JP2004269635A - Flame-retardant film, incombustible laminate, and incombustible laminate structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a fascia, such as an internally illuminated one, having excellent flame retardancy and being resistant to staining by penetrated rainwater and to the growth of e.g., mold. <P>SOLUTION: A flame-retardant film is prepared from a composition formed by formulating a flexible fluroresin with titanium oxide. This film is high in water repellency, light resistance, flame retardancy, and whiteness since it is prepared from the composition formed by formulating the fluororesin inherently having a high limiting oxygen index and excellent weathering resistance with the titanium oxide. Therefore, a laminate 5 prepared by laminating the film on either surface of a glass fiber fabric and laminating a coat layer based on a thermoplastic resin or a silicone resin on the other surface is a membrane material being excellent in water repellency, light resistance, and weathering resistance, having such flame retardancy as to be determined as an incombustible material, having high flexibility, excellent processability, and nonproblematic in cracking and placeability, and suited as the fascia when set up with e.g., a fastener 6. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００６２】
【表２】

【００６３】
【表３】

【００６４】
各フッ素樹脂の限界酸素指数（カタログ値）は、上記したようにフッ素樹脂１で４３、フッ素樹脂２で４３、フッ素樹脂３で６５、フッ素樹脂４で７２であり、最低でも４３であったが、各実施例および比較例のフィルムのように薄く（厚み０．１５ｍｍ）に成膜すると、表１〜表３に示すように限界酸素指数の測定値は樹脂本来の限界酸素指数に達しない。これは、不燃性である鉄であってもスチールウールは空気中で燃えたり、アルミニュームの微粉末が粉塵爆発を起こすのと同様の現象である。
【００６５】
フッ素樹脂に無機添加剤を添加することにより、限界酸素指数の理論値および測定値が向上する。フッ素樹脂１とフッ素樹脂２との混合樹脂に対して、無機添加剤の添加量がゼロである比較例１では限界酸素指数の測定値（以下、限界酸素指数測定値という）が３０．３であるのに対し、炭酸カルシュームを８部添加した比較例２では限界酸素指数測定値３１．１となる。フッ素などのハロゲン元素の存在下で卓越した難燃効果を呈する三酸化アンチモンを３部添加した比較例３では、比較例２における炭酸カルシュームの添加量より少ない添加量でも、比較例２よりも高い限界酸素指数測定値３８．２となっている。いわゆるハロゲン化アンチモンとしての難燃効果が発現するためと思われる。ガラスビーズを３部添加した比較例４でも限界酸素指数測定値３２．９と僅かながら向上している。
【００６６】
同じくフッ素樹脂１とフッ素樹脂２との混合樹脂に対して、無機添加剤として酸化チタンＡ（ルチル型）を添加した実施例１〜７では、添加量がわずか０．２部である実施例１でも限界酸素指数測定値５０．９と格段に向上し、物質混合則による限界酸素指数の理論値４３を遙かにしのぐ高い値が得られた。また添加量にほぼ比例して限界酸素指数測定値の向上が見られたが、添加部数２部以上で測定器の限界（限界酸素指数７０）に達した。
【００６７】
同じくフッ素樹脂１とフッ素樹脂２との混合樹脂に対して、無機添加剤として酸化チタンＢ（アナターゼ型）を添加した実施例８〜１４においても、添加量がわずか０．２部である実施例８で限界酸素指数４１．７が得られ、添加量にほぼ比例して限界酸素指数の向上が見られた。
【００６８】
フッ素樹脂１とフッ素樹脂３との混合樹脂に対して、無機添加剤として酸化チタンＡ（ルチル型）を添加した実施例１５〜２１においても、添加量が０．２部である実施例１５で限界酸素指数６７．５が得られ、添加量０．５部以上で測定器の限界（限界酸素指数７０）に達した。
【００６９】
フッ素樹脂１とフッ素樹脂３との混合樹脂に対して、無機添加剤として酸化チタンＢ（アナターゼ型）を添加した実施例２２〜２８においても、添加量が０．２部である実施例２２で限界酸素指数４６．５が得られ、添加量にほぼ比例して限界酸素指数の向上が見られた。
【００７０】
フッ素樹脂３とフッ素樹脂４との混合樹脂に対して、無機添加剤として酸化チタンＢ（アナターゼ型）を添加した実施例２９においては、添加量０．２部で限界酸素指数６１．８が得られた。酸化チタンＡ（ルチル型）の添加によっては、より高い限界酸素指数が得られるものと予想される。
【００７１】
以上のように、本来は燃えにくい樹脂であるのに薄いフィルム状に成膜した場合に燃え易くなる（軟質）フッ素樹脂に対して、極微量の酸化チタンを配合することにより、難燃性の向上した難燃性フィルムを形成できる。フッ素樹脂という高価な樹脂の成膜品の難燃性を向上できる非常に有用な技術である。
【００７２】
しかも軟質フッ素樹脂を用いるため、フッ素樹脂に共通する撥水性、耐候性は有し、かつ、加工性に優れる、低温での加工が可能である、柔軟である等の利点を具備したものとなる。
【００７３】
同じくフッ素樹脂であるＰＴＦＥ（ポリテトラフルオロエチレン）は、限界酸素指数が９５と高く、特に難燃化を図らなくとも充分な難燃性能を有しているが、成膜しにくい、加工温度が高い、硬いなどの欠点を持っていることは周知である。
【００７４】
本発明の難燃性フィルムは、難燃性の点ではＰＴＦＥには及ばないものの、ＰＴＦＥにない多くの利点を備えており、ＰＴＦＥが利用されている分野の一部は好適に代替可能である。
【００７５】
本発明の難燃性フィルムをガラス繊維布帛に積層して、内照式看板などに用いる積層体を作成することができる。内照式看板においては光透過性が重要な課題である。透明性が高すぎると、基材たるガラス繊維布帛が透けて見え、品位上好ましくない。
【００７６】
そのため従来は、中空ガラスビーズを添加することによって光拡散を生起し、ガラス繊維布帛を見えなくする手法が採られていた（表１に示した比較例４はその一例である）。しかしビーズは、カレンダー法等、材料に高いせん断力（シェアー）が加わる加工に於いては微粉砕されてしまう危険性が高く、シェアー状態の管理が難しかった。
【００７７】
これに対し本発明に用いる酸化チタンは、極微量に配合するだけでよいので、（軟質）フッ素樹脂の持っている透明性はさほど損なわず、さらには高い隠蔽力を持っていて、その添加量により自由に隠蔽性をコントロール可能である。粒径も細かくて分散も容易であるため、加工時のせん断力のコントロールなどの煩わしい管理も必要ではなく、また熱濃硫酸以外に対して化学的に安定であるため後段で悪影響が出る恐れもない。
【００７８】
酸化チタンを微量に添加することで、フィルムに高い難燃性を付与できるだけでなく、その添加量によって光透過量の制御を容易に行なうことができ、そのような難燃性フィルムをガラス繊維布帛に積層した積層体に、不燃材料と判定される品質を持たせること、またガラス繊維布帛を遮蔽してシルキーな外観を持たせ、高品位を付与することが可能となるのである。
【００７９】
以下、本発明の積層体について説明する。
（実施例３０）
ガラス繊維製布帛（カネボウ株式会社製 ガラス繊維織物 ＧＶ８１８Ｊ 糸密度３３×４３／吋 平織り組織生地重量１９０ｇ／ｍ^２の一方の面を、ウレタン樹脂溶液を固形分３０ｇ／ｍ^２となるように塗布し１５０℃で乾燥させることにより、接着処理した。ウレタン樹脂溶液は次のようにして調製した：水性ウレタン樹脂（大日本インキ製 インプラニールディスパージョンＤＬＦ）１００質量部に対して、増粘剤０．５質量部、シランカップリング剤（信越化学製 シランカップリング剤 ＫＢＭ４０３）１質量部を加えた。
【００８０】
この接着処理済みのガラス繊維製布帛に難燃性フィルムを積層した。難燃性フィルムの積層は次のようにして行った：上述した実施例３の処方（フッ素樹脂１を８０質量部、フッ素樹脂２を２０質量部、酸化チタンＡを０．６質量部）に滑剤としての燐酸フォスフェート０．５質量部を加えた材料（比重約１．９）を、１７０℃に設定された試験ロールで溶融混合し、試験ロールとゴムロールの線圧２０ｋｇ／ｃｍとして、ロール上で厚み０．１２ｍｍの溶融フィルムを成膜しつつ、布帛上に貼り合わせた。
【００８１】
ガラス繊維製布帛のもう一方の面に熱可塑性樹脂を主体とするコート層を積層し、１８０℃で一分間乾燥させた。熱可塑性樹脂を主体とするコート層の積層は次のようにして行った：オレフィン系ディスパージョン（三井化学製 ケミパールＳ１００ 固形分２７％）３７０質量部（固形分１００質量部相当）、水酸化マグネシューム（協和化学工業製 キスマ５Ａ）１００部、撥水剤Ａ（日華化学製 フッ素系撥水剤 ＮＧＴ６７１Ｆ）１０部、防かび剤Ａ（ローム・アンド・ハース デュロテックス７６０３）４質量部をディスパーにて高速攪拌し、しかる後に脱泡し、塗布した。塗布量は６０ｇ／ｍ^２であった。
【００８２】
得られた実施例３０の積層体について次の試験を行った。
１）実施例３０の積層体のコート層表面（ガラス繊維製布帛に背反する面）の撥水性をＪＩＳ Ｌ１０９６により試験した。
【００８３】
２）実施例３０の積層体から２０ｃｍ角の試料を切り取り、その試料の対角線上の角を掴んでそれぞれ手揉み１０回した後に樹脂の剥離脱落の有無を調べた。
３）実施例３０の積層体より縦糸方向及び横糸方向から幅３ｃｍ長さ２０ｃｍの試料を切り取り、その下端を２ｃｍ市販の万年筆用赤インクに浸して、毛細管現象によるインクの上昇を目視で確認した。
【００８４】
４）実施例３０の積層体から２０ｃｍ角の試料を切り取り、その試料をガストーチ（プリンス社のＷＥＬＤＩＮＧ ＴＯＲＣＨ ＧＢ２００１）により１０ｃｍの距離から３０秒間加熱し、表面の無機物残差の有無と繊維の露出状態を目視で判定した。これは、「防火上有害な裏面に達する亀裂、損傷の発生がないこと」を判定する代用試験として行なった。
