JP4310715B2 - Sheet-shaped incombustible molded body - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明はシート状不燃成形体に関し、更に詳しくは、高度の不燃性と優れた機械的強度を併せ持ち、かつ柔軟性に富み、曲面下地に対して良好な施工性を有するシート状不燃成形体に関する。
【０００２】
【従来の技術】
従来より、曲面下地に不燃材を施工する場合、溝加工を施した不燃材をＲ型台に当てがい必要な曲率半径を確保した上で溝にセメント等の充填材を充填し硬化せしめた後に、所定の曲面下地にはり付けるという方法が採られているが、工程数が多くなるとともに、施工が繁雑でやっかいなものであった。
また、ケイ酸カルシウム板等の一部にこのような溝加工によらない方法も見られるが、適用できる曲率半径に制約（せいぜい１０００ｍｍ以上）があり、かなりゆるやかな曲面しか得ることができなかった。
【０００３】
さらには、柔軟性を有し屈曲自在な不燃裏打材上にケイ酸カルシウム板等の不燃基材を接着し、該不燃基材の表面に溝を所定間隔で形成し、かつ溝底が前記した不燃裏打材に至るように施したものがある。
しかしながら、かかる方法は、▲１▼不燃裏打材と不燃基材との接着工程が必要であり、加工工程が繁雑である。▲２▼不燃裏打材と不燃基材を接着するのに有機系接着剤を使用することが多いため、不燃性の悪化を来しやすい。▲３▼柔軟性を有し、屈曲自在な不燃裏打材としてはガラスクロス、各種無機繊維系不織布、アラミド繊維シートなどが用いられるが、かかる不燃裏打材は一般に極めて高価であるなどの難点を有する。
従って、前記した溝加工あるいは屈曲自在な不燃裏打材の接着等を施さずとも曲がりの急な曲面施工を施すことのできる不燃材の開発が急がれていた。
【０００４】
そこで、本発明者は、かかる課題を解決すべく、鋭意試行錯誤を繰り返したところ、多量の含水無機化合物あるいは多量の含水無機化合物と炭酸塩及び所定量のセルロース繊維を含有し、さらに、特定の硬化特性を有するフェノール樹脂と無機繊維の所定量を含有するシート状熱成形体が、高度の不燃性と優れた機械的強度を併せ持ち、かつ柔軟性に富み、曲面下地に対して良好な施工性を有することを見い出し、本発明を完成した。
【０００５】
本発明に係るシート状不燃成形体は、含水無機化合物を固形分で６０〜９５重量％と、セルロース繊維を固形分で２〜３０重量％と、無機繊維を固形分で１〜２０重量％と、熱硬化性樹脂を固形分で１〜２０重量％とを含有するシート状熱成形体であって、前記熱硬化性樹脂の内、固形分で３０重量％以上がキュラストメータによる１７５℃での硬化速度が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するものである。
【０００６】
また、本発明に係るシート状不燃成形体は、含水無機化合物と炭酸塩を固形分で合計６０〜９５重量％と、セルロース繊維を固形分で２〜３０重量％と、無機繊維を固形分で１〜２０重量％と、熱硬化性樹脂を固形分で１〜２０重量％とを含有し、かつ含水無機化合物／炭酸塩が固形分重量比で５０／５０より含水無機化合物過多側であるシート状熱成形体であって、前記熱硬化性樹脂の内、固形分で３０重量％以上がキュラストメータによる１７５℃での硬化速度が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するものである。
【０００７】
上記した含水無機化合物としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、二水和石こう及びアルミン酸化カルシウム等を挙げることができる。これらの化合物は何れも分子内に結晶水を持ち化学的に類似した構造を有する。また、含水無機化合物は、その種類によって分解温度及び吸熱量に幾分差があるが、高温加熱時に分解して吸熱作用により不燃化効果を示すという点では全く共通している。従って、基本的に前記した含水無機化合物のいずれを用いてもよいが入手価格等の経済性をも考慮すると水酸化アルミニウムが最適である。
【０００８】
本発明で使用する炭酸塩としては、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、炭酸ストロンチウム、炭酸ベリリウム、炭酸亜鉛等の中から少なくとも１種類を選択して使用する。これらの炭酸塩はその種類により、分解温度等に幾分差があるが、高温加熱時に分解して吸熱作用により難燃効果を示すという点では全く共通している。従って、基本的に前記した炭酸塩のいずれを用いてもよいが、価格の面から炭酸カルシウムが最適である。なお、炭酸塩配合によるもう１つの重要な効果として本発明者が特開平５−１１２６５９号公報で指摘したところの発煙量低減効果を挙げることができる。
【０００９】
本発明に係るシート状不燃成形体中の含水無機化合物あるいは含水無機化合物と炭酸塩の合計の含有率範囲は固形分で６０〜９５重量％、好ましくは７０〜９２重量％、さらに好ましくは７５〜８８重量％である。その含有率が６０重量％未満では十分な不燃性が得られない。反対に、９５重量％を超えた場合は含水無機化合物あるいは含水無機化合物と炭酸塩の合計量の過多により十分な機械的強度あるいは曲面施工性が得られず不適である。なお、シート状不燃成形体中の含水無機化合物あるいは含水無機化合物と炭酸塩の合計の含有率を７０〜９２重量％の範囲とすることで十分な不燃性と機械的強度あるいは曲面施工性を確保しやすくなり、７５〜８８重量％の範囲とすることで一層、十分な不燃性と機械的強度あるいは曲面施工性を確保しやすくなる。また、含水無機化合物／炭酸塩の含有重量比率は固形分で５０／５０、好ましくは６０／４０よりも含水無機化合物過多側としなければならない。５０／５０よりも含水無機化合物過少側とした場合、不燃性が低下することがあり不適である。なお、含水無機化合物／炭酸塩の含有重量比率を固形分で６０／４０よりも含水無機化合物過多側とすることでより十分な不燃性を確保しやすくなる。
【００１０】
上記したセルロース繊維としては、針葉樹系あるいは広葉樹系の化学パルプ、機械パルプ、セミケミカルパルプ等の木材パルプあるいは木綿パルプ、麻パルプ、各種古紙などの中から選ばれる１種類あるいは２種類以上を併用して使用すればよい。木材パルプは供給量および品質が安定しており価格も比較的安価であることから最も使いやすいセルロース繊維原料である。木綿パルプ及び麻パルプは供給量が不安定であり価格も高価であるが、本発明におけるような含水無機化合物あるいは含水無機化合物と炭酸塩を多量に含有するシート状成形体においては、必要に応じて該木綿パルプあるいは麻パルプを使用することによりシート状成形体の機械的強度の低下を最小限にとどめることができる。
【００１１】
本発明のシート状不燃成形体中のセルロース繊維の含有率範囲は固形分で２〜３０重量％、好ましくは４〜２０重量％、さらに好ましくは７〜１５重量％である。その含有率が２重量％未満ではセルロース繊維の過少により十分な抄紙性あるいは機械的強度並びに曲面施工性が得られず、また３０重量％を超えた場合は有機物質の過多により十分な不燃性を得ることができない。なお、シート状不燃成形体中のセルロース繊維の含有率を４〜２０重量％の範囲とすることで、十分な抄紙性、機械的強度、曲面施工性及び不燃性を確保しやすくなり、７〜１５重量％の範囲とすることで、一層十分な抄紙性、機械的強度、曲面施工性及び不燃性を確保しやすくなる。
