JP2004035378A - Heat expandable refractory material composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 60
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- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 25
- 239000002657 fibrous material Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 239000000057 synthetic resin Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
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- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
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Landscapes
- Building Environments (AREA)
- Ceramic Products (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Lining And Supports For Tunnels (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ビル構築用の鉄骨を始めとする各種構造材、建物の内外壁や天井部、間仕切り、屋外通路壁、トンネル内壁、建具、器壁等の耐火被覆層ならびに耐火充填層形成に用いる熱発泡性耐火材組成物に関する。
【０００２】
【従来の技術】
近年、都市におけるビルの高層化や地下街の大規模化が進み、これに伴って防災対策の必要性が高まっており、特に火災への備えが重要になっている。しかるに、各種構造材に対する耐火被覆として旧来汎用されていたアスベストは粉塵吸入による発癌性の問題で使用できなくなっており、またロックウールについても同様の健康被害の懸念があって嫌忌すべきものになっている上、これらは耐火性能面でも充分ではなかった。
【０００３】
そこで、前記のアスベストやロックウールに代わる耐火被覆材料として、火災時の受熱で発泡して断熱発泡層を形成し、遮炎・遮熱作用を発揮する熱発泡性耐火塗料が種々提案されている。このような熱発泡性耐火塗料には、水溶性アルカリ珪酸塩を主成分として硬化剤や骨材成分が配合され、含有水分の気化によって発泡を生じる無機系のもの、結合剤樹脂に炭化剤とポリリン酸アンモニウムの如き発泡剤が配合され、発泡と共に炭化層を形成する有機系のもの、水溶性シリケートとアルコキシシラン誘導体やオルガノシリカゾルとの反応物を主体としたもの、水溶性アルカリ珪酸塩と紫外線硬化型樹脂成分を混合したもの等があるが、これらの殆どは実用化しておらず、実際の使用例は有機系のものだけである。
【０００４】
しかるに、上記使用実績のある有機系のものは、火災時に結合剤樹脂の溶融と共に発泡剤の分解によるガスが発生することにより、フォーム状に膨張した炭化層を生成するが、そのガス成分に有毒なアンモニアガスが高率で含まれるため、被災環境を却って害する懸念がある上、肝心な耐火性能も充分とは言えない。因みに、普通鋼の耐熱温度は３５０℃、耐火鋼でも６００℃に過ぎず、それ以上の高温では軟化してしまうため、鉄骨構造として火災温度１０００℃に耐えるためには極めて強力な熱遮断性を発揮する耐火被覆が必要である。
【０００５】
上述の情況に照らし、本発明者は先に、長期にわたる綿密な実験研究のもとに、鉄骨構造用の耐火被覆として充分な熱遮断性を発揮し得る画期的な無機系の耐火性コーティング剤を究明し、これを特願２００１−３５４８５８号として出願中である。この耐火性コーティング剤は、水溶性アルカリ珪酸塩及びホルマイト系鉱物粉末と、これら以外のＳｉＯ２ 付与成分とを必須成分として含有する水性ペーストからなり、その塗膜が火災時の受熱によって発泡して断熱発泡層を生成するが、発泡のタイミングとスピードの絶妙なバランスにより、塗膜全体に偏りなく生じた細かい気泡の安定した成長に伴って塗膜全体が均一に膨張し、均一で厚い発泡断熱層を生成する上、発泡後の流動点が高いために垂れ落ちを生じにくく、優れた熱遮断性を長く持続できるという特徴を備えている。
【０００６】
【発明が解決しようとする課題】
しかるに、前記耐火性コーティング剤においても、当然のことながら様々な面で改良の余地を残している。特に、このような耐火性コーティング剤による耐火被覆層は一般的に層厚５ｍｍ以上といった厚いものになるため、塗工時の垂れ落ちや塗工後の重力による変形を生じたり、塗膜自体の硬化収縮に伴う亀裂、硬化後の基材側の温度変化に伴う伸縮による亀裂、火災時の受熱に伴う割れ等を発生する場合がある。そして、上記の垂れ落ちや変形があると、耐火被覆層の厚みが不均一になって耐火断熱性能の低下を招いたり、外観が悪化することになり、また耐火被覆層に亀裂が存在すると、火炎時に亀裂を通して下地の基材に直接に高熱が及ぶことになるため、耐火被覆としての信頼性が得られず、また火災時の受熱に伴う割れが発生すると、やはり下地の基材に高熱が及んで耐火性の低下を招くことになる。
【０００７】
本発明者は、上記の耐火性コーティング剤に係る技術を基本にして、更に性能や施工性を高めるべく鋭意検討を重ねた結果、水溶性アルカリ珪酸塩と無機質粉末とを主成分とする熱発泡性材料に短繊維物質を含有させた場合に、上記の垂れ落ちや変形、亀裂を防止でき、しかも火災時の割れも生じにくく熱発泡の均一性が向上することを見出し、本発明を達成したものである。
【０００８】
【課題を解決するための手段】
すなわち、請求項１の発明は、水溶性アルカリ珪酸塩と無機質粉末とを主成分とし、平均繊維長０．５〜１５ｍｍの短繊維物質を含有してなる熱発泡性耐火材組成物に係る。しかして、このような熱発泡性耐火材組成物では、短繊維物質の存在により、基材に塗工した際に垂れ落ちや重力による変形を生じず、形成した耐火層の寸法安定性及び保形性がよく、施工性も向上すると共に、耐火層の硬化収縮に伴う亀裂や基材の温度変化に伴う伸縮による亀裂が防止される。しかも、火災時に耐火層が溶融発泡する際、気泡同士の合体が抑制され、この合体による空洞部の形成や合体した気泡の破裂が防止され、また受熱による割れも防止される。また、短繊維物質が適度な繊維長であることから、熱発泡性材料の各成分を混合する際、繊維同士の絡まり合いが抑制され、もって耐火層全体に短繊維物質を均一に含有させることができる。
