, generation | occurrence | production of this microcrack becomes a cause of the communicating body structure where cells connected, As a result, the convection of the gas inside a cell will increase and the heat insulation of a foam will fall. By blending heat resistant fibers, the foam is less likely to shrink even at high temperatures, and microcracks can be prevented from occurring. The heat-resistant fiber that can be blended is preferably an inorganic fiber, and more preferably at least one selected from the group consisting of potassium titanate fiber, boron fiber, and silica fiber.
[0027]
Organic fibers such as vinylon fiber, polypro fiber, and aramid fiber may carbonize and burn in the high temperature range, and glass fibers made of E glass have low heat resistance and melt and soften in the high temperature range. It is not always appropriate to add these fibers to the composition of the present invention. However, these are conventionally known reinforcing fibers, and in order to improve the strength of the molded body and also improve the shape retention, these fibers are added to 2 parts by weight of the reactive inorganic powder. There is no problem if it is added in a range less than parts by weight. If it exceeds 2 parts by weight, the kneadability and foamability of the composition deteriorate due to the increase in viscosity.
[0028]
Regarding the fiber length and fiber diameter of such heat-resistant fibers, the ratio of fiber length to fiber diameter, so-called aspect ratio, is preferably in the range of 20 to 2000, more preferably 50 to 1000. When the aspect ratio is less than 20, the intended reinforcing effect cannot be obtained. On the other hand, when the aspect ratio is greater than 2000, the viscosity of the raw material liquid composed of each component used in the present invention becomes too high, and a predetermined amount of heat-resistant fiber is added. When added, the raw material liquid may not be uniformly stirred. However, even when the ratio of the fiber length to the fiber diameter, that is, the aspect ratio is within the above range, when fibers having a fiber diameter of 15 μm or more are added, the presence of heat-resistant fibers is less than the cell wall of the foam. Therefore, the effect of preventing cracking of the cell wall at a high temperature cannot be obtained.
[0029]
In addition, you may add a foaming auxiliary material to the composition of this invention as needed. The foaming aid is not particularly limited as long as foaming foam is stabilized while being fine. Examples include fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate, zinc maleate, calcium maleate, castor oil surfactants, animal proteins such as casein, and the like. These may be used alone or in combination of two or more.
[0030]
Then, the quantity of each component which comprises the foamable composition of this invention is demonstrated. First, the amount of the alkali metal silicate is preferably 10 to 100 parts by weight, more preferably 20 to 60% by weight with respect to 100 parts by weight of the aluminum silicate-based reactive inorganic powder. When the amount of the alkali metal silicate is larger than this, the molded body tends to be brittle, while when the amount of the alkali metal silicate is small, the curing reaction with the aluminum silicate-based reactive inorganic powder is delayed. As described above, the alkali metal silicate is preferably added in the form of an aqueous solution. For example, when a 50% aqueous solution of the alkali metal silicate is used, 100 parts by weight of the aluminum silicate-based reactive inorganic powder is used. It is preferable to add 20 to 200 parts by weight.
[0031]
Moreover, it is preferable that the quantity of a foaming agent shall be 0.05-5 weight part with respect to 100 weight part of aluminum silicate type reactive inorganic powder. When a foaming agent is a peroxide, 0.2 to 3 weight% is preferable, More preferably, it is 0.5 to 2 weight%. For example, when hydrogen peroxide is used as the peroxide, if the amount of hydrogen peroxide is larger than this, bubble breakage progresses due to abnormal foaming, and the foam cells become open-celled and the heat insulation performance decreases. Moreover, since it becomes a density smaller than a suitable density, the molded object which has sufficient intensity | strength cannot be obtained. On the other hand, when the amount of hydrogen peroxide is small, foaming is small and the density of the molded body is high, and although strength and closed cells can be secured, the lightness is impaired and the heat insulating performance is inferior. In the present invention, it is preferable to mix hydrogen peroxide as an aqueous solution, that is, hydrogen peroxide water in consideration of the safety of workers. For example, a commercially available 35% aqueous solution is appropriately diluted with water and used. Is preferred. When hydrogen peroxide solution having a concentration of 10% is used, it is preferable to add 2 to 30 parts by weight with respect to 100 parts by weight of the aluminum silicate-based reactive inorganic powder. When the foaming agent is a metal foaming agent, 0.05 to 5 parts by weight is preferable, and 0.1 to 3 parts by weight is particularly preferable. If it is less than 0.05 weight, the density of the obtained foam becomes too high, and the heat insulation performance deteriorates, which is not preferable. On the other hand, when the amount exceeds 5 parts by weight, foaming is excessive and normal foam cells cannot be formed, the density becomes too low, the molded product becomes too brittle, and good heat insulation performance cannot be obtained.
[0032]
The amount of the infrared-impermeable powder is preferably 4 to 40 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the aluminum silicate reactive inorganic powder. If the amount is less than 4 parts by weight, heat transfer due to radiation cannot be sufficiently suppressed. Conversely, if the amount exceeds 40 parts by weight, the strength of the resulting foam is weakened, and cracking may occur at high temperatures. In the present invention, the upper limit of the blending amount is 40 parts by weight regardless of whether one kind of infrared impermeable powder is used alone or two or more kinds are used in combination. .