本発明で使用するフェノール樹脂は、その全部または一部をキュラストメータによる１７５℃での硬化速度が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満、好ましくは、０．１ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満、さらに好ましくは０．１５ｋｇ・ｃｍ／分以上０．３５ｋｇ・ｃｍ／分未満なる硬化特性を有するものとしなければならない。フェノール樹脂の全量が、前記硬化速度０．０５ｋｇ・ｃｍ／分未満のものの場合、得られるシート状成形体の機械的強度が不十分となる。また、フェノール樹脂の全量が前記硬化速度０．４ｋｇ・ｃｍ／分以上のものの場合、得られるシート状成形体の柔軟性が低下し、十分な曲面施工性を得ることができない。本発明で使用するフェノール樹脂の全部または一部をキュラストメータによる１７５℃での硬化速度が０．１ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するものとすることで、後述する互いに背反する、優れた機械的強度と良好な曲面施工性を両立しやすくなり、０．１５ｋｇ・ｃｍ／分以上０．３５ｋｇ・ｃｍ／分未満なる硬化特性を有するものとすることで、一層、優れた機械的強度と良好な曲面施工性を両立しやすくなる。さらに、本発明で使用するフェノール樹脂として、キュラストメータによる１７５℃での硬化速度が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するものと、これ以外のフェノール樹脂を併用して用いる場合、前記硬化特性を有するフェノール樹脂以外のフェノール樹脂を選択するに当っては、後述するところの互いに背反の関係にある、優れた機械的強度と良好な曲面施工性の両方を満足できるように配慮してその種類及び配合量を選択しなければならない。
【００１２】
上記したフェノール樹脂は、加熱処理に伴う流動硬化作用により不燃性素材に各種成形賦形効果もしくは諸強度の発現効果または曲面施工性さらには含水無機化合物あるいは炭酸塩の脱落防止効果等を与える。前記で使用するフェノール樹脂の硬化温度は併用する含水無機化合物あるいは炭酸塩の分解温度よりも低くなるようにするのが望ましい。
【００１３】
本発明のシート状不燃成形体中のフェノール樹脂の含有率範囲は固形分で１〜２０重量％、好ましくは３〜１７重量％以上、さらに好ましくは５〜１５重量％である。その含有率が１重量％未満では十分な機械的強度あるいは曲面施工性が得られず、また２０重量％を超えた場合は有機物質の過多により十分な不燃性を得ることができない。なお、シート状不燃成形体中のフェノール樹脂の含有率を３〜１７重量％の範囲とすることで、十分な機械的強度、曲面施工性及び不燃性を確保しやすくなり、５〜１５重量％の範囲とすることで、一層、十分な機械的強度、曲面施工性及び不燃性を確保しやすくなる。使用するフェノール樹脂の全量に占める前記硬化特性を有するフェノール樹脂の割合は固形分で３０重量％以上とするのが好ましく、より好ましくは５０重量％以上、さらに好ましくは６０重量％以上とするのがよい。３０重量％未満では得られるシート状成形体の曲面施工性及び機械的強度のどちらか一方あるいは両方が不十分となることがある。なお、使用するフェノール樹脂の全量に占める前記硬化特性を有するフェノール樹脂の割合を５０重量％以上とすることで、曲面施工性と機械的強度の両立をさらに図りやすくなり、６０重量％以上とすることで、なお一層、曲面施工性と機械的強度の、両立を図りやすくなる。また、この場合、前記硬化特性を有するフェノール樹脂以外のフェノール樹脂を選択するに当っては、後述するところの互いに背反の関係にある、優れた機械的強度と良好な曲面施工性の両方を満足できるように配慮してその種類及び配合量を選択しなければならない。
【００１４】
上記した無機繊維としては、ロックウール繊維、ガラス繊維、セラミック繊維あるいは炭素繊維などの中から少なくとも１種類を選択して使用する。特にロックウール繊維を用いると得られるシート状成形体の曲面施工性が一段と向上するので好ましい。
本発明のシート状不燃成形体中の無機繊維の含有率範囲は固形分で１〜２０重量％、好ましくは１〜１５重量％、さらに好ましくは２〜１０重量％である。その含有量が１重量％未満では、ＪＩＳ Ａ１３２１の表面試験において亀裂を発生しやすくなり、２０重量％を超えると十分な抄紙性が得られず、得られるシート状成形体中に無機繊維を均一に分布せしめることができない。なお、シート状不燃成形体中の無機繊維の含有率を１〜１５重量％の範囲とすることで無機繊維を均一に分布せしめやすくなるとともに、ＪＩＳ Ａ１３２１の表面試験で亀裂を回避しやすくなり、２〜１０重量％の範囲とすることで、一層、無機繊維を均一に分布せしめやすくなるとともに、ＪＩＳ Ａ１３２１の表面試験で亀裂を回避しやすくなる。
【００１５】
本発明に係るシート状不燃成形体は、上記配合のもとに含水無機化合物あるいは含水無機化合物と炭酸塩／セルロース繊維／無機繊維／フェノール樹脂という構成であればよくその製造法としては、湿式抄造法、乾式成形法などの任意の方法が適用可能であり、特定の製造法に限定するものではないが、湿式抄造法が最も好ましい。以下において、湿式抄造法を適用した場合を例にとって製造法にも言及しながらさらに詳述する。
【００１６】
本発明に係るシート状不燃成形体は含水無機化合物または炭酸塩の歩留を向上させるための各種歩留向上剤あるいは必要に応じて合成繊維または着色のための合成染料などを含有していてもよい。また、用途によっては機械的強度もしくは後加工適性の改善等を図るべく乾燥または湿潤紙力増強剤、サイズ剤、耐水化剤、撥水剤等を含有せしめるべきことは言うまでもない。
【００１７】
本発明のシート状不燃成形体にフェノール樹脂を含有せしめる方法としては、フェノール樹脂の液状物、繊維状物あるいは粒状物等を原料中に内添したり、紙層形成後に塗布または含浸するなどすればよい。含水無機化合物または炭酸塩を含有せしめる方法としては、含水無機化合物または炭酸塩を含有する塗料を基材に塗布あるいは含浸せしめるなどの方法も考えられるが、所定の含浸量を確保し、あるいは厚さ方向での品質の均一化を図るためには、原料スラリ−中に含水無機化合物または炭酸塩を粉体状あるいはスラリ−状にて内添する方法が最も好ましい。この場合、含水無機化合物、炭酸塩、セルロース繊維、無機繊維及びフェノール樹脂の添加方法及び添加順序等は任意であり、必要に応じて叩解処理等を施してもよい。
【００１８】
こうして得た原料スラリ−を用いて本発明に係るシート状不燃成形体を製造するには、通常の抄造法及び熱成形法によればよい。すなわち抄造については長網、円網あるいは傾斜網等の抄造網上に前記スラリ−を供給し、濾過、脱水した後、圧搾、乾燥すればよい。また、必要により各種コンビネ−ション網や、多槽円網及び各種ラミネ−タ−などにより紙層を２層以上重ね合わせてもよい。熱成形については、従来慣用の熱圧プレス成形、高周波加熱成形などを単独であるいは２種以上組み合わせて適用すればよい。
【００１９】
さらに用途によっては、得られたシート状不燃成形体に各種塗料の吹付けもしくは塗布あるいは印刷などの表面処理を施したり、化粧紙、レザー、合成樹脂膜、突板、金属板もしくは金属箔等の柔軟性のある面材を貼り合わせるなどして固着せしめ、該シート状不燃成形体の付加価値を一段と高めることができることは言うまでもない。
【００２０】
本発明のシート状不燃成形体は、含水無機化合物と無機繊維を含有するか、または含水無機化合物と炭酸塩と無機繊維を含有するだけで優れた不燃性を発揮するが、従来慣用の難燃剤の使用を妨げるものではない。併用可能な難燃剤としては、有機リン化合物、含リン含窒素有機化合物、スルファミン酸グアニジン等のスルファミン酸塩、無機リン酸塩、含ハロゲン化合物及びアンチモン系化合物等の公知の難燃剤を挙げることができる。また、該難燃剤の使用方法としては、原料スラリ−中に内添せしめるか抄造工程中もしくは抄造後または成形後に塗布または含浸せしめる等の方法が挙げられる。ただし、この場合、含水無機化合物と無機繊維の含有率または含水無機化合物と炭酸塩と無機繊維の含有率等を考慮して難燃剤の含有量を定めるべきことは当然である。
【００２１】
【作用】