【００８５】
５）上記４）におけるガストーチによる加熱の際に、積層体からの炎の発生状態を観察した。大きな炎の発生があった時に×、僅かな炎の発生があった時に△、炎が殆ど認められなかった時に○と判定した。これは、建築基準法第２条９号に於ける「２００ｋｗ／ｍ^２の発熱が１０秒間を越えてはならない」を判定する代用試験として行なった。
この積層体の処方および試験結果は表４に示した。
【００８６】
（実施例３１）
ガラス繊維製布帛（カネボウ株式会社製 ＧＶ８１８Ｊ 糸密度 ３３×４３本／吋 平織り組織生地重量 １９０ｇ／ｍ^２の一方の面を実施例３０と同様にして接着処理した。
【００８７】
この接着処理済みのガラス繊維製布帛に、実施例３０と同様の溶融フィルムを貼り合わせた。
ガラス繊維製布帛のもう一方の面にシリコーン樹脂組成物を塗布し、１３０℃で一分間乾燥させた。シリコーン樹脂組成物は次のように調製した：シリコーン樹脂（東芝ＧＥシリコーン社製 ＫＭ２００Ｔ）１００質量部、タルク２０質量部、防かび剤Ｂ（ローム・アンド・ハース社製 ｖｉｎｙｚｅｎｅ）５質量部をディスパーにて高速攪拌し、しかる後に脱泡した。シリコーン樹脂自体に撥水性が有るため撥水剤は添加していない。塗布量は８０ｇ／ｍ^２とした。
得られた積層体について実施例３０と同様の試験を行った。
この積層体の処方および試験結果は表４に示した。
【００８８】
（実施例３２）
ガラス繊維製布帛（カネボウ株式会社製 ＧＶ８１８Ｊ 糸密度 ３３×４３本／吋 平織り組織生地重量 １９０ｇ／ｍ^２）の一方の面を実施例３０と同様にして接着処理した。
【００８９】
この接着処理済みのガラス繊維製布帛に、実施例３０と同様の溶融フィルム（ただし厚み０．１１ｍｍ）を貼り合わせた。
ガラス繊維製布帛のもう一方の面に熱可塑性樹脂組成物を塗布し、１８０℃で一分間乾燥させた。熱可塑性樹脂組成物は次のようにして調製した：アクリル系樹脂溶液（大日本インキ化学株式会社製 溶剤型アクリル樹脂 クリスコートＰ１３３０ 固形分３０％）３３３質量部（固形分１００質量部相当）、カタルポ（丸尾カルシュウム社製 カタルポ）５０質量部、撥水剤Ｂ（日本油脂株式会社製 フッ素系撥水剤 モディパーＦ６００）２０部、防かび剤Ｃ（大日本インキ化学株式会社製 バイオカット−Ｚ）４質量部、粘度調整用トルエン適量、をディスパーにて高速攪拌し、しかる後に脱泡した。塗布量は４０ｇ／ｍ^２とした。
【００９０】
この積層体について実施例３０と同様の試験を行った。
またコーンカロリーメーターで発熱量を測定し、３．１ＭＪの実測値を得た。
また理論発熱量を次のように算出し実測値と比較した。
【００９１】
条件１：フッ素樹脂層について、フッ素樹脂１およびフッ素樹脂２に含まれる炭素量を分子構造から約３０％と想定し、その全てが燃焼により二酸化炭素に変わるものとして酸素消費量を求める。
【００９２】
条件２：接着処理に用いたウレタン樹脂溶液と裏面コート層について、有機物成分の組成は全て炭素と水素であると仮定し、また実際の構造とは異なるがＣｎＨ_２ｎの飽和炭化水素構造であると仮定し、その炭素および水素の全てが燃焼により二酸化炭素及び水に変わるものとして酸素消費量を求める。
【００９３】
計算：
フッ素樹脂層は厚み０．１１ｍｍ、比重１．９であるから積層体１ｍ^２のフッ素樹脂量は２０９ｇ／ｍ^２であり、炭素の含有量を約３０％と仮定すると、炭素量は６２．７ｇ／ｍ^２となる。この炭素を二酸化炭素とするのに必要な酸素量はその２．６７倍（原子量Ｃ＝１２ Ｏ_２＝１６×２から、３２／１２＝２．６７）の１６７ｇ／ｍ^２である。Ｈｕｇｇｅｔｔ（米国）とＰａｋｅｒ（米国）の理論より酸素消費量１ｋｇ当たりの発熱量１３．１ＭＪであるから、理論発熱量は１３．１ＭＪ×０．１６７ｋｇ／１ｋｇの式より２．１９ＭＪと概算できる。
【００９４】
ウレタン樹脂溶液はほぼ全て有機物成分からなり、付着量３０ｇ／ｍ^２であるから、酸素消費量はその３．４３倍の１０３ｇ、発熱量は１．３５ＭＪ＝１３．１ＭＪ×０．１０３ｋｇとなる。
【００９５】
裏面コート層は付着量４０ｇ／ｍ^２であるが、無機物成分であるカタルポを２９％含むため有機物成分は実質２８．５ｇ／ｍ^２であり、酸素消費量はその３．４３倍の９８ｇ、発熱量は１．２８ＭＪ＝１３．１ＭＪ×０．０９８ｋｇとなる。
【００９６】
したがって積層体全体の理論発熱量は、４．８２ＭＪ＝２．１９ＭＪ＋１．３５ＭＪ＋１．２８ＭＪと算出される。
この積層体の処方、試験結果および計算結果は表４に示した。
【００９７】
【表４】

【００９８】
上記したように、実施例３２の積層体で発熱量理論値４．８２ＭＪ、発熱量実測値３．１０ＭＪが得られており、両値とも、建築基準法２条９号に規定される不燃性能を備えるための条件８ＭＪ以下を満足する値である。実施例３０の積層体でも同様にして、理論発熱量１．３８，発熱量理論値５．１２が算出される。
【００９９】
実測値が理論値よりも低い値となったのは、１）燃焼後の試料（大部分はガラス繊維布帛である）に煤が幾分か見られ完全燃焼していなかった、２）接着層、裏面コート層の有機物成分が飽和炭化水素構造をとっていなかった、ことに基づく誤差と見られる。
【０１００】
このようにして、コーンカロリーメーターによる実測試験を行わずとも、また用いる熱可塑性材料の種類にかかわらず、理論計算によって総発熱量の概略を知ることができ、積層量のコントロールに役立てることができる。
【０１０１】
（実施例３３）
図１は本発明の一実施形態における積層体構造体の断面図、図２は同積層体構造体の一部拡大断面図である。
図１および図２に示すように、積層体構造体１は、内照式看板として構成されており、照明器具２を内側に配置し、建物の外壁３に取り付けた看板枠体４に対して、膜材たる積層体５が固定具６を介して展張されている。積層体５は上述したようなものであり、５ａは不燃性フィルム、５ｂはガラス繊維製布帛、５ｃはコート層である。
【０１０２】
図３にも示すように、固定具６は、断面Ｕ形の溝部７ａを有した樋状の固定具本体７と、溝部７ａ内に配置された積層体５の周縁部を溝部７ａ内面に対して押える押え金具８と、押え金具８と積層体５との間に配置された緩衝材としての弾性体９とで構成されており、押え金具８，弾性体９，積層体５，固定具本体７を貫通する押えビス１０，固定ビス１１によって、看板枠体４に固定されている。固定具６はカバー１２によって覆われている。固定具本体７，押え金具８は例えばアルミニューム，鉄，ステインレススチール，ジュラルミン，チタンなどの金属で作製され、弾性体９は合成ゴム，熱可塑性エラストマーなどからなる。
【０１０３】
固定具本体７においては、溝部７ａを挟んだ一側から溝部底部にわたる壁体７ｂが厚く形成されていて、展張された積層体５はこの一側の壁体７ｂによってコート層５ｃ側から支持される。この壁体７ｂは中空状に形成され、補強リブ７ｃが配されていて、それにより固定具本体７の強度確保および重量低減が図られている。溝部７ａを挟んだ他側の壁体７ｄは、看板枠体１０の外側面と面一をなすように、溝部７ａの開口端に相応する位置から外方へ、次いで下方へとＬ形に折り曲げ形成されている。
【０１０４】
この固定具本体７の一側の壁体７ｂは、溝部７ａに臨んだ上端縁部および対向配置された固定具本体７に臨んだ縁部が、溝部底部と同じ曲率半径Ｒ＝５ｍｍを持つ曲面形状に形成されている。溝部７ａを挟んだ他側の壁体７ｄも、溝部７ａに臨んだ上端縁部が曲率半径Ｒ＝３ｍｍを持つ曲面形状に形成されている。
【０１０５】
押え金具８は、溝部７ａの内面にほぼ沿う外形を有し、曲率半径Ｒ＝５ｍｍの溝部底部に対応する部分は、その溝部底部よりも一回り小さい曲率半径Ｒ＝４ｍｍを持つ曲面形状に形成されている。この押え金具８も中空状に形成されている。弾性体９は、溝部底部に沿う彎曲形状を持ったシートして形成されている。
【０１０６】
ここで、固定具６に展張した積層体５は、固定具６の丸みＲによっては劣化し易く、割れたり切断したりする懸念がある。このため予め固定具６の丸みＲと積層体５の劣化について予め検討した。
【０１０７】
この種の劣化に関する試験方法としては、ＪＩＳ Ｐ ８１１５（紙及び板紙のＭＩＴ形試験機による耐折れ強さ試験方法）がある。図４（ａ）を参照しながら概略を説明する。ＭＩＴ試験機に備わる断面扇形の一対の固定具１３の間に試料１４を挟み込み、この試料１４に垂直方向（試料１４の厚み方向に直交する方向）の張力Ｔを１ｋｇｆ（約９．８Ｎ）加える。そして、その状態で固定具１３を扇形中心部分を軸として左右９０度、都合１８０度にわたり回転させて、試料１４を扇形中心部分を折り線として左右に折り曲げる動作を、１７５回／分の速度で繰り返す。折り曲げ強度の弱い材料であればその間に割れたり切断したりする。
【０１０８】
この試験方法等を用いて固定具１３の丸みＲが膜材に及ぼす影響を試験した。
試験装置：ＴＭＩＴ型耐折試験機（上島製作所製）
試料：実施例３２で作成した積層体
固定具： 従来より用いられている標準のＲ＝０．１〜０．２ｍｍのもの、および、比較のために特別に作成したＲ＝２ｍｍ、Ｒ＝３ｍｍ、Ｒ＝５ｍｍ、Ｒ＝１０ｍｍのもの。Ｒは図４（ｂ）に示した扇形中心部分の曲率半径を意味する。
【０１０９】
試験方法１： ＪＩＳ Ｐ ８１１５に準ずる。試験条件として、試料サイズ１５ｍｍ×１５０ｍｍ、張力１．０ｋｇ×１５ｍｍ、折り曲げ回数１００回、１０００回、１０万回、折り曲げサイクル１７５回／分を使用する。評価は、試料の表面状態の変化を目視にて確認することで行う。
【０１１０】
試験方法２：強度変化を確認するために、ＪＩＳ Ｌ１０９６（一般織物試験方法）６．１２．１（１）法に規定されたストリップ法の重布類に準じて、定速伸長形試験にて引張強度を測定し、強度保持率を計算する。試料巾は１５ｍｍとする。
結果を表５に示す。
【０１１１】
【表５】

【０１１２】
表５からわかるように、Ｒ＝３ｍｍ〜１０ｍｍで良好な結果が得られた。Ｒ＝３ｍｍ未満のものでは、Ｒ＝３ｍｍ，５ｍｍ，１０ｍｍのものに比べて生地の劣化が格段に進んでいる。Ｒ＝０．１〜０．２ｍｍの標準固定具では１００回程度の屈曲で著しい強度劣化が発生している。Ｒ＝１０を越えるものでもＲ＝１０のものと同様の良好な結果が得られるが、Ｒを大きくすると、それだけ固定具１３の厚みを大きくせざるを得ず、実用に際して、重くなり、デザイン上も好ましくないなどの不都合が生じる。Ｒ＝３ｍｍ〜５ｍｍの範囲が好ましい。
【０１１３】
したがって、膜材を展張する際に、Ｒ＝３ｍｍ〜５ｍｍの適度な丸みをつけた固定具を用いることで、膜材が風によるはためきを繰り返す間に劣化したり、取り付けの際に摩擦によって裏面が削れる事態を回避することができ、膜材本来の強度を発揮させることが可能となる。Ｒ＝３ｍｍ〜５ｍｍの固定具であれば、膜材の取り付け時も低摩擦で展張することができ、取り付け作業が容易になる。Ｒ＝０．１〜０．２ｍｍの標準固定具を用いると、膜材本来の強度を発揮できない。
【０１１４】
先に図１〜図３を用いて説明した固定具６では、積層体５が彎曲して圧接する部位は全てＲ５としているので、積層体５の劣化は生じにくく、本来の強度を発揮できると言える。さらに固定具６の全体に丸みを付けているので、荷重が一点に集中せずに全面に分散することになり、全体としての保持力も向上する。
【０１１５】
ただし、必ずしも固定具６の全体に丸みを付ける必要はなく、少なくとも、積層体５が彎曲して圧接する部位に丸みをつければよい。