【０００９】
請求項２の発明は、上記請求項１の熱発泡性耐火材組成物において、前記短繊維物質が合成樹脂繊維からなる構成としている。この場合、火災時に耐火層中の合成樹脂繊維は高熱で炭化するが、この炭化物によって耐火層の断熱性がより向上することになる。
【００１０】
請求項３の発明は、上記請求項２の熱発泡性耐火材組成物において、前記合成樹脂繊維がビニロン繊維であるものとしている。この場合、火災時に耐火層中のビニロン繊維は溶融して直ちに炭化するため、燃焼ガスを殆ど発生しない。
【００１１】
請求項４の発明は、上記請求項１の熱発泡性耐火材組成物において、前記短繊維物質が非有機質繊維であるものとしている。この場合、火災時に耐火層が溶融発泡する際、原形を保った非有機質繊維によって溶融発泡層の垂れ落ちが防止されると共に、空洞の発生や加熱割れも確実に防止できる。
【００１２】
請求項５の発明は、上記請求項１又は２の熱発泡性耐火材組成物において、前記短繊維物質が固化状態の耐火材組成物全量中の０．０１〜２．０重量％を占める割合で含有されてなるものとしている。この場合、耐火層の火災時の溶融発泡性を阻害しない範囲で、短繊維物質の既述作用が充分に発現することになる。
【００１３】
請求項６の発明は、上記請求項１〜５のいずれかの熱発泡性耐火材組成物において、前記水溶性アルカリ珪酸塩が固化状態の耐火材組成物全量中の３０〜８０重量％を占める割合で含有されてなる構成としている。この場合、耐火層の火災時の溶融発泡性とそれによる耐火断熱性能を良好に確保できる。
【００１４】
請求項７の発明は、上記請求項１〜６のいずれかの熱発泡性耐火材組成物において、前記無機質粉末として微粒子状シリカを含む構成としている。この場合、耐火層の火災時の溶融発泡性とそれによる耐火断熱性能がより向上すると共に、耐火層の形成時の硬化が速くなる。
【００１５】
請求項８の発明は、上記請求項７の熱発泡性耐火材組成物において、前記無機質粉末として、微粒子状シリカと共に、炭酸カルシウム粉末、水酸化アルミニウム粉末、焼成クレー、メタカオリン粉末より選ばれる少なくとも一種を含む構成としている。すなわち、炭酸カルシウムは熱分解によって炭酸ガスを放出し、水酸化アルミニウムは加熱の初期段階で水を発生し、共に耐火層３の熱発泡を補助する作用があり、また焼成クレーは熱伝導率が低いために耐火層３の断熱性を高める作用があり、更にメタカオリン粉末はＳｉＯ２ 付与成分として効果的に機能し、これらの使用によって耐火層の耐火断熱性能が向上することになる。
【００１６】
【発明の実施の形態】
本発明に係る熱発泡性耐火材組成物は、既述のように水溶性アルカリ珪酸塩と無機質粉末とを主成分として短繊維物質を含有するものであり、硬化前の原料組成物では一般的にクリーム状ないしパテ状の水性ペースト形態であり、各種基材の表面に塗工して厚い耐火被覆層を形成したり、各種基材の中空部に注入して耐火充填層を形成できるが、その硬化時に亀裂を生じず、また硬化後に温度変化によって基材が伸縮しても亀裂を生じにくいため、耐火層としての高い信頼性が得られる。しかも、この熱発泡性耐火材組成物は、基材に塗工した際に垂れ落ちや重力による変形を生じにくく、形成層の寸法安定性及び保形性が良好であるから、均一な厚みで外観に優れ、且つ耐火断熱性能の局所的な偏りがない耐火被覆層を形成できると共に、その施工性も良好である。
【００１７】
しかして、本発明の熱発泡性耐火材組成物よりなる耐火層は、火災時の受熱によって発泡して厚い断熱発泡層を生成するが、この発泡過程での気泡同士の合体を生じにくく、溶融物全体に生じた細かい気泡群が独立気泡のまま膨張してゆくため、断熱発泡層中に気泡の合体による大きな空洞部を生じたり、合体した気泡が破裂したり、加熱割れを生じることがなく、もって該断熱発泡層は全体的に均一な発泡状態となって極めて卓越した熱遮断性を発揮する。
【００１８】
このような熱発泡性耐火材組成物の優れた特徴は専ら含有する短繊維物質に依拠しているが、該短繊維物質には平均繊維長が０．５〜１５ｍｍの範囲にあるものを用いる必要がある。すなわち、この平均繊維長が０．５ｍｍ未満のものでは、前記の亀裂防止、寸法安定性、垂れ止め、保形性等の作用が充分に発現しない。一方、該平均繊維長が１５ｍｍを越えるものでは、各成分を混合して原料組成物を調製する際に、繊維同士が絡み合って塊になり易く、短繊維物質が耐火層全体に均一に分散含有されないため、やはり前記作用が充分に発現しない。また、該短繊維物質の太さについては、特に制約はないが、繊維径（フィラメント径）で５〜１００μｍの範囲が好適であり、細過ぎては強度に乏しいために充分な配合効果が得られず、逆に太過ぎては硬く曲がりにくいために組成物素地に対する結着性が弱くなって前記作用を充分に発揮できない。
【００１９】
上記の短繊維物質としては、特に制約はなく、合成樹脂繊維、非有機質繊維、動物性繊維、植物性繊維等の種々のものを使用可能であるが、特に合成樹脂繊維及び非有機質繊維が好適である。すなわち、合成樹脂繊維を含む耐火層では、火災時に合成樹脂繊維が高熱で炭化するが、この炭化物の高い断熱性によって耐火層自体の耐火断熱性能が向上する。また、非有機質繊維を含む耐火層では、高熱下でも非有機質繊維が原形を保つため、火災時の受熱で溶融発泡する際に溶融発泡層の垂れ落ちや気泡の合体による空洞部の発生が確実に防止されると共に、形成された断熱発泡層の加熱割れが防止され、もって耐火断熱性能がより向上することになる。
【００２０】
上記の合成樹脂繊維としては、種々の材質のものを使用できるが、特にビニロン繊維（ポリビニルアルコール繊維）は火災時に溶融して直ちに炭化し、燃焼ガスを殆ど発生しないという利点がある。一方、非有機質繊維としては、ガラス繊維、炭素繊維、金属繊維、人工セラミック繊維等を好適に使用できる。
【００２１】
短繊維物質の含有量は、固化状態の耐火材組成物全量中の０．０１〜２．０重量％を占める割合がよく、少な過ぎては使用効果が充分に発現せず、逆に多過ぎては耐火層の火災時の溶融発泡性が阻害される懸念がある。しかして、材質が合成樹脂繊維である場合は、その比重が小さいために少ない重量でも量的には多くなるから、特に前記含有量を０．０１〜０．２重量％の範囲にすることが推奨される。
【００２２】
本発明の熱発泡性耐火材組成物における主成分の一つである水溶性アルカリ珪酸塩は、塗膜に熱発泡性をもたらすための基本成分であり、火災時の受熱によって溶融状態となって気化した含有水分を気泡化させて層内に留まらせ、もって耐火層の発泡層への転化を可能にするものである。また、原料組成物においても、その水溶液がベースとして他の配合成分を分散ないし溶存させる液媒体となる。従って、この水溶性アルカリ珪酸塩は、耐火材組成物の水を除く成分中の３０〜８０重量％を占める割合で用いることが好ましく、この割合が少な過ぎては充分な熱発泡性が得られず、逆に多過ぎても熱発泡が不均一になって生成する発泡層の断熱性能が低下する。