本発明の重要な点は、特定の硬化特性を有するフェノール樹脂を用いることにより、多量の含水無機化合物及びセルロース繊維と無機繊維の所定量を含有するか、あるいは多量の含水無機化合物と炭酸塩及びセルロース繊維と無機繊維の所定量を含有し、さらに所定量の前記フェノール樹脂を含有するシート状熱成形体が熱成形により硬化することにより優れた機械的強度を発現するにもかかわらず、柔軟性に富み良好な曲面施工性を有する点にある。
【００２２】
フェノール樹脂は少量の配合で機械的強度を発現でき、かつ、フェノール樹脂そのものも比較的耐熱性に優れているため、高度の不燃性を必要とする材料には好適であるといえよう。
【００２３】
しかし、フェノール樹脂を含有した組成物は、熱成形した際含有されるフェノール樹脂の硬化作用により硬質化するため機械的強度が向上する反面、柔軟性は低下してしまうのが一般的である。
【００２４】
そこで、本発明者は、多量の含水無機化合物あるいは含水無機化合物と炭酸塩と比較的少量のフェノール樹脂を含有し、高度の不燃性を有するシート状成形体において、本来、背反の関係にある優れた機械的強度と良好な柔軟性（曲面施工性）を両立すべく、多数次の実験を行ったところ、特定の硬化特性を有するフェノール樹脂を用いることにより、かかる目的を達成することができることを見出した。すなわち、キュラストメータによる１７５℃での硬化速度（以下において、この意味で単に硬化速度と言うことがある。）が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するフェノール樹脂がかかる目的に適うことを見出したのである。
【００２５】
比較的フェノール樹脂の含有率の少ない組成物中のフェノール樹脂を効率的に熱硬化させ強度発現等の機能を十分に発揮させようとした場合、通常は、より硬化速度の速いフェノール樹脂を用いた方が有利と判断されるところであるが、あえて０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満というかなり遅い硬化速度を有するフェノール樹脂を用いることにより、優れた機械的強度と良好な柔軟性（曲面施工性）を両立せしめることができたのである。
【００２６】
次に、後述する実施例での実験結果に基づき説明する。後述の実施例１、実施例４、比較例１及び比較例３に係るシート状成形体は互いにほとんど同一の組成を有し、いずれもＪＩＳ−Ａ１３２１の表面試験での１級（建築基準法に規定する不燃材料に相当）に合格する高度の不燃性を有する。そして用いたフェノール樹脂の硬化速度は、実施例１が０．２１ｋｇ・ｃｍ／分、実施例４が０．３４ｋｇ・ｃｍ／分、比較例１が０．７１ｋｇ・ｃｍ／分、比較例３が１．４０ｋｇ・ｃｍ／分である。曲面施工性の判断指標である曲率半径は比較例１が１４０ｍｍ、比較例３が１７０ｍｍであるのに対し、実施例１が６０ｍｍ、実施例４が５０ｍｍであり、適用可能曲率半径が比較例１及び３に比べ実施例１及び４では１／２〜１／３となり柔軟性が大きく向上し、優れた曲面施工性が得られることがわかる。
【００２７】
また、機械的強度についても、裂断長では、比較例１に比べ実施例１、４は２５〜３０％程度低いが、比較例３と比べると実施例１、４は４０〜５０％程度向上している。また曲げ強度では、比較例１に比べ実施例１、４は１５〜３０％程度低いが、比較例３と比べると５０〜６０％程度向上している。従って、実施例１、４に係るシート状成形体は機械的強度においても十分に優れている。さらに、実施例１、４の曲率半径５０ｍｍあるいは６０ｍｍという曲面施工性は、後述する比較例６に示した市販のケイ酸カルシウム板について同様に評価した１５００ｍｍに比べると１／２５〜１／３０に当たり、本願発明のシート状不燃成形体がきわめて良好な曲面施工性を有していることがわかる。また機械的強度面でも実施例１、４が比較例６よりも裂断長で１．１〜１．２倍、曲げ強度で１．５〜１．７倍と優位である。
【００２８】
すなわち、多量の含水無機化合物あるいは含水無機化合物と炭酸塩と比較的少量のフェノール樹脂を含有し、高度の不燃性を有するシート状成形体においては、使用するフェノール樹脂の硬化速度を０．０５ｋｇ・ｃｍ／分以上、０．４ｋｇ・ｃｍ／分未満の範囲に特定することによりはじめて、優れた機械的強度と良好な柔軟性（曲面施工性）を兼ね備えたシート状不燃成形体を得ることができる。
【００２９】
硬化速度が０．０５ｋｇ・ｃｍ／分以上、０．４ｋｇ・ｃｍ／分未満なるフェノール樹脂を用いた場合に、かかる好結果の得られる作用・機構の詳細は未だ不明であるが、本願発明のシート状不燃成形体中の骨格構成要素であるセルロース繊維と無機繊維による網状構造に対し、０．０５ｋｇ・ｃｍ／分以上、０．４ｋｇ・ｃｍ／分未満なる硬化速度を有するフェノール樹脂が前記網状構造を効果的に補強する形で硬化し、フェノール樹脂の硬化物に特有の硬質化を極力伴わずに強度発現がなされるため本来は背反の関係にある、優れた機械的強度と良好な柔軟性（曲面施工性）を両立できるものと推定される。
【００３０】
【実施例】
次に本発明を以下の実施例に基づいてさらに具体的に説明する。本実施例中の各項目の測定は次の方法によった。
(１) 厚さ及び密度；ＪＩＳ Ｐ−８１１８による。
(２) 不燃性；ＪＩＳ Ａ−１３２１の表面試験による。
(３) 裂断長；ＪＩＳ Ａ−８１１３による。繊維配向性がある場合、繊維配向方向とこれに直角をなす方向にていて測定し、両者の平均を求めた。
(４) 曲げ強度；ＪＩＳ Ａ−５９０７による。繊維配向性がある場合、繊維配向方向とこれに直角をなす方向にていて測定し、両者の平均を求めた。
(５) 局面施工性；４０、５０、６０、７０、８０、９０、１００、１１０、１２０、１３０、１４０、１５０、１７０、２００、３００、４００、６００、８００、１０００、１５００、２０００なる曲率半径を有する成形合板を用いて模擬下地を構成し、この模擬下地に試験体（５ｃｍ×２５ｃｍ、繊維配向性がある場合、繊維配向方向に２５ｃｍとなるようにした。）を２５ｃｍの辺が曲率半径の方向に沿うようにあてがい破断あるいはひび割れ等の施工上の不具合を発生しなかった最も小さい曲率半径をもって評価した。
また、フェノール樹脂のキュラストメータによる１７５℃での硬化速度は硬化曲線上の最大トルクの１０％に達した点（トルクＦ10（ｋｇ・ｃｍ）、時間Ｔ10（分））と最大トルクの９０％に達した点（トルクＦ90（ｋｇ・ｃｍ）、時間Ｔ90（分））とを結んだ直線の傾き、すなわち、（Ｆ90−Ｆ10）／（Ｔ90−Ｔ10）ｋｇ・ｃｍ／分で与えられる。
【００３１】
実施例１
市販の針葉樹系未晒硫酸塩パルプと繊維長７ｍｍのロックウール繊維（以下、無機繊維ａと略称する。）を離解機にて離解して得たセルロース繊維と無機繊維の混合分散液の所定量を取り、これに水酸化アルミニウム粉体（平均粒径５．７μｍである。以下同じ）、炭酸カルシウム粉体（平均粒径１．５μｍである。以下同じ）及びキュラストメータによる１７５℃での硬化速度が０．２１ｋｇ・ｃｍ／分であるフェノ−ル樹脂（以下、フェノ−ル樹脂ａと略称する。）を添加し、撹拌機にて十分に分散混合後、角型テスト抄紙機にて抄造し、圧搾、乾燥した後、熱プレスにて加熱処理（温度１７５℃、圧力５ｋｇ／ｃｍ2 、時間３分）し、シート状成形体Ａを得た。シート状成形体Ａについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３２】
実施例２
実施例１において、無機繊維ａに代えて、繊維長３ｍｍのロックウール繊維（以下、無機繊維ｂと略称する。）を用いた以外は実施例１と同様にしてシート状成形体Ｂを得た。
シート状成形体Ｂについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３３】
実施例３
実施例１において、無機繊維ａに代えて、繊維長１ｍｍのロックウール繊維（以下、無機繊維ｃと略称する。）を用い、フェノール樹脂ａに代えて、キュラストメータによる１７５℃での硬化速度が０．３４ｋｇ・ｃｍ／分であるフェノ−ル樹脂（以下、フェノ−ル樹脂ｂと略称する。）を用いた以外は実施例１と同様にしてシート状成形体Ｃを得た。シート状成形体Ｃについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３４】
