JP4082453B2 - Architectural curing mesh sheet and manufacturing method thereof - Google Patents

Description

【００３５】
ｖ）．ポリリン酸アンモニウムとしては、（ＮＨ₄ ＰＯ₃ ）_n で示される、重合度ｎが３０〜１２００のものが好ましい。また、ポリリン酸アンモニウムは、メラミン樹脂、尿素樹脂、トリアジン樹脂などの窒素含有樹脂から選ばれた１種以上により表面被覆耐水化されたものを使用することが好ましい。vi）．ポリリン酸アンモニウム誘導体化合物としては、リン酸アンモニウムと、メラミン、尿素、トリアジンなどの含窒素化合物との縮合物である縮合系リン酸塩化合物で、これらは例えば、メラミン変性ポリリン酸アンモニウム、ポリリン酸メラミン、リン酸メラミンなどが好ましく使用できる。上記リン原子含有化合物のなかでも、特にリン酸エステル類、芳香族縮合リン酸エステル類、及びポリリン酸アンモニウム、ポリリン酸アンモニウム誘導体などが好ましく、さらに、これらのリン原子含有化合物は窒素原子含有化合物と併用して用いることが防炎効果と耐久性との観点において好ましい。
【００３６】
また、本発明に使用する難燃化樹脂層には必要に応じて、粒径０．１〜２０μｍ、特に０．５〜１０μｍの、ｉ）．シリカ、合成非晶質シリカ（二酸化ケイ素）、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸カルシウム、ケイ藻土などのケイ素化合物、ii）．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、水酸化バリウム、水酸化ジルコニウム、塩基性炭酸マグネシウム、ドロマイト、ヒドロキシスズ酸亜鉛、酸化スズ水和物、ホウ砂などの金属水酸化物、iii)．酸化アルミニウム、酸化マグネシウム、酸化バリウム、酸化チタン、酸化亜鉛、酸化スズ、酸化ジルコニウム、酸化モリブデン、酸化アンチモン、ジルコニウム−アンチモン複合酸化物などの金属酸化物、iv）．炭酸亜鉛、炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、炭酸マグネシウム−カルシウムなどの金属炭酸塩化合物、ｖ）．硫酸アルミニウム、硫酸バリウムなどの金属硫酸塩化合物、vi）．ホウ酸亜鉛、メタホウ酸亜鉛、メタホウ酸バリウム、ホウ酸アルミニウムなどのホウ酸化合物、vii)．アルミナ水和物、ゼオライト、セピオライト、ハイドロタルサイト、ヒドロキシアパタイト、ケイ藻土などの無機系化合物複合体などの無機系化合物の適量を併用することもできる。
【００３７】
本発明のメッシュシートの難燃化樹脂層には無機系顔料、及び有機系顔料を用いて任意に着色することができる。例えば無機系顔料としては、酸化亜鉛（亜鉛華）、酸化チタン（ルチル型、アナターゼ型）、三酸化アンチモン、酸化鉄（鉄黒、べんがら）、黄色酸化鉄、フエロシアン化鉄（紺青）、スピネル構造酸化物、またアルミニウム粉、ブロンズ粉、ニッケル粉、ステンレス粉などの金属顔料やパール顔料など、有機系顔料としては、不溶性モノアゾ顔料、不溶性ジスアゾ顔料、アゾレーキ顔料、縮合アゾ顔料、金属錯塩アゾ顔料、フタロシアニン顔料、酸性染料レーキ顔料、塩基性染料レーキ顔料、アントラキノン系顔料、チオインジゴ系顔料、ペリノン系顔料、ペリレン系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリノン系顔料、キノフタロン系顔料、イソインドリン系顔料、アリザリンレーキ顔料、金属錯塩アゾメチン顔料、アニリン系顔料など公知の顔料が挙げられる。また、本発明の難燃化樹脂層には、屋外耐久性を向上させる目的で、紫外線吸収剤、酸化防止剤、光安定剤などを適量添加することが好ましい。紫外線吸収剤としてはベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸系化合物及び、アニリド系化合物の紫外線吸収剤が使用でき、酸化防止剤としてはヒンダードフェノール系化合物、アミン系化合物、及びフォスファイト系化合物の酸化防止剤が使用できる。また光安定剤としてはヒンダードアミン系化合物の光安定剤が使用できる。
【００３８】
本発明のメッシュシートに使用する粗目織編物は、繊維糸条の交錯によって形成された糸条間空隙（粗目織編物の面積に対し５〜６５％の空隙面積）を有する織布または編布から選ばれる。織布の織組織に限定はないが特に平織織物、模紗織物、綾織物、朱子織物などであると得られるメッシュシートの縦緯物性バランスに優れ好ましい。編布としてはラッセル編の緯糸挿入トリコットが好ましい。また粗目織編物を形成する糸条には合成繊維、天然繊維、半合成繊維、無機繊維、またはこれらの２種以上から成る混用繊維のいずれでもよいが、加工性、汎用性を考慮するとポリプロピレン繊維、ポリエチレン繊維、ポリビニルアルコール繊維、ポリエステル繊維、ポリアミド（ナイロン）繊維などの合成繊維を用いることが好ましい。また、糸条の形態としてはマルチフィラメント糸条、モノフィラメント糸条、短繊維紡績（スパン）糸条、スプリットヤーン糸条、テープヤーン糸条など、何れの糸条を用いてもよいが、なかでも引張強力と引裂強力とに優れているポリエステル繊維、ポリアミド繊維、及びこれらの混合混用繊維などから形成されたマルチフィラメント糸条による粗目織編物、モノフィラメント糸条による粗目織編物、または短繊維紡績（スパン）糸条による粗目織編物が好ましい。
【００３９】
本発明に使用する粗目織編物の糸条原料には、特にテレフタル酸とエチレングリコールとの重縮合によって得られるポリエチレンテレフタレート（ＰＥＴ）、テレフタル酸とブチレングリコールとの重縮合によって得られるポリブチレンテレフタレート（ＰＢＴ）などのポリエステル繊維が好ましく、中でもＰＥＴ樹脂から紡糸されるポリエステル繊維（マルチフィラメント糸条）が紡糸性と機械的強度に優れ好ましい。また、このＰＥＴ樹脂紡糸原料には上記モノマー以外にイソフタル酸、ナフタレンジカルボン酸、アジピン酸、ジエチレングリコールなどの共重合モノマーを５重量％程度含んだものも使用できる。特に必要に応じて、例えば、ポリ−ｐ−フェニレンテレフタルアミド（ＰＰＴＡ）繊維糸条をＰＥＴ繊維糸条の間に等間隔で配置して織組織が｛ＰＰＴＡ−ＰＥＴ−ＰＥＴ−ＰＥＴ｝を繰り返し単位とする織組織とした引張強度と引裂強度を重視した特別な織物を使用することもできる。これらの粗目織編物の製織は、シャットル織機、シャットルレス織機（レピア方式、グリッパ方式、ウオータージェット方式、エアジェット方式）などの従来公知の織機を用いて製織することができる。また、製織に用いる繊維糸条は、紡糸工程時に有機系顔料、無機系顔料、染料などの着色剤を添加して得られた原着繊維であることができ、特にモノフィラメント糸条に適している。また、あるいは繊維糸条、または粗目織編物を後工程で有機系顔料、無機系顔料、染料などによる着色処理、及びこれらを含む樹脂バインダーで処理して着色されていてもよい。さらにこれらの粗目織編物には例えば、精練処理、漂白処理、柔軟化処理、糊剤処理、撥水処理、防水処理、防カビ処理、防炎処理、カレンダー処理、バインダー樹脂処理など、公知の繊維処理加工を併用することができる。
【００４０】
本発明に使用する粗目織編物を構成するマルチフィラメント糸条、又はモノフィラメント糸条には２７７〜３３３３dtexの繊度の糸条が使用できる。これらの糸条は１本で用いられることもあれば、２〜５本好ましくは２〜３本を合撚して１本の糸条を構成したもの、あるいは２〜５本好ましくは２〜３本を並列して見掛け１本の糸条を構成したものなどで用いることができる。２類クラスの建築養生メッシュシートの場合、例えば、２７７dtexのマルチフィラメント糸条を１インチ当たり経糸２４〜２６本、緯糸２５〜２８本打ち込んだ平織織布、５５６dtexのマルチフィラメント糸条を１インチ当たり経糸１８〜２０本、緯糸１８〜２０本打ち込んだ平織織布であり、１類クラスの建築養生メッシュシートの場合、例えば、８３３dtexのマルチフィラメント糸条３本を合撚した糸条を１インチ当たり経糸１０〜１２本、緯糸１０〜１２本打ち込んだ平織織布、１１１１dtexのマルチフィラメント糸条３本を合撚した糸条を１インチ当たり経糸６〜８本、緯糸６〜８本打ち込んだ平織織布、２２２２dtexのマルチフィラメント糸条を１インチ当たり経糸１２〜１４本、緯糸１２〜１４本打ち込んだ平織織布、１６６６dtexのマルチフィラメント糸条を１インチ当たり経糸１５〜１７本、緯糸１５〜１７本打ち込んだ平織織布、３３３３dtexのマルチフィラメント糸条２本を合撚した糸条を１インチ当たり経糸４〜５本、緯糸４〜５本打ち込んだ平織織布などが特に好ましく使用できる。特にＪＩＳ Ａ８９５２に規定される鋼管落下による耐貫通試験を必要とする１類クラスのメッシュシートでは、経緯構成糸条の繊度が１１１１dtex未満では不適合となることがある。また粗目織編物（２軸織物）の経糸及び緯糸の打込み本数は、２類クラスのメッシュシートで例えば、２７７〜５５６dtexのマルチフィラメント糸条、またはモノフィラメント糸条を１インチ当たり１６〜３０本、好ましくは１８〜２６本、１類クラスのメッシュシートで例えば、１６６６〜３３３３dtexのマルチフィラメント糸条、またはモノフィラメント糸条を１インチ当たり６〜２０本、好ましくは７〜１６本である。本発明のメッシュシートに用いる粗目織編物は経糸・緯糸構成からなる粗目２軸織物が好ましい。また、本発明に使用する粗目織編物には１９７dtex（３０番手）〜５９１dtex（１０番手）の短繊維紡績糸条を組み合わせて使用できる。
【００４１】
また本発明のメッシュシートに用いる粗目織編物は、３軸織物及び、４軸織物を使用することもできる。３軸織物としては上記マルチフィラメント糸条、又はモノフィラメント糸条による３方向の糸条から構成され、互いの糸条の交差角が６０°となるように製織された織布である。３軸織物としては経糸を含み、これに２方向のバイアス（斜）糸を絡めて構成される織布が加工方向の織組織の安定性に優れ好ましい。この３軸織物の組織は２本綾織の応用によるバスケット織であることもできる。一方、４軸織物としては上記マルチフィラメント糸条、又はモノフィラメント糸条による４方向の糸条から構成され、互いに直交する経糸と緯糸とを含み、さらに経糸と緯糸とに４５°の角度で交差する２方向のバイアス糸とを含み、必要に応じて５５〜１６６dtex程度のモノフィラメントからなる絡糸を用いて製織された織布（編物）である。特に本発明に３軸織物、または４軸織物を用いることによって、メッシュシートには多方向からの外力に対する安定した抵抗力を備えることを可能とし、建築現場の張囲いシートとして、より安全性の高いメッシュシートを得ることができる。これら３軸織物及び、４軸織物による粗目織編物の経糸、緯糸、バイアス糸の打込み本数に特に限定はないが、２７７〜３３３３dtexのマルチフィラメント糸条、又はモノフィラメント糸条を各方向、１インチ当たり４〜３０本、好ましくは７〜２４本打込んで得られる織布、が使用できる。
【００４２】
これらの本発明に用いる粗目織編物の合計空隙面積率は、５〜６５％であることが好ましく、特に１０〜４０％のものが好ましく適している。空隙面積は繊維糸条の交錯によって形成される空隙（粗目）であり、空隙面積率は織編物の面積に対する値である。空隙面積率が５％未満であると得られるメッシュシートの透視性と通気性とが不十分になり、また、空隙面積率が６５％を越えると、繊維糸条の含有密度が小さくなり、得られるメッシュシートの引裂強度が不十分になりそれと同時に、ＪＩＳ Ａ８９５２に規定される鋼管落下による耐貫通試験に不適合となることがある。空隙面積率は粗目織編物の単位面積に対し、繊維糸条の占める面積を百分率として求め、１００から差し引いた値として求めることができる。空隙面積率は経方向１０cm×緯方向１０cmを単位面積として求めることができ、必要に応じて市販の複写機を用いて拡大印刷した画像から面積を算出したり、あるいは複写画像の切り抜きを糸条部と空隙部とに種別し、これらの質量比率を根拠に、これを空隙面積率と同各に見なし充当したものであってもよい。
【００４３】
また、本発明のメッシュシートにおいては、特に粗目織編物には、１）．ホスホン酸系化合物によって下処理が施されていることが防炎性の観点において好ましく、これによってメッシュシートの難燃化樹脂層に配合する難燃性付与剤の総和量を削減させることができる。ホスホン酸系化合物としては、例えば、ビニルホスホン酸ジメチルエステル、ビニルホスホン酸ジフェニルエステル、メチルホスホン酸モノビニルエステル、フェニルホスホン酸モノビニルエステルなどのホスホン酸エステル、及び環式ホスホン酸エステル類、また例えば、ビニルホスホン酸、アリルホスホン酸、ブテニルホスホン酸、ビニルフェニルホスホン酸、２−アクリロイロキシエチルホスホン酸、２−メタアクリロイロキシエチルホスホン酸、ビス（２−メタクロイロキシエチル）ホスホン酸などのホスホン酸誘導体が挙げられるが、特に環式ホスホン酸エステル類が好ましい。特に好ましい環式ホスホン酸エステルとしては、前記化学式（１）及び（２）の化合物の少なくとも１種が用いられる。
【００４４】
ホスホン酸系化合物による粗目織編物の下処理は、ホスホン酸系化合物を０．５〜１０質量％濃度、好ましくは１．０〜５質量％濃度で含む溶液からなる下処理剤浴中に上記粗目織編物を浸漬し、粗目織編物を構成する繊維糸条の繊維間にホスホン酸系化合物を侵入させ、これを引き上げると同時にゴム製マングルロールで粗目織編物を圧搾し、余分な処理剤を除去した後、熱風炉内で乾燥させ、さらに１３０〜２１０℃の熱処理を施して、繊維のミクロ構造内にホスホン酸系化合物を吸着させて定着させる公知の方法が挙げられる。本発明において粗目織編物は、ホスホン酸系化合物による下処理を１９０〜２００℃の熱条件で施し、繊維に定着させたポリエステルフィラメント織物、及びポリエステル短繊維紡績織物であることが好ましい。
【００４５】