【００２３】
このような水溶性アルカリ珪酸塩としては、珪酸ナトリウム、珪酸カリウム、珪酸リチウム等が挙げられるが、水ガラスとしての水溶液形態の市販品を好適に使用できる。しかして、この水溶性アルカリ珪酸塩は、Ｍ２ Ｏ・ｎＳｉＯ２ （Ｍはアルカリ金属）の構造式で表され、化合物の種類や水ガラスでのグレードによってＭ２ ＯとＳｉＯ２ のモル比に幅がある。
【００２４】
上記の水溶性アルカリ珪酸塩と共に主成分として併用する無機質粉末としては、従来より無機及び有機コーティング剤の骨材や充填剤に使用されている種々の無機化合物及び天然鉱物の粉末を使用でき、例えば、ホワイトカーボンやコロイダルシリカの如き微粒子状シリカ、炭酸カルシウム粉末、水酸化アルミニウム粉末、酸化チタン粉末、セピオライトの如きホルマイト系鉱物粉末、バーミュキュライトの如き加水雲母類粉末、珪酸カルシウム粉末、天然ガラス粉末、パーライトの如き真珠岩類の粉末、カオリン類やシリマナイトの如きクレー及びこれらの焼成クレー、亜硫酸カルシウム粉末、中空状アルミノシリケート粒子等が挙げられ、これらは２種以上を併用可能である。
【００２５】
上記の無機質粉末の中でも、微粒子状シリカは、耐火層の溶融発泡時の垂れ防止と、該耐火層形成時の硬化促進に寄与することから、特に好適なものとして推奨される。すなわち、水溶性アルカリ珪酸塩を含む無機質の熱発泡性材料では、水溶性アルカリ珪酸塩のＳｉＯ２ ／Ｍ２ Ｏ（Ｍはアルカリ金属）のモル比でＳｉＯ２ の比率が高いほど発泡後の流動点（流動温度）は高くなる傾向があり、それだけ火災時の受熱から垂れ落ちを生じるまでに時間を要し、もって発泡層による優れた熱遮断効果が長く持続することが判明している。しかるに、例えばＪＩＳ−３号水ガラスの同モル比が３．２程度であるように、水溶性アルカリ珪酸塩単独ではＳｉＯ２ の比率を高くできないが、微粒子状シリカの使用によって該比率を高く設定することが可能となる。また、本発明の熱発泡性耐火材組成物は硬化前には一般的にクリーム状ないしパテ状の水性ペーストをなすが、その硬化は微粒子状シリカの存在によって速まることが認められており、それだけ耐火層形成の作業能率が向上することになる。
【００２６】
しかして、微粒子状シリカの配合量は、水溶性アルカリ珪酸塩との合量におけるＳｉＯ２ ／Ｍ２ Ｏ（Ｍはアルカリ金属）のモル比を３．７〜８とする割合に設定するのがよく、少な過ぎては使用効果が充分に発現せず、逆に多過ぎては原料組成物の硬化が速過ぎて使用困難になる。なお、他のＳｉＯ２ 成分を含む化合物や鉱物では、後述するメタカオリン粉末を除いて、前記溶融発泡後の垂れ防止に寄与するＳｉＯ２ 付与成分として作用しにくいことが判明している。
【００２７】
また、他の好適な無機質粉末として、炭酸カルシウム粉末、水酸化アルミニウム粉末、焼成クレー、メタカオリン粉末が挙げられる。これらの内、炭酸カルシウム粉末は、９００℃程度で熱分解して炭酸ガスを発生し、これが耐火層の受熱による発泡時に気泡となるため、発泡助剤として機能する。水酸化アルミニウム粉末は、２００〜３００℃程度で水を発生し、これに伴って気化熱を奪って冷却効果をもたらすため、初期段階での耐火層の昇温抑制に寄与する。また、焼成クレーは、熱伝導率が低いため、耐火層の断熱作用を高める作用がある。更に、メタカオリン粉末は、カオリンを９００℃程度で焼成したものであるが、前記の微粒子状シリカ以上にＳｉＯ２ 付与成分として機能する。しかして、これらの好適な無機質粉末は、その１種又は２種以上を前記微粒子状シリカと併用することが特に推奨される。
【００２８】
他の無機質粉末として、酸化チタン粉末は、一般的に白色顔料として知られるが、本発明の熱発泡性耐火材組成物においてはその充填性を高めると共に防黴作用があるため、好適なものである。その他、セピオライトの如きホルマイト系鉱物の粉末は、繊維状組織を有するため、耐火層の保湿と熱発泡前及び熱発泡後の亀裂防止に効果がある。バーミュキュライトの如き加水雲母類粉末は、層状粒子からなるために保湿機能に優れる。亜硫酸カルシウム粉末は、硬化促進剤として、耐火層の形成において水溶性アルカリ珪酸塩と反応して硬化を速める機能がある。更に、これら以外の無機質粉末として、珪酸カルシウム粉末、天然ガラス粉末、パーライトの如き真珠岩類の粉末、中空状アルミノシリケート粒子、シリマナイト粉末等が挙げられる。
【００２９】
なお、本発明の先行技術である前記耐火性コーティング剤ではホルマイト系鉱物粉末と他のＳｉＯ２ 付与成分という組み合わせを必須としているが、本発明組成物では該組み合わせは必須ではない。これは、本発明組成物にあっては短繊維物質が火災時の耐火層の均一な溶融発泡を促進するため、それだけ熱発泡条件が緩和されて使用する無機質粉末の選択肢が拡がることを意味する。
【００３０】
本発明に係る熱発泡性耐火材組成物は、既述のように水溶性アルカリ珪酸塩と無機質粉末とを主成分として短繊維物質を含有するものであるが、必要に応じて他の各種添加剤を耐火層本来の特性を阻害しない少量範囲で使用することができる。このような添加剤としては、過度な乾燥による耐火層内の水分喪失を防ぐ保湿剤、水濡れの可能性がある部位に使用する場合の溶出を防止する撥水剤、基材表面に対する常温下もしくは高温下の接着性を高める接着性付与剤、着色剤、粘度調整剤等が挙げられる。
【００３１】
本発明の熱発泡性耐火材組成物を調製するには、水溶性アルカリ珪酸塩の水溶液に上述した他の配合成分を添加混合すればよい。しかして、この混合にて調製される原料組成物は水性ペーストであるが、概してクリーム状ないしパテ状をなし、そのままでもスプレーガンによる吹き付け塗装、刷毛塗り塗装、スリットからの流延塗装等で基材表面に塗工したり、注入具を用いて基材の中空部に注入充填することが可能であるが、これら塗工や注入を容易にするために必要とあらば、適当な粘度になるように水を加えて希釈してもよい。また、塗工では所要の厚みに設定する上で重ね塗りを行うことも可能である。
【００３２】
かくして基材の表面に塗工したり中空部に充填した熱発泡性耐火材組成物は、一定時間（通常４８時間程度）放置することによって表面的に硬化し、更に日数を経て完全硬化して非常に強靱で硬い耐火層となる。この硬化は、余剰水分の蒸発と共に、水溶性アルカリ珪酸塩がバインダーとして働いて無機質粉末粒子をアルカリの作用で結着することによってなされる。
【００３３】