なお、上記した積層体構造体１の形状や材料は単なる例示であり、これに限定されるものではない。
【０１１６】
【発明の効果】
以上のように本発明によれば、本来高い限界酸素指数を有し、且つ耐候性に優れる軟質フッ素樹脂に酸化チタンを配合することにより、限界酸素指数が著しく向上した難燃性フィルムを得ることができる。
【０１１７】
上記した難燃性フィルムをガラス繊維製布帛の一方の面に積層し、他方の面に熱可塑性樹脂またはシリコーン樹脂を主体としたコート層を積層して積層体を構成することにより、高耐候耐光性、優れた難燃性を持たせることができ、雨水の染み込みによるシミ、カビの問題も回避できる。
【０１１８】
上記した不燃性積層体を所定の丸みを付けた固定具で展張して積層体構造体を構成することにより、劣化しにくいものとすることができ、袖看板、内照式看板などとして利用する場合も長期にわたって高品位に維持可能となる。この種の用途に従来用いられてきたアクリル、ポリカーボネート等の膜材で懸念されていた割れや破片の飛散等の事故の恐れもなく、安全である。
【図面の簡単な説明】
【図１】本発明の一実施形態における積層体構造体の断面図
【図２】図１の積層体構造体の一部拡大断面図
【図３】図１の積層体構造体に用いられた固定具の各部材を示した断面図
【図４】固定具のＲが積層体の劣化に及ぼす影響を調べる試験方法を説明する模式図
【符号の説明】
１ 積層体構造体
２ 照明器具
３ 外壁
４ 看板枠体
５ 積層体
６ 固定具
７ 固定具本体
７ａ 溝部
８ 押え金具
９ 弾性体[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant film, a non-combustible laminate, and a non-combustible laminate structure used for a signboard or the like.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, many signboards such as internally illuminated signboards are made of a laminate obtained by laminating a thermoplastic resin such as an acrylic resin, a polycarbonate resin, or a soft vinyl chloride on a synthetic fiber or a glass fiber. When acrylic resin or polycarbonate resin is used as the film material, there is no flexibility, there is a risk of breaking when an object collides or the fragments may be scattered and injure people, and it is difficult to create a large signboard On the other hand, a laminate using a synthetic fiber or a glass fiber as a base material is rich in flexibility, excellent in workability, and free from problems of cracking and workability.
[0003]
In recent years, internally illuminated signboards have become larger and are often mounted as advertising media on the outer walls of buildings, so that high security has been required as part of building structures. Needless to say, measures to prevent cracks and shards from scattering are increasing. In many cases, high flame retardancy and non-combustibility are required to ensure safety in the event of fire.
[0004]
As a material having high flame retardancy and non-flammability, and also usable for an internally illuminated signboard, for example, a laminate in which a silicone resin or a fluororesin is laminated on glass fiber can be seen (for example, Patent Document 1, Patent Document 1). 2, see Patent Document 3).
[0005]
[Patent Document 1]
JP 2001-55646 A
[0006]
[Patent Document 2]
JP-A-8-259637
[0007]
[Patent Document 3]
JP-A-8-290528
[0008]
[Problems to be solved by the invention]
The Building Standards Law was revised in 1998, and the use of materials that are determined to be non-combustible in the tests specified in Article 2.9 of the Building Standards Law for new applications such as internally illuminated signboards is required. Have been.
[0009]
An outline of the above test will be described. 0 to 100 kW / m from a distance of 25 mm for a 100 × 100 mm sample ² At the same time as applying uniform heat radiation and heating, a high-voltage spark is generated to ignite and burn flammable gas gradually generated from the sample, and the total amount of heat generated from the sample within a predetermined time, the maximum heat generation rate And the damage of the sample. Use a corn calorimeter for the measurement.
[0010]
The requirements for non-combustible materials are as follows.
1) Total heating value within 8 minutes after starting heating ² It must be:
2) 200 KW / m maximum heating rate for 10 seconds within 20 minutes after starting heating ² Do not exceed.
3) There should be no crack or damage reaching the backside which is harmful to fire protection within 20 minutes after the start of heating.
[0011]
Although the term "non-combustible material" suggests a material that does not burn at all, the revised Building Standards Law emphasizes the time required for people to safely evacuate during an actual fire, and some burns Any material that clears the criteria is open to practical use as a safe material.
[0012]
The laminates disclosed in Patent Documents 1, 2, and 3 are all nonflammable. This is speculation based on the fact that glass fibers are nonflammable, and silicone resins and fluororesins have a high limiting oxygen index and are considered to be flame retardant. The limiting oxygen index of a resin is important as an index of flame retardancy, and a resin with a high limiting oxygen index is useful both in the design of laminates and when used as part of a building structure. is there.
[0013]
The resin commonly mentioned in Examples of Documents 1, 2, and 3 has a limiting oxygen index of 54, and certainly has higher flame retardancy than a general thermoplastic resin. However, when the resin is formed into a thin film, the limiting oxygen index generally decreases. In Examples of Document 3 (Japanese Patent Application Laid-Open No. Hei 8-290528), the heat resistance when held for 1000 hours in a constant temperature bath at 80 ° C. is evaluated, and is not considered to be flame retardant.