実施例４
実施例３において、無機繊維ｃに代えて、繊維長０．１５ｍｍのロックウール繊維（以下、無機繊維ｄと略称する。）を用いた以外は実施例３と同様にしてシート状成形体Ｄを得た。
シート状成形体Ｄについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３５】
実施例５
実施例１において、無機繊維ａに代えて、繊維長３ｍｍのガラス繊維（以下、無機繊維ｅと略称する。）を用いた以外は実施例１と同様にしてシート状成形体Ｅを得た。
シート状成形体Ｅについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３６】
実施例６
実施例１において、無機繊維ａに代えて、繊維長５ｍｍのガラス繊維を用い、水酸化アルミニウム粉体に代えて水酸化マグネシウム粉体（平均粒径１０μｍである。以下同じ）を用いた以外は実施例１と同様にして、シート状成形体Ｆを得た。
シート状成形体Ｆについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３７】
実施例７
実施例１において、炭酸カルシウム粉体を配合しない以外は実施例１と同様にして、シート状成形体Ｇを得た。
シート状成形体Ｇについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３８】
実施例８
実施例１において、フェノール樹脂ａとフェノール樹脂ｃをフェノール樹脂ａ／フェノール樹脂ｃ＝３／２なる固形分重量比率で配合した以外は実施例１と同様にして、シート状成形体Ｈを得た。
シート状成形体Ｈについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００３９】
比較例１
実施例１において、フェノ−ル樹脂ａに代えて、キュラストメータによる１７５℃での硬化速度が０．７１ｋｇ・ｃｍ／分であるフェノ−ル樹脂（以下、フェノ−ル樹脂ｃと略称する。）を用いた以外は実施例１と同様にしてシート状成形体Ｉを得た。シート状成形体Ｉについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４０】
比較例２
実施例５において、フェノ−ル樹脂ａに代えて、フェノール樹脂ｃを用いた以外は実施例５と同様にしてシート状成形体Ｊを得た。
シート状成形体Ｊについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４１】
比較例３
実施例１において、フェノ−ル樹脂ａに代えて、キュラストメータによる１７５℃での硬化速度が１．４０ｋｇ・ｃｍ／分であるフェノール樹脂（以下、フェノール樹脂ｄと略称する。）を用いた以外は実施例１と同様にしてシート状成形体Ｋを得た。シート状成形体Ｋについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４２】
比較例４
実施例５において、フェノ−ル樹脂ａに代えて、フェノール樹脂ｄを用いた以外は実施例５と同様にしてシート状成形体Ｌを得た。
シート状成形体Ｌについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４３】
実施例９
市販の針葉樹系未晒硫酸塩パルプと無機繊維ａをパルパーにて離解し、これに水酸化アルミニウム粉体、炭酸カルシウム粉体及びフェノール樹脂ａを添加し十分に分散混合後、長網／ワインドアップロール構成の巻取板紙抄紙機にてシート層を２０層積層させて抄造し、圧搾、乾燥した後、熱プレス処理（温度１７５℃、圧力１０ｋｇ／ｃｍ2 、時間１０分）し、シート状成形体Ｍを得た。
シート状成形体Ｍについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４４】
実施例１０
実施例９において、各成分の配合量を変えた以外は実施例９と同様にして、シート状成形体Ｎを得た。
シート状成形体Ｎについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４５】
比較例５
実施例９において、フェノ−ル樹脂ａに代えてフェノール樹脂ｄを用いた以外は実施例９と同様にして、シート状成形体Ｏを得た。
シート状成形体Ｏについて、各成分の含有率を表１に示すとともに、厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４６】
比較例６
市販のケイ酸カルシウム板について厚さ、密度、裂断長、曲げ強度、不燃性及び曲面施工性をそれぞれ測定し、その結果を表１に示した。
【００４７】
【表１】
【発明の効果】
本発明のシート状成形体は含水無機化合物あるいは含水無機化合物と炭酸塩／セルロース繊維／無機繊維／フェノール樹脂という構成で各成分を特定量含有し、かつフェノール樹脂の全部または一部をキュラストメータによる１７５℃での硬化速度が０．０５ｋｇ・ｃｍ／分以上０．４ｋｇ・ｃｍ／分未満なる硬化特性を有するものとしたので、高度の不燃性と優れた機械的強度を併せ持ち、かつ柔軟性に富み、曲面下地に対して良好な施工性を有するシート状不燃成形体が得られる。すなわち、本発明のシート状不燃成形体は、ＪＩＳ
Ａ−１３２１の表面試験の１級（これは建築基準法で規定する不燃材料に相当する）に合格できる高度の不燃性を有し、かつ、ケイ酸カルシウム板のごとき従来の不燃材に比べ優れた機械的強度を有する上に、溝加工あるいは屈曲自在な不燃裏打材との接着等を施さずとも、曲率半径５０〜１００ｍｍといったきわめて曲がりの急な曲面施工性を施すことができるという利点を有する。
【００４９】
さらに、本発明のシート状不燃成形体の少なくとも片面に化粧紙、レザー、合成樹脂膜、突板、金属板もしくは金属箔等の柔軟性のある面材を貼り合わせ等により固着せしめることで、両者共に柔軟性がありなじみがよいために表面強度、平滑性及び光沢感などの表面品位、意匠性等が付与され、さらに曲面施工が可能な付加価値の一段と高まったシート状不燃成形体を得ることができる。
特に、金属板を貼合した場合、得られるシート状不燃成形体はきわめて高強度を有するとともに耐割裂性にも優れ、同時に柔軟性を有し各種曲面施工にも適用できることから内外装材として好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sheet-like incombustible molded article, and more particularly, to a sheet-like incombustible molded article having a high degree of incombustibility and excellent mechanical strength, and being rich in flexibility and having good workability for a curved substrate. .
[0002]
[Prior art]
Conventionally, when applying a non-combustible material to a curved substrate, after applying the grooved non-combustible material to the R-type table and securing the necessary radius of curvature, the groove is filled with a filler such as cement and cured. Although a method of pasting on a predetermined curved base is adopted, the number of processes is increased and construction is complicated and troublesome.