本発明の熱発泡性耐火材組成物は、鉄骨の如き鋼材を始めとする各種構造材、建物の内外壁や天井部、間仕切り、屋外通路壁、トンネル内壁、建具、器壁等の耐火被覆層の形成、ならびに多重管の内外筒間や中空パネル等の中空部に充填する耐火充填層の形成に好適に使用できるが、その用途的及び形態的な制約はない。また、これら耐火被覆層や耐火充填層を形成する基材の材質についても特に制約はなく、不燃物及び可燃物のいずれでもよく、例えば、鉄を始めとする各種金属、スレート、コンクリート、木材、合板、紙管、ダンボール、圧縮板紙、合成樹脂、ＦＲＰ等の広範な材質が対象となる。
【００３４】
【実施例】
【００３５】
実施例２
実施例１の配合組成におけるビニロン短繊維の配合量を０．０２部に変更した以外は、実施例１と同様にして耐火被覆層を形成した。
【００３６】
【００３７】
【００３８】
実施例５
ＪＩＳ−３号水ガラス（実施例１と同） ・・・７４．０部
ホワイトカーボン（実施例４と同） ・・・６．０部
セピオライト粉末（実施例４と同） ・・・５．０部
メタカオリン粉末（実施例４と同） ・・・５．０部
パーライト粉末（実施例４と同） ・・・５．０部
酸化チタン粉末（実施例１と同） ・・・５．０部
カーボン短繊維（実施例４と同） ・・・０．１部
上記成分を混合してクリーム状の水性ペーストを調製し、これを用いて実施例１と同様にして耐火被覆層を形成した。
【００３９】
比較例１
実施例１の配合組成におけるビニロン短繊維を配合しなかった以外は、実施例
と同様にして耐火被覆層を形成した。
【００４０】
比較例２
実施例３の配合組成におけるガラス短繊維を配合しなかった以外は、実施例３と同様にして耐火被覆層を形成した。
【００４１】
比較例３
実施例５の配合組成におけるカーボン短繊維を配合しなかった以外は、実施例５と同様にして耐火被覆層を形成した。
【００４２】
以上の実施例及び比較例にて耐火被覆層を形成したＨ形鋼の各１０点について、塗工１０日後の耐火被覆層の状態を観察した。その結果、実施例１〜５のＨ形鋼では、各１０点の全てで耐火被覆層の変形や亀裂が認められなかった。しかるに、比較例１のＨ形鋼の３点、比較例２のＨ形鋼の５点、比較例３のＨ形鋼の２点には、耐火被覆層にコーナー部に沿う亀裂が認められた。
【００４３】
〔耐火性試験〕
実施例１，３，５で耐火被覆層を形成したＨ形鋼の各１点と、比較例１〜３で耐火被覆層を形成したＨ形鋼中の前記亀裂を生じなかったもの各１点を試験用サンプルとし、ＩＳＯ−８３４に基づく耐火性能評価試験方法に準じ、当該試験用サンプルを試験炉内に塗膜形成面が垂直になるように配置し、この試験炉内をガスバーナーにて直火で加熱すると共に、熱電対を介してＨ形鋼の温度と炉内の温度を加熱開始から６０分まで測定すると共に、測定後に試験炉から取り出したサンプルの表面状態を観察したところ、次の表１に示す結果が得られた。なお、表中の『実』は実施例、『比』は比較例を意味する。
【００４４】
【表１】
表１の結果から、耐火被覆層に短繊維物質を含有する実施例１，３，５のＨ形鋼は、炉内温度が９００℃に至っても１００℃前後の低温を保っており、優れた断熱作用を示すことが明らかである。これに対し、耐火被覆層に短繊維物質を含有しない比較例１〜３のＨ形鋼は、いずれも硬化段階での亀裂がないにもかかわらず急激な温度上昇を生じており、試験後の平面部に割れが認められることから、加熱途上で生じた割れを通してＨ形鋼自体に高熱が及んでいるものと推測される。なお、この耐火性試験において、いずれの耐火被覆層も加熱開始から約１０分後に発泡による膨張が始まり、１５分後には膨張によって熱電対が埋まり、試験後の接炎位置の層厚は元の層厚の３倍弱に達していた。
【００４６】
【発明の効果】
請求項１の発明によれば、火災時の受熱によって発泡して遮炎断熱機能を発揮する熱発泡性耐火材組成物として、主成分の水溶性アルカリ珪酸塩と無機質粉末と共に特定繊維長の短繊維物質を含有することから、基材に塗工した際に垂れ落ちや重力による変形を生じにくく、形成した耐火層の寸法安定性及び保形性がよく、施工性も良好であると共に、該耐火層の硬化収縮に伴う亀裂や基材の温度変化に伴う伸縮による亀裂発生が防止され、しかも火災時に熱遮断性に優れた発泡層を形成でき、熱発泡性耐火材として高い信頼性を備えたものが提供される。
【００４７】
請求項２の発明によれば、上記の熱発泡性耐火材組成物において、合成樹脂繊維からなる短繊維物質を含むことから、火災時の耐火層の断熱性がより向上するという利点がある。
【００４８】
請求項３の発明によれば、上記の熱発泡性耐火材組成物において、短繊維物質としてビニロン繊維を含むことから、火災時に短繊維物質の燃焼ガスが殆ど発生しないという利点がある。
【００４９】
請求項４の発明によれば、上記の熱発泡性耐火材組成物において、短繊維物質として非有機質繊維を含むとから、耐火層が溶融発泡する際に垂れ落ちを生じず、且つ形成される断熱発泡層の亀裂を防止でき、もって火災時の遮炎断熱性がより向上するという利点がある。
【００５０】
請求項５の発明によれば、上記の熱発泡性耐火材組成物において、短繊維物質が特定の割合で含有されていることから、耐火層の火災時の溶融発泡性と短繊維物質による垂れ防止及び亀裂防止作用とが共に良好になるという利点がある。
【００５１】
請求項６の発明によれば、上記の熱発泡性耐火材組成物において、アルカリ珪酸塩を特定割合で含むことから、耐火層の火災時の溶融発泡性とそれによる耐火断熱性能を良好に確保できるという利点がある。
【００５２】
請求項７の発明によれば、上記の熱発泡性耐火材組成物において、無機質粉末として微粒子状シリカを含むことから、耐火層の火災時の溶融発泡性とそれによる耐火断熱性能がより向上すると共に、耐火層の形成時の硬化が速くなるという利点がある。
【００５３】
請求項８の発明によれば、上記の熱発泡性耐火材組成物において、無機質粉末として微粒子状シリカと共に特定種のものを含むことから、耐火層の耐火断熱性能がより向上するという利点がある。[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is used for forming various structural materials including steel frames for building construction, inner and outer walls and ceilings of buildings, partitions, outdoor passage walls, inner walls of tunnels, fittings, container walls, and other fireproof coating layers and fireproof filling layers. The present invention relates to a thermally foamable refractory composition.