[0014]
This type of laminate in which a glass fiber and a fluororesin are laminated has been registered and used since 1987 as a membrane material type A that satisfies the “Japan Membrane Structure Association Technical Standards for Specific Membrane Structures”. The membrane material type A is shown as a standard having a content of tetrafluoroethylene (PTFE, known as Teflon (registered trademark)) of 90% or more. It has very high flame retardancy. However, a laminate satisfying the standard of the film material type A is very hard and is suitable as a material for a large structure represented by Tokyo Dome, but is also difficult to use for a small signboard or the like.
[0015]
As for the silicone resin, there is a description that "it does not easily burn out even when approaching a flame, but there is a defect that it keeps burning once it is ignited."("New silicone and its application: Toshiba Silicone Co., Ltd. April 1, 1994 ").
[0016]
On the other hand, many of the signboards are used outdoors, and there is a concern that rainwater or the like may enter inside the signboard while being exposed to rain, snow, or the like. Water cannot penetrate in a signboard made of acrylic resin or polycarbonate resin, but in a signboard made of a laminated material mainly composed of glass fiber, rainwater etc. will be generated by the capillary phenomenon from the cross section of the glass fiber fabric. May penetrate. If there is no resin coating layer on the back side of the glass fiber fabric (that is, on the inside of the signboard), rainwater or the like easily penetrates over a wide range of the fabric, causing stains, molds, and the like, and causing a deterioration in appearance.
[0017]
Even with a fluororesin / glass fiber / fluororesin structure in which a fluororesin is laminated on both sides of a glass fiber fabric, it is almost impossible to impregnate the resin into each of the glass fiber multifilaments. Infiltration of rainwater from the cross section cannot be completely eliminated. Also, by laminating the fluororesin on both sides, it becomes harder and harder to bend. There is also a problem that the price of the fluororesin is high because the price is high.
[0018]
In a laminate in which the silicone resin is laminated on both sides of the glass fiber, the silicone resin is very flexible and easily damaged by scratching from the outside. Further, when a signboard of such a laminate is installed outdoors, a small amount of low-molecular siloxane or the like contained in the silicone resin may migrate to the surface, and this may become a trace of a rain streak, resulting in poor appearance. This is similar to the traces of black rain streaks seen under window frames when silicone resin is used as a caulking agent in building window frames.
[0019]
In general, a film material is stretched and fixed at the time of manufacturing and constructing a signboard. However, a laminate made of glass fiber as a base material has a low elongation and is difficult to stretch and fix. If it is pulled too strongly, it will break, and if it is too loose, the film material will loosen, which is undesirable in appearance. At the time of expansion, the fixing device is rubbed against the fixing device, and is scraped or broken, and the strength of the original laminate may be impaired. Depending on the fixing device, the frictional strength may be increased and the expansion may be difficult.
[0020]
[Means for Solving the Problems]
The present inventors have studied to solve the above problems, and as a result, found that, by mixing titanium oxide with a fluororesin, a film having excellent light resistance, high flame retardancy, and high whiteness can be formed. Was completed.
[0021]
That is, the present invention provides a flame-retardant film obtained by blending titanium oxide with a soft fluororesin.
Further, the present invention, the melting point of 85 ℃ ~ 160 ℃, and flexural modulus of 700MPa measured by ISO 178 to 100 parts by weight of a soft fluororesin, added 0.2 parts by weight of titanium oxide to 4 parts by weight, A flame-retardant film having a thickness of 0.05 mm to 0.3 mm and having a limiting oxygen index of 50 or more is laminated on one surface of a glass fiber fabric, and the other surface is coated with a thermoplastic resin or a silicone resin. The present invention provides a non-combustible laminate in which layers are laminated.
[0022]
Further, the present invention is a non-combustible laminate structure in which the above-described non-combustible laminate is extended by a fixture, wherein a predetermined fixing region of the non-combustible laminate is arranged in a groove formed in a fixture body. Supporting the non-combustible laminate with a support formed in a curved shape having a radius of curvature of 3 mm to 10 mm on the wall of the fixture body along the groove, and fixing the fixing region of the non-combustible laminate in the groove with an elastic body. The present invention provides a non-combustible laminate structure pressed against the inner surface of the groove by a pressing tool through the inside.
[0023]
Fluororesin is a resin originally having a high critical oxygen index, but by adding a small amount of titanium oxide, the critical oxygen index can be significantly improved.
Of course, it is not possible to suppress the total amount of heat enough to pass the test of Building Standard Law Article 2.9 by only improving the limiting oxygen index, but the maximum heat generation speed is 200 kW / m. ² It is important that the limiting oxygen index be increased so as to have a characteristic of gradual combustion in order not to exceed 10 seconds continuously. In a combustion mode in which flashover occurs at once, it is difficult to take time for a person to safely evacuate, and the danger is high.
[0024]
The reason that the titanium oxide used in the present invention greatly contributes to the improvement of the limiting oxygen index as compared with other inorganic substances, for example, antimony trioxide which is a similar metal oxide, is due to the high thermal stability of the titanium oxide. It is presumed to be due to the following catalytic action.
[0025]
In the combustion of a polymer, heat from a fire source causes a part of the polymer to be gasified and turned into radicals that easily react with oxygen in the air. The radicals combine with oxygen to start burning, and the heat of combustion is added. Further, the generation of radicals from the polymer is further promoted, and the combustion is continued. Stopping combustion by suppressing the generation of radicals is one theory of flame retardancy.
[0026]
It is presumed that titanium oxide itself is an oxide and does not burn, but captures generated radicals or promotes recombination of radicals, thereby exerting an effect on flame retardancy. Academic elucidation of the flame retardant effect of titanium oxide on soft fluororesin could not be found in various documents.
[0027]
There are two types of titanium oxide, rutile type and anatase type, but rutile type is preferable. The rutile type shows higher performance in improving the oxygen index and shows higher light fastness. Titanium oxide has a high effect of blocking ultraviolet rays and is used as so-called white powder (white powder) in women's cosmetics, and also has the effect of improving the weather resistance and weather resistance of the resin used in the laminate this time.
[0028]
The correlation between the amount of titanium oxide added and the improvement of the limiting oxygen index exhibits an effect far exceeding at least the mixing rule of substances. The amount of titanium oxide added to improve the limiting oxygen index is 0.2 to 4 parts by mass based on 100 parts by mass of the soft fluororesin. With such an addition amount, a critical oxygen index of 50 or more can be achieved. The limit oxygen index of 50 or more is set as a safety factor based on approximately twice the oxygen concentration of 23% by mass in the air.
[0029]
If the amount is less than 0.2 parts by mass, a sufficient oxygen index improving effect cannot be obtained. If the amount is more than 4 parts by mass, the compatibility with the resin becomes insufficient and bloom (powder blowing) occurs. In addition, when the laminated product is used for an internally illuminated signboard, the light transmittance becomes insufficient. The addition of 0.2 to 2 parts by mass is more preferred.
[0030]
The soft fluororesin used in the present invention is not particularly limited, and examples thereof include terpolymers and copolymers obtained by copolymerizing polyvinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene at various monomer ratios. For example, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and the like can be used. These terpolymers or copolymers can be used alone or as a mixture, or further mixed with a polymer of polyvinylidene fluoride or hexafluoropropylene. The use of a mixture facilitates the adjustment of flexibility and film-forming properties. Those having a melting point of 85 ° C. to 160 ° C. and a flexural modulus of 700 MPa or less measured according to ISO 178 are preferred.
[0031]
A resin having a melting point of less than 85 ° C. may have insufficient heat resistance. With a resin having a melting point exceeding 160 ° C., film formation by the calendar method cannot be easily performed. In the case of a resin having a melting point of more than 160 ° C., it is necessary to set the actual calender film forming temperature to 200 ° C. or higher in order to obtain good film forming properties, and many resin additives such as processing aids. And the resin additive has a smaller number of options in consideration of heat resistance. For film formation by the calender method, a resin having a melting point of 145 to 85 ° C is more preferable.
[0032]
A film forming method using a T-die, which is generally used for a resin having a high melting point, is also possible, but this film forming method causes a large amount of discharge loss at the time of adjusting the resin film thickness and warming up the processing machine. Fluororesins are very expensive compared to general-purpose resins, so that economic losses increase.
[0033]
It is also possible to dissolve the resin in an organic solvent such as methyl ethyl ketone and laminate it on the substrate by coating.However, after the organic solvent evaporates, micro-bubbles tend to remain and the density of the resin layer tends to be low. It is not preferable from the viewpoints of a decrease in mechanical strength and easiness of contamination.
[0034]
A resin having a flexural modulus of 700 MPa or less as measured according to ISO 178 is preferable in order to impart flexibility to a film formed from the resin. Forming a film with a resin having a higher flexural modulus causes problems such as difficulty in bending and easy occurrence of bending whitening.
[0035]
When constructing the laminate, the above-described flame-retardant film is laminated on one surface of the glass fiber cloth. The bonding may be performed using a general adhesive, a silane coupling agent, or a titanate coupling agent. Such a bonding method is a conventional means for bonding an inorganic substance and an organic substance, and is also used as a conventional means for bonding a glass fiber and a soft fluororesin used in the present invention. (In the 1995 edition of the Shin-Etsu Silicone Silane Coupling Agent catalog or technical data T11-5A and "New Silicones and Their Applications: Toshiba Silicone Co., Ltd., April 1, 1994" It is introduced as a dry processing method and a wet processing method.)