２）．また前記１）に記載の下処理剤にはバインダー樹脂を混用することもでき、例えば、酢酸ビニル成分、（メタ）アクリル酸（エステル）成分、（無水）マレイン酸、（無水）フマル酸、（無水）イタコン酸などの極性成分を含有するエチレン系共重合体樹脂、及びアクリル系共重合体樹脂、アイオノマー樹脂、スチレン系共重合体樹脂、ポリウレタン系樹脂などの熱可塑性樹脂溶液中にホスホン酸系化合物を含有させたものを用いることによって、繊維表面にホスホン酸系化合物を定着することもできる。このバインダーは有機系溶剤中に可溶化、または分散されたもの、もしくは水中に乳化分散されたバインダー樹脂含有液体の何れであってもよく、バインダー樹脂の固形分濃度は１〜３０質量％、特に３〜１５質量％であることが下処理作業の観点において好ましい。この時併用するホスホン酸系化合物はバインダー樹脂含有液体に対して１〜１０質量％濃度で使用することができる。このバインダーを伴う下処理（塗工、含浸、被覆）には公知の加工方法、例えば、ディッピング法、ディップコート法、ドクターナイフコート法、グラビアコート法、ロータリースクリーンコート法、スプレーコート法などにて処理剤を１回以上、含浸及び／又は塗布することによって実施することができ、乾燥は自然乾燥、もしくは３０〜１２０℃、特に６０〜１００℃の熱風乾燥によって行うことが好ましい。ホスホン酸系化合物を含むバインダーの付着量は粗目織編物の質量に対し１〜３０質量％、特に２〜１５質量％であることが好ましい。付着量が１％未満だと、得られるメッシュシートの防炎性が不十分となることがあり、また付着量が３０％を越えると防炎性を返って悪くすることがある。また上記２）の下処理液には難燃化樹脂層に用いる難燃性付与剤と同一のものをさらに適量含んでいても良く、これらはａ）．赤リン、金属リン酸塩、金属有機リン酸塩、リン酸誘導体、ポリリン酸アンモニウム、及びポリリン酸アンモニウム誘導体化合物などのリン原子含有化合物、ｂ）．（イソ）シアヌレート系化合物、（イソ）シアヌル酸系化合物、グアニジン系化合物、尿素系化合物、及び、これらの誘導体化合物などの窒素原子含有化合物、ｃ）．ケイ素化合物、金属水酸化物、金属酸化物、金属炭酸塩化合物、金属硫酸塩化合物、ホウ酸化合物、及び無機系化合物複合体などの無機系化合物から選ばれた１種以上である。
【００４６】
本発明のメッシュシートの製造は、１）．粗目織編物、またはホスホン酸系化合物によって下処理が施された粗目織編物を、液粘度が、０．１〜１０Pa・ｓ（１０〜５０℃／０．５〜３時間）、０．５〜１０Pa・ｓ（２０℃／０．５時間）であり、特に好ましくは０．５〜５Pa・ｓ（２０〜５０℃／０．５〜３時間）、１〜５Pa・ｓ（２０℃／０．５時間）の、難燃性付与剤含有ポリウレタン前駆体組成物液バス中に浸漬（ディッピング）し、粗目織編物を構成する繊維糸条の少なくとも露出外周全域にポリウレタン前駆体組成物を付着させ、これを引き上げると同時にゴム製マングルロールで粗目織編物を圧搾し、ポリウレタン前駆体組成物を繊維糸条に含浸させた後、１００℃以上で５〜３０分、好ましくは１５０〜２３０℃で１〜１０分間熱風炉内で熱処理を施して、ブロックイソシアネート化合物のブロック化剤を解離させて再生するイソシアネート基と、活性水素基との硬化反応によって前記ポリウレタン前駆体組成物を難燃化ポリウレタン系樹脂（前記難燃樹脂被覆層に対して、前記難燃性付与剤を１０〜５０質量％含有する）に転化し、これを難燃樹脂被覆層とする製造方法によって得ることができる。
【００４７】
２）．また本発明のメッシュシートの製造は、粗目織編物、またはホスホン酸系化合物によって下処理が施された粗目織編物の表裏面に、液粘度が０．１〜１０Pa・ｓ（１０〜５０℃／０．５〜３時間）、０．５〜１０Pa・ｓ（２０℃／０．５時間）、特に好ましくは０．５〜５Pa・ｓ（１０〜５０℃／０．５〜３時間）、１〜５Pa・ｓ（２０℃／０．５時間）の、難燃性付与剤含有ポリウレタン前駆体組成物液組成物を、ナイフコート、グラビア転写コート、ロータリースクリーンコート、クリアランスコート、スプレーコートなどの塗工方法によって表裏面に塗布し、粗目織編物を構成する繊維糸条の少なくとも露出外周面全域にポリウレタン前駆体組成物を含浸付着させた後、１００℃以上で５〜３０分、好ましくは１５０〜２３０℃で１〜１０分間熱風炉内で熱処理を施して、ブロックイソシアネート化合物のブロック化剤を解離させて再生するイソシアネート基と、活性水素基との硬化反応によって前記ポリウレタン前駆体組成物を難燃化ポリウレタン系樹脂（前記難燃樹脂被覆層に対して、前記難燃性付与剤を１０〜５０質量％含有する）に転化し、これを難燃樹脂被覆層とする製造方法によって得ることができる。
【００４８】
３）．本発明のメッシュシートの製造は、上記１）及び２）の製造方法において、必要に応じてポリウレタン前駆体組成物に、希釈溶剤、及び／又は可塑剤を粘度調整剤として含み、液粘度が０．１〜１０Pa・ｓ（１０〜５０℃／０．５〜３時間）、０．５〜１０Pa・ｓ（２０℃／０．５時間）、特に好ましくは０．５〜５Pa・ｓ（１０〜５０℃／０．５〜３時間）、１〜５pa・ｓ（２０℃／０．５時間）に調整された、難燃性付与剤含有ポリウレタン前駆体組成物液を用いて製造することもできる。
【００４９】
上記１〜３）に記載の製造方法において、難燃性付与剤含有ポリウレタン前駆体組成物液の液粘度の要件、０．１〜１０Pa・ｓ（１０〜５０℃／０．５〜３時間）、０．５〜１０Pa・ｓ（２０℃／０．５時間）とは、１０〜５０℃の温度範囲内で難燃性付与剤を含有するポリウレタン前駆体組成物液の液粘度が０．１〜１０Pa・ｓであり、この液粘度を０．５〜３時間維持可能なものを意味するものである。粘度の測定は塩ビペーストゾルの粘度測定に用いられるブルックフィールド型回転式粘度計（ＢＬ，ＢＭ，ＢＨ）を用いて行うことができる。特に難燃性付与剤を含有するポリウレタン前駆体組成物液の液粘度は、４号ローターを装着したＢＭ型粘度計を用いて、回転数１２rpm での６０秒後の数値（×５００cP）で決定すること、または６号ローターを装着したＢＨ型粘度計を用いて、回転数４rpm での６０秒後の数値（×２５００cP）で決定することができる。このときcPとPa・ｓとの関係は１Pa・ｓ＝１０００cPである。ポリウレタン前駆体組成物の液粘度が１０Pa・ｓ（１０〜５０℃／０．５〜３時間）、１０Pa・ｓ（２０℃／０．５時間）よりも大きいと、難燃性付与剤を含有するポリウレタン前駆体組成物の流動性が悪くなり、本発明のメッシュシートの製造が困難となることがある。また、ポリウレタン前駆体組成物の液粘度が０．１Pa・ｓ（１０〜５０℃／０．５〜３時間）よりも小さくなると難燃性付与剤を配合して含有するポリウレタン前駆体組成物の、粗目織編物に対する吸収にムラを生じて難燃性付与剤が分離することがあり、本発明のメッシュシートの製造が困難となる。５０℃の液粘度が必要な理由は、常温時に５Pa・ｓを越えるポリウレタン前駆体組成物が５０℃を上限とする加温によって低粘度化したり、または常温時に固体状態のポリウレタン前駆体組成物が液体化するなどして、本発明のメッシュシートの製造可能範囲に包含されるためである。またこの時、５０℃を上限とする加温によって一旦低粘度化したポリウレタン前駆体組成物が短時間で増粘したり、ゲル化を生じると本発明のメッシュシートの製造が不能となるため、ポリウレタン前駆体組成物の調整後０．５時間を起点として加工可能範囲のポットライフを３時間とした。また、ポリウレタン前駆体組成物の加温が５０℃を越えると、加工可能範囲の液粘度のポットライフが短くなり本発明のメッシュシートの製造に支障をもたらすことがある。
【００５０】
また本発明のメッシュシートの製造を通常実施する際に、使用するポリウレタン前駆体組成物の液粘度をより明確にするために、２０℃／０．５時間条件の粘度を併記した。また、ポリウレタン前駆体組成物の熱処理硬化条件、（１００℃以上で５〜３０分、好ましくは１５０〜２３０℃で１〜１０分間）は用いるポリウレタン前駆体組成物のブロック化剤解離温度と、製造に使用するディッピング機、コーティング機などの加工機に附帯する熱風炉の熱容量と炉長とによって任意設定可能な条件である。また、上記製造方法によって得られるメッシュシートの質量に占める難燃樹脂被覆層の割合は１０〜６０質量％、好ましくは２５〜５０質量％である。難燃樹脂被覆層の割合が１０質量％に満たないと、得られるメッシュシートの耐洗濯性と防炎性が不十分となる。また、空隙面積率５〜６５％を維持しながら難燃樹脂被覆層の割合が６０質量％を越えるメッシュシートの製造は困難となる。得られたメッシュシートは例えば１ピースが１．８ｍ幅×３．４ｍ長、１．８ｍ幅×３．６ｍ長、１．８ｍ幅×５．１ｍ長、１．８ｍ幅×５．４ｍ長、３．６ｍ幅×５．４ｍ長などの規格で縫製され、各々縁部がほつれ防止の折り返し縫製補強されたもので、必要に応じて縁部には接続用縫込みロープを有するもの、あるいは特にウレタン樹脂被覆シートなどのスリット支持体を折り返し部に挿入縫製し、この縁部全体に定間隔で設けられるハトメの固定強度を強化したものなどが使用できる。縁部の縫製は、ミシン縫製、または高周波ウエルダー縫製などによって実施することができる。
【００５１】
【実施例】
次ぎに実施例、及び比較例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの例の範囲に限定されるものではない。下記実施例、及び比較例において得られたメッシュシートの評価に適用した試験方法は以下の通りである。
（Ｉ）．粘度測定
４号ローターを装着したＢＭ型回転粘度計（（株）トキメック社製）を用いて、ポリウレタン前駆体組成物（液温度２０と５０℃でそれぞれ０．５時間後、及び３．０時間後）の粘度を、回転数１２rpm での６０秒後の数値（×５００cP）で決定した。（必要に応じて６号ローターを装着したＢＨ型回転粘度計（（株）トキメック社製）を用いて、回転数４rpm での６０秒後の数値（×２５００cP）で決定した。）このときcPとPa・ｓとの関係は１Pa・ｓ＝１０００cPである。
【００５２】
（II）．防炎性
ＪＩＳ Ｌ−１０９１により試験し、下記の判定基準により評価した。（質量４５０ｇ／ｍ² 以下はＡ−１法の区分３、質量４５０ｇ／ｍ² を越えるものはＡ−２法の区分３を適用した。）
○：炭化面積４０cm² 以下、残炎時間５秒以下、残じん時間２０秒以下、炭化距離２０cm以下である。
×：炭化面積、残炎時間、残じん時間、炭化距離の項目の１項目以上が規格数値を超えている。
【００５３】
(III)．耐貫通試験［（社）仮設工業会認定基準］
ＪＩＳ Ａ８９５２に規定される３０°傾斜試験枠に固定したメッシュシートの中央部を標的に、高さ３ｍから質量５kgの鋼管落体（ＪＩＳ Ａ８９５２規格適合品）を自由落下させて、メッシュシートの耐貫通性、及び破損（破断）状態を観察した。
○：鋼管落体の貫通なし。
△：鋼管落体の貫通はないが、メッシュシートの亀裂破損が大きい。
×：鋼管落体がメッシュシートを破り完全に貫通する。
（IV）．耐洗濯性
容量４５０Ｌの工業用回転式洗濯機を用い、未使用のメッシュシート縫製品（１．８ｍ幅×３．６ｍ長：長さ方向８ツ折り×幅方向４ツ折り）の耐洗濯性を評価した。洗濯は、弱アルカリ性の工業用洗剤（商標：ゲンブナイス：［成分］界面活性剤として直鎖アルキルベンゼンスルホン酸ナトリウム、工程化剤として硫酸塩、アルカリ剤として珪酸塩、及び炭酸塩、水転化剤としてアルミノ珪酸塩、及び蛍光増白剤：ゲンブ（株））５００ｇと、アルカリ剤としてメタ珪酸ナトリウム９水塩（三宝化学工業（株））１００ｇを４０℃の温水３００Ｌ中に溶解させたものを使用し、３０分間洗濯した直後の外観を観察した。
○：樹脂被覆層の脱落、膨潤などの外観異常なし。
△：樹脂被覆層の膨潤が認められる。
×：樹脂被覆層が膨潤し、部分的に脱落している。
【００５４】
（Ｖ）．洗濯後の防炎性
上記（IV）で試験したメッシュシートを工業用水で５分間濯ぎ洗いし、これを常温で２４時間乾燥させたものを試験体として、上記（II）と同一の防炎試験を行った。
（VI）．洗濯後の耐貫通試験
上記（IV）で試験したメッシュシートを工業用水で５分間濯ぎ洗いし、これを常温で２４時間乾燥させたものを試験体として、上記（III)耐貫通試験と同一の防炎試験を行った。
【００５５】
［実施例１]
ｉ）．ポリウレタン前駆体組成物（１）
ウレトジオン基含有ＨＭＤＩ（１，６−ヘキサメチレンジイソシアネート）誘導体と、活性水素基含有化合物として、数平均分子量５００、平均官能基数２．０のポリテトラメチレンエーテルポリオールとを、活性水素基／イソシアネート当量比１．３で含み、かつ、ポリウレタン前駆体中のウレトジオン基／活性水素基当量比が０．７２であるポリウレタン前駆体１００質量部に対して、ウレトジオン基開環触媒として１，５−ジアザビシクロ（４，３，０）ノネン−５（ＤＢＮ）０．５質量部と、酸化防止剤と耐候安定剤との複合添加剤として、商標：チヌビンＢ−７５（チバ・スパシャルティ・ケミカルズ（株））１．０質量部と、着色剤としてルチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部と、難燃性付与剤（窒素原子含有化合物（ｂ−１））としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））３０質量部、難燃性付与剤（リン原子含有化合物ｂ−２−１）として、ホスホン酸化合物（商標：Ｋ−１９Ａ、前記化学式（１）又は（２）のホスホン酸化合物の混合物：明成化成（株））１０質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン前駆体組成物（１）を得た。このポリウレタン前駆体組成物（１）の液粘度（ＢＭ型回転粘度計による計測値）は、３．６Pa・ｓ（２０℃／０．５時間）、３．９Pa・ｓ（２０℃／３．０時間）、１．２Pa・ｓ（５０℃／０．５時間）、１．８Pa・ｓ（５０℃／３．０時間）であった。
【００５６】
ii ）．メッシュシートの製造
次に、液温度５０℃のポリウレタン前駆体組成物（１）を充填した浴中に、下記下処理を施したポリエステル粗目模紗織物基布（１１１１dtex／３本のマルチフィラメント糸条：経糸打込み密度７本／２．５４cm×緯糸打込み密度７本／２．５４cm：質量１８５ｇ／ｍ² ：空隙率３４％）をディップ（浸漬）し、ポリウレタン前駆体組成物（１）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（１）を粗目模紗織物基布の全面に含浸付着させた後、２００℃の熱風乾燥炉で６分間熱処理し、厚さ０．７４mm、質量４１０ｇ／ｍ² のメッシュシートを得た。