In addition, there is a method that does not depend on such groove processing on a part of the calcium silicate plate or the like, but there is a limitation on the applicable radius of curvature (at most 1000 mm or more), and only a fairly gentle curved surface could be obtained. .
[0003]
Further, a non-combustible base material such as a calcium silicate plate is bonded onto a flexible and flexible non-combustible backing material, grooves are formed on the surface of the non-combustible base material at predetermined intervals, and the groove bottom is as described above. Some have been applied to reach non-combustible backing materials.
However, this method requires (1) an adhesion process between the incombustible backing material and the incombustible substrate, and the processing process is complicated. (2) Since an organic adhesive is often used to bond the non-combustible backing material and the non-combustible base material, the non-combustibility tends to deteriorate. (3) Glass cloth, various inorganic fiber-based nonwoven fabrics, aramid fiber sheets, etc. are used as flexible and flexible non-combustible backing materials. However, such non-combustible backing materials are generally very expensive. .
Accordingly, there has been an urgent need to develop a non-combustible material that can be subjected to a sharp curved surface construction without applying the groove processing or bonding of a flexible non-combustible backing material.
[0004]
Therefore, the present inventor repeated intensive trial and error in order to solve such problems, and contained a large amount of a water-containing inorganic compound or a large amount of a water-containing inorganic compound and carbonate and a predetermined amount of cellulose fiber, Has curing propertiesPhenolic resinAnd a sheet-like thermoformed product containing a predetermined amount of inorganic fibers have a high degree of incombustibility and excellent mechanical strength, and are found to be flexible and have good workability for curved substrates, The present invention has been completed.
[0005]
The sheet-shaped incombustible molded article according to the present invention has a water-containing inorganic compound in a solid content of 60 to 95% by weight, a cellulose fiber in a solid content of 2 to 30% by weight, and an inorganic fiber in a solid content of 1 to 20% by weight. , A sheet-like thermoformed product containing 1 to 20% by weight of a solid content of a thermosetting resin, the thermosetting resinOf which, 30% by weight or more in terms of solid contentIt has a curing characteristic that the curing rate at 175 ° C. by a curast meter is 0.05 kg · cm / min or more and less than 0.4 kg · cm / min.
[0006]
Moreover, the sheet-like incombustible molded body according to the present invention comprises a water-containing inorganic compound and a carbonate in a total content of 60 to 95% by weight, cellulose fibers in a solid content of 2 to 30% by weight, and inorganic fibers in a solid content. 1 to 20% by weight and a sheet containing 1 to 20% by weight of a thermosetting resin in solid content, and the water-containing inorganic compound / carbonate is on the water-containing inorganic compound excess side from 50/50 in the solid content weight ratio A thermoformed body, the thermosetting resinOf which, 30% by weight or more in terms of solid contentIt has a curing characteristic that the curing rate at 175 ° C. by a curast meter is 0.05 kg · cm / min or more and less than 0.4 kg · cm / min.
[0007]
Examples of the above-mentioned water-containing inorganic compound include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, dihydrate gypsum and calcium aluminate. These compounds all have crystal water in the molecule and have a chemically similar structure. In addition, the hydrous inorganic compounds have some differences in decomposition temperature and endothermic amount depending on the type, but they are quite common in that they decompose upon high temperature heating and exhibit an incombustible effect due to endothermic action. Therefore, basically any of the above-mentioned water-containing inorganic compounds may be used, but aluminum hydroxide is optimal in view of economics such as an acquisition price.
[0008]
As the carbonate used in the present invention, at least one selected from calcium carbonate, magnesium carbonate, barium carbonate, strontium carbonate, beryllium carbonate, zinc carbonate and the like is used. These carbonates have some differences in decomposition temperature and the like depending on their types, but they are quite common in that they decompose upon high temperature heating and exhibit a flame retardant effect due to endothermic action. Therefore, basically, any of the carbonates described above may be used, but calcium carbonate is optimal from the viewpoint of cost. In addition, the smoke generation amount reducing effect pointed out by the present inventor in Japanese Patent Application Laid-Open No. 5-112659 can be given as another important effect obtained by blending carbonate.
[0009]
The total content range of the water-containing inorganic compound or the water-containing inorganic compound and the carbonate in the non-combustible molded article according to the present invention is 60 to 95% by weight, preferably 70 to 92% by weight, more preferably 75 to 95% by solid content. 88% by weight. If the content is less than 60% by weight, sufficient nonflammability cannot be obtained. On the other hand, if it exceeds 95% by weight, it is unsuitable because sufficient mechanical strength or curved surface workability cannot be obtained due to the excessive amount of the water-containing inorganic compound or the water-containing inorganic compound and the carbonate. It should be noted that sufficient non-flammability and mechanical strength or curved surface workability is ensured by setting the total content of the water-containing inorganic compound or the water-containing inorganic compound and carbonate in the sheet-like non-combustible molded body to be in the range of 70 to 92% by weight. It becomes easy to secure, and it becomes easy to ensure sufficient nonflammability, mechanical strength, or curved surface construction property by setting it as the range of 75 to 88 weight%. Further, the content ratio by weight of the hydrated inorganic compound / carbonate must be 50/50, preferably 60/40, in excess of the hydrated inorganic compound in terms of solid content. If the water-containing inorganic compound is less than 50/50, the nonflammability may be lowered, which is unsuitable. In addition, it becomes easy to ensure sufficient nonflammability by making content weight ratio of a water-containing inorganic compound / carbonate into a water content inorganic compound excess side rather than 60/40 by solid content.
[0010]
As the above-mentioned cellulose fiber, one or more kinds selected from wood pulp such as softwood or hardwood chemical pulp, mechanical pulp, semi-chemical pulp, cotton pulp, hemp pulp, and various used papers are used in combination. Can be used. Wood pulp is the most easy-to-use cellulose fiber material because of its stable supply and quality and relatively low price. Cotton pulp and hemp pulp are unstable in supply and expensive in price, but in a sheet-like molded body containing a large amount of a water-containing inorganic compound or a water-containing inorganic compound and carbonate as in the present invention, as required. Thus, by using the cotton pulp or hemp pulp, the decrease in the mechanical strength of the sheet-like molded product can be minimized.
[0011]
The content range of the cellulose fiber in the non-combustible molded article of the present invention is 2 to 30% by weight, preferably 4 to 20% by weight, and more preferably 7 to 15% by weight in terms of solid content. If the content is less than 2% by weight, sufficient paper-making properties or mechanical strength and curved surface workability cannot be obtained due to the shortage of cellulose fibers, and if it exceeds 30% by weight, sufficient nonflammability is caused by an excess of organic substances. Can't get. In addition, it becomes easy to ensure sufficient paper-making property, mechanical strength, curved surface workability, and nonflammability by making the content rate of the cellulose fiber in a sheet-like incombustible molding into the range of 4-20 weight%, 7- By making it the range of 15 weight%, it becomes easy to ensure more sufficient paper-making property, mechanical strength, curved surface workability, and nonflammability.