[0002]
[Prior art]
In recent years, the rise of buildings in cities and the scale of underground shopping centers have been increasing, and accordingly, the necessity of disaster prevention measures has increased, and preparations for fires have become particularly important. However, asbestos, which was previously widely used as a fire-resistant coating for various structural materials, cannot be used due to the carcinogenicity of dust inhalation, and rock wool has also been disliked due to similar health concerns. In addition, they were not sufficient in terms of fire resistance.
[0003]
Therefore, as a fire-resistant coating material replacing the asbestos and rock wool, various heat-foamable fire-resistant paints that form a heat-insulating foam layer by foaming upon receiving heat during a fire and exhibit a flame-shielding / heat-shielding action have been proposed. . Such a heat-foamable refractory paint contains a water-soluble alkali silicate as a main component, and a curing agent and an aggregate component are blended. A foaming agent such as ammonium polyphosphate is blended, and an organic one that forms a carbonized layer together with foaming, a product mainly composed of a reaction product of a water-soluble silicate and an alkoxysilane derivative or an organosilica sol, a water-soluble alkali silicate and an ultraviolet ray There is a mixture of a curable resin component and the like, but most of them have not been put into practical use, and the actual use examples are only organic ones.
[0004]
However, the organic type that has been used above generates a carbonized layer expanded in the form of a foam due to the generation of gas due to the decomposition of the foaming agent together with the melting of the binder resin at the time of fire, but is toxic to the gas component. Because of the high ammonia gas content, there is a concern that the affected environment may be harmed, and the essential fire resistance is not sufficient. By the way, the heat resistance temperature of ordinary steel is 350 ° C, and even fire-resistant steel is only 600 ° C, and if it is higher than that, it will be softened. Requires a refractory coating to work.
[0005]
In view of the above-mentioned circumstances, the present inventor has previously made a groundbreaking inorganic refractory coating capable of exhibiting sufficient heat barrier properties as a refractory coating for steel structures based on long-term and detailed experimental research. An agent has been investigated, and this has been filed as Japanese Patent Application No. 2001-354858. This refractory coating agent is composed of a water-soluble alkali silicate and formite-based mineral powder, and SiO 2 other than these. 2 It is composed of an aqueous paste containing an imparting component as an essential component, and the coating film foams by receiving heat in the event of a fire to form a heat insulating foam layer.However, due to the exquisite balance of timing and speed of foaming, the film is biased to the entire coating film. The entire coating film expands uniformly with the stable growth of the fine bubbles that have been generated, forming a uniform and thick foamed heat insulating layer, and the pour point after foaming is high, so that it does not easily sag, and excellent heat It has a feature that it can maintain the blocking property for a long time.
[0006]
[Problems to be solved by the invention]
However, the refractory coating agent still has room for improvement in various aspects. In particular, since a fire-resistant coating layer made of such a fire-resistant coating agent generally has a thickness as large as 5 mm or more, it may sag during coating, or may be deformed by gravity after coating, or the coating film itself may be damaged. A crack due to curing shrinkage, a crack due to expansion and contraction due to a temperature change on the substrate side after curing, a crack due to heat reception in a fire, and the like may occur. And, if there is the above-mentioned dripping or deformation, the thickness of the fire-resistant coating layer becomes non-uniform and causes a decrease in fire-resistant heat insulation performance, or the appearance deteriorates, and if there is a crack in the fire-resistant coating layer, Since high heat is directly applied to the base material through a crack at the time of a flame, reliability as a fireproof coating cannot be obtained, and if cracks occur due to heat reception during a fire, the high heat will also be applied to the base material. As a result, the fire resistance is reduced.
[0007]
The present inventor has conducted intensive studies based on the technology relating to the above-mentioned refractory coating agent to further enhance the performance and workability, and as a result, has found that thermal foaming containing water-soluble alkali silicate and inorganic powder as main components is performed. When a short fiber substance is contained in the conductive material, the above-mentioned sagging, deformation, and cracks can be prevented, cracks are less likely to occur at the time of fire, and uniformity of thermal foaming is improved, and the present invention has been achieved. Things.
[0008]
[Means for Solving the Problems]
That is, the invention of claim 1 relates to a heat-expandable refractory material composition comprising a water-soluble alkali silicate and an inorganic powder as main components and a short fiber substance having an average fiber length of 0.5 to 15 mm. However, in such a thermally foamable refractory composition, the presence of the short fiber material does not cause dripping or deformation due to gravity when applied to a base material, and the dimensional stability and protection of the formed refractory layer. The shape is good, the workability is improved, and the crack due to the curing shrinkage of the refractory layer and the crack due to the expansion and contraction due to the temperature change of the base material are prevented. Moreover, when the refractory layer is melted and foamed in a fire, coalescence of the bubbles is suppressed, the formation of a cavity due to the coalescence and the rupture of the coalesced bubbles are prevented, and cracking due to heat reception is also prevented. In addition, since the short fiber substance has an appropriate fiber length, when mixing each component of the thermofoamable material, the entanglement of the fibers is suppressed, so that the short fiber substance is uniformly contained in the entire refractory layer. Can be.
[0009]
According to a second aspect of the present invention, in the thermally foamable refractory composition of the first aspect, the short fiber material is made of synthetic resin fibers. In this case, at the time of fire, the synthetic resin fibers in the refractory layer are carbonized by high heat, and this carbide further improves the heat insulation of the refractory layer.
[0010]
According to a third aspect of the present invention, in the thermally foamable refractory composition of the second aspect, the synthetic resin fibers are vinylon fibers. In this case, during the fire, the vinylon fibers in the refractory layer are melted and immediately carbonized, so that almost no combustion gas is generated.
[0011]
According to a fourth aspect of the present invention, in the thermally foamable refractory composition of the first aspect, the short fiber material is an organic fiber. In this case, when the refractory layer is melt-foamed during a fire, the non-organic fibers that maintain their original shape can prevent the melt-foamed layer from sagging, and can also reliably prevent cavities and heat cracks.
[0012]
According to a fifth aspect of the present invention, in the thermally foamable refractory composition according to the first or second aspect, the proportion of the short fiber material occupying 0.01 to 2.0% by weight of the total amount of the solidified refractory material composition. It is assumed that it is contained in. In this case, the above-described action of the short fiber material is sufficiently exhibited as long as the melt-foamability of the refractory layer at the time of fire is not impaired.
[0013]
According to a sixth aspect of the present invention, in the thermally foamable refractory composition according to any one of the first to fifth aspects, the water-soluble alkali silicate accounts for 30 to 80% by weight based on the total amount of the solidified refractory material composition. It is configured to be contained at a ratio. In this case, the fire resistance of the refractory layer at the time of fire and the fire insulation performance can be satisfactorily secured.