On the other surface of the glass fiber cloth, a coat layer of a thermoplastic resin or a silicone resin is laminated. This is to protect the glass fiber cloth and to prevent the occurrence of stains and molds due to rainwater soaked by the capillary phenomenon.
[0036]
By laminating the flame-retardant film and the coat layer, a laminate having properties that can be used as a film material for an internally illuminated signboard, etc., that is, a non-flammability that passes the Building Standard Law Article 2.9 is obtained. Thus, it is possible to realize a laminated body that is flexible, easy to use, and has high designability without generating mold, stains, and the like.
[0037]
The thermoplastic resin can be used without particular limitation as long as it is excellent in weather resistance. For example, acrylic resin, polyurethane resin, olefin resin, polyester resin, styrene elastomer, dispersion, emulsion Alternatively, a solution in an organic solvent is laminated by a method such as coating.
[0038]
The silicone-based resin is a polymer formed by linking silicon having an organic group through siloxane bonds, but may be any as long as it forms a film. For example, a rubber-type resin such as a millable rubber compound or a liquid rubber; As a gel type or a silicone resin, a varnish type, a paint type, a molding resin and the like can be used. These materials are laminated by coating or laminating a film.
[0039]
It is preferable to use those resins dissolved and dispersed in an organic solvent. The use of the organic solvent makes it easier to penetrate into the glass fiber fabric, so that the penetration of rainwater or the like can be effectively prevented. In the case of an aqueous resin, the wetness is deteriorated by deposits such as an oil agent and a sizing agent remaining on the glass fiber, and the resin is difficult to penetrate.
[0040]
The reason that the thermoplastic resin or the silicone-based resin can be freely selected and used as described above is that the total calorific value due to combustion is almost the same regardless of the type of the resin. This is supported by the report by Huggett and Baker (USA) that "many organic materials generate 13.1 MJ of energy per kilogram of oxygen consumed during combustion, with an error within 5%". The theory.
[0041]
In the non-combustible material test described in Article 2-9 of the Building Standards Law described above, a 10 × 10 cm specimen was 100 kw / m from a distance of 25 mm. ² Although heat radiation is given, even in a laminate using glass fiber as a base material, most of the coating resin disappears due to such high heat radiation, and the fiber remains in the remaining glass fiber base material. A phenomenon of losing weight occurs. Flame penetrates through small gaps in the tissue as the glass fibers become thinner. In this state, it is determined that the condition that “there is no crack or damage reaching the back surface that is harmful to fire protection within the required time (within 20 minutes) after the start of heating” is not satisfied.
[0042]
For this reason, special measures are required for the woven structure of the glass fiber, for example. It is effective to increase the weaving density of the fiber or to use a weaving method in which the amount of yarn per unit area is large, such as twill weaving or satin weaving, and the fiber opening treatment disclosed in Japanese Patent Application Laid-Open No. 2001-55646. Etc. are also effective.
[0043]
However, if a glass fiber cloth woven by using a general plain weaving loom and raising the fiber density to the upper limit thereof can be used as it is, it is technically and economically advantageous. In the laminate of the present invention, a plain-woven glass fiber cloth having an increased fiber density is used, and an inorganic filler and at least one of a metal hydrate and a metal oxide are added to the coat layer. Prevent cracks, damage reaching the backside, harmful on fire protection. These inorganic additives remain as inorganic residues on the surface of the glass fiber cloth even after the resin of the coat layer is burned down or decomposed, and play a role of filling the eyes of the cloth.
[0044]
As the inorganic filler, calcium carbonate, clay, talc, magnesium silicate, silica and the like can be used. As the metal hydrate, magnesium hydroxide or aluminum hydroxide having water of crystallization can be used. As the metal oxide, antimony compounds such as antimony trioxide and antimony tetroxide, zinc borate, zinc stannate, molybdenum compounds, zirconium compounds and the like can be used.
[0045]
Metal hydrates are conventionally used as flame retardants to release water of crystallization during combustion to suppress heat generation, and metal oxides are also conventionally used as flame retardants for various polymers. It can be said that both have the effects of the inorganic filler and the flame retardant. By using these metal hydrates and / or metal oxides in combination with the inorganic filler, not only can the eyes of the glass fiber cloth be filled, but also the flame retardancy of the resin can be improved.
[0046]
The fact that the flame retardancy of the resin can be improved is based on the above-mentioned non-combustible material test in Building Standard Law Article 2.9, "The maximum heat generation rate is 200 KW / m for 10 seconds within the required time (within 20 minutes) after the start of heating. ² Is not important. In an actual fire, this is to prevent a flash-over or paper-burning fire.
[0047]
Inorganic fillers, metal hydrates and metal oxides have more important effects. By including these inorganic substances in the coat layer, the limiting oxygen index of the coat layer can be improved, and the total calorific value of the coat layer can also be reduced.
[0048]
In other words, it is inferred from the above-mentioned report by Huggett and Parker (USA) that "many organic substances generate 13.1 MJ of energy for 1 kg of oxygen consumed during combustion, and the error is within 5%". As described above, when the inorganic substance is mixed with the organic material of the coat layer, and the mixing ratio of the inorganic substance increases, the calorific value decreases.
[0049]
This effect can be similarly obtained when a thermoplastic resin (a general organic substance) is used for the coat layer or when a silicone resin having a smaller amount of carbon atoms and hydrogen atoms in the molecule is used. Most of the inorganic materials used in the present invention are inexpensive compared to resins, and in other cases, the amount is small, which leads to a reduction in material costs.
[0050]
However, on the other hand, the inorganic additive basically causes a decrease in resin strength, and therefore the upper limit is 200 parts by mass based on 100 parts by mass of the resin component (resin solids). The range of 20 parts by mass to 200 parts by mass is an appropriate amount for enabling a required amount of inorganic residue while maintaining practical resin strength. If it exceeds 200 parts by mass, the resin strength is significantly reduced, and if it is less than 20 parts by mass, a required amount of inorganic residue is not generated. Preferably, 50 to 150 parts by mass is added.
[0051]
When a thermoplastic resin is used for the coat layer, a water repellent is added to prevent stains such as stains caused by rainwater infiltration during outdoor use. The type of the water repellent is not particularly limited, but a fluorine-based or silicon-based water-repellent is preferred from the viewpoint of performance. The amount of addition may be the value recommended by the manufacturer.
[0052]
Even when high water repellency is imparted to the coat layer itself, when nutrients of mold are dissolved in water droplets and dew particles when rainwater infiltration or dew condensation occurs inside, the mold that ingests the nutrients is laminated This is because they may adhere to the surface of the glass fiber or penetrate between the glass fiber multifilaments from the cross section of the laminate due to the capillary phenomenon and grow there. Especially when the laminate is used for an internally illuminated signboard, the inside of the signboard becomes a considerably hot and humid atmosphere due to the heat and humidity of the light source, and it is easy to create an environment where mold easily grows. It is necessary to do.
[0053]
Examples of the fungicide include thiazoline compounds, dithiocarbamate compounds, N-phenylmaleimide resin, salicylamide, 2.3.4.6-methoxycarbonylaminobenzimidazole, 2-methoxycarbonylaminobenzimidazole, acrylic acid polymer , An organotin compound, a nitrogen compound, p-chloromethaxylenol, 2- (4-thiazolyl) -benzimidazole, 10,10'-oxybisphenoxyarsine, N (fluorodichloromethylthio) -phthalimide, N-dimethyl- N'-phenyl (N'-fluorodichloromethylthio) -sulfamide, dodecyldimethylpentylammonium chloride, cyclic nitrogen compounds, silver-based inorganic antibacterial agents, inorganic / organic hybrid fungicides, and the like can be used alone or Mix To use. The amount of the fungicide to be added may be the value recommended by the manufacturer.
[0054]
The lamination amount of the flame-retardant film composed of a soft fluororesin and titanium oxide is 100 g / m ² ~ 550g / m ² Is desirable. 100g / m ² If it is less than 3, it cannot be said that the film has sufficient film strength against external factors such as ultraviolet rays and wind and rain when used outdoors, and it is difficult to control the thickness in film formation by the calendar method. 550g / m ² Exceeds 8 MJ / m, together with the backside thermoplastic resin or silicone resin-based coating layer. ² Easy to cross. A total calorific value of 8 MJ or less is a condition for providing non-combustibility specified in Article 2.9 of the Building Standards Act. Even a fluororesin having a high limiting oxygen index contains carbon as a component, and if the resin is extremely thick, a calorific value exceeding 8 MJ is reached, so that the amount is naturally limited. 550g / m ² If it exceeds, uniform film formation by the calendering method becomes difficult, and the film becomes hard. 200g / m ² To 250g / m ² Is more desirable.
[0055]
Lamination amount of the coating layer mainly composed of thermoplastic resin or silicone resin is 20 to 200 g / m ² Is desirable. When a signboard or the like is produced, the film material is spread by uniformly applying tension using a fixture. In the laminate of the present invention, the coat layer on the back surface plays a role of protecting the glass fiber cloth. The amount of the coating layer laminated is 20 g / m ² If it is less than this, the glass fiber fabric will be damaged at the time of attachment, and the strength tends to decrease. 200g / m ² If it exceeds, the calorific value together with the flame-retardant film on the surface will increase.