（ポリエステル粗目模紗織物基布の下処理）
商標：Ｋ−１９Ａ、化学式（１）及び（２）のホスホン酸
化合物の混合物：明成化成（株） ５質量部
希釈剤：水 ９５重量部
上記下処理剤浴中にポリエステル粗目模紗織物基布をディップし、引上げると同時に高硬度ゴムのニップロールで余分な下処理剤を絞り落とし、１２０℃の熱風乾燥炉で１分間乾燥させた後、２００℃の熱風乾燥炉で１分間熱処理し、ホスホン酸化合物を繊維に定着させた。（基布に対するホスホン酸化合物の定着量は、２．５ｇ／ｍ² であった。）
【００５７】
［実施例２］
ｉ）．ポリウレタン前駆体組成物（２）
実施例１のポリウレタン前駆体の活性水素基含有化合物（ポリテトラメチレンエーテルポリオール）を、数平均分子量２０００、平均官能基数２．０のポリブチレンアジペートに変更し、活性水素基／イソシアネート当量比１．２で含み、かつ、ポリウレタン前駆体中のウレトジオン基／活性水素基当量比が０．５９であるポリウレタン前駆体１００質量部を得た。これ以外は実施例１と同一配合としてグレー色のポリウレタン前駆体組成物（２）を得た。このポリウレタン前駆体組成物（２）の液粘度（ＢＭ型回転粘度計による計測値）は、３．８Pa・ｓ（２０℃／０．５時間）、４．１Pa・ｓ（２０℃／３．０時間）、１．４Pa・ｓ（５０℃／０．５時間）、２．０Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度５０℃のポリウレタン前駆体組成物（２）を充填した浴中に、実施例１と同一のホスホン酸化合物下処理を施したポリエステル粗目３軸織物基布（１１１１dtex／２本のマルチフィラメント糸条：経糸打込み密度１３本／２．５４cm×バイアス糸打込み密度１３本／２．５４cm：質量２２５ｇ／ｍ² ＜ホスホン酸化合物の定着量２．５ｇ／ｍ² ＞：空隙率２２％）をディップ（浸漬）し、ポリウレタン前駆体組成物（２）を付着させた粗目３軸織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（２）を粗目３軸織物基布の全面に含浸付着させた後、２００℃の熱風乾燥炉で６分間熱処理し、厚さ０．７４mm、質量４２８ｇ／ｍ² のメッシュシートを得た。
【００５８】
［実施例３］
ｉ）．ポリウレタン前駆体組成物（３）
実施例１のポリウレタン前駆体の活性水素基含有化合物（ポリテトラメチレンエーテルポリオール）を、数平均分子量１０００、平均官能基数２．０のポリプロピレンエーテルポリオールに変更し、活性水素基／イソシアネート当量比１．４で含み、かつ、ポリウレタン前駆体中のウレトジオン基／活性水素基当量比が０．４９であるポリウレタン前駆体１００質量部を得た。これ以外は実施例１と同一配合としてグレー色のポリウレタン前駆体組成物（３）を得た。このポリウレタン前駆体組成物（３）の液粘度（ＢＭ型回転粘度計による計測値）は、３．５Pa・ｓ（２０℃／０．５時間）、３．８Pa・ｓ（２０℃／３．０時間）、１．５Pa・ｓ（５０℃／０．５時間）、２．１Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度５０℃のポリウレタン前駆体組成物（３）を充填した浴中に、実施例１と同一のホスホン酸化合物下処理を施したポリエステル粗目模紗織物基布（８３３dtex／３本のマルチフィラメント糸条：経糸打込み密度１１本／２．５４cm×バイアス糸打込み密度１１本／２．５４cm：質量２２５ｇ／ｍ² ＜ホスホン酸化合物の定着量２．５ｇ／ｍ² ＞：空隙率１４％）をディップ（浸漬）し、ポリウレタン前駆体組成物（３）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（３）を粗目模紗織物基布の全面に含浸付着させた後、２００℃の熱風乾燥炉で６分間熱処理し、厚さ０．７４mm、質量４３６ｇ／ｍ² のメッシュシートを得た。
【００５９】
［実施例４］
ｉ）．ポリウレタン前駆体組成物（４）
１，６−ヘキサメチレンジイソシアネート（ＨＭＤＩ）系イソシアヌレート変性ポリイソシアネート（商標：タケネートＤ−１７０Ｎ：イソシアネート基含有量２０．７質量％、固形分１００質量％：武田薬品工業（株））１００質量部にメチルエチルケトオキシム３５質量部を加えて得た固形分６０質量％のブロックイソシアネート化合物（１）（※遊離のメチルエチルケトオキシム当量比はブロックイソシアネート１当量あたり０．０３当量：キシレン溶媒）４４質量部と、活性水素基含有樹脂としてアクリルポリオール（商標：アクリデックＡ−８０１：水酸基価１００mgＫＯＨ／ｇ、固形分５０質量％：トルエン／酢酸ブチル溶媒：大日本インキ化学工業（株））１４８質量部とを配合してなる当量比０．１５のポリウレタン前駆体１９２質量部（固形分５２．２質量％）に対し、ブロック化剤解離触媒としてスズ系化合物（商標：フォーメートＫ：固形分１０質量％：武田薬品工業（株））５質量部、架橋剤としてカルボジイミド化合物（商標：カルボジライトＴ−０２、カルボジイミド当量２７７：日清紡（株））１質量部、酸化防止剤と耐候安定剤との複合添加剤として商標：チヌビンＢ−７５（チバ・スペシャルティ・ケミカルズ（株））を１．０質量部、着色剤としてルチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部、難燃性付与剤（窒素原子含有化合物）としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））２０質量部、難燃性付与剤として、リン原子含有化合物−１）：ホスホン酸化合物（商標：Ｋ−１９Ａ、化学式（１）又は（２）のホスホン酸化合物の混合物：明成化成（株））１０質量部、及びリン原子含有化合物−２：メラミン被覆ポリリン酸アンモニウム（重合度ｎ＝１０００）（商標：エクソリットＡＰ４６２：クラリアントジャパン（株））１０質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン前駆体組成物（４）を得た。このポリウレタン前駆体組成物（４）の液粘度（ＢＭ型回転粘度計による計測値）は、４．０Pa・ｓ（２０℃／０．５時間）、４．４Pa・ｓ（２０℃／３．０時間）、２．１Pa・ｓ（５０℃／０．５時間）、３．２Pa・ｓ（５０℃／３．０時間）であった。
【００６０】
ii ）．メッシュシートの製造
次に、液温度２０℃のポリウレタン前駆体組成物（４）を充填した浴中に、実施例１と同一の（ホスホン酸化合物下処理）ポリエステル粗目模紗織物基布をディップ（浸漬）し、ポリウレタン前駆体組成物（４）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（４）を粗目模紗織物基布の全面に含浸付着させ、１８０℃の熱風乾燥炉で３分間熱処理した後、このメッシュシートを再度ポリウレタン前駆体組成物（４）充填浴中にディップし、１回目のディップ−熱処理と同様の手順を経て、厚さ０．７４mm、質量４２２ｇ／ｍ² のメッシュシートを得た。
【００６１】
［実施例５］
ｉ）．ポリウレタン前駆体組成物（５）
実施例４のブロックイソシアネート化合物（１）４４質量部を、下記のブロックイソシアネート化合物（２）４４質量部に変更した。このブロックイソシアネート化合物（２）は、１，６−ヘキサメチレンジイソシアネート（ＨＭＤＩ）系ビウレット変性ポリイソシアネート（商標：タケネートＤ−１６５Ｎ９０ＰＸ：イソシアネート基含有量２１．０質量％、固形分９０質量％：武田薬品工業（株））１００質量部にメチルエチルケトオキシム３５質量部を加えて得た固形分６０質量％のキシレン溶液であった。（※遊離のメチルエチルケトオキシム当量比はブロックイソシアネート１当量あたり０．０３当量）これ以外は実施例４と同一として得られたグレー色のポリウレタン前駆体組成物（５）の液粘度（ＢＭ型回転粘度計による計測値）は、４．２Pa・ｓ（２０℃／０．５時間）、４．８Pa・ｓ（２０℃／３．０時間）、２．６Pa・ｓ（５０℃／０．５時間）、３．６Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度２０℃のポリウレタン前駆体組成物（５）を充填した浴中に、実施例２と同一の（ホスホン酸化合物下処理）ポリエステル粗目３軸織物基布をディップ（浸漬）し、ポリウレタン前駆体組成物（５）を付着させた粗目３軸織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（５）を粗目３軸織物基布の全面に含浸付着させ、１８０℃の熱風乾燥炉で３分間熱処理した後、このメッシュシートを再度ポリウレタン前駆体組成物（５）充填浴中に、ディップし、１回目のディップ−熱処理と同様の手順を経て、厚さ０．７４mm、質量４３５ｇ／ｍ² のメッシュシートを得た。
【００６２】
［実施例６］
ｉ）．ポリウレタン前駆体組成物（６）
実施例４のブロックイソシアネート化合物（１）４４質量部を、下記のブロックイソシアネート化合物（３）７０質量部に変更、また、実施例４のアクリルポリオール（商標：アクリデックＡ−８０１：固形分５０質量％：大日本インキ化学工業（株））１４８質量部を１１７質量部に変更した。ブロックイソシアネート化合物（３）は、イソホロンジイソシアネート（ＩＰＤＩ）系トリメチロールプロパン・アダクト変性ポリイソシアネート（商標：タケネートＤ−１４０Ｎ：イソシアネート基含有量１０．５質量％、固形分７５質量％：武田薬品工業（株））１００質量部にメチルエチルケトオキシム３５質量部を加えて得た固形分６０質量％のキシレン溶液であった。（※遊離のメチルエチルケトオキシム当量比はブロックイソシアネート１当量あたり０．０３当量）このポリウレタン前駆体（固形分５３．６質量％）１８７質量部を基準とし、実施例４と同一の配合（ブロック化剤解離触媒、複合添加剤、着色剤、難燃性付与剤）を行って得られたグレー色のポリウレタン前駆体組成物（６）の液粘度（ＢＭ型回転粘度計による計測値）は、４．４Pa・ｓ（２０℃／０．５時間）、４．９Pa・ｓ（２０℃／３．０時間）、２．５Pa・ｓ（５０℃／０．５時間）、３．９Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度２０℃のポリウレタン前駆体組成物（６）を充填した浴中に、実施例３と同一の（ホスホン酸化合物下処理）ポリエステル粗目模紗織物基布をディップ（浸漬）し、ポリウレタン前駆体組成物（６）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（６）を粗目模紗織物基布の全面に含浸付着させ、１８０℃の熱風乾燥炉で３分間熱処理した後、再度ポリウレタン前駆体組成物（６）充填浴中にメッシュシートをディップし、１回目のディップ−熱処理と同様の手順を経て、厚さ０．７４mm、質量４４２ｇ／ｍ² のメッシュシートを得た。
【００６３】
［実施例７］
ｉ）．ポリウレタン前駆体組成物（７）
１，３−ビス（イソシアナトメチル）シクロヘキサン（Ｈ₆ ＸＤＩ）の３量体ベースの（メチルエチルケトオキシム）ブロックイソシアネート化合物（４）（商標：タケネートＢ−８４２Ｎ、有効イソシアネート基含有量９．７質量％、固形分７０質量％、ソルベンツ＃１００・酢酸ブチル溶媒：武田薬品工業（株））４０質量部と、活性水素基含有樹脂としてアクリルポリオール（商標：タケラックＵＡ−７０２：水酸基価５０mgＫＯＨ／ｇ、固形分５０質量％：トルエン／酢酸ブチル溶媒：武田薬品工業（株））１４５質量部とを配合してなる当量比０．１５のポリウレタン前駆体１８５質量部（固形分５４．３質量％）に対して、ブロック化剤解離触媒としてスズ系化合物（商標：フォーメートＫ：固形分１０質量％：武田薬品工業（株））５質量部と、酸化防止剤と耐候安定剤との複合添加剤として商標：チヌビンＢ−７５（チバ・スペシャルティ・カミカルズ（株））を１．０質量部、着色剤としてルチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部、難燃性付与剤（窒素原子含有化合物）としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））３０質量部、難燃性付与剤（リン原子含有化合物−１）として、ホスホン酸化合物（商標：Ｋ−１９Ａ、化学式（１）及び（２）のホスホン酸化合物の混合物：明成化成（株））１０質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン前駆体組成物（７）を得た。このポリウレタン前駆体組成物（７）の液粘度（ＢＭ型回転粘度計による計測値）は、３．７Pa・ｓ（２０℃／０．５時間）、４．２Pa・ｓ（２０℃／３．０時間）、３．０Pa・ｓ（３５℃／０．５時間）、３．６Pa・ｓ（３５℃／３．０時間）、２．２Pa・ｓ（５０℃／０．５時間）、２．７Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度３５℃のポリウレタン前駆体組成物（７）を充填した浴中に、実施例１と同一の（ホスホン酸化合物下処理）ポリエステル粗目模紗織物基布をディップ（浸漬）し、ポリウレタン前駆体組成物（７）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（７）を粗目模紗織物基布の全面に含浸付着させ、１８０℃の熱風乾燥炉で３分間熱処理した後、このメッシュシートを再度ポリウレタン前駆体組成物（７）充填浴中にディップし、１回目のディップ−熱処理と同様の手順を経て、厚さ０．７４mm、質量４２５ｇ／ｍ² のメッシュシートを得た。
【００６４】
［実施例８］
ｉ）．ポリウレタン前駆体組成物（８）