[0014]
A seventh aspect of the present invention is the heat-expandable refractory composition according to any one of the first to sixth aspects, wherein the inorganic powder contains finely divided silica. In this case, the fire resistance of the refractory layer in the event of a fire and the heat insulation performance of the refractory layer are further improved, and the hardening of the refractory layer at the time of formation is quickened.
[0015]
The invention according to claim 8 is the heat-expandable refractory composition according to claim 7, wherein the inorganic powder is at least one selected from calcium carbonate powder, aluminum hydroxide powder, calcined clay, and metakaolin powder together with particulate silica. Is included. That is, calcium carbonate releases carbon dioxide gas by thermal decomposition, aluminum hydroxide generates water in the initial stage of heating, and both have an effect of assisting thermal foaming of the refractory layer 3, and calcined clay has a thermal conductivity. It has the effect of increasing the heat insulating property of the refractory layer 3 because of its low content. 2 It functions effectively as an imparting component, and the use thereof improves the fire-insulating performance of the fire-resistant layer.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
The heat-expandable refractory composition according to the present invention contains a short fiber substance containing water-soluble alkali silicate and inorganic powder as main components as described above, and is generally used in a raw material composition before curing. In the form of a creamy or putty-like aqueous paste, it can be coated on the surface of various substrates to form a thick refractory coating layer, or can be injected into the hollow portion of various substrates to form a refractory filler layer. Since no cracks are formed during the curing, and even if the base material expands and contracts due to a temperature change after the curing, cracks are hardly generated, so that high reliability as a fire-resistant layer can be obtained. In addition, the heat-foamable refractory composition has a uniform thickness because it is less likely to sag or deform due to gravity when applied to a substrate, and has good dimensional stability and shape retention of a formed layer. It is possible to form a fire-resistant coating layer which is excellent in appearance and has no local deviation of fire-insulation performance, and has good workability.
[0017]
Thus, the refractory layer made of the heat-foamable refractory composition of the present invention foams by receiving heat during a fire to form a thick heat-insulating foam layer. Because the fine bubbles generated in the entire object expand as closed cells, they do not create a large cavity due to the coalescence of the bubbles in the heat insulating foam layer, do not burst the coalesced bubbles, and do not cause heat cracking Thus, the heat-insulating foamed layer is in a uniform foamed state as a whole, and exhibits extremely excellent heat insulation properties.
[0018]
The excellent characteristics of such a heat-expandable refractory material composition mainly depend on the contained short fiber material, and the short fiber material having an average fiber length in the range of 0.5 to 15 mm is used. There is a need. That is, if the average fiber length is less than 0.5 mm, the above-mentioned effects such as crack prevention, dimensional stability, non-sagging, and shape retention properties are not sufficiently exhibited. On the other hand, when the average fiber length exceeds 15 mm, the fibers tend to be entangled with each other to form a lump when mixing the components to prepare a raw material composition, and the short fiber material is uniformly dispersed and contained throughout the refractory layer. Therefore, the effect is not sufficiently exhibited. Further, the thickness of the short fiber material is not particularly limited, but the fiber diameter (filament diameter) is preferably in the range of 5 to 100 μm. On the contrary, if it is too thick, it is hard and hard to bend, so that the binding property to the composition base material is weak and the above-mentioned effect cannot be sufficiently exhibited.
[0019]
The short fiber material is not particularly limited, and various types of synthetic resin fibers, non-organic fibers, animal fibers, plant fibers, and the like can be used. Particularly, synthetic resin fibers and non-organic fibers are preferable. It is. That is, in the fireproof layer containing synthetic resin fibers, the synthetic resin fibers are carbonized by high heat at the time of fire, and the high heat insulating property of the carbide improves the fireproof heat insulating performance of the fireproof layer itself. In the refractory layer containing non-organic fibers, the non-organic fibers retain their original shape even under high heat, so that when the resin is melted and foamed by receiving heat during a fire, it is ensured that the molten foam layer drips and a cavity is formed due to coalescence of bubbles. In addition to this, heat cracking of the formed heat-insulating foam layer is prevented, and the fire-resistant heat insulating performance is further improved.
[0020]
As the above-mentioned synthetic resin fibers, various materials can be used. In particular, vinylon fibers (polyvinyl alcohol fibers) have the advantage that they are melted at the time of fire and immediately carbonized, and almost no combustion gas is generated. On the other hand, as the non-organic fiber, glass fiber, carbon fiber, metal fiber, artificial ceramic fiber and the like can be suitably used.
[0021]
The content of the short fiber substance is preferably 0.01 to 2.0% by weight based on the total amount of the refractory material composition in the solidified state. If the content is too small, the effect of use is not sufficiently exhibited, and conversely, the content is too large. Therefore, there is a concern that the melt-foamability of the refractory layer at the time of a fire may be impaired. When the material is a synthetic resin fiber, the specific gravity is small, so that even a small weight increases the quantity, so that the content is particularly preferably in the range of 0.01 to 0.2% by weight. Recommended.
[0022]
The water-soluble alkali silicate, which is one of the main components in the thermally foamable refractory composition of the present invention, is a basic component for bringing thermal foamability to the coating film, and becomes a molten state by receiving heat during a fire. The vaporized water content is bubbled and retained in the layer, thereby enabling the refractory layer to be converted to a foamed layer. Also, in the raw material composition, the aqueous solution is used as a base to serve as a liquid medium in which other components are dispersed or dissolved. Therefore, the water-soluble alkali silicate is preferably used in a proportion occupying 30 to 80% by weight of the components of the refractory material excluding water, and if this proportion is too small, sufficient thermal foaming properties can be obtained. On the contrary, if the amount is too large, the thermal foaming becomes non-uniform, and the heat insulation performance of the foamed layer generated is reduced.
[0023]
Examples of such a water-soluble alkali silicate include sodium silicate, potassium silicate, and lithium silicate. Commercially available products in the form of an aqueous solution as water glass can be suitably used. Thus, this water-soluble alkali silicate is M 2 On SiOn 2 (M is an alkali metal), and depending on the type of compound and grade in water glass, M 2 O and SiO 2 Has a wide range of molar ratios.
[0024]
As the inorganic powder used in combination with the water-soluble alkali silicate as a main component, powders of various inorganic compounds and natural minerals conventionally used for aggregates and fillers of inorganic and organic coating agents can be used. , Fine particle silica such as white carbon and colloidal silica, calcium carbonate powder, aluminum hydroxide powder, titanium oxide powder, formite mineral powder such as sepiolite, hydromica powder such as vermiculite, calcium silicate powder, natural glass Powders, powders of perlites such as perlite, clays such as kaolins and sillimanite, and calcined clays thereof, calcium sulfite powders, hollow aluminosilicate particles, and the like can be used in combination.