[0033]
When heat-resistant fibers (inorganic fibers) are further added to the foamable composition of the present invention, 0.3 to 5 parts by weight of heat-resistant fibers may be added to 100 parts by weight of the reactive powder. preferable. If the amount of heat-resistant fiber is too small, the effect of preventing the occurrence of microcracks at high temperatures cannot be obtained, and if too large, kneading cannot be performed well. Moreover, also when mix | blending a heat resistant fiber (inorganic fiber) with a foamable composition, it is preferable that the quantity of infrared rays impervious powder shall be 4-40 weight part with respect to 100 weight part of reactive powder. .
[0034]
In addition to the above-described components, the foamable composition of the present invention can also contain inorganic heat-resistant hollow particles such as shirasu balloons and ceramic balloons as long as the object of the present invention is not impaired.
[0035]
The characteristics of the foamable composition of the present invention can be confirmed by the following method according to the fire resistance test of ISO 834. That is, when one side of a foam obtained from the foamable composition is heated for a predetermined time under a temperature rise condition according to the ISO 834 heating temperature curve, the average temperature of the opposite side, that is, the non-heated side of the foam When the difference between the maximum temperature of the foam non-heated surface and the room temperature is 180 ° C. or less, a foam excellent in fire resistance and heat insulation at high temperatures is obtained. Can be evaluated. In addition, the apparatus which can reproduce a fireproof test furnace or a fireproof test furnace can be used for the heating of the foam obtained from the foamable composition of this invention.
[0036]
Here, when a foam is generally used for the fireproof structure, a high density is not preferable because the porosity in the foam is low and the thermal conductivity is high. In addition, when the density is low, the cell size in the foam increases, convection increases in the cell, and the thermal conductivity increases. In the present invention, by adding an infrared opaque powder to the foam, a foam having excellent heat insulation in a wide range from low density to high density can be obtained. 100-700kg / m Three It is also possible to use a foam.
[0037]
As described above, the present invention adds infrared impermeable powder in the foam to reduce heat transfer due to radiation, and if necessary, by adding a heat-resistant fiber that is stable even at high temperatures as a reinforcing material, It prevents microcracking and reduces heat transfer by convection. Therefore, the foam of this invention is used suitably as a fireproof heat insulating material for civil engineering construction, a fireproof filler, a sound absorbing material, and a heat resistant heat insulating material for industrial materials.
[0038]
In order to obtain a foam from the foamable composition of the present invention, for example, an aqueous solution of an alkali metal silicate, an aluminum silicate-based reactive inorganic powder and an infrared-impermeable powder, and further, if necessary, inorganic fibers and foaming aids. It is possible to employ a method in which an agent is mixed to form a slurry, an aqueous solution of a peroxide as a foaming agent is added and mixed, and filled into a predetermined shape by an ordinary method and foamed and cured. Alternatively, for example, an aluminum silicate-based reactive inorganic powder, a metal-based foaming agent and an infrared-impermeable powder, and further mixed with inorganic fibers and a foaming aid as necessary to form a uniform powder, and an alkali metal A method in which an aqueous solution of silicate is added and mixed to form a slurry, which is filled in a predetermined shape and foam-cured by an ordinary method, can be employed.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail, but the present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0040]
Fire test furnace experiment
The foams obtained in the following Examples and Comparative Examples were sufficiently dried for 24 hours with a 50 ° C. dryer. After drying, the specimen was cut into a 1000 × 1000 × 40 mm specimen, the density of the specimen was measured according to JIS K7222, and the specimen was installed in a 1 m refractory furnace. The heating temperature of the test body was programmed so as to be a temperature increase condition according to ISO834 (fire resistance test method for building structure / member) heating temperature curve. As shown in FIG. 1, 0.32 mm chromel alumel thermocouples are fixed at predetermined positions (four locations indicated by ●) on the non-heated surface (back surface) of the test specimen, and each thermoelectric power is changed every one minute. The temperature of the non-heated surface of the test body at the opposite position was measured, and the maximum average temperature and the maximum temperature of the test body non-heated surface up to the heating end time were obtained. The heating time was 72 minutes. The case where the difference between the maximum average temperature of the foam non-heated surface and room temperature is 140 ° C or less and the difference between the maximum temperature of the foam non-heated surface and room temperature is 180 ° C or less is defined as "good", otherwise The case of was evaluated as “impossible”.
[0041]
Examples 1-3, Comparative Examples 1-2
According to the formulation shown in Table 1, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter 30 μm) were mixed with a hand mixer into a slurry obtained. After adding hydrogen peroxide (concentration 10%) and further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. In the foams of Examples 1 to 3, it was confirmed that the infrared-impermeable powder was present along the cell wall surface. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 1.