実施例４で用いたブロックイソシアネート化合物（１）と、活性水素基含有化合物として、数平均分子量５００、平均官能基数２．０のポリテトラメチレンエーテルポリオールとを、活性水素基／イソシアネート当量比１．３で含み、かつ、ポリウレタン前駆体中のブロックイソシアネート基／活性水素基当量比が０．７２であるポリウレタン前駆体１００質量部に対して、ブロック化剤解離触媒としてスズ系化合物（商標：フォーメートＫ：固形分１０質量％：武田薬品工業（株））５質量部と、酸化防止剤と耐候安定剤との複合添加剤として商標：チヌビンＢ−７５（チバ・スペシャルティ・ケミカルズ（株））を１．０質量部、着色剤としてリチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部、難燃性付与剤（窒素原子含有化合物）としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））３０質量部、難燃性付与剤（リン原子含有化合物−１）として、ホスホン酸化合物（商標：Ｋ−１９Ａ、化学式（１）及び（２）のホスホン酸化合物の混合物：明成化成（株））１０質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン前駆体組成物（８）を得た。このポリウレタン前駆体組成物（８）の液粘度（ＢＭ型回転粘度計による計測値）は、３．３Pa・ｓ（２０℃／０．５時間）、３．６Pa・ｓ（２０℃／３．０時間）、２．６Pa・ｓ（３５℃／０．５時間）、３．１Pa・ｓ（３５℃／３．０時間）、２．１Pa・ｓ（５０℃／０．５時間）、２．５Pa・ｓ（５０℃／３．０時間）であった。
ii ）．メッシュシートの製造
次に、液温度３５℃のポリウレタン前駆体組成物（８）を充填した浴中に、実施例３と同一のホスホン酸化合物下処理を施したポリエステル粗目模紗織物基布をディップ（浸漬）し、ポリウレタン前駆体組成物（８）を付着させた粗目模紗織物基布を引上げると同時にマングルロールでニップ（圧搾）し、ポリウレタン前駆体組成物（８）を粗目模紗織物基布の全面に含浸付着させた後、２００℃の熱風乾燥炉で６分間熱処理し、厚さ０．７４mm、質量４４４ｇ／ｍ² のメッシュシートを得た。
【００６５】
実施例１〜８の試験結果を表１に記す。
【表１】

【００６６】
［比較例１］
実施例１のポリウレタン前駆体（１）を水系ポリウレタン樹脂（１）に変更し、更に難燃性付与剤の一部を変更、及び増量した。すなわちポリウレタン系樹脂（１）（商標：アデカボンタイターＨＵＸ−２９０Ｎ：エステル系ポリウレタン樹脂エマルジョン：固形分５０質量％：旭電化工業（株））２００質量部（固形分換算１００質量部）に対し、酸化防止剤と耐候安定剤との複合添加剤として商標：チヌビンＢ−７５（チバ・スペシャルティ・ケミカルズ（株））を１．０質量部、着色剤としてルチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部、難燃性付与剤（窒素原子含有化合物）としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））１００質量部、難燃性付与剤（リン原子含有化合物−３）として、芳香族縮合リン酸エステル（商標ＣＲ−７４７：粘度３９００cP／４０℃：大八化学（株））３０質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン（１）組成物を得た。このポリウレタン（１）組成物の液粘度（ＢＭ型回転粘度計による計測値）は、３．２Pa・ｓ（２０℃／０．５時間）、３．５Pa・ｓ（２０℃／３．０時間）、２．８Pa・ｓ（５０℃／０．５時間）、３．３Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１２ｇ／ｍ² のメッシュシートを得た。
【００６７】
［比較例２］
比較例１のポリウレタン（１）組成物中にカルボジイミド系架橋剤（商標：カルボジライトＶ−０２、有効成分量４０質量％：日清紡（株））１０質量部（固形分換算４質量部）を追加配合した以外は比較例１と同一組成とした。このポリウレタン（１）組成物の液粘度（ＢＭ型回転粘度計による計測値）は、３．０Pa・ｓ（２０℃／０．５時間）、４．４Pa・ｓ（２０℃／３．０時間）、２．７Pa・ｓ（５０℃／０．５時間）、７．６Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１５ｇ／ｍ² のメッシュシートを得た。
【００６８】
［比較例３］
実施例１のポリウレタン前駆体（１）を水系酢酸ビニル−エチレン共重合体樹脂に変更し、更に難燃性付与剤の一部を変更、及び増量した。すなわち酢酸ビニル−エチレン共重合体樹脂（商標：スミカフレックスＳ−５００：固形分５５質量％：住友化学工業（株））１８２質量部（固形分換算１００質量部）に対し、比較例１と同一、同量の複合添加剤、着色剤、及び難燃性付与剤を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色の酢酸ビニル−エチレン共重合体樹脂組成物を得た。この酢酸ビニル−エチレン共重合体樹脂組成物の液粘度（ＢＭ型回転粘度計による計測値）は、２．７Pa・ｓ（２０℃／０．５時間）、３．１Pa・ｓ（２０℃／３．０時間）、２．５Pa・ｓ（５０℃／０．５時間）、２．８Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１０ｇ／ｍ² のメッシュシートを得た。
【００６９】
［比較例４］
実施例１のポリウレタン前駆体（１）を水系ポリウレタン樹脂（２）に変更し、更に難燃性付与剤の一部を変更、及び増量した。すなわちポリウレタン系樹脂（２）（商標：パーミュセンＲＵ−４０−３５０：ポリカーボネート系ポリウレタン樹脂エマルジョン：固形分４０質量％：スタール・ジャパン（株））２５０質量部（固形分換算１００質量部）に対し、酸化防止剤と耐候安定剤との複合添加剤として商標：チヌビンＢ−７５（チバ・スペシャルティ・ケミカルズ（株））を１．０質量部、着色剤としてリチル型酸化チタン顔料４．０質量部とカーボンブラック顔料０．８質量部、難燃性付与剤（窒素原子含有化合物）としてメラミン・シアヌレート（商標：ＭＣ−６１０：平均粒子径１〜５μｍ：日産化学（株））６０質量部、難燃性付与剤として、リン原子含有化合物−３）：芳香族縮合リン酸エステル（商標ＣＲ−７４７：粘度３９００cP／４０℃：大八化学（株））２０質量部、及びリン原子含有化合物−４）：赤リン（商標：ヒシガードホワイトＣＰ、赤リン含有量３３質量％の酸化チタンコート消色品：日本化学（株））１５質量部を配合したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のポリウレタン（２）組成物を得た。このポリウレタン（２）組成物の液粘度（ＢＭ型回転粘度計による計測値）は、１．８Pa・ｓ（２０℃／０．５時間）、２．１Pa・ｓ（２０℃／３．０時間）、１．５Pa・ｓ（５０℃／０．５時間）、１．９Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１０ｇ／ｍ² のメッシュシートを得た。
【００７０】
［比較例５］
比較例４のポリウレタン（２）組成物中にカルボジイミド系架橋剤（商標：カルボジライトＶ−０２、有効成分量４０質量％：日清紡（株））１０質量部（固形分換算４質量部）を追加配合した以外は比較例４と同一組成とした。このポリウレタン（２）組成物の液粘度（ＢＭ型回転粘度計による計測値）は、１．７Pa・ｓ（２０℃／０．５時間）、２．０Pa・ｓ（２０℃／３．０時間）、２．２Pa・ｓ（５０℃／０．５時間）、７．４Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１７ｇ／ｍ² のメッシュシートを得た。
【００７１】
［比較例６］
実施例１のポリウレタン前駆体（１）を水系アクリル系樹脂に変更し、更に難燃性付与剤の一部を変更、及び増量した。すなわちアクリル系樹脂（商標：ウルトラゾールＢ−８００：固形分５５質量％：ガンツ化成（株））１８２質量部（固形分換算１００質量部）に対し、比較例４と同一、同量の複合添加剤、着色剤、及び難燃性付与剤を配当したものを基本組成とし、これをブレンダーで均一撹拌してグレー色のアクリル系樹脂組成物を得た。このアクリル系樹脂組成物の液粘度（ＢＭ型回転粘度計による計測値）は、１．６Pa・ｓ（２０℃／０．５時間）、１．８Pa・ｓ（２０℃／３．０時間）、１．３Pa・ｓ（５０℃／０．５時間）、１．８Pa・ｓ（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例４と同一の方法と手順により、厚さ０．７４mm、質量４１２ｇ／ｍ² のメッシュシートを得た。
【００７２】
※比較例１〜６で得たメッシュシートは、未使用状態においては、消防法施工規則第４条（ＪＩＳ Ｌ１０９１Ａ法）の防炎性能と、ＪＩＳ Ａ８９５２及び（社）仮設工業会認定基準に規定される性能（鋼管落下による耐貫通試験）とを満足するものであったが、何れも水系樹脂エマルジョンを使用して加工を行ったものであるため、根本的に耐水性に優れるものではなく、洗濯によって膨潤した樹脂被覆層が擦れ合って脱落劣化することによって鋼管落下による耐貫通試験に不合格となったり、また、洗濯時に樹脂被覆層の膨潤に伴なって難燃性付与剤が系外に抽出されることによって防炎性が得られなくなるものであった。従ってこれらのメッシュシートでは１度の洗濯によって防炎効果や耐貫通性が容易に失われてしまうため、繰り返し使用することができないものであった。
【００７３】
［比較例７］
実施例４のポリウレタン前駆体に用いたブロックイソシアネート化合物（１）のフロック化剤を省いた組成系とした。すなわち１，６−ヘキサメチレンジイソシアネート（ＨＭＤＩ）系イソシアヌレート変性ポリイソシアネート（商標：タケネートＤ−１７０Ｎ：イソシアネート基含有量２０．７質量％、固形分１００質量％：武田薬品工業（株））をそのまま用いた。このイソシアネート化合物の変更以外は実施例４と同一とし、グレー色のポリウレタン前駆体組成物（９）を得た。このポリウレタン前駆体組成物（９）の液粘度（ＢＭ型回転粘度計による計測値）は、４．４Pa・ｓ（２０℃／０．５時間）、７．１Pa・ｓ（２０℃／３．０時間）、５．３Pa・ｓ（３５℃／０．５時間）、１２．８Pa・ｓ（３５℃／３．０時間）、１８．５Pa・ｓ（５０℃／０．５時間）、ゲル化測定不能（５０℃／３．０時間）であった。次に実施例１で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例７と同一の方法と手順によりメッシュシートを得ようとしたが、加工直後から液粘度が上昇しポリウレタン前駆体組成物（９）の流動性が著しく低くなりその結果、加工が困難となり、正常樹脂付着、及び正常外観のメッシュシートは得られなかった。
【００７４】
［比較例８］
実施例４のポリウレタン前駆体に用いたブロックイソシアネート化合物（１）のフロック化剤を省いた組成系とした。すなわち１，６−ヘキサメチレンジイソシアネート（ＨＭＤＩ）系イソシアヌレート変性ポリイソシアネート（商標：タケネートＤ−１７０Ｎ：イソシアネート基含有量２０．７質量％、固形分１００質量％：武田薬品工業（株））をそのまま用いた。このイソシアネート化合物の変更以外は実施例４と同一とし、グレー色のポリウレタン前駆体組成物（１０）を得た。このポリウレタン前駆体組成物（１０）の液粘度（ＢＭ型回転粘度計による計測値）は、４．６Pa・ｓ（２０℃／０．５時間）、７．３Pa・ｓ（２０℃／３．０時間）、５．５Pa・ｓ（３５℃／０．５時間）、１１．３Pa・ｓ（３５℃／３．０時間）、１５．４Pa・ｓ（５０℃／０．５時間）、ゲル化測定不能（５０℃／３．０時間）、であった。次に実施例３で用いた下処理ポリエステル粗目模紗織物基布を使用して、実施例８と同一の方法と手順によりメッシュシートを得ようとしたが、加工直後から液粘度が上昇しポリウレタン前駆体組成物（１０）の流動性が著しく低くなり、その結果、加工が困難となり、正常樹脂付着、及び正常外観のメッシュシートは得られなかった。
【００７５】
比較例１〜８の試験結果を表２に記す。
【表２】

【００７６】
【発明の効果】
上記、実施例及び、比較例により明らかなように、本発明によって得られる建築養生メッシュシートは通気性と採光性を有し、また消防法施工規則第４条（ＪＩＳ Ｌ１０９１Ａ法）の防炎性能と、ＪＩＳ Ａ８９５２及び（社）仮設工業会認定基準に規定される性能（鋼管落下による耐貫通試験）とを満足するものであった。特に本発明によって得られる建築養生メッシュシートは、過酷な洗濯にも十分な耐性を有し、洗濯によって難燃化ポリウレタン樹脂による被覆層が膨潤して脱落したり、難燃性付与剤が系外抽出減量したりする不都合は観察されなかった。また、本発明のメッシュシートは１度の洗濯によって容易に防炎効果が失われたり、鋼管落下による耐貫通試験に簡単に不合格となるようなことはないので、汚れたメッシュシートを回収・洗濯して繰り返し再使用することが可能である。従って本発明の建築養生メッシュシートは、従来のポリ塩化ビニル樹脂使用のメッシュシートと同様に使用でき、しかも火災時に有毒なハロゲン化水素ガスを発生させる心配がないため、極めて有用性の高いものである。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a building mesh sheet used for a building construction site, a building enclosure demolition work site, and the like and a manufacturing method thereof. More specifically, the present invention can be used for a long time mainly on a construction site covering sheet, can be washed and reused after use, and burns if an unexpected fire is encountered. The present invention also relates to a non-vinyl chloride building curing mesh sheet that does not generate hydrogen halide gas and a method for producing the same.