[0025]
Among the above-mentioned inorganic powders, finely divided silica is recommended as a particularly preferable one because it contributes to prevention of dripping of the refractory layer at the time of melting and foaming and acceleration of hardening at the time of forming the refractory layer. That is, in the case of an inorganic thermally foamable material containing a water-soluble alkali silicate, the water-soluble alkali silicate SiO 2 2 / M 2 O (M is an alkali metal) molar ratio of SiO 2 The higher the ratio, the higher the pour point (flow temperature) after foaming, and the longer it takes to get dripping from the heat received in the event of a fire, so that the excellent thermal barrier effect of the foam layer lasts longer Has been found to be. However, for example, the water-soluble alkali silicate alone can be used to form SiO 2 so that the same molar ratio of JIS-3 water glass is about 3.2. 2 Cannot be increased, but the use of finely divided silica allows the ratio to be set higher. In addition, the heat-expandable refractory composition of the present invention generally forms a creamy or putty-like aqueous paste before curing, but it has been recognized that the curing is accelerated by the presence of fine-particle silica, and only that. The work efficiency of the formation of the refractory layer is improved.
[0026]
Thus, the compounding amount of the particulate silica is SiO 2 in the total amount with the water-soluble alkali silicate. 2 / M 2 It is preferable to set the molar ratio of O (M is an alkali metal) to a ratio of 3.7 to 8. When the amount is too small, the effect of use is not sufficiently exhibited, and when it is too large, the curing of the raw material composition is performed. Is too fast and difficult to use. In addition, other SiO 2 In compounds and minerals containing components, except for metakaolin powder described below, SiO that contributes to prevention of sagging after the melt foaming is used. 2 It has been found that it does not easily act as an imparting component.
[0027]
Other suitable inorganic powders include calcium carbonate powder, aluminum hydroxide powder, calcined clay, and metakaolin powder. Of these, the calcium carbonate powder thermally decomposes at about 900 ° C. to generate carbon dioxide gas, which becomes bubbles when foaming due to heat reception of the refractory layer, and thus functions as a foaming aid. The aluminum hydroxide powder generates water at about 200 to 300 ° C., thereby taking away heat of vaporization and providing a cooling effect, and thus contributes to suppressing the temperature rise of the refractory layer in the initial stage. Further, calcined clay has a low thermal conductivity, and thus has an effect of enhancing the heat insulating effect of the refractory layer. Furthermore, the metakaolin powder is obtained by calcining kaolin at about 900 ° C. 2 Functions as an imparting component. It is particularly recommended that one or more of these suitable inorganic powders be used in combination with the finely divided silica.
[0028]
As other inorganic powders, titanium oxide powder is generally known as a white pigment. However, in the heat-expandable refractory composition of the present invention, it is preferable to increase the filling property and to have a fungicidal action. is there. In addition, since the powder of the hormite-based mineral such as sepiolite has a fibrous structure, it is effective in moisturizing the refractory layer and preventing cracks before and after thermal foaming. Hydromica powder such as vermiculite is excellent in moisturizing function because it is composed of layered particles. Calcium sulfite powder has a function as a curing accelerator to accelerate curing by reacting with a water-soluble alkali silicate in the formation of a refractory layer. Further, other inorganic powders include calcium silicate powder, natural glass powder, perlite rock powder such as perlite, hollow aluminosilicate particles, and sillimanite powder.
[0029]
In the refractory coating agent, which is a prior art of the present invention, formite-based mineral powder and other SiO 2 Although the combination of the imparting components is essential, the combination is not essential in the composition of the present invention. This means that in the composition of the present invention, the short fiber material promotes uniform melting and foaming of the refractory layer at the time of fire, so that the thermal foaming conditions are alleviated and the choice of the inorganic powder to be used is expanded. .
[0030]
The heat-expandable refractory composition according to the present invention contains a short-fiber substance containing water-soluble alkali silicate and inorganic powder as main components as described above. The agent can be used in a small amount range that does not interfere with the inherent properties of the refractory layer. Examples of such additives include a humectant that prevents moisture loss in the refractory layer due to excessive drying, a water repellent that prevents elution when used in a site that may be wetted with water, and a normal temperature to the substrate surface. Alternatively, an adhesiveness-imparting agent, a coloring agent, a viscosity adjuster, etc., which enhance the adhesiveness at a high temperature may be used.
[0031]
In order to prepare the thermally foamable refractory composition of the present invention, the above-mentioned other components may be added to and mixed with an aqueous solution of a water-soluble alkali silicate. Although the raw material composition prepared by this mixing is an aqueous paste, it is generally in the form of a cream or putty, and can be used as it is by spray coating with a spray gun, brush coating, casting from a slit, etc. It is possible to apply to the surface of the material or to inject and fill the hollow part of the base material using a pouring tool, but if necessary to facilitate these coating and pouring, it will have an appropriate viscosity As described above, water may be added for dilution. In the coating, it is also possible to perform recoating after setting the required thickness.
[0032]
Thus, the thermally foamable refractory composition applied to the surface of the base material or filled in the hollow portion is surface-cured by leaving it for a certain period of time (usually about 48 hours), and further cured completely after several days. Very tough and hard refractory layer. This curing is carried out by evaporating excess water and binding the inorganic powder particles by the action of alkali by the water-soluble alkali silicate acting as a binder.
[0033]
The heat-expandable refractory composition of the present invention includes various structural materials including steel such as steel frames, inner and outer walls and ceilings of buildings, partitions, outdoor passage walls, tunnel inner walls, fittings, container walls, etc. And the formation of a refractory packing layer to be filled between the inner and outer cylinders of the multi-tube or in a hollow portion such as a hollow panel, but there is no limitation in application and form. In addition, there is no particular limitation on the material of the base material forming the fire-resistant coating layer and the fire-resistant filling layer, and may be any of incombustibles and combustibles. For example, various metals including iron, slate, concrete, wood, A wide range of materials such as plywood, paper tubes, cardboard, compressed paperboard, synthetic resin, FRP, etc. are targeted.
[0034]
【Example】
[0035]
Example 2
A fire-resistant coating layer was formed in the same manner as in Example 1, except that the amount of vinylon short fibers in the composition of Example 1 was changed to 0.02 parts.
[0036]
[0037]
[0038]
Example 5
JIS-3 water glass (same as in Example 1) 74.0 parts
White carbon (same as Example 4) ... 6.0 parts
Sepiolite powder (same as in Example 4) ... 5.0 parts
Metakaolin powder (same as in Example 4) ... 5.0 parts
Pearlite powder (same as in Example 4) ... 5.0 parts
Titanium oxide powder (same as in Example 1) ... 5.0 parts
Short carbon fiber (same as in Example 4) 0.1 part
The above components were mixed to prepare a creamy aqueous paste, and a refractory coating layer was formed in the same manner as in Example 1 using this.
[0039]
Comparative Example 1
Example 1 except that vinylon short fibers in the composition of Example 1 were not blended.