[0056]
In order to prevent a decrease in the strength of the laminate, a structure is adopted in which an elastic body is interposed by a fixture and sandwiched. Thereby, the laminated body can be securely fixed to prevent displacement, and strength deterioration due to repeated fatigue caused by flapping by wind can be prevented. By using a fixing tool having a radius of R = 3 mm or more at a contact portion where the laminate is bent and pressed, the stretching is facilitated, and the deterioration of the strength of the laminate can be more effectively prevented. If R is less than 3 mm, rubbing or shaving during stretching is likely to occur, and if it exceeds 10 mm, sharpness will be lost and the stretched material will be easily loosened.
[0057]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described with reference to examples and comparative examples.
The non-combustible film of the present invention will be described.
(Examples 1-29, Comparative Examples 1-4)
The pellets of the soft fluororesin and the inorganic additives (products) were melt-mixed with test rolls at the compositions shown in Tables 1 to 3 to form films of Examples 1 to 29 and Comparative Examples 1 to 4. The thickness was 0.15 mm. The critical oxygen index LOI value of the obtained film was measured under the following test conditions. The measurement was performed by "Japan Chemical Fiber Inspection Association".
[0058]
<Test conditions>
JIS K-7201
Test specimen classification: B-1
Determination of oxygen index: When burning continues for 50 mm or more
Ignition heat source: Natural gas
For reference, assuming that the limiting oxygen index of the inorganic additive (substance) is 100, the theoretical value of the limiting oxygen index according to the substance mixing rule was determined according to the following equation.
Critical oxygen index = (resin oxygen index x number of prescriptions + number of inorganic additives (things) x 100) / total prescription
The theoretical values and measured values of the obtained limiting oxygen index are also shown in Tables 1 to 3.
[0059]
The details of various soft fluororesins in the table and the limiting oxygen index (catalog value) of the resin alone are as follows.
Fluororesin 1: Kynar 2820 [PVDF (polyvinylidene fluoride) -HFP (hexafluoropropylene) copolymer] manufactured by elf atchem;
Fluororesin 2: Kynar 9301 [PVDF (polyvinylidene fluoride) -HFP (hexafluoropropylene) -TFE (tetrafluoroethylene) terpolymer] manufactured by elf atochem;
Fluororesin 3: dyneon THV200G manufactured by Sumitomo 3M Limited;
Fluororesin 4: dyneon THV400G manufactured by Sumitomo 3M Limited;
[0060]
Details of the inorganic additives in the table are as follows.
Calcium carbonate: Calcium carbonate SS80 manufactured by Nitto Powder Co., Ltd .;
Antimony trioxide: Antimony trioxide PATOX-M manufactured by Nippon Seiko Co., Ltd.
Inorganic filler: HSC-110C hollow glass beads, manufactured by Toshiba Baroteini Co., Ltd.
Titanium oxide A: Titanium oxide JR401 manufactured by Teika Co., Ltd.
Titanium oxide B: Titanium oxide JA-1 manufactured by Teica Corporation.
[0061]
[Table 1]

[0062]
[Table 2]

[0063]
[Table 3]

[0064]
As described above, the limiting oxygen index (catalog value) of each fluororesin was 43 for fluororesin 1, 43 for fluororesin 2, 65 for fluororesin 3, and 72 for fluororesin 4, and at least 43. When the film is formed to be thin (0.15 mm in thickness) like the films of Examples and Comparative Examples, the measured value of the limiting oxygen index does not reach the original limiting oxygen index of the resin as shown in Tables 1 to 3. This is similar to the phenomenon in which steel wool burns in the air even with non-flammable iron, or a fine powder of aluminum causes a dust explosion.
[0065]
By adding an inorganic additive to the fluororesin, the theoretical value and measured value of the limiting oxygen index are improved. In Comparative Example 1 in which the amount of the inorganic additive added was zero with respect to the mixed resin of the fluororesin 1 and the fluororesin 2, the measured value of the critical oxygen index (hereinafter referred to as the critical oxygen index measured value) was 30.3. On the other hand, in Comparative Example 2 in which 8 parts of calcium carbonate was added, the measured value of critical oxygen index was 31.1. In Comparative Example 3 in which 3 parts of antimony trioxide exhibiting an excellent flame retardant effect in the presence of a halogen element such as fluorine was added, the addition amount was smaller than that of Comparative Example 2 even if the addition amount of calcium carbonate in Comparative Example 2 was smaller than that of Comparative Example 2. The measured limit oxygen index value is 38.2. This is probably because the so-called antimony halide exhibits a flame retardant effect. In Comparative Example 4 in which 3 parts of glass beads were added, the measured value of the limiting oxygen index was 32.9, which is slightly improved.
[0066]
Similarly, in Examples 1 to 7 in which titanium oxide A (rutile type) was added as an inorganic additive to a mixed resin of fluororesin 1 and fluororesin 2, the amount of addition was only 0.2 part. However, the limit oxygen index measured value was remarkably improved to 50.9, and a high value far exceeding the theoretical value 43 of the limit oxygen index according to the substance mixing rule was obtained. Although the measured value of the limit oxygen index was improved almost in proportion to the amount added, the limit (limit oxygen index: 70) of the measuring device was reached when the number of added parts was 2 or more.
[0067]
Similarly, in Examples 8 to 14 in which titanium oxide B (anatase type) was added as an inorganic additive to a mixed resin of fluororesin 1 and fluororesin 2, only 0.2 part was added. At 8 the critical oxygen index 41.7 was obtained, and the limiting oxygen index was improved almost in proportion to the amount added.
[0068]
In Examples 15 to 21 in which titanium oxide A (rutile type) was added as an inorganic additive to the mixed resin of the fluororesin 1 and the fluororesin 3, Example 15 in which the addition amount was 0.2 part was used. A limiting oxygen index of 67.5 was obtained, and the limit of the measuring instrument was reached (a limiting oxygen index of 70) when the added amount was 0.5 part or more.
[0069]
In Examples 22 to 28 in which titanium oxide B (anatase type) was added as an inorganic additive to the mixed resin of the fluororesin 1 and the fluororesin 3, the addition amount was 0.2 parts in Example 22. A limiting oxygen index of 46.5 was obtained, and the limiting oxygen index was improved almost in proportion to the added amount.
[0070]
In Example 29 in which titanium oxide B (anatase type) was added as an inorganic additive to a mixed resin of the fluororesin 3 and the fluororesin 4, a limiting oxygen index of 61.8 was obtained with an addition amount of 0.2 part. Was done. It is expected that a higher limiting oxygen index can be obtained by adding titanium oxide A (rutile type).
[0071]
As described above, by blending a very small amount of titanium oxide with a (soft) fluororesin, which is inherently hard to burn but becomes easily flammable when formed into a thin film, the flame retardant An improved flame retardant film can be formed. This is a very useful technique that can improve the flame retardancy of a film formed of an expensive resin such as a fluororesin.
[0072]
Moreover, since a soft fluororesin is used, it has the same water repellency and weather resistance as the fluororesin, and has advantages such as excellent workability, processing at a low temperature, and flexibility. .
[0073]
PTFE (polytetrafluoroethylene), which is also a fluororesin, has a high limiting oxygen index of 95, and has sufficient flame-retardant performance even if it is not particularly flame-retardant. It is well known that it has drawbacks such as high hardness.
[0074]
Although the flame-retardant film of the present invention is inferior to PTFE in terms of flame retardancy, it has many advantages not found in PTFE, and some of the fields where PTFE is used can be suitably replaced. .
[0075]
The flame retardant film of the present invention can be laminated on a glass fiber fabric to produce a laminate used for an internally illuminated signboard or the like. Light transmission is an important issue for internally illuminated signboards. If the transparency is too high, the glass fiber fabric as the base material is seen through, which is not preferable in terms of quality.
[0076]
Therefore, conventionally, a method of causing light diffusion by adding hollow glass beads to make the glass fiber fabric invisible has been adopted (Comparative Example 4 shown in Table 1 is one example). However, beads have a high risk of being finely pulverized in a process such as a calendering method in which a material is subjected to a high shearing force (shear), and it is difficult to control the shear state.
[0077]
On the other hand, the titanium oxide used in the present invention only needs to be added in a very small amount, so that the transparency of the (soft) fluororesin does not deteriorate so much, and furthermore, it has a high hiding power. The concealment can be controlled freely by using. Since the particle size is fine and easy to disperse, no cumbersome management such as control of shear force during processing is necessary, and there is a risk that adverse effects may occur in the later stage because it is chemically stable to other than hot concentrated sulfuric acid. Absent.
[0078]
By adding a small amount of titanium oxide, not only can the film be imparted with high flame retardancy, but also the amount of light added can be easily controlled to control the amount of light transmission. It is possible to give the laminated body laminated with a quality determined to be a non-combustible material, and to provide a silky appearance by shielding the glass fiber fabric, thereby giving high quality.
[0079]
Hereinafter, the laminate of the present invention will be described.
(Example 30)
Glass fiber fabric (glass fiber fabric GV818J manufactured by Kanebo Co., Ltd. Yarn density 33 × 43 / inch Plain weave fabric weight 190 g / m ² Of the urethane resin solution with a solid content of 30 g / m ² Then, the coating was performed at 150 ° C. to perform an adhesive treatment. A urethane resin solution was prepared as follows: 0.5 part by mass of a thickener and 100 parts by mass of an aqueous urethane resin (Dip Nippon Ink's Inplanil Dispersion DLF), a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass of a silane coupling agent KBM403) was added.