[0002]
[Prior art]
Polyvinyl chloride resin is flexible and tough, and has excellent durability, workability, and cost. Therefore, it is widely used in a wide range of applications. Among them, the polyvinyl chloride resin paste composition is in a liquid state and thus has a wide range of processing applications, and is suitable for coating and dipping, for example. In particular, mesh sheets used for building construction sites and building demolition construction sites are obtained by dipping coarse polyester fiber fabric with a polyvinyl chloride resin paste composition and gelling the polyvinyl chloride resin paste composition. Industrial material. This mesh sheet has breathability and daylighting, and also has the flameproof performance specified in Article 4 (JIS L1091A method) of the Fire Service Act construction regulations, and the performance (tensile) specified by JIS A8952 and the Temporary Industry Association certification standards. It is the most commonly used mesh-curing sheet for building construction at the construction site by satisfying the following: strength × elongation, tensile strength, strength of joints, penetration test by dropping steel pipe).
[0003]
When these mesh sheets are used for long-term enclosures, they are contaminated by dust and dirt, and at the same time, paints scattered during spray coating on the exterior walls of buildings are often accompanied by dirt. . However, this has no particular effect on the performance of the mesh sheet itself, so the mesh sheet removed after completion of the building is specially washed by the manufacturer with an alkaline detergent and then used for the next construction site. Has been reused. Since the mesh sheet reused 2 to 3 times in this way is unavoidably accompanied by a deterioration in strength, it is finally discarded. However, easy incineration treatment of polyvinyl chloride resin products is not preferable because of concerns about the generation of dioxins, and in the case of landfill treatment, plasticizers and metal stabilizers contained in soft polyvinyl chloride resin As a result, there is a growing concern that recent plastic products have as little environmental impact as possible and can be easily recycled when disposed of.
[0004]
In response to these social demands, recently, there has been a demand for a mesh sheet for building enclosures that does not use polyvinyl chloride resin. As a result of studying a resin solution having a dipping property similar to that of a polyvinyl chloride resin paste composition, a flame retardant was added to an aqueous resin (for example, resin emulsion or resin dispersion). Non-vinyl chloride flameproof mesh sheets based on the composition have been proposed and used in some applications. These are for example i). A flameproof mesh sheet coated with a flame retardant comprising a polyolefin resin dispersion containing red phosphorus and an ammonium polyphosphate compound (see, for example, Patent Document 1), ii). Flameproof mesh sheet coated with a flame retardant comprising an ethylene-vinyl acetate copolymer aqueous dispersion containing red phosphorus and ammonium polyphosphate compound (see, for example, Patent Document 2), iii). Flameproof mesh sheet coated with a flame retardant comprising an ethylene-vinyl acetate copolymer aqueous dispersion containing red phosphorus, ammonium polyphosphate compound, and phosphate ester (see, for example, Patent Document 3), iv). Flameproof mesh sheet coated with a flame retardant comprising a polyolefin resin dispersion and an ammonium polyphosphate compound and a metal hydroxide (see, for example, Patent Document 4), v). Flameproof mesh sheet coated with a flame retardant comprising polyolefin resin dispersion containing red phosphorus, melamine sulfate and metal hydroxide (for example, see Patent Document 5), vi). A mesh sheet such as a flameproof mesh sheet (for example, see Patent Document 6) comprising a polyurethane resin aqueous dispersion mixed with a non-halogen organic phosphate ester and coated with a flame retardant containing an oxazoline group-containing aqueous crosslinking agent. is there.
[0005]
However, the mesh sheets of i) to vi) are essentially inferior in water resistance due to the use of an aqueous dispersion, and the resin coating layer swells and rubs when washed with an alkaline detergent for reuse. As a result, the resin coating layer easily falls off and has a disadvantage that it cannot be reused. In addition, among the mesh sheets of the above i) to iii) and v) in which red phosphorus must be used as a flame retardant component, the problem of being unable to freely color due to the effect of reddish brown of red phosphorus itself, There is a problem that the color of the red phosphorus is decolored by sunlight and the hue of the mesh sheet changes, and further, there is a problem that the red phosphorus is hydrolyzed by rain, and the durability is generally poor. On the other hand, the mesh sheet of vi) improves the water resistance of the coating resin to some extent by using a cross-linking agent. However, it still does not reach a level that can withstand washing with an alkaline detergent. Easily hydrolyzing the used non-halogen organic phosphate ester is a serious problem from the viewpoint of flameproofness during reuse.
[0006]
On the other hand, a fabric having a recumbent texture using an original flame-retardant polyester fiber copolymerized with a bifunctional phosphorus compound has been proposed as a mesh sheet for construction work (for example, Patent Document 7, Patent Document 8, Patent Document 9). Etc.) Certainly, these mesh sheets are composed of a special recumbent tissue, so they will not be misaligned even after washing, and they are also lightweight, but these mesh sheets cause misalignment. Because it requires a robust recumbent structure to prevent it from being made, the voids of the weave are extremely small compared to conventional construction construction tension sheets, and thus the air permeability and lighting are insufficient. There are drawbacks. In addition, it is possible to design a large void portion of the woven fabric in order to improve the air permeability and the daylighting property of the mesh sheet of the recumbent tissue. However, this not only tends to cause misalignment, but also JIS A8952 Therefore, the mesh sheet of the recumbent structure using the original flame-retardant polyester fiber cannot help being inferior in air permeability and daylighting. In addition, since the mesh sheet is used with bare fibers, it is easy to be scratched at the construction site, which may cause the standard strength to be unsatisfactory, or may be incompatible with the penetration test due to steel pipe dropping. In addition, for example, even if an ultraviolet absorbent is included in the fiber, light degradation due to sunlight is unavoidable in the long term, and there is a great risk of hydrolysis during alkaline washing.
[0007]
[Patent Document 1]
JP 11-036602 A, pages 2-5
[Patent Document 2]
JP-A-11-117175, pages 2-6
[Patent Document 3]
JP-A-11-172806, pp. 2-6
[Patent Document 4]
JP 2000-063841 A, pp. 2-6
[Patent Document 5]
JP 2000-178559 A, pages 2-6
[Patent Document 6]
JP 2002-069293, pages 2-5
[Patent Document 7]
JP-A-8-109541, pages 2-7, FIGS. 1-3
[Patent Document 8]
JP-A-8-269850, pages 2-6
[Patent Document 9]
JP-A-10-169205, pages 2-6
[0008]
[Problems to be solved by the invention]
The present invention solves the problem of the washing resistance of the non-vinyl chloride building curing mesh sheet for construction fences at the construction site, which has been a problem of the above prior art, and is reusable for washing. It is intended to provide a non-vinyl chloride building curing mesh sheet that satisfies the flameproof performance of Article 4 (JIS L1091A method) and can maintain the performance specified in JIS A8952 and the temporary industry association certification standard. .
[0009]
[Means for Solving the Problems]
As a result of repeated research and investigations to solve the above-mentioned problems, the present invention forms an impregnated coating on the entire surface of a coarse-textured knitted fabric with a polyurethane precursor containing a specific amount of a specific flame retardant and a specific liquid viscosity. The mesh sheet obtained by converting this polyurethane precursor composition into a flame retardant polyurethane-based resin by a thermosetting reaction and making it a flame retardant resin coating layer has excellent durability, and is washed and reused. This is a book that can be used and that it can satisfy the flameproof performance of Article 4 (JIS L1091A method) of the Fire Service Act construction regulations and the performance specified in JIS A8952 and the Temporary Manufacturers Association Certification Standard even in reuse. The invention has been completed.
[0010]
  The architectural curing mesh sheet of the present invention comprises fiber yarns, and has a coarse woven knitted fabric having gaps between yarns formed by the crossing thereof, and at least the entire exposed surface of the fiber yarns of the coarse woven knitted fabric. A flame retardant resin coating layer formed by impregnation or coating, wherein the flame retardant resin coating layer is formed by a thermosetting reaction of a composition of a polyurethane precursor and a flame retardant imparting agent,
  (A) The polyurethane precursor has (a) at least one selected from a polyol monomer compound (a-1) having active hydrogen and a polyol polymer (a-2), and (b) a blocked isocyanate group. A liquid mixture ((a) + (b)) comprising at least one selected from the compound (b-1) having and the compound (b-2) having a uretdione group,
  (B) The flame retardant imparting agent includes at least one selected from an organic compound (c-1) containing a nitrogen atom and an organic compound (c-2) having a phosphorus atom,
  (C) The composition of the polyurethane precursor and the flame retardant imparting agent has a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours),
  (D) Content of the said flame-retarding agent with respect to the total mass of the said flame-retardant resin coating layer is 10-50 mass%, It is characterized by the above-mentioned.
  In the architectural curing mesh sheet of the present invention, the isocyanate group-containing compound (b-1) for polyurethane precursor is preferably selected from compounds having a blocked isocyanate group.
  In the architectural curing mesh sheet of the present invention, the organic compound (c-1) containing a nitrogen atom is an (iso) cyanurate compound, an (iso) cyanuric acid compound, a guanidine compound, a urea compound, and derivatives thereof. Preferably selected from compounds.
  In the architectural curing mesh sheet of the present invention, the organic compound (c-2) containing phosphorus atoms is preferably selected from red phosphorus, (metal) (organic) phosphate, phosphoric acid derivative, and ammonium polyphosphate. .
  In the architectural curing mesh sheet of the present invention, the coarse woven fabric may be selected from a biaxial woven fabric, a triaxial woven fabric, and a 4-axial woven fabric knitted by crossing the fiber yarns in 2 to 4 directions. preferable.
  In the architectural curing mesh sheet of the present invention, the coarse woven fabric preferably has a total void area of 5 to 65% with respect to the surface area of the coarse woven fabric.
  In the architectural curing mesh sheet of the present invention, it is preferable that the coarse woven or knitted fabric is subjected to a flame retardant treatment with a phosphonic acid compound.
  The method for producing a building-curing mesh sheet of the present invention comprises a coarse yarn knitted fabric which is composed of fiber yarns and has a yarn gap formed by the crossing thereof.In,
  (A) (a) having active hydrogenPolyolMonomer compound (a-1) andPolyolPolymer (a-2)Chosen fromAt least one, and (b)blockCompound (b-1) having isocyanate group and compound (b-2) having uretdione groupChosen fromIncluding at least oneLiquid mixture ((a) + (b))A polyurethane precursor comprising:
  (B) including a flame retardant imparting agent including at least one selected from an organic compound (c-1) containing a nitrogen atom and an organic compound (c-2) having a phosphorus atom;
  (C) Impregnation or coating treatment with a flame retardant polyurethane precursor composition having a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours)ApplyAndnextThe flame retardant polyurethane precursor composition impregnated or coated on at least the entire exposed surface of the fiber yarn of the coarse woven or knitted fabric is subjected to heat treatment, and this is subjected to heat treatment. To form a flame retardant resin coating layer, wherein the content of the flame retardant imparting agent with respect to the total mass of the flame retardant resin coating layer is adjusted to 10 to 50% by mass It is.
  In the method for producing an architectural curing mesh sheet of the present invention, the flame retardant polyurethane precursor composition may not contain a dilution solvent.
  In the method for producing an architectural curing mesh sheet of the present invention, the flame retardant polyurethane precursor composition may contain a diluent solvent.
  In the method for producing an architectural curing mesh sheet of the present invention, it is preferable that the flame retardant polyurethane precursor composition is impregnated or coated at 20 to 50 ° C., and the heat treatment is performed at a temperature of 100 ° C. or higher.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  The architectural curing mesh sheet of the present invention is a composite of a coarse woven knitted fabric having inter-yarn gaps formed by crossing fiber yarns, and a flame retardant resin coating layer formed by impregnating and covering the entire surface of the coarse woven knitted fabric. The flame retardant resin coating layer is formed by converting the flame retardant imparting agent-containing polyurethane precursor composition into a flame retardant polyurethane resin by a thermosetting reaction, and (A) the polyurethane precursor composition Have (a) an active hydrogen groupPolyol monomerCompound (a-1) and / orPolyol polymer(A-2) and (b)block(B-1) containing an isocyanate group and / or a compound (b-2) containing a uretdione group, and (B) an organic compound (c-1) in which the flame retardant agent has a nitrogen atom and / or Or the organic compound (c-2) containing a phosphorus atom and having a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), the flame-retardant resin coating layer is It contains 10-50% by mass of the flame retardant imparting agent.
[0012]
  In addition, the method for producing a building-curing mesh sheet of the present invention comprises a coarse knitted knitted fabric which is composed of fiber yarns and has a yarn gap formed by crossing them.In,
  (A) (a) having active hydrogenPolyolMonomer compound (a-1) andPolyolAt least one polymer (a-2), and (b)blockA polyurethane precursor comprising a mixture containing at least one of a compound (b-1) having an isocyanate group and a compound (b-2) having a uretdione group, and
  (B) a flame retardant imparting agent comprising at least one of an organic compound (c-1) containing a nitrogen atom and an organic compound (c-2) having a phosphorus atom;
  (C) having a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours),
Impregnation or coating treatment with flame retardant polyurethane precursor compositionApplyAndnext
  The flame retardant polyurethane precursor composition impregnated or coated on at least the entire exposed surface of the fiber yarn of the coarse woven or knitted fabric is subjected to heat treatment, and this is subjected to heat treatment. To form a flame retardant resin coating layer, wherein the content of the flame retardant imparting agent with respect to the total mass of the flame retardant resin coating layer is adjusted to 10 to 50% by mass It is.
[0013]
  The polyurethane precursor composition used for the flame retardant resin coating layer of the architectural curing mesh sheet of the present invention contains an active hydrogen group in the molecule.PolyolMonomer compound (a-1),And / orContains active hydrogen groups in the moleculePolyolA polymer (a-2);blockIt is a mixture with the polyisocyanate compound component (b), and the polyisocyanate compound component (b)blockCompound (b-1) containing an isocyanate group,And / orSelected from compounds having a uretdione group in the molecule (b-2)Thethis houseCompound(A-1) is a low molecular polyol having a number average molecular weight of 62 to less than 500.As the polymer (a-2),A polymer polyol having a number average molecular weight of 500 to 30,000 can be used.