The phenol resin used in the present invention has a curing rate of 0.05 or less at 175 ° C. using a curastometer.kg · cm / min0.4 or morekg · cm / minLess, preferably 0.1kg · cm / min0.4 or morekg · cm / minLess, more preferably 0.15kg · cm / min0.35 or morekg · cm / minIt shall have a curing property of less than. The total amount of phenol resin is the curing rate of 0.05kg · cm / minIn the case of less than the above, the mechanical strength of the obtained sheet-like molded product becomes insufficient. Further, the total amount of the phenol resin is the curing rate of 0.4.kg · cm / minIn the case of the above thing, the softness | flexibility of the obtained sheet-like molded object falls and sufficient curved surface workability cannot be obtained. All or part of the phenol resin used in the present invention has a curing rate of 0.1 at 175 ° C. measured by a curastometer.kg · cm / min0.4 or morekg · cm / minBy having a curing characteristic of less than, it becomes easy to achieve both excellent mechanical strength and good curved surface workability, which are mutually contradictory, which will be described later,kg · cm / min0.35 or morekg · cm / minBy having less curing properties, it becomes easier to achieve both excellent mechanical strength and good curved surface workability. Further, as the phenol resin used in the present invention, the curing rate at 175 ° C. by a curastometer is 0.05.kg · cm / min0.4 or morekg · cm / minIn the case of using a phenolic resin other than this having a curing characteristic that is less than this, in selecting a phenolic resin other than the phenolic resin having the curing characteristic, there is a contradictory relationship as described later. The type and blending amount must be selected so that both excellent mechanical strength and good curved surface workability can be satisfied.
[0012]
AbovePhenolic resin,Accompanying heat treatmentFluidized hardening provides non-flammable materials with various molding shaping effects, various strength development effects, curved surface workability, and hydrated inorganic compounds or carbonates to prevent falling off, etc.give. Phenolic resin used aboveCuring temperatureIsThan the decomposition temperature of the hydrous inorganic compound or carbonate used togetherIt is desirable to make it low.
[0013]
In the non-combustible molded article of the present inventionPhenolic resinThe content range of is 1 to 20% by weight, preferably 3 to 17% by weight or more, and more preferably 5 to 15% by weight in terms of solid content. If the content is less than 1% by weight, sufficient mechanical strength or curved surface workability cannot be obtained, and if it exceeds 20% by weight, sufficient nonflammability cannot be obtained due to excessive organic substances. In the sheet-like incombustible molded bodyPhenolic resinBy making the content ratio of 3 to 17% by weight, it becomes easy to ensure sufficient mechanical strength, curved surface workability and nonflammability, and by making it the range of 5 to 15% by weight, more sufficient It becomes easy to ensure mechanical strength, curved surface workability and nonflammability. usePhenolic resinHaving the above-mentioned curing characteristics in the total amount ofPhenolic resinIs preferably 30% by weight or more in terms of solid content, more preferably 50% by weight or more, and still more preferably 60% by weight or more. If it is less than 30% by weight, either or both of the curved surface workability and mechanical strength of the obtained sheet-like molded product may be insufficient. UsePhenolic resinHaving the above-mentioned curing characteristics in the total amount ofPhenolic resinBy setting the ratio of 50% by weight or more, it becomes easier to achieve both curved surface workability and mechanical strength, and by setting it to 60% by weight or more, both curved surface workability and mechanical strength are further improved. It becomes easy to plan. Also, in this case, it has the curing characteristicsPhenolic resinOther thanPhenolic resinWhen choosing a, there is a contradictory relationship as described laterIt is in,The type and blending amount must be selected in consideration of satisfying both excellent mechanical strength and good curved surface workability.
[0014]
As the above-mentioned inorganic fiber, at least one kind selected from rock wool fiber, glass fiber, ceramic fiber or carbon fiber is used. In particular, the use of rock wool fibers is preferable because the curved surface workability of the obtained sheet-like molded product is further improved.
The content range of the inorganic fibers in the sheet-shaped incombustible molded article of the present invention is 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 10% by weight in terms of solid content. If the content is less than 1% by weight, cracks are likely to occur in the surface test of JIS A1321, and if it exceeds 20% by weight, sufficient paper-making properties cannot be obtained, and inorganic fibers are uniformly distributed in the obtained sheet-like molded product. Cannot be distributed. In addition, it becomes easy to uniformly distribute the inorganic fibers by making the content of the inorganic fibers in the sheet-shaped incombustible molded body in the range of 1 to 15% by weight, and it is easy to avoid cracks in the surface test of JIS A1321, By setting the content in the range of 2 to 10% by weight, the inorganic fibers can be more easily uniformly distributed, and cracks can be easily avoided in the surface test of JIS A1321.
[0015]
The sheet-shaped incombustible molded article according to the present invention is a water-containing inorganic compound or a water-containing inorganic compound and carbonate / cellulose fiber / inorganic fiber /Phenolic resinAs the manufacturing method, any method such as a wet papermaking method or a dry molding method can be applied, and the manufacturing method is not limited to a specific manufacturing method, but the wet papermaking method is most preferable. Hereinafter, the case where the wet papermaking method is applied will be described in detail with reference to the manufacturing method.
[0016]
The sheet-like incombustible molded article according to the present invention may contain various yield improvers for improving the yield of the hydrous inorganic compound or carbonate, or if necessary, synthetic fibers or synthetic dyes for coloring. Good. In addition, it goes without saying that a dry or wet paper strength enhancer, a sizing agent, a water-proofing agent, a water-repellent agent and the like should be included in order to improve mechanical strength or suitability for post-processing depending on applications.
[0017]
In the sheet-like incombustible molded article of the present inventionPhenolic resinAs a method of containing,Phenolic resinA liquid material, a fibrous material, or a granular material may be internally added to the raw material, or may be applied or impregnated after forming the paper layer. As a method of adding a water-containing inorganic compound or carbonate, a method of applying or impregnating a base material with a paint containing a water-containing inorganic compound or carbonate is also conceivable. In order to make the quality uniform in the direction, the method of internally adding a hydrated inorganic compound or carbonate in the form of powder or slurry in the raw material slurry is most preferable. In this case, a hydrous inorganic compound, carbonate, cellulose fiber, inorganic fiber andPhenolic resinThe addition method and the order of addition are optional, and beating treatment may be performed if necessary.
[0018]
In order to produce the sheet-shaped incombustible molded body according to the present invention using the raw material slurry thus obtained, a normal papermaking method and a thermoforming method may be used. That is, for papermaking, the slurry may be supplied onto a papermaking net such as a long net, a circular net or an inclined net, filtered and dehydrated, and then compressed and dried. Further, if necessary, two or more paper layers may be overlapped by various combination nets, multi-tank circular nets, various laminators and the like. For thermoforming, conventional hot press molding, high-frequency thermoforming, etc. may be applied alone or in combination of two or more.
[0019]
In addition, depending on the application, the obtained sheet-shaped non-combustible molded product may be subjected to surface treatment such as spraying, application or printing of various paints, or soft paper such as decorative paper, leather, synthetic resin film, veneer, metal plate or metal foil. Needless to say, it is possible to further increase the added value of the sheet-like non-combustible molded article by adhering a sticky face material.
[0020]
The sheet-like incombustible molded article of the present invention contains a water-containing inorganic compound and inorganic fiber, or exhibits excellent incombustibility only by containing a water-containing inorganic compound, carbonate and inorganic fiber. It does not prevent the use of. Examples of flame retardants that can be used in combination include known flame retardants such as organic phosphorus compounds, phosphorus-containing nitrogen-containing organic compounds, sulfamates such as guanidine sulfamate, inorganic phosphates, halogen-containing compounds, and antimony compounds. it can. Examples of the method of using the flame retardant include a method in which it is internally added in a raw material slurry, or is applied or impregnated during a paper making process, after paper making, or after molding. However, in this case, it is natural that the content of the flame retardant should be determined in consideration of the content of the hydrous inorganic compound and the inorganic fiber or the content of the hydrous inorganic compound, the carbonate and the inorganic fiber.
[0021]
[Action]
An important aspect of the present invention is that it has specific curing propertiesPhenolic resinContaining a large amount of a water-containing inorganic compound and a predetermined amount of cellulose fibers and inorganic fibers, or a large amount of a water-containing inorganic compound and carbonate, a predetermined amount of cellulose fibers and inorganic fibers, and a predetermined amount of SaidPhenolic resinAlthough the sheet-like thermoformed body containing the resin exhibits excellent mechanical strength by being cured by thermoforming, it is rich in flexibility and has good curved surface workability.