[0080]
A flame-retardant film was laminated on the glass fiber fabric that had been subjected to the bonding treatment. The lamination of the flame-retardant film was carried out as follows: to the above-described formulation of Example 3 (80 parts by mass of fluororesin 1, 20 parts by mass of fluororesin 2, and 0.6 parts by mass of titanium oxide A). A material (specific gravity of about 1.9) to which 0.5 part by mass of phosphate phosphate as a lubricant was added was melt-mixed with a test roll set at 170 ° C., and the test roll and rubber roll were subjected to a linear pressure of 20 kg / cm. While a molten film having a thickness of 0.12 mm was formed thereon, the film was bonded to a cloth.
[0081]
A coat layer mainly composed of a thermoplastic resin was laminated on the other surface of the glass fiber fabric, and dried at 180 ° C. for 1 minute. Lamination of the coating layer mainly composed of a thermoplastic resin was carried out as follows: 370 parts by mass (corresponding to 100 parts by mass of solid content) of olefin-based dispersion (Kemipearl S100 manufactured by Mitsui Chemicals, 27% solid content), magnesium hydroxide 100 parts of (Kisuma 5A manufactured by Kyowa Chemical Industry), 10 parts of water repellent A (fluorinated water repellent NGT671F manufactured by Nikka Kagaku), and 4 parts by mass of fungicide A (Rohm and Haas Durotex 7603) to a disper. The mixture was stirred at high speed, and then defoamed and applied. Application amount is 60 g / m ² Met.
[0082]
The following test was performed on the obtained laminate of Example 30.
1) The water repellency of the surface of the coat layer (the surface opposite to the glass fiber fabric) of the laminate of Example 30 was tested according to JIS L1096.
[0083]
2) A sample of 20 cm square was cut out from the laminate of Example 30, the diagonal corners of the sample were gripped, hand-rubbed 10 times each, and the presence or absence of peeling-off of the resin was examined.
3) A sample having a width of 3 cm and a length of 20 cm was cut out from the laminate of Example 30 in the warp direction and the weft direction, and the lower end was immersed in a commercially available red ink for fountain pens, and the rise of the ink due to the capillary phenomenon was visually confirmed. .
[0084]
4) A 20 cm square sample was cut from the laminate of Example 30, and the sample was heated with a gas torch (WELDING TORCH GB2001, Prince Company) from a distance of 10 cm for 30 seconds, and the presence or absence of inorganic residue on the surface and the exposed state of the fiber. Was visually determined. This was carried out as a substitute test for judging that "there is no crack or damage reaching the backside which is harmful to fire protection".
[0085]
5) At the time of heating by the gas torch in the above 4), the state of occurrence of flame from the laminate was observed. When a large flame was generated, it was evaluated as X, when a slight flame was generated, as △, and when almost no flame was recognized, as ○. This is "200 kw / m" in Article 2.9 of the Building Standards Act. ² The heat generation must not exceed 10 seconds. "
Table 4 shows the formulation and test results of this laminate.
[0086]
(Example 31)
Glass fiber fabric (GV818J manufactured by Kanebo Co., Ltd. Thread density 33 × 43 / inch Plain weave fabric weight 190 g / m ² Was subjected to an adhesive treatment in the same manner as in Example 30.
[0087]
The same molten film as in Example 30 was bonded to this bonded glass fiber fabric.
The other side of the glass fiber fabric was coated with the silicone resin composition and dried at 130 ° C. for 1 minute. The silicone resin composition was prepared as follows: 100 parts by mass of silicone resin (KM200T, manufactured by Toshiba GE Silicones), 20 parts by mass of talc, and 5 parts by mass of fungicide B (vinylize, manufactured by Rohm and Haas) were dispersed. , And defoamed. No water repellent was added because the silicone resin itself has water repellency. 80 g / m ² And
The same test as in Example 30 was performed on the obtained laminate.
Table 4 shows the formulation and test results of this laminate.
[0088]
(Example 32)
Glass fiber fabric (GV818J manufactured by Kanebo Co., Ltd. Thread density 33 × 43 / inch Plain weave fabric weight 190 g / m ² ) Was subjected to an adhesive treatment in the same manner as in Example 30.
[0089]
The same molten film (thickness: 0.11 mm) as in Example 30 was bonded to the glass fiber fabric that had been subjected to the bonding treatment.
The other side of the glass fiber fabric was coated with the thermoplastic resin composition and dried at 180 ° C. for 1 minute. The thermoplastic resin composition was prepared as follows: 333 parts by mass of an acrylic resin solution (solvent type acrylic resin, Chris Coat P1330 manufactured by Dainippon Ink and Chemicals, Inc., solid content 30%) (equivalent to 100 parts by mass of solid content); 50 parts by mass of catarpo (catarpo manufactured by Maruo Calschum Co., Ltd.), 20 parts of water repellent B (fluorinated water repellent Modiper F600 manufactured by NOF Corporation), fungicide C (Biocut-Z manufactured by Dainippon Ink and Chemicals, Inc.) 4 parts by mass and an appropriate amount of toluene for viscosity adjustment were stirred at high speed with a disper, and then defoamed. Coating amount is 40 g / m ² And
[0090]
The same test as in Example 30 was performed on this laminate.
The calorific value was measured with a corn calorimeter, and an actual measured value of 3.1 MJ was obtained.
The theoretical calorific value was calculated as follows and compared with the actually measured value.
[0091]
Condition 1: The amount of carbon contained in the fluororesin 1 and the fluororesin 2 is assumed to be about 30% from the molecular structure of the fluororesin layer, and the oxygen consumption is determined assuming that all of the carbon is converted to carbon dioxide by combustion.
[0092]
Condition 2: Regarding the urethane resin solution and the back coat layer used for the bonding treatment, it is assumed that the compositions of the organic components are all carbon and hydrogen. ₂ Assuming a saturated hydrocarbon structure of n, oxygen consumption is determined assuming that all of its carbon and hydrogen are converted to carbon dioxide and water by combustion.
[0093]
Calculation:
Since the fluororesin layer has a thickness of 0.11 mm and a specific gravity of 1.9, the laminate 1 m ² Of fluorine resin is 209 g / m ² And assuming a carbon content of about 30%, the carbon content is 62.7 g / m ² It becomes. The amount of oxygen required to convert this carbon to carbon dioxide is 2.67 times that (atomic weight C = 12 O ₂ = 16 × 2, 32/12 = 2.67) of 167 g / m ² It is. Since the calorific value per kg of oxygen consumption is 13.1 MJ based on the theory of Huggett (USA) and Paker (USA), the theoretical calorific value can be roughly estimated to be 2.19 MJ from the formula of 13.1 MJ × 0.167 kg / kg.
[0094]
Almost all urethane resin solutions consist of organic components, and the amount of adhesion is 30 g / m ² Therefore, the oxygen consumption is 103 g, 3.43 times that of the above, and the calorific value is 1.35 MJ = 13.1 MJ × 0.103 kg.
[0095]
The back coat layer has an adhesion amount of 40 g / m. ² However, the organic component is substantially 28.5 g / m2 because it contains 29% of catalpo which is an inorganic component. ² The oxygen consumption is 3.43 times that of 98 g, and the calorific value is 1.28 MJ = 13.1 MJ × 0.098 kg.
[0096]
Therefore, the theoretical calorific value of the entire laminate is calculated as 4.82 MJ = 2.19 MJ + 1.35 MJ + 1.28 MJ.
Table 4 shows the formulation, test results and calculation results of the laminate.
[0097]
[Table 4]

[0098]
As described above, in the laminate of Example 32, a theoretical calorific value of 4.82 MJ and a measured calorific value of 3.10 MJ were obtained, and both values show the nonflammability performance specified in Article 2-9 of the Building Standards Act. Is a value that satisfies the condition of 8 MJ or less for satisfying the condition. Similarly, a theoretical calorific value of 1.38 and a theoretical calorific value of 5.12 are calculated for the laminate of Example 30.
[0099]
The measured values were lower than the theoretical values. 1) Some soot was observed in the sample after burning (mostly a glass fiber fabric), and the sample was not completely burned. 2) The adhesive layer This is considered to be an error based on the fact that the organic component of the back coat layer did not have a saturated hydrocarbon structure.
[0100]
In this way, without performing an actual measurement test using a cone calorimeter, and irrespective of the type of thermoplastic material used, it is possible to know an outline of the total calorific value by theoretical calculation and to help control the amount of lamination. .
[0101]
(Example 33)
FIG. 1 is a cross-sectional view of a laminated structure according to an embodiment of the present invention, and FIG. 2 is a partially enlarged cross-sectional view of the laminated structure.
As shown in FIGS. 1 and 2, the laminated body structure 1 is configured as an internally illuminated signboard, and has a lighting fixture 2 disposed inside and a signboard frame 4 attached to an outer wall 3 of a building. The laminate 5 as a film material is stretched via a fixture 6. The laminate 5 is as described above, 5a is a non-combustible film, 5b is a glass fiber fabric, and 5c is a coat layer.
[0102]
As shown in FIG. 3, the fixing device 6 has a gutter-shaped fixing device main body 7 having a U-shaped groove 7 a and a peripheral portion of the laminated body 5 arranged in the groove 7 a with respect to the inner surface of the groove 7 a. The holding member 8 is composed of a holding member 8 for pressing and holding, and an elastic body 9 as a cushioning material disposed between the holding member 8 and the laminated body 5. 7 are fixed to the signboard frame 4 by holding screws 10 and fixing screws 11 penetrating therethrough. The fixture 6 is covered by a cover 12. The fixing body 7 and the holding member 8 are made of a metal such as aluminum, iron, stainless steel, duralumin or titanium, and the elastic body 9 is made of synthetic rubber, thermoplastic elastomer, or the like.