[0014]
Among these, as the low molecular polyol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-butanediol, Pentanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, Decamethylene glycol, diethylene glycol, dipropylene glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1, 3-pentanediol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2- Tylene glycol, 2-n-eicosane-1,2-ethylene glycol, 2-n-octacosane-1,2-ethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, Cationic properties such as bisphenol A, hydrogenated bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A, ethylene oxide or propylene oxide adduct of hydrogenated bisphenol A, trimethylpropane, glycerin, hexanetriol, quadrol, pentaerythritol, sorbitol Group-free low molecular polyols, 2,2-dimethylolpropionic acid, carboxylic acid group-containing low molecular polyols such as 2,2-dimethylolbutanoic acid, carboxylic acid group-containing Salts of molecular polyols with ammonia, organic amines, alkali metals, alkaline earth metals, etc., sulfonic acid group-containing low molecules such as 2-sulfo-1,3-propanediol and 2-sulfo-1,4-butanediol Examples include polyols, salts of sulfonic acid group-containing low molecular weight polyols with ammonia, organic amines, alkali metals, alkaline earth metals, and the like. Particularly, those compounds having a side chain are polyurethane precursor compositions From the viewpoints of compatibility and viscosity stability.
[0016]
Examples of the polymer polyol for the polymer compound (a-2) include polyester polyol, polyamide ester polyol, polycarbonate polyol, polyether polyol, polyether ester polyol, polyolefin polyol, and fluorine polyol.
[0017]
Of these, polyester polyols are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, succinic acid, adipic acid 1,4-cyclohexyldicarboxylic acid, hydromuconic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and other cationic group-free polycarboxylic acids, 5-sulfo-isophthalic acid and other sulfonic acid group-containing poly One or more of carboxylic acids and salts of these sulfonic acid group-containing polycarboxylic acids with ammonia, organic amines, alkali metals, alkaline earth metals, etc., their acid anhydrides, acid halides, dialkyl esters, etc. And those obtained by reaction with molecular polyols. Furthermore, the polyester polyol is subjected to ring-opening polymerization of lactones such as ε-caprolactone, alkyl group-substituted ε-caprolactone, δ-valerolactone, and alkyl group-substituted δ-valerolactone, using the above-described low molecular weight polyol as an initiator. Examples thereof include lactone polyester polyols obtained. Furthermore, it replaces with a part of low molecular polyol, and the polyamide ester polyol obtained using low molecular polyamines, such as hexamethylenediamine, isophoronediamine, and monoethanolamine, and low molecular amino alcohol. Examples of the polycarbonate polyol include those obtained from a dealcoholization reaction or a dephenol reaction between one or more of the aforementioned low-molecular polyols and ethylene carbonate, diethyl carbonate, or diphenyl carbonate.
[0018]
As the polyether polyol, the low molecular polyol, low molecular polyamine or low molecular amino alcohol described above is used as an initiator, an alkylene oxide such as ethylene oxide or propylene oxide, an epoxide such as tetrahydrofuran, or a simple or mixture of cyclic ethers. What is obtained by polymerizing is mentioned.
Examples of polyether ester polyols include copolyols obtained from the aforementioned polyether polyols and the aforementioned polycarboxylic acids. Moreover, the thing obtained by reaction with the above-mentioned polyester and polycarbonate, epoxide, and cyclic ether is mentioned.
[0019]
Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. Examples of the fluorine polyol include fluoroolefins, cyclohexyl vinyl ethers, hydroxyalkyl vinyl ethers, hydroxyalkyl vinyl ethers, vinyl monocarboxylates as disclosed in JP-A-57-34107 and JP-A-61-275111. It is a copolymer such as an ester. Further, as long as the number average molecular weight is 500 or more and the compound has one or more active hydrogen groups in one molecule, a dimer acid polyol, a hydrogenated dimer acid polyol, or the like may be used. The component (a-1) described above is not particularly limited to one type.
[0021]
  In the moleculeblockAs the compound component (b-1) containing an isocyanate group, a polyisocyanate compound is reacted with an active hydrogen group-containing compound such as water, polycarboxylic acid, polyol, polyamine, amino alcohol, or urea, urethanized, or amide. Isocyanate group-containing modified product obtained by the formation of an isocyanate group, or an isocyanate group-containing modified product in which an isocyanate group is dimerized by a uretdione bond or a carbodiimide bond at the same time or after these reactions, or an isocyanate group is trimerized by an isocyanurate bond Isocyanate group-containing modified products, isocyanate group-containing modified products in which isocyanate groups are highly polymerized by uretonimine bonds, etc., and isocyanate group-terminated prepolymers obtained by reacting active hydrogen group-containing compounds, or Mixture of isocyanurate-urethane-modified isocyanates such asofThose whose isocyanate group is protected by a blocking agent described laterIs. Particularly, among the components (b-1) used in the present invention, those having at least a part of structural units derived from hexamethylene diisocyanate (HMDI) as the blocked isocyanate compound from the viewpoint of the liquid requirements of the obtained polyurethane precursor Is preferred. The component (b-1) is preferably obtained by a known reaction between a polyisocyanate compound (modified product) and a blocking agent. Examples of the polyisocyanate compound include isocyanurate-modified polyisocyanate, burette-modified polyisocyanate, trimethylolpropane-modified polyisocyanate, urethane-modified polyisocyanate, diisocyanate, triisocyanate, and the like. From the viewpoint of layer strength and washing resistance, isocyanurate-modified polyisocyanate (especially HMDI), burette-modified polyisocyanate (especially HMDI), trimethylolpropane-modified polyisocyanate (especially HMDI) and the like are preferred. The effective isocyanate group content of these blocked isocyanate compounds is 5.0 to 20% by mass, particularly 7.0 to 18% by mass in terms of solid content of the blocked isocyanate compound, and the flame retardancy of the mesh sheet is obtained. It is preferable in terms of the strength of the resin coating layer and the washing resistance.
[0022]
  Also,blockThe polyisocyanate compound (b) may be modified with a hydroxyl compound during synthesis. Examples of the hydroxyl compound include monohydroxyl compounds such as methanol, ethanol, isopropanol, and phenol, dihydroxyl compounds such as ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol, hexanediol, cyclohexanediol, and neopentylglycol, Low molecular polyhydric alcohols such as trimethylolpropane, glycerin and pentaerythritol; high molecular weight polyhydric alcohols such as aliphatic hydrocarbon polyols, polyether polyols and polyester polyols. These isocyanate compounds are aliphatic or aliphatic (including aromatic water additives) derived from the viewpoint of the liquid requirements of the polyurethane precursor used in the present invention, and the resulting mesh sheet The aliphatic diisocyanate can be a compound having 4 to 24 carbon atoms, preferably 6 to 12 carbon atoms, and the alicyclic diisocyanate can be a compound having 8 to 24 carbon atoms, preferably 8 to 16 carbon atoms. These include, for example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate Methyl-3,5,5-trimethylcyclohexyliso Aneto (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) - cyclohexane, 4,4'-dicyclohexylmethane diisocyanate. (B-1) component of the said description is not specifically limited only to 1 type, Aromatic diisocyanate can also be used together in an appropriate amount as needed.
[0023]
Examples of the blocking agent for protecting the isocyanate group in the component (b-1) include alcohols, phenols, active methylenes, mercaptans, acid amides, acid imides, imidazoles, ureas, oximes, Examples include amine-based compounds, imide-based compounds, pyridine-based compounds, and pyrazole-based compounds. Among them, specific examples of alcohol-based blocking agents include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, and methyl. Carbitol, benzyl alcohol, cyclohexanol, etc. are used. Specific examples of phenolic blocking agents include phenol, cresol, ethylphenol, butylphenol, nonylphenol, styrenated phenol, hydroxybenzoate. Acid esters are used. Specific examples of the active methylene blocking agent include dimethyl malonate, diethyl malonate, methyl acetoacetate, and acetylacetone. Specific examples of the mercaptan blocking agent include butyl mercaptan. , Dodecyl mercaptan, etc. are used, and specific examples of the acid amide blocking agent include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc. Specifically, succinimide, maleic imide and the like are used, imidazole blocking agent is specifically used, imidazole, 2-methylimidazole and the like are specifically used, and urea blocking agent is specifically urea. , Thiourea, ethylene urea, etc. Specific examples of oxime blocking agents include formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Specific examples of amine blocking agents include diphenylamine, aniline, and carbazole. In particular, ethyleneimine, polyethyleneimine, etc. are used as imine blocking agents, and 2-hydroxypyridine, 2-hydroxyquinoline, etc. are specifically used as pyridine blocking agents. As the pyrazole-based blocking agent, specifically, 3,5-dimethylpyrazole is used. Of these, oxime-based, active methylene-based, phenol-based, and pyrazole-based blocking agents can be preferably used. Particularly, among oxime-based compounds, preferably acetooxime and methylethylketoxime are used, and among pyrazole-based compounds, 3, 5-dimethylpyrazole can be preferably used. The reaction between the polyisocyanate compound and the blocking agent can be carried out regardless of the presence or absence of a solvent. The blocking reaction is carried out using organometallic salts such as tin, zinc and lead, and tertiary amines as catalysts. It can also be used. This blocking reaction is preferably carried out under the conditions of 0 to 100 ° C., particularly 20 to 80 ° C. If the reaction temperature exceeds 100 ° C, side reactions may occur and the blocking agent may not function normally. If the reaction temperature is below 0 ° C, the reaction rate may decrease and the blocking agent may not be added normally. The blocking agent is added in an amount of 0.15-3.0 equivalents, preferably 0.2-2.0 equivalents, per equivalent of blocked isocyanate. If the addition amount is less than 0.15 equivalent, the resulting polyurethane precursor is inferior in liquid viscosity stability, and if it exceeds 3.0 equivalent, curing failure may occur during thermal curing.
[0024]
In converting the polyurethane precursor composition used in the present invention into a flame retardant resin coating layer by a thermosetting reaction, the blocking agent of the blocked isocyanate compound component (b-1) is dissociated to efficiently regenerate the isocyanate groups. It is preferable to use a catalyst in combination for the purpose and to promote the reaction between the active hydrogen group-containing compound (a) and the regenerated isocyanate group. Examples of the catalyst include ditintin dilaurate, dioctyltin dilaurate, stannous octoate, and other organic tin catalysts, triethylenediamine, triethylamine, N, N, N ′, N′-tetramethylpropylenediamine, N-methylmorpholine, 1, Amine-based catalysts such as 2-dimethylimidazole and 1,5-diaza-bicyclo (4,3,0) nonene-5, and amines such as borane salts, phenol salts, octylates and carbonates of these amine catalysts A salt catalyst, a carboxylic acid metal salt catalyst such as lead naphthenate, magnesium naphthenate and potassium acetate, a phosphorus catalyst such as triethylphosphine and tribenzylphosphine, and an alkoxide catalyst such as sodium methoxide can be used. The use of the catalyst is not particularly limited to one type, and two or more types may be used in combination as required. Moreover, the addition amount of a catalyst is 1.0 mass% or less with respect to the total amount of (a) and (b), Preferably it is 0.001-0.5 mass%. When the amount of the catalyst added exceeds 1.0% by mass, not only the difference in effect is not observed, but also the liquid viscosity of the polyurethane precursor composition increases, or gelation occurs during storage of the liquid. There is not preferable. These catalysts are preferably used by adding an appropriate amount to the polyurethane precursor at the time of production of the mesh sheet, and if necessary, the catalyst is diluted to the desired concentration with the above-mentioned organic solvent or plasticizer. You can also.
[0025]
  In the polyurethane precursor composition used in the present invention, the compound component (a) containing active hydrogen groups in the molecule: (a-1 and / or a-2), and in the moleculeblockThere is no particular limitation on the mixing ratio with the polyisocyanate compound component (b-1) containing an isocyanate group, but the molar ratio of the active hydrogen group contained in (a) and the effective isocyanate group contained in (b-1). Is preferably in the range of 1: 9 to 9: 1, particularly 2: 8 to 8: 2, from the viewpoint of the strength, washing resistance, and processability of the flame-retardant resin coating layer of the mesh sheet. Outside this range, the strength and washing resistance of the flame retardant resin coating layer of the resulting mesh sheet may be inferior.
[0026]
As the compound component (b-2) having a uretdione group in the molecule, an aliphatic diisocyanate having 4 to 24 carbon atoms, preferably 6 to 12 carbon atoms, an alicyclic diisocyanate having 8 to 24 carbon atoms, preferably 8 to 16 carbon atoms. Uretdione dimer or polyuretdione, etc. can be preferably used, such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis ( Isocyanatomethyl) -cyclohexane A urethodionation dimers and 4,4'-dicyclohexylmethane diisocyanate or Poriuretojion body (including isocyanurate trimers.). These (b-2) compounds are, for example, trialkylphosphines such as triethylphosphine, dibutylethylphosphine, tri-n-propylphosphine, triamylphosphine, tribenzylphosphine, or the presence of a uretdiation catalyst such as pyridines. Below, it can manufacture at the reaction temperature of 0-90 degreeC. This production reaction may be carried out in the absence of a solvent, or may be carried out in the presence of an organic solvent such as an aromatic solvent, a ketone solvent or an ester solvent, and a solvent such as a plasticizer. it can. The component (b-2) in the above description is not particularly limited to one type, and is a mixture of a uretdione dimer and a polyuretdione, or a mixture of other isocyanate components as necessary. Also good.
[0027]
  The polyurethane precursor composition used in the present invention comprises a compound component (a): (a-1 and / or a-2) containing an active hydrogen group in the molecule,blockPolyisocyanate compound component containing isocyanate group(B-1) and a compound component having a uretdione group(B-2) is reacted under an excess of active hydrogen groups with an equivalent ratio of uretdione groups to isocyanate groups exceeding 1.0, and the equivalent ratio of uretdione groups to active hydrogen groups is 0.25. Active hydrogen group excess composition in the range of -1.0, preferably 0.35-0.75. When this equivalent ratio is less than 0.25, the chain extension effect and the crosslinking density are insufficient, and the strength and washing resistance of the flame-retardant resin coating layer of the resulting mesh sheet may be insufficient. On the other hand, if the equivalent ratio exceeds 1.0, gelation may occur during storage of the polyurethane precursor composition. In particular, when the (b-2) compound is used in the polyurethane precursor composition, the catalyst for ring opening of the uretdione group is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the polyurethane precursor composition. In particular, the inclusion of 0.3 to 3.0 parts by mass is preferable from the viewpoint of a conversion reaction to a flame-retardant polyurethane resin by a thermosetting reaction. When the addition amount of the uretdione group ring-opening catalyst is less than 0.1 part by mass, the ring-opening reaction of the uretdione group is not sufficiently promoted and the strength and washing resistance of the flame-retardant resin coating layer of the mesh sheet are insufficient. May be. Moreover, even if the addition amount of the ring-opening catalyst exceeds 5.0 parts by mass, the ring-opening acceleration reaches a peak, and as a component remaining in the flame-retardant resin coating layer of the resulting mesh sheet, strength and washing resistance, etc. May have a negative effect. Specific examples of the ring-opening catalyst include 1,5-diazabicyclo (4,3,0) nonene-5 (DBN) and a fatty acid salt of DBN or a phenol salt of DBN. Fatty acids include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, and unsaturated acids such as acrylic acid, crotonic acid, isocrotonic acid, oleic acid, erucic acid, sorbic acid, and linoleic acid In addition to fatty acids, isoalkyl fatty acids and oxy fatty acids can be used without particular limitation. Examples of phenols include phenol, cresols, xylenols, naphthols, alkyl-substituted phenols (such as methyl, ethyl, butyl, and propyl), and these include DBN and fatty acids and / or phenols. Can be obtained by equivalent reaction.