[0042]
Examples 4-6, Comparative Examples 3-4
According to the formulation shown in Table 2, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size 30 μm) were mixed with a hand mixer. Hydrogen oxide water (concentration 10%) was added, and after further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. In order to adjust the density, the amount of each component excluding hydrogen peroxide was three times that of Comparative Examples 1-2 and Examples 1-3. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 2.
[0044]
Examples 7-9, Comparative Examples 5-6
According to the formulation shown in Table 3, blast furnace slag (composition SiO 2 : Al 2 O Three = 2: 1 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size 30 μm) were mixed with a hand mixer. Hydrogen oxide water (concentration 10%) was added, and after further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 3.
[0046]
Examples 10-12, Comparative Example 7
According to the formulation shown in Table 4, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), a slurry obtained by mixing zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide (manufactured by Teika Co., Ltd., average particle size 0.3 μm) with a hand mixer. Hydrogen peroxide water (concentration 10%) was added to the mixture, and after further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 4.
[0048]
Examples 13 to 15 and Comparative Example 8
According to the formulation shown in Table 5, blast furnace slag (composition SiO 2 : Al 2 O Three = 2: 1 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), a slurry obtained by mixing zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide (manufactured by Teika Co., Ltd., average particle size 0.3 μm) with a hand mixer. Hydrogen peroxide water (concentration 10%) was added to the mixture, and after further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 5.
[0050]
Examples 16-17, Comparative Example 9
According to the formulation shown in Table 6, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter 30 μm) and titanium oxide (manufactured by Teika Co., Ltd., average particles) Hydrogen peroxide solution (concentration 10%) was added to the resulting slurry mixed with a hand mixer (diameter 0.3 μm), and after further mixing, it was poured into a mold of 1100 × 1100 × 40 mm, foamed and cured, and inorganic A foam was obtained. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 6.
[0052]
Examples 18-19, Comparative Examples 10-11
According to the formulation shown in Table 7, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries), zirconium oxide (manufactured by Wako Pure Chemical Industries, average particle size 30 μm) and potassium titanate fiber (trade name: TISMO-D, 1100 × 1100 after adding hydrogen peroxide water (concentration 10%) to the resulting slurry obtained by mixing Otsuka Chemical Co., Ltd., average fiber length / fiber diameter average ratio 70) with a hand mixer. It was poured into a 40 mm mold and foamed and cured to obtain an inorganic foam. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 7.
[0054]
Examples 20-22, Comparative Examples 12-13
According to the formulation shown in Table 8, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size 30 μm) were mixed with a hand mixer into a slurry obtained. After adding 12.0 to 14.0 μm aluminum powder and further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. In the foams of Examples 20 to 22, it was confirmed that the infrared-impermeable powder was present along the cell wall surface. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 8.
[0056]
Examples 23-25, Comparative Examples 14-15
According to the formulation shown in Table 9, fly ash (composition SiO 2 : Al 2 O Three = 11: 5 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter of 30 μm) were mixed with a hand mixer. After adding 0.01 to 14.0 μm aluminum powder and further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. In order to adjust the density, the blending amount of each component excluding the aluminum powder was three times that of Examples 20 to 22 and Comparative Examples 12 to 13. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 9.
[0058]
Examples 26-28, Comparative Examples 16-17
According to the formulation shown in Table 10, blast furnace slag (composition SiO 2 : Al 2 O Three = 2: 1 (weight ratio), average particle size 10 μm), sodium silicate aqueous solution (composition SiO) 2 / Na 2 O = 1.5, concentration 55%), zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter of 30 μm) were mixed with a hand mixer into the resulting slurry. After adding 0.01 to 11.0 μm aluminum powder and further mixing, it was poured into a mold of 1100 × 1100 × 40 mm and foamed and cured to obtain an inorganic foam. Using the obtained foam, the physical properties were evaluated according to the above methods. The results are shown in Table 10.
[0060]
【The invention's effect】
By using the foamable composition of the present invention, it is possible to obtain a foam having excellent fire and heat insulation properties even at high temperatures.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic diagram showing the positions of thermocouples (four locations in black circles) installed on a non-heated surface of a fireproof test specimen.
Claims (9)
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| JP5002825B2 (en) * | 2005-07-07 | 2012-08-15 | 株式会社ジェイエスピー | Method for producing inorganic foam |
| JP4676827B2 (en) * | 2005-07-07 | 2011-04-27 | 株式会社アスクテクニカ | Porous molded body and method for producing the same |
| JP2007120159A (en) * | 2005-10-28 | 2007-05-17 | Ehime Univ | Heat insulating and soundproof material |
| JP4714640B2 (en) * | 2006-06-07 | 2011-06-29 | 新日本製鐵株式会社 | Manufacturing method of heat insulating gradient material |
| JP6960814B2 (en) * | 2017-09-25 | 2021-11-05 | ライト工業株式会社 | Filler and manufacturing method of filler |
| JP2019059633A (en) * | 2017-09-25 | 2019-04-18 | ライト工業株式会社 | Filler and method for producing filler |
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2003
- 2003-03-26 JP JP2003084661A patent/JP4378675B2/en not_active Expired - Lifetime
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