A refractory coating layer was formed in the same manner as described above.
[0040]
Comparative Example 2
A fire-resistant coating layer was formed in the same manner as in Example 3, except that the short glass fiber in the composition of Example 3 was not used.
[0041]
Comparative Example 3
A fire-resistant coating layer was formed in the same manner as in Example 5, except that the short carbon fibers in the composition of Example 5 were not used.
[0042]
The state of the fire-resistant coating layer 10 days after application was observed for each of the 10 points of the H-section steel having the fire-resistant coating layer formed in the above Examples and Comparative Examples. As a result, in the H-section steels of Examples 1 to 5, no deformation or crack of the refractory coating layer was observed at all 10 points. However, at the three points of the H-section steel of Comparative Example 1, the five points of the H-section steel of Comparative Example 2, and the two points of the H-section steel of Comparative Example 3, cracks were found along the corners in the refractory coating layer. .
[0043]
(Fire resistance test)
One point of each of the H-section steels having the fire-resistant coating layer formed in Examples 1, 3, and 5, and one point of each of the H-section steels having the fire-resistant coating layer formed in Comparative Examples 1 to 3 in which the crack did not occur. Is used as a test sample, and the test sample is arranged in a test furnace so that the coating film forming surface is vertical according to the fire resistance performance evaluation test method based on ISO-834. While heating with an open flame, the temperature of the H-section steel and the temperature in the furnace were measured up to 60 minutes from the start of heating via a thermocouple, and the surface state of the sample taken out of the test furnace after the measurement was observed. The results shown in Table 1 were obtained. In the table, "actual" means an example, and "ratio" means a comparative example.
[0044]
[Table 1]
From the results shown in Table 1, the H-shaped steels of Examples 1, 3, and 5 containing the short fiber material in the refractory coating layer maintained a low temperature of about 100 ° C. even when the furnace temperature reached 900 ° C. It is clear that it exhibits adiabatic effect. On the other hand, the H-section steels of Comparative Examples 1 to 3 in which the refractory coating layer does not contain the short fiber substance have a sharp temperature rise despite the absence of any cracks in the hardening stage. Since cracks were observed in the flat portion, it is presumed that high heat was applied to the H-section steel itself through cracks generated during heating. In this fire resistance test, each of the refractory coating layers began to expand due to foaming about 10 minutes after the start of heating, and after 15 minutes, the thermocouple was buried by the expansion, and the layer thickness at the flame contact position after the test was restored. It had reached less than three times the layer thickness.
[0046]
【The invention's effect】
According to the first aspect of the present invention, a heat-foamable refractory composition which foams by receiving heat during a fire to exhibit a flame-insulating and heat-insulating function is provided, together with a water-soluble alkali silicate as a main component and an inorganic powder, having a short specific fiber length. Since it contains a fibrous substance, it is unlikely to be sagged or deformed by gravity when applied to a base material, and the formed fire-resistant layer has good dimensional stability and shape retention, good workability, and Prevents cracks caused by curing shrinkage of the refractory layer and cracks caused by expansion and contraction due to temperature change of the base material.Moreover, it can form a foam layer with excellent heat insulation in the event of a fire, and has high reliability as a heat foaming refractory material. Is provided.
[0047]
According to the second aspect of the present invention, since the heat-foamable refractory composition contains a short fiber material made of synthetic resin fiber, there is an advantage that the heat insulating property of the fire-resistant layer at the time of fire is further improved.
[0048]
According to the third aspect of the present invention, since the heat-foamable refractory composition contains vinylon fibers as the short fiber material, there is an advantage that combustion gas of the short fiber material is hardly generated at the time of fire.
[0049]
According to the invention of claim 4, in the above-mentioned heat-foamable refractory material composition, since the non-organic fiber is contained as the short fiber material, the refractory layer does not sag when melt-foamed and is formed. There is an advantage that cracks in the heat-insulating foam layer can be prevented, so that the fire-insulation and heat-insulating properties at the time of fire are further improved.
[0050]
According to the fifth aspect of the present invention, since the short-fiber substance is contained in the heat-foamable refractory composition at a specific ratio, the refractory layer has a melt-foaming property at the time of a fire and sags due to the short-fiber substance. There is an advantage that both the prevention and crack prevention effects are improved.
[0051]
According to the sixth aspect of the present invention, in the above-mentioned thermally foamable refractory composition, the alkali silicate is contained in a specific ratio, so that the fire-resistant layer of the refractory layer at the time of fire and the fire insulation and heat insulation performance due thereto are well secured. There is an advantage that you can.
[0052]
According to the seventh aspect of the present invention, since the heat-expandable refractory material composition contains finely divided silica as the inorganic powder, the fire-resistant melt foaming property of the fire-resistant layer and the fire insulation performance thereof are further improved. At the same time, there is an advantage that curing at the time of forming the refractory layer is quickened.
[0053]
According to the invention of claim 8, since the heat-expandable refractory material composition contains a specific type of inorganic powder together with the particulate silica as the inorganic powder, there is an advantage that the fire-resistant insulation performance of the fire-resistant layer is further improved. .
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002198917A JP2004035378A (en) | 2002-07-08 | 2002-07-08 | Heat expandable refractory material composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002198917A JP2004035378A (en) | 2002-07-08 | 2002-07-08 | Heat expandable refractory material composition |
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| JP2004035378A true JP2004035378A (en) | 2004-02-05 |
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| JP2002198917A Pending JP2004035378A (en) | 2002-07-08 | 2002-07-08 | Heat expandable refractory material composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011104006A3 (en) * | 2010-02-24 | 2011-10-20 | TDH - GmbH Technischer Dämmstoffhandel | Heat-insulating refractory molded article |
| JP2013500364A (en) * | 2009-07-30 | 2013-01-07 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Silica-based polyurea composition |
| CN107162627A (en) * | 2015-10-10 | 2017-09-15 | 董晓娜 | A kind of multifunctional green construction material |
| JP2021101013A (en) * | 2016-02-02 | 2021-07-08 | 積水化学工業株式会社 | Fire-resistant resin composition |
-
2002
- 2002-07-08 JP JP2002198917A patent/JP2004035378A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013500364A (en) * | 2009-07-30 | 2013-01-07 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Silica-based polyurea composition |
| WO2011104006A3 (en) * | 2010-02-24 | 2011-10-20 | TDH - GmbH Technischer Dämmstoffhandel | Heat-insulating refractory molded article |
| CN107162627A (en) * | 2015-10-10 | 2017-09-15 | 董晓娜 | A kind of multifunctional green construction material |
| CN107162627B (en) * | 2015-10-10 | 2020-10-20 | 浙江新业置业有限公司 | Multifunctional green building material |
| JP2021101013A (en) * | 2016-02-02 | 2021-07-08 | 積水化学工業株式会社 | Fire-resistant resin composition |
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