[0028]
  In the polyurethane precursor composition used in the present invention, (i). Contains active hydrogen groups in the moleculePolyolCompound component (a): (a-1 and / or a-2) and in the moleculeblockPolyisocyanate compound component (b) containing an isocyanate group:(B-1)And / orCompound (b-2) having uretdione group((A) + (b)) is a liquid polyurethane precursor composition containing no organic solventAndThat is, both (a) and (b) are liquidOrOr either (a) or (b) is liquid, and the liquid viscosity of this composition is 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), 0.5 to 10 Pa.・ S (20 ° C./0.5 hours), especially 0.5 to 5 Pa · s (10 to 50 ° C./0.5 to 3 hours), 1 to 5 Pa · s (20 ° C./0.5 hours) It is preferable from the viewpoint of manufacturing the mesh sheet of the present invention. ii). If necessary, the mixture of (a) and (b) may contain an organic solvent and / or a plasticizer as a viscosity modifier, and the liquid viscosity of this composition is 0.1 to 10 Pa.・ S (10-50 ° C./0.5-3 hours) is preferable, 0.5-10 Pa · s (20 ° C./0.5 hours) is more preferable, and the mesh sheet of the present invention is particularly preferable. From the viewpoint of production, 0.5 to 5 Pa · s (10 to 50 ° C./0.5 to 3 hours) and 1 to 5 Pa · s (20 ° C./0.5 hours) are more preferable.
[0029]
In addition, in the polyurethane precursor composition used in the present invention, a carbodiimide compound, an oxazoline compound, if necessary, in order to further improve the durability of the flame retardant resin coating layer (wear strength, washing resistance, etc.) One or more kinds of crosslinking agents selected from an aziridine compound and a diamine compound can be blended, whereby the crosslinking density of the flame retardant resin coating layer of the resulting mesh sheet can be increased. Examples of the carbodiimide compound include compounds obtained by converting an organic diisocyanate compound into carbodiimide, such as dipyrpyrcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, di-p-toluoylcarbodiimide, triisopropylbenzene polycarbodiimide, and the like. In particular, polyfunctional compounds such as polycarbodiimide can be preferably used. As the aziridine compound, for example, diphenylmethane-bis-4,4′-N, N′-diethyleneurea, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] can be used. . The oxazoline compound is a compound derived from oxazole obtained by decarboxylation of oxazole-4-carboxylic acid as a raw material, such as 2-oxazoline, 4-methyl-2-oxazoline, 2,2 A polyfunctional oxazoline polymer obtained by grafting an oxazolyl group using a polymer such as' -bis (2-oxazoline), a styrene resin, or an acrylic resin as a trunk can be used. As the diamine compound, ethylenediamine, hexamethylenediamine, isophoronediamine, mensendiamine, 4,4'-diphenylmethanediamine, 4,4'-diaminodiphenylsulfone, metaxylenediamine, piperazine and the like can be used. These crosslinking agents are preferably contained in an amount of about 0.2 to 10 parts by weight, particularly about 0.5 to 5.0 parts by weight, based on 100 parts by weight of the polyurethane precursor composition. When the addition ratio of the crosslinking agent is less than 0.2 parts by weight, the effect of improving the durability (wear strength, washing resistance, etc.) of the resulting mesh sheet does not appear clearly, and when it exceeds 10 parts by weight, the resulting mesh sheet is obtained. In some cases, the flame retardant resin layer becomes too hard and may not conform to the penetration resistance test by dropping a steel pipe specified in JIS A8952.
[0030]
The polyurethane precursor composition used in the present invention contains at least one organic compound containing a nitrogen atom and / or a phosphorus atom as a flame retardant imparting agent (c), and is converted into a converted flame retardant resin coating layer. The flame retardant imparting agent is contained in an amount of 10 to 50% by mass, particularly 20 to 35% by mass. The organic compound (c-1) containing a nitrogen atom is at least one selected from (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivative compounds thereof. In addition, the organic compound (c-2) containing a phosphorus atom is at least one selected from red phosphorus, (metal) (organic) phosphate, phosphoric acid derivative, and ammonium polyphosphate. . If the content of the flame retardant imparting agent is less than 10% by mass, the flameproof performance of Article 4 of the Fire Service Act Regulations (JIS L1091A method) cannot be satisfied, and the content exceeds 50% by mass. In addition, the workability of the mesh sheet of the present invention may be deteriorated, and the durability of the flame retardant resin layer may be insufficient. The liquid viscosity of the polyurethane precursor composition containing the flame retardant imparting agent is 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), 0.5 to 10 Pa · s (20 ° C / 0.5 hours), particularly 0.5-5 Pa · s (10-50 ° C / 0.5-3 hours), 1-5 Pa · s (20 ° C / 0.5 hours). From the viewpoint of production of the mesh sheet of the present invention, the polyurethane precursor containing the flame retardant imparting agent as necessary can contain an organic solvent and / or a plasticizer as a viscosity modifier. The liquid viscosity in this case is 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), 0.5 to 10 Pa · s (20 ° C./0) in terms of the production of the mesh sheet of the present invention. 0.5 hours), and particularly preferably 0.5 to 5 Pa · s (10 to 50 ° C./0.5 to 3 hours) and 1 to 5 Pa · s (20 ° C./0.5 hours). The liquid temperature is particularly preferably in the range of 20 to 50 ° C., but particularly at 35 to 50 ° C., the polyurethane precursor has a low viscosity, which is suitable for producing a mesh sheet. Moreover, if it is excellent in the stability of liquid viscosity, it can also process in the high temperature range over 50 degreeC. Dilution solvents used for liquid viscosity adjustment include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, and cycloaliphatic solvents such as cyclopentane, cyclohexane, and methylcyclohexane. Hydrocarbon solvents, acetone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as diethyl ether, 1,4-dioxane and tetrahydrofuran, cellosolve solvents such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether, acetic acid Use organic solvents such as ester solvents such as ethyl and butyl acetate, aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone alone or in combination. It is possible to use. As the plasticizer, general-purpose plasticizers used for plasticizers of soft vinyl chloride resins, for example, phthalic acid esters such as dibutyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate , Fatty acid dibasic esters such as di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl sebacate, phosphate esters such as tricresyl phosphate, cresyl diphenyl phosphate, aromatic condensed phosphate esters And the like. When the liquid viscosity of the polyurethane precursor composition is greater than 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), particularly 10 Pa · s (20 ° C./0.5 hour), a flame retardancy imparting agent is added. The fluidity of the polyurethane precursor-impregnated coating liquid that is blended and contained may deteriorate, making it difficult to produce the mesh sheet of the present invention. Further, when the liquid viscosity of the polyurethane precursor composition is less than 0.1 Pa · s (10 to 50 ° C./0.5 to 3 hours), the polyurethane precursor composition containing the flame retardant imparting agent is contained. In some cases, the absorption to the coarse woven or knitted fabric may be uneven and the flame retardant imparting agent may be separated, making it difficult to produce the mesh sheet of the present invention.
[0031]
As the nitrogen atom-containing compound (c-1), i). Cyanurate derivatives such as trimethyl cyanurate and triethyl cyanurate, and composites of these (iso) cyanurate derivatives and melamine compounds (for example, melamine cyanurate), (iso) cyanurate derivatives such as trimethyl isocyanurate and triethyl isocyanurate, ii). Melamine (cyanuric acid amide), guanamine, benzoguanamine, melamine sulfate, trimethylolmelamine, cyanuric acid trimethyl ester, cyanuric acid triethyl ester, cyanuric acid monoamide, cyanuric acid diamide, and 1,3,5-triazine, 2,4,6 -Cyanuric acid derivatives such as trioxy-1,3,5-triazine, isocyanuric acid monoimide, isocyanuric acid diimide, isocyanuric acid triimide, calcium cyanamide (lime nitrogen), trimethyl dicyanamide, triethyl dicyanamide, tricarbimide, and Isocyanuric acid derivatives such as dicyanamide trimer (melon), iii). And guanidine derivatives such as dicyandiamide, dicyandiamidicin, guanidine, guanidine sulfamate, guanidine phosphate, guanidine sulfate, and diguanide, iv). In addition, urea compounds such as urea, thiourea, dimethylolurea, diacetylurea, ethyleneurea, trimethylurea, N-benzoylurea, and guanylurea phosphate, and composites of these nitrogen-containing compounds are included. v). Also, complex salts of these nitrogen-containing compound (c-1) and phosphorus-containing compound (c-2), for example, (poly) phosphoric acid and melamine compound complex salt, (poly) phosphoric acid and melamine compound 2 Complex salt with ˜trimer, complex salt of phosphonic acid and melamine compound, complex salt of phosphonic acid and melamine compound 2-3 trimer, complex salt of phosphinic acid and melamine, phosphinic acid and melamine compound And a complex salt of sulfamic acid and a melamine compound. As other nitrogen-containing compounds, heterocyclic compounds such as pyrroles, indoles, oxazoles, oxazines, thiazines and pyridazines can be used. Among the above nitrogen atom-containing compounds, (iso) cyanuric acid derivatives, composites of (iso) cyanurate derivatives and melamine compounds (for example, melamine cyanurate) and the like are preferable, and these nitrogen atom-containing compounds are particularly phosphate esters. It is preferable from the viewpoints of flameproofing effect and durability to be used in combination with benzene, aromatic condensed phosphates, ammonium polyphosphate, ammonium polyphosphate derivatives and the like.
[0032]
Of the phosphorus atom-containing compound (c-2), i). Red phosphorus is powdery red phosphorus having an average particle diameter of 5 to 25 μm, which is obtained by converting yellow phosphorus into red phosphorus by heating at 250 to 350 ° C. in an inert gas atmosphere. In particular, red phosphorus includes powdered red phosphorus having an average particle diameter of 5 to 25 μm and surface-stabilized with a nitrogen-containing resin such as melamine resin, urea resin, and triazine resin, and titanium oxide, zinc oxide, and water. It is preferable to use powdered red phosphorus having an average particle diameter of 5 to 25 μm and surface-whitened with an inorganic metal compound such as aluminum oxide. ii). Examples of the metal phosphate include metal salts such as phosphoric acid, phosphorous acid, and hypophosphorous acid. Examples of the metal forming the salt include Na, K, Li, Ca, Ba, Mg, Al, and Zn. Yes, specifically, calcium dihydrogen phosphate (lime phosphate), calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, phosphorous Examples include monopotassium acid, dipotassium phosphite, and potassium hypophosphite. iii). Examples of metal organic phosphates include PO (OR) (OH), such as octyl potassium phosphate and hexyl calcium phosphate.₂ In addition, a metal salt of a monoalkyl phosphate represented by PO (OR) such as dibutyl potassium phosphate and dihexyl calcium phosphate₂ Metal salts of dialkyl phosphates represented by OH, dioctyl potassium phosphite, butyl calcium phosphite, etc., P (OR) (OH)₂ A metal salt of a monoalkyl phosphite represented by the following formula: P (OR) such as potassium dododecyl phosphite and dibutyl calcium phosphite₂ Examples thereof include metal salts of dialkyl phosphite represented by OH, and the metal that forms a salt with them is Na, K, Li, Ca, Ba, Mg, Al, Zn or the like. (* R represents an alkyl group)
[0033]
iv). Examples of phosphoric acid derivatives include a). Phosphate esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, and aromatic condensed phosphate esters, b). Examples of phosphonic acid compounds include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, butylphosphonic acid, dimethyl phosphonate, vinylphosphonic acid diphenyl ester, methylphosphonic acid monovinyl ester, and phenylphosphonic acid monovinyl ester. And phosphonic acid esters such as vinylphosphonic acid, allylphosphonic acid, butenylphosphonic acid, vinylphenylphosphonic acid, 2-acryloyloxyethylphosphonic acid, 2-methacryloyloxyethylphosphone Examples thereof include phosphonic acid derivatives such as acid and bis (2-methacryloxyethyl) phosphonic acid, and cyclic phosphonic acid esters represented by the following formulas (1) and (2) are particularly preferable. Arbitrariness. C). In addition, phosphinic acids such as dimethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, phenylphosphinic acid, and phosphonates of nitrogen-containing compounds (melamine, melamine dimer, melamine trimer, etc.), or Examples include phosphinates.
[0034]
[Chemical 1]

[0035]
v). As ammonium polyphosphate, (NH_Four PO_Three )_n And those having a polymerization degree n of 30 to 1200 are preferred. In addition, it is preferable to use ammonium polyphosphate that has been surface coated with water resistance by at least one selected from nitrogen-containing resins such as melamine resin, urea resin, and triazine resin. vi). The ammonium polyphosphate derivative compound is a condensed phosphate compound that is a condensate of ammonium phosphate and a nitrogen-containing compound such as melamine, urea, or triazine. These include, for example, melamine-modified ammonium polyphosphate, melamine polyphosphate Melamine phosphate and the like can be preferably used. Among the phosphorus atom-containing compounds, phosphate esters, aromatic condensed phosphate esters, ammonium polyphosphate, ammonium polyphosphate derivatives, and the like are particularly preferable. Further, these phosphorus atom-containing compounds are nitrogen atom-containing compounds and Use in combination is preferable from the viewpoint of the flameproofing effect and durability.
[0036]
The flame retardant resin layer used in the present invention may have a particle size of 0.1 to 20 μm, particularly 0.5 to 10 μm, i). Silica, synthetic amorphous silica (silicon dioxide), silicon compounds such as aluminum silicate, magnesium silicate, calcium silicate, diatomaceous earth, ii). Metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, zinc hydroxystannate, tin oxide hydrate, borax, etc., iii). Metal oxides such as aluminum oxide, magnesium oxide, barium oxide, titanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, antimony oxide, zirconium-antimony composite oxide, iv). Metal carbonate compounds such as zinc carbonate, calcium carbonate, barium carbonate, magnesium carbonate, magnesium carbonate-calcium, v). Metal sulfate compounds such as aluminum sulfate and barium sulfate, vi). Boric compounds such as zinc borate, zinc metaborate, barium metaborate, aluminum borate, vii). An appropriate amount of an inorganic compound such as an inorganic compound complex such as alumina hydrate, zeolite, sepiolite, hydrotalcite, hydroxyapatite, or diatomaceous earth can also be used in combination.