[0022]
Phenolic resinCan express mechanical strength with a small amount of formulation, andPhenolic resinSince it itself is relatively excellent in heat resistance, it can be said that it is suitable for materials that require a high degree of nonflammability.
[0023]
But,Phenolic resinThe composition containing is contained when thermoformedPhenolic resinIn general, the mechanical strength is improved because the material is hardened by the hardening action, but the flexibility is generally lowered.
[0024]
Therefore, the inventor of the present invention is a sheet-like molded article that contains a large amount of a water-containing inorganic compound or a water-containing inorganic compound, a carbonate, and a relatively small amount of a phenol resin, and has a high degree of nonflammability, and is inherently in a contradictory relationship. In order to achieve both mechanical strength and good flexibility (curved surface workability), a number of experiments were conducted, and it was found that such a purpose could be achieved by using a phenolic resin having specific curing characteristics. I found it. That is, the curing rate at 175 ° C. by a curastometer (hereinafter, this may simply be referred to as the curing rate) is 0.05.kg · cm / min0.4 or morekg · cm / minIt has been found that a phenolic resin having a curing property of less than this is suitable for this purpose.
[0025]
When a phenol resin in a composition having a relatively low content of phenol resin is efficiently thermally cured to fully exert functions such as strength development, a phenol resin having a higher curing speed is usually used. However, 0.05kg · cm / min0.4 or morekg · cm / minBy using a phenol resin having a considerably slow curing rate of less than 1, it was possible to achieve both excellent mechanical strength and good flexibility (curved surface workability).
[0026]
Next, a description will be given based on experimental results in examples described later. The sheet-like molded bodies according to Example 1, Example 4, Comparative Example 1 and Comparative Example 3 to be described later have almost the same composition, and both are first grades in the surface test of JIS-A1321 (according to the Building Standards Act). Equivalent to non-combustible material to be specified). The curing rate of the phenol resin used was 0.21 in Example 1.kg · cm / minExample 4 was 0.34kg · cm / minComparative Example 1 is 0.71kg · cm / minComparative Example 3 is 1.40kg · cm / minIt is. The radius of curvature, which is a judgment index for curved surface workability, is 140 mm in Comparative Example 1 and 170 mm in Comparative Example 3, whereas it is 60 mm in Example 1 and 50 mm in Example 4, and the applicable curvature radius is Comparative Example 1. In comparison with Examples 3 and 3, in Examples 1 and 4, it is 1/2 to 1/3, and the flexibility is greatly improved, and excellent curved surface workability is obtained.
[0027]
Further, regarding the mechanical strength, the breaking lengths of Examples 1 and 4 were lower by about 25 to 30% than Comparative Example 1, but Examples 1 and 4 were improved by about 40 to 50% compared to Comparative Example 3. is doing. Further, in terms of bending strength, Examples 1 and 4 are lower by about 15 to 30% than Comparative Example 1, but are improved by about 50 to 60% compared to Comparative Example 3. Therefore, the sheet-like molded bodies according to Examples 1 and 4 are sufficiently excellent in mechanical strength. Furthermore, the curved surface workability of 50 mm or 60 mm in the curvature radius of Examples 1 and 4 is 1/25 to 1/30 compared to 1500 mm similarly evaluated for a commercially available calcium silicate plate shown in Comparative Example 6 described later. It can be seen that the sheet-like non-combustible molded article of the present invention has extremely good curved surface workability. In terms of mechanical strength, Examples 1 and 4 are superior to Comparative Example 6 in 1.1 to 1.2 times in breaking length and 1.5 to 1.7 times in bending strength.
[0028]
That is, in a sheet-shaped molded article containing a large amount of a water-containing inorganic compound or a water-containing inorganic compound and carbonate and a relatively small amount of a phenol resin, and having a high degree of incombustibility, the curing rate of the phenol resin used is set to 0.05.kg · cm / min0.4kg · cm / minThe sheet-shaped incombustible molded article having both excellent mechanical strength and good flexibility (curved surface workability) can be obtained only by specifying in the range below.
[0029]
Curing speed 0.05kg · cm / min0.4kg · cm / minThe details of the action / mechanism to obtain such a favorable result when using a phenol resin of less than that are still unclear, but the network structure of cellulose fibers and inorganic fibers, which are the skeleton constituent elements in the sheet-like incombustible molded article of the present invention 0.05 against structurekg · cm / min0.4kg · cm / minThe phenolic resin having a curing speed of less than 50% is cured in a form that effectively reinforces the network structure, and strength development is achieved without the hardening peculiar to the cured product of the phenolic resin as much as possible. It is estimated that a certain excellent mechanical strength and good flexibility (curved surface workability) can be achieved at the same time.
[0030]
【Example】
Next, the present invention will be described more specifically based on the following examples. Measurement of each item in this example was performed by the following method.
(1) Thickness and density: According to JIS P-8118.
(2) Nonflammability: According to the surface test of JIS A-1321.
(3) Breaking length: According to JIS A-8113. When there was fiber orientation, it measured in the fiber orientation direction and the direction perpendicular | vertical to this, and calculated | required the average of both.
(4) Bending strength: According to JIS A-5907. When there was fiber orientation, it measured in the fiber orientation direction and the direction perpendicular | vertical to this, and calculated | required the average of both.
(5) Phase workability; curvature of 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 170, 200, 300, 400, 600, 800, 1000, 1500, 2000 A simulated base is formed using a molded plywood having a radius, and the test base (5 cm × 25 cm, if there is fiber orientation, the length is 25 cm in the fiber orientation direction when the fiber is oriented) has a 25 cm side curvature. The evaluation was performed with the smallest radius of curvature that did not cause any inconvenience in construction such as breaking or cracking along the radius direction.
In addition, the curing rate of phenol resin at 175 ° C with a curastometer is the maximum on the curing curve.torquePoints that reached 10% of (torqueF10 (kg · cm), Time T10 (min)) and maximumtorque90% of the points (torqueF90 (kg · cm), The slope of the straight line connecting time T90 (minutes)), ie, (F90-F10) / (T90-T10)kg · cm / minGiven in.
[0031]
Example 1
A predetermined amount of a mixed dispersion of cellulose fibers and inorganic fibers obtained by disaggregating commercially available softwood unbleached sulfate pulp and rock wool fibers having a fiber length of 7 mm (hereinafter abbreviated as “inorganic fibers a”) with a disaggregator. In this, aluminum hydroxide powder (average particle size is 5.7 μm, the same applies hereinafter), calcium carbonate powder (average particle size is 1.5 μm, the same applies hereinafter) and a curastometer at 175 ° C. Curing speed is 0.21kg · cm / minThe phenol resin (hereinafter abbreviated as phenol resin a) is added, sufficiently dispersed and mixed with a stirrer, then formed with a square test paper machine, pressed and dried, and then heated. Heat treatment with a press (temperature 175 ° C., pressure 5 kg / cm2 3 hours), and a sheet-like molded product A was obtained. About the sheet-like molded object A, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0032]
Example 2
In Example 1, instead of the inorganic fiber a, a sheet-like molded body B was obtained in the same manner as in Example 1 except that rock wool fiber having a fiber length of 3 mm (hereinafter abbreviated as inorganic fiber b) was used. .