[0103]
In the fixture body 7, the wall 7b extending from one side sandwiching the groove 7a to the bottom of the groove is formed thick, and the expanded laminate 5 is supported by the wall 7b on one side from the coat layer 5c side. You. The wall 7b is formed in a hollow shape, and is provided with a reinforcing rib 7c, so that the strength of the fixture main body 7 is ensured and the weight is reduced. The wall 7d on the other side sandwiching the groove 7a is bent in an L shape outward from a position corresponding to the opening end of the groove 7a and then downward so as to be flush with the outer surface of the sign frame 10. Is formed.
[0104]
The wall 7b on one side of the fixture body 7 has a curved surface having an upper edge facing the groove 7a and an edge facing the fixture body 7 arranged opposite to the groove bottom having the same radius of curvature R = 5 mm as the groove bottom. It is formed in a shape. The wall 7d on the other side sandwiching the groove 7a is also formed in a curved shape having an upper edge facing the groove 7a with a radius of curvature R = 3 mm.
[0105]
The presser fitting 8 has an outer shape substantially along the inner surface of the groove 7a, and a portion corresponding to the groove bottom having a radius of curvature R = 5 mm is formed into a curved surface having a radius of curvature R = 4 mm, which is slightly smaller than the groove bottom. Have been. The holding member 8 is also formed in a hollow shape. The elastic body 9 is formed as a sheet having a curved shape along the bottom of the groove.
[0106]
Here, the laminated body 5 spread on the fixture 6 is easily deteriorated depending on the roundness R of the fixture 6, and there is a concern that the laminate 5 may be broken or cut. For this reason, the roundness R of the fixture 6 and the deterioration of the laminate 5 were examined in advance.
[0107]
As a test method for this kind of deterioration, there is JIS P 8115 (a method for testing the bending strength of paper and paperboard using an MIT type tester). The outline will be described with reference to FIG. A sample 14 is sandwiched between a pair of fixtures 13 having a sector shape provided in the MIT tester, and a tension T of 1 kgf (about 9.8 N) in a vertical direction (a direction orthogonal to the thickness direction of the sample 14) is applied to the sample 14. . Then, in this state, the fixture 13 is rotated 90 degrees to the left and right around the fan-shaped central portion, and 180 degrees for convenience, and the operation of bending the sample 14 right and left around the fan-shaped central portion as a folding line is performed at a speed of 175 times / minute. repeat. If the material has low bending strength, it is cracked or cut in the meantime.
[0108]
Using this test method and the like, the effect of the roundness R of the fixture 13 on the film material was tested.
Testing equipment: TMIT type folding tester (Kamishima Seisakusho)
Sample: laminated body prepared in Example 32
Fixture: Standard R = 0.1-0.2 mm conventionally used, and R = 2 mm, R = 3 mm, R = 5 mm, R = 10 mm specially prepared for comparison. . R means the radius of curvature of the central portion of the sector shown in FIG.
[0109]
Test method 1: According to JIS P 8115. As test conditions, a sample size of 15 mm × 150 mm, a tension of 1.0 kg × 15 mm, a number of bending times of 100 times, 1000 times, 100,000 times, and a bending cycle of 175 times / minute are used. The evaluation is performed by visually confirming a change in the surface state of the sample.
[0110]
Test method 2: In order to confirm the change in strength, a constant-speed elongation test was performed in accordance with the heavyweight fabrics of the strip method specified in JIS L1096 (General woven fabric test method) 6.12.1 (1). Measure the tensile strength and calculate the strength retention. The sample width is 15 mm.
Table 5 shows the results.
[0111]
[Table 5]

[0112]
As can be seen from Table 5, good results were obtained with R = 3 mm to 10 mm. In the case of R = 3 mm or less, the deterioration of the cloth is remarkably advanced as compared with the case of R = 3 mm, 5 mm, and 10 mm. In the case of the standard fixture with R = 0.1 to 0.2 mm, remarkable strength deterioration occurs after bending about 100 times. Although a good result similar to that of R = 10 can be obtained with a material exceeding R = 10, if R is increased, the thickness of the fixture 13 must be increased accordingly. However, such disadvantages as undesirable are also caused. R is preferably in the range of 3 mm to 5 mm.
[0113]
Therefore, when the film material is spread, by using an appropriately rounded fixing tool of R = 3 mm to 5 mm, the film material is deteriorated during repeated flapping by wind, or the back surface is rubbed by friction during mounting. Can be avoided, and the original strength of the film material can be exhibited. If the fixing tool has an R of 3 mm to 5 mm, the film can be spread with low friction even when the film material is mounted, and the mounting work becomes easy. When a standard fixture with R = 0.1 to 0.2 mm is used, the original strength of the film material cannot be exhibited.
[0114]
In the fixture 6 described above with reference to FIGS. 1 to 3, all the portions where the laminate 5 is bent and pressed are R5, so that the laminate 5 is hardly deteriorated and the original strength can be exhibited. I can say. Furthermore, since the fixture 6 is rounded as a whole, the load is dispersed over the entire surface without being concentrated at one point, and the holding force as a whole is also improved.
[0115]
However, it is not always necessary to round the entire fixture 6, but it is sufficient to at least round the portion where the laminate 5 is bent and pressed.
In addition, the shape and material of the above-mentioned laminated body structure 1 are merely examples, and are not limited thereto.
[0116]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a flame-retardant film having a significantly improved limiting oxygen index by blending titanium oxide with a soft fluororesin which originally has a high limiting oxygen index and has excellent weather resistance. Can be.
[0117]
By laminating the above-described flame-retardant film on one surface of a glass fiber fabric and laminating a coat layer mainly composed of a thermoplastic resin or a silicone resin on the other surface to form a laminate, high weather resistance and light resistance are obtained. Properties and excellent flame retardancy, and avoids spots and molds caused by rainwater infiltration.
[0118]
The above-described non-combustible laminate is stretched by a fixture having a predetermined roundness to form a laminate structure, which can be hardly deteriorated, and is used as a sleeve signboard, an internally illuminated signboard, or the like. In this case, high quality can be maintained for a long time. It is safe without the risk of accidents such as cracks and scattering of fragments, which have been concerned with film materials such as acrylic and polycarbonate conventionally used for this type of application.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a laminate structure according to an embodiment of the present invention.
FIG. 2 is a partially enlarged cross-sectional view of the laminate structure of FIG. 1;
FIG. 3 is a cross-sectional view showing each member of a fixture used in the laminate structure of FIG. 1;
FIG. 4 is a schematic view for explaining a test method for examining the effect of the R of the fixture on the deterioration of the laminate.
[Explanation of symbols]
1 laminate structure
2 Lighting equipment
3 outer wall
4 Signboard frame
5 laminate
6 Fixture
7 Fixture body
7a Groove
8 Holding bracket
9 Elastic body

Claims (9)

Flame-retardant film made by blending titanium oxide with soft fluororesin. 2. A film having a thickness of 0.05 mm to 0.3 mm by adding 0.2 to 4 parts by mass of titanium oxide to 100 parts by mass of a soft fluororesin, and having a limiting oxygen index of 50 or more. The flame-retardant film according to the above. Melting point 85 ° C. to 160 ° C. and 100 parts by mass of a soft fluororesin having a flexural modulus of 700 MPa or less measured by ISO 178, 4 parts by mass of titanium oxide 0.2 to 4 parts by mass are added, and the thickness is 0.05 mm. The flame-retardant film according to claim 2, which is formed to a thickness of 0.3 mm and has a limiting oxygen index of 50 or more. The flame-retardant film according to any one of claims 1 to 3, wherein the soft fluororesin is one or a mixture of polyvinylidene fluoride-hexafluoropropylene copolymer and polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer. . Melting point 85 ° C. to 160 ° C. and 100 parts by mass of a soft fluororesin having a flexural modulus of 700 MPa or less measured by ISO 178, 4 parts by mass of titanium oxide 0.2 to 4 parts by mass are added, and the thickness is 0.05 mm. A non-flammable film formed by laminating a flame-retardant film having a critical oxygen index of 50 or more on one surface of a glass fiber cloth and a coat layer made of a thermoplastic resin or a silicone resin on the other surface. Laminate. A flame-retardant film is formed by adding 0.2 to 4 parts by mass of titanium oxide to one or a mixture of polyvinylidene fluoride-hexafluoropropylene copolymer and polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer. The coating layer is made of an acrylic resin, a polyurethane resin, an olefin resin, a polyester resin, a styrene elastomer, a thermoplastic resin or a silicone resin, or an inorganic filler and a metal hydrate. And at least one of the metal oxides is added in a total amount of 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the solid content of the thermoplastic resin or 100 parts by mass of the silicone resin, and the thermoplastic resin is used. 6. The non-combustible material according to claim 5, which is sometimes formed by further adding a water repellent. Sotai. The non-combustible laminate according to claim 6, wherein the coat layer contains a fungicide. Stacking amount of the flame-retardant film is ^{100g / m 2 ~550g / m 2} , the amount of lamination of the coating layer according to any one of claims 7 to claim 5 which is a ^20g / ^{m 2 ~200g} / m 2 Non-combustible laminate. A non-combustible laminate structure obtained by extending the non-combustible laminate according to any one of claims 5 to 8 with a fixture, wherein a peripheral edge of the non-combustible laminate is provided in a groove formed in a fixture body. A portion is arranged, and the non-combustible laminate is supported by a support portion formed in a curved shape with a radius of curvature R3 mm to 10 mm on a wall portion of the fixture main body along the groove portion. A non-combustible laminate structure in which a peripheral portion is pressed against an inner surface of a groove by a pressing tool via an elastic body.

Images