About the sheet-like molded object B, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0033]
Example 3
In Example 1, a rock wool fiber having a fiber length of 1 mm (hereinafter abbreviated as “inorganic fiber c”) was used in place of the inorganic fiber a, and the curing rate at 175 ° C. with a curastometer was used in place of the phenol resin a. Is 0.34kg · cm / minA sheet-like molded product C was obtained in the same manner as in Example 1 except that a phenol resin (hereinafter abbreviated as phenol resin b) was used. About the sheet-like molded object C, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, incombustibility, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0034]
Example 4
In Example 3, instead of the inorganic fiber c, a sheet-like molded product D was prepared in the same manner as in Example 3 except that rock wool fiber having a fiber length of 0.15 mm (hereinafter abbreviated as inorganic fiber d) was used. Obtained.
About the sheet-like molded object D, while showing the content rate of each component in Table 1, thickness, a density, fracture length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0035]
Example 5
In Example 1, instead of the inorganic fiber a, a sheet-like molded body E was obtained in the same manner as in Example 1 except that glass fiber having a fiber length of 3 mm (hereinafter abbreviated as “inorganic fiber e”) was used.
About the sheet-like molded object E, while showing the content rate of each component in Table 1, thickness, a density, fracture length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0036]
Example 6
In Example 1, glass fiber having a fiber length of 5 mm was used in place of the inorganic fiber a, and magnesium hydroxide powder (average particle size of 10 μm; the same applies hereinafter) was used in place of the aluminum hydroxide powder. In the same manner as in Example 1, a sheet-like molded product F was obtained.
About the sheet-like molded object F, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0037]
Example 7
In Example 1, a sheet-like molded body G was obtained in the same manner as in Example 1 except that calcium carbonate powder was not blended.
About the sheet-like molded object G, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0038]
Example 8
In Example 1, a sheet-like molded body H was obtained in the same manner as in Example 1 except that the phenol resin a and the phenol resin c were blended at a solid content weight ratio of phenol resin a / phenol resin c = 3/2. .
About the sheet-like molded object H, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0039]
Comparative Example 1
In Example 1, instead of the phenol resin a, the curing rate at 175 ° C. by a curastometer was 0.71.kg · cm / minA sheet-like molded product I was obtained in the same manner as in Example 1 except that a phenol resin (hereinafter abbreviated as phenol resin c) was used. About the sheet-like molded object I, while showing the content rate of each component in Table 1, thickness, a density, fracture length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0040]
Comparative Example 2
In Example 5, a sheet-like molded product J was obtained in the same manner as in Example 5 except that the phenol resin c was used instead of the phenol resin a.
About the sheet-like molded object J, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0041]
Comparative Example 3
In Example 1, instead of the phenol resin a, the curing rate at 175 ° C. by a curastometer was 1.40.kg · cm / minA sheet-like molded body K was obtained in the same manner as in Example 1 except that a phenol resin (hereinafter abbreviated as phenol resin d) was used. About the sheet-like molded object K, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0042]
Comparative Example 4
In Example 5, a sheet-like molded body L was obtained in the same manner as in Example 5 except that the phenol resin d was used instead of the phenol resin a.
About the sheet-like molded object L, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0043]
Example 9
Commercial softwood unbleached sulfate pulp and inorganic fiber a are disaggregated with a pulper, aluminum hydroxide powder, calcium carbonate powder and phenolic resin a are added to this and thoroughly dispersed and mixed. 20 sheet layers were laminated on a roll-type paperboard paper machine, pressed, dried, and then hot pressed (temperature 175 ° C., pressure 10 kg / cm).2 , Time 10 minutes) to obtain a sheet-like molded product M.
About the sheet-like molded object M, while showing the content rate of each component in Table 1, thickness, a density, fracture length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0044]
Example 10
In Example 9, a sheet-like molded body N was obtained in the same manner as in Example 9 except that the amount of each component was changed.
About the sheet-like molded object N, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0045]
Comparative Example 5
In Example 9, a sheet-like molded product O was obtained in the same manner as in Example 9 except that the phenol resin d was used instead of the phenol resin a.
About the sheet-like molded object O, while showing the content rate of each component in Table 1, thickness, a density, tearing length, bending strength, nonflammability, and curved surface workability were measured, respectively, and the result was shown in Table 1. .
[0046]
Comparative Example 6
The thickness, density, breaking length, bending strength, incombustibility, and curved surface workability of each commercially available calcium silicate plate were measured, and the results are shown in Table 1.
[0047]
[Table 1]
【The invention's effect】
The sheet-like molded article of the present invention contains a specific amount of each component in the structure of a water-containing inorganic compound or a water-containing inorganic compound and carbonate / cellulose fiber / inorganic fiber / phenol resin, and a curastometer for all or part of the phenol resin. Cure rate at 175 ° C. by 0.05kg · cm / min0.4 or morekg · cm / minSince it has less curing properties, a sheet-like incombustible molded article having a high degree of incombustibility and excellent mechanical strength, having high flexibility, and good workability with respect to a curved substrate can be obtained. That is, the sheet-like incombustible molded article of the present invention is JIS
It has high incombustibility that can pass the first grade of surface test of A-1321 (this corresponds to the incombustible material specified by the Building Standards Act) and is superior to conventional incombustible materials such as calcium silicate board. In addition to having high mechanical strength, there is an advantage that it is possible to perform curved surface workability with an extremely sharp curvature such as a radius of curvature of 50 to 100 mm without performing groove processing or bonding with a flexible nonflammable backing material. .
[0049]
Furthermore, by adhering a flexible face material such as decorative paper, leather, synthetic resin film, veneer, metal plate or metal foil to at least one side of the sheet-shaped incombustible molded article of the present invention, Because it is flexible and familiar, surface quality such as surface strength, smoothness and glossiness, design properties, etc. are given, and it is possible to obtain a further increased value-added sheet-like non-combustible molded body capable of curved surface construction it can.
In particular, when a metal plate is bonded, the obtained sheet-shaped non-combustible molded body has extremely high strength and is excellent in splitting resistance, and at the same time has flexibility and can be applied to various curved surface constructions, so it is suitable as an interior / exterior material. Can be used.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21796897A JP4310715B2 (en) | 1997-07-29 | 1997-07-29 | Sheet-shaped incombustible molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21796897A JP4310715B2 (en) | 1997-07-29 | 1997-07-29 | Sheet-shaped incombustible molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1143543A JPH1143543A (en) | 1999-02-16 |
| JP4310715B2 true JP4310715B2 (en) | 2009-08-12 |
Family
ID=16712563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21796897A Expired - Fee Related JP4310715B2 (en) | 1997-07-29 | 1997-07-29 | Sheet-shaped incombustible molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4310715B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002052680A (en) * | 2000-08-09 | 2002-02-19 | Toyota Tsusho Corp | Decorative sheet |
| JP4782301B2 (en) * | 2001-04-11 | 2011-09-28 | 北越紀州製紙株式会社 | Sheet-like incombustible molded body and method for producing the same |
| JP4678631B2 (en) * | 2001-05-17 | 2011-04-27 | 北越紀州製紙株式会社 | Sheet-like incombustible cosmetic material |
| JP4782308B2 (en) * | 2001-05-18 | 2011-09-28 | 北越紀州製紙株式会社 | Sheet-like incombustible molded body and method for producing the same |
| JP4969948B2 (en) * | 2006-08-18 | 2012-07-04 | 北越紀州製紙株式会社 | Lighting adjustment tool sheet and lighting adjustment tool using the sheet |
| MY165595A (en) * | 2014-03-31 | 2018-04-16 | Aica Kogyo Co Ltd | Decorative board |
| CN107848263B (en) * | 2015-07-10 | 2020-10-09 | 爱克工业株式会社 | Decorative sheet |
-
1997
- 1997-07-29 JP JP21796897A patent/JP4310715B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1143543A (en) | 1999-02-16 |
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