[0037]
The flame retardant resin layer of the mesh sheet of the present invention can be arbitrarily colored using an inorganic pigment and an organic pigment. For example, inorganic pigments include zinc oxide (zinc white), titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide (iron black, red rose), yellow iron oxide, iron ferrocyanide (bitumen), spinel structure Organic pigments such as oxides, metal powders such as aluminum powder, bronze powder, nickel powder and stainless steel and pearl pigments, insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments, Phthalocyanine pigment, acid dye lake pigment, basic dye lake pigment, anthraquinone pigment, thioindigo pigment, perinone pigment, perylene pigment, quinacridone pigment, dioxazine pigment, isoindolinone pigment, quinophthalone pigment, isoindoline Pigment, alizarin lake pigment, metal complex azomethine face , It includes known pigments such as aniline pigments. In addition, it is preferable to add an appropriate amount of an ultraviolet absorber, an antioxidant, a light stabilizer and the like to the flame retardant resin layer of the present invention for the purpose of improving outdoor durability. UV absorbers such as benzophenone compounds, benzotriazole compounds, salicylic acid compounds and anilide compounds can be used as UV absorbers, and hindered phenol compounds, amine compounds, and phosphite compounds as antioxidants. Antioxidants can be used. As the light stabilizer, a light stabilizer of a hindered amine compound can be used.
[0038]
The coarse woven fabric used in the mesh sheet of the present invention is a woven fabric or a knitted fabric having a gap between yarns formed by crossing fiber yarns (a void area of 5 to 65% with respect to the area of the coarse woven fabric). To be elected. Although there is no limitation on the woven structure of the woven fabric, it is excellent in the balance of physical properties of the mesh sheet obtained when it is a plain woven fabric, imitation fabric, twill fabric, satin fabric, etc. As the knitted fabric, Russell knitted weft insertion tricot is preferable. The yarn forming the coarse woven or knitted fabric may be any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber, or a mixed fiber composed of two or more of these, but polypropylene fiber is considered in consideration of processability and versatility. It is preferable to use synthetic fibers such as polyethylene fiber, polyvinyl alcohol fiber, polyester fiber, and polyamide (nylon) fiber. In addition, as the form of the yarn, any yarn such as multifilament yarn, monofilament yarn, short fiber spinning (spun) yarn, split yarn yarn, tape yarn yarn, etc. may be used. Coarse woven knitted fabric with multifilament yarn, monofilament yarn woven fabric, or short fiber spinning (spun) formed from polyester fiber, polyamide fiber, and mixed and mixed fibers that have excellent tensile strength and tear strength ) A coarse woven or knitted fabric with yarn is preferred.
[0039]
The yarn raw material of the coarse woven fabric used in the present invention includes, in particular, polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol, and polybutylene terephthalate obtained by polycondensation of terephthalic acid and butylene glycol ( Polyester fibers such as PBT are preferred, and polyester fibers (multifilament yarns) spun from PET resin are particularly preferred because of their excellent spinnability and mechanical strength. In addition to the above-mentioned monomers, the PET resin spinning raw material containing about 5% by weight of a copolymerization monomer such as isophthalic acid, naphthalene dicarboxylic acid, adipic acid, diethylene glycol and the like can be used. In particular, if necessary, for example, poly-p-phenylene terephthalamide (PPTA) fiber yarns are arranged at equal intervals between PET fiber yarns, and the woven structure is a repeating unit of {PPTA-PET-PET-PET}. It is also possible to use a special woven fabric that emphasizes the tensile strength and tear strength of the woven structure. These coarse-textured knitted fabrics can be woven using a conventionally known loom such as a shuttle loom, a shuttleless loom (rapier method, gripper method, water jet method, air jet method). Further, the fiber yarn used for weaving can be an original fiber obtained by adding a colorant such as an organic pigment, an inorganic pigment, or a dye during the spinning process, and is particularly suitable for a monofilament yarn. . Alternatively, the fiber yarn or the coarse woven or knitted fabric may be colored by a subsequent treatment with an organic pigment, an inorganic pigment, a dye or the like, and a resin binder containing them. Furthermore, these coarse-textured knitted fabrics include, for example, known fibers such as a scouring treatment, a bleaching treatment, a softening treatment, a paste treatment, a water repellency treatment, a waterproof treatment, an antifungal treatment, a flameproof treatment, a calendar treatment, and a binder resin treatment Processing can be used in combination.
[0040]
A yarn having a fineness of 277 to 3333 dtex can be used for the multifilament yarn or monofilament yarn constituting the coarse woven or knitted fabric used in the present invention. These yarns may be used alone, or 2-5, preferably 2-3, are twisted to form one yarn, or 2-5, preferably 2-3. It can be used in such a manner that a single thread is formed by arranging books in parallel. In the case of class 2 architectural curing mesh sheet, for example, a plain weaving fabric in which 277-dtex multifilament yarns are punched 24 to 26 warps per inch and 25-28 wefts per inch, 556 dtex multifilament yarns per inch A plain woven fabric in which 18 to 20 warps and 18 to 20 wefts are driven, and in the case of a class 1 architectural curing mesh sheet, for example, a yarn obtained by twisting three 833 dtex multifilament yarns per inch Plain weave fabric with 10-12 warp yarns, 10-12 weft yarns driven in, 3-1111 dtex multifilament yarns twisted, 6-8 warp yarns per inch, 6-8 weft yarns A plain woven fabric in which 12 to 14 warp yarns and 12 to 14 weft yarns are printed per inch, 2122 dtex multifilament yarn, 1666 dtex 15 to 17 warp yarns per inch, 15 to 17 warp yarns weaved, 15 to 17 weft yarns, 4 to 5 warp yarns per inch, twisted together with two 3333 dtex multifilament yarns A plain woven fabric or the like in which 4 to 5 pieces are driven can be particularly preferably used. In particular, in a class 1 mesh sheet that requires a penetration resistance test by dropping a steel pipe as defined in JIS A8952, there may be cases where the fineness of the weft constituting yarn is less than 1111 dtex. Further, the number of warp and weft threads of coarse knitted fabric (biaxial woven fabric) is a class 2 mesh sheet, for example, 16 to 30 multifilament yarns of 277 to 556 dtex or monofilament yarns per inch, preferably 18 to 26, 1 class mesh sheet, for example, 1666 to 3333 dtex multifilament yarns, or monofilament yarns 6 to 20 yarns per inch, preferably 7 to 16 yarns. The coarse woven fabric used in the mesh sheet of the present invention is preferably a coarse biaxial woven fabric having a warp / weft structure. The coarse knitted fabric used in the present invention can be used in combination with short fiber spun yarns of 197 dtex (30th) to 591 dtex (10th).
[0041]
Moreover, the coarse-textured knitted fabric used for the mesh sheet of this invention can also use a triaxial fabric and a 4-axis fabric. The triaxial woven fabric is a woven fabric composed of the above-mentioned multifilament yarn or monofilament yarn in three directions, and woven so that the crossing angle between the yarns is 60 °. As the triaxial woven fabric, a woven fabric including warp yarns and entangled with two-direction bias (oblique) yarns is preferable because of excellent stability of the woven structure in the processing direction. The structure of this triaxial woven fabric can also be a basket weave by applying two twills. On the other hand, the four-axis woven fabric is composed of the above-described multifilament yarns or four-direction yarns of monofilament yarns, and includes warp yarns and weft yarns orthogonal to each other, and further intersects the warp yarns and the weft yarns at an angle of 45 °. It is a woven fabric (knitted fabric) woven using a twin yarn comprising monofilaments of about 55 to 166 dtex as necessary, including a bi-directional bias yarn. In particular, by using a triaxial woven fabric or a four-axial woven fabric in the present invention, the mesh sheet can be provided with a stable resistance against external forces from multiple directions, and can be used more safely as a construction sheet covering sheet. A high mesh sheet can be obtained. There is no particular limitation on the number of warps, wefts, and bias yarns of the coarse knitted knitted fabric by these triaxial woven fabrics and 4-axial woven fabrics, but 277 to 3333 dtex multifilament yarns or monofilament yarns in each direction per inch. A woven fabric obtained by implanting 4 to 30, preferably 7 to 24 can be used.
[0042]
The total void area ratio of the coarse woven or knitted fabric used in the present invention is preferably 5 to 65%, particularly preferably 10 to 40%. The void area is a void (coarse) formed by the intersection of the fiber yarns, and the void area ratio is a value relative to the area of the woven or knitted fabric. When the void area ratio is less than 5%, the resulting mesh sheet has insufficient transparency and air permeability, and when the void area ratio exceeds 65%, the content density of the fiber yarn becomes small, and The tear strength of the resulting mesh sheet becomes insufficient, and at the same time, it may become incompatible with the penetration resistance test due to the steel pipe dropping specified in JIS A8952. The void area ratio can be obtained as a value obtained by subtracting the area occupied by the fiber yarn as a percentage with respect to the unit area of the coarse woven fabric. The void area ratio can be obtained as a unit area of 10 cm in the warp direction and 10 cm in the weft direction. If necessary, the area can be calculated from the enlarged print image using a commercially available copying machine, or the copy image can be cut out as a thread. It may be classified into a portion and a void portion, and based on these mass ratios, this may be regarded as the same as the void area ratio and applied.
[0043]
In the mesh sheet of the present invention, particularly for coarse woven fabrics, 1). From the viewpoint of flame resistance, it is preferable that the phosphonic acid-based compound is subjected to a pretreatment, whereby the total amount of the flame retardant imparting agent blended in the flame retardant resin layer of the mesh sheet can be reduced. Examples of phosphonic acid compounds include phosphonic acid esters such as vinylphosphonic acid dimethyl ester, vinylphosphonic acid diphenyl ester, methylphosphonic acid monovinyl ester, and phenylphosphonic acid monovinyl ester, and cyclic phosphonic acid esters, and also, for example, vinylphosphonic acid. Phosphonic acid derivatives such as acid, allylphosphonic acid, butenylphosphonic acid, vinylphenylphosphonic acid, 2-acryloyloxyethylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, bis (2-methacryloxyethyl) phosphonic acid Among them, cyclic phosphonic acid esters are particularly preferable. As a particularly preferred cyclic phosphonic acid ester, at least one of the compounds represented by the chemical formulas (1) and (2) is used.
[0044]
The pretreatment of the coarse woven fabric with the phosphonic acid compound is carried out in the above roughening agent bath comprising a solution containing the phosphonic acid compound at a concentration of 0.5 to 10% by mass, preferably 1.0 to 5% by mass. Immerse the woven or knitted fabric, infiltrate the phosphonic acid compound between the fibers of the fiber yarn constituting the coarse knitted fabric, pull it up, and simultaneously squeeze the coarse woven fabric with a rubber mangle roll to remove excess treatment agent. Then, it is dried in a hot air oven and further subjected to a heat treatment at 130 to 210 ° C. to adsorb and fix the phosphonic acid compound in the fiber microstructure. In the present invention, the coarse woven fabric is preferably a polyester filament woven fabric and a polyester short fiber spun woven fabric, which are pretreated with a phosphonic acid compound under a heat condition of 190 to 200 ° C. and fixed to the fiber.
[0045]
2). In addition, a binder resin can be mixed with the pretreatment agent described in 1), for example, vinyl acetate component, (meth) acrylic acid (ester) component, (anhydrous) maleic acid, (anhydrous) fumaric acid, ( Anhydrous) Ethylene copolymer resins containing polar components such as itaconic acid, and phosphonic acid solutions in thermoplastic resin solutions such as acrylic copolymer resins, ionomer resins, styrene copolymer resins, polyurethane resins By using a compound containing a compound, a phosphonic acid compound can be fixed on the fiber surface. This binder may be any of a binder resin-containing liquid solubilized or dispersed in an organic solvent, or an emulsion-dispersed liquid in water. The solid content concentration of the binder resin is 1 to 30% by mass, particularly 3 to 15% by mass is preferable from the viewpoint of the pretreatment work. At this time, the phosphonic acid compound used in combination can be used at a concentration of 1 to 10% by mass relative to the binder resin-containing liquid. For the pretreatment (coating, impregnation, coating) involving this binder, known processing methods such as dipping method, dip coating method, doctor knife coating method, gravure coating method, rotary screen coating method, spray coating method, etc. It can be carried out by impregnating and / or applying the treatment agent at least once, and drying is preferably performed by natural drying or by hot air drying at 30 to 120 ° C., particularly 60 to 100 ° C. The adhesion amount of the binder containing the phosphonic acid compound is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, based on the mass of the coarse woven or knitted fabric. If the adhesion amount is less than 1%, the resulting mesh sheet may have insufficient flameproofing properties. If the adhesion amount exceeds 30%, the flameproofing properties may be reversed and worsened. Further, the above-mentioned 2) pretreatment liquid may further contain an appropriate amount of the same flame retardant imparting agent used for the flame retardant resin layer, and these include a). Phosphorus atom-containing compounds such as red phosphorus, metal phosphates, metal organic phosphates, phosphate derivatives, ammonium polyphosphate, and ammonium polyphosphate derivative compounds, b). Nitrogen-containing compounds such as (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivatives thereof, c). One or more selected from inorganic compounds such as silicon compounds, metal hydroxides, metal oxides, metal carbonate compounds, metal sulfate compounds, boric acid compounds, and inorganic compound complexes.
[0046]
Production of the mesh sheet of the present invention is 1). A coarse-textured knitted fabric or a coarse-textured knitted fabric that has been pretreated with a phosphonic acid compound has a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), 0.5 to 10 Pa · s (20 ° C./0.5 hours), particularly preferably 0.5 to 5 Pa · s (20 to 50 ° C./0.5 to 3 hours), and 1 to 5 Pa · s (20 ° C./0.00 hours). 5 hours), dipping in a flame retardant imparting agent-containing polyurethane precursor composition liquid bath, and attaching the polyurethane precursor composition to at least the entire exposed outer periphery of the fiber yarn constituting the coarse woven fabric, At the same time, the coarse knitted fabric is squeezed with a rubber mangle roll and impregnated into the fiber yarn with the polyurethane precursor composition, and then at 100 ° C. or higher for 5 to 30 minutes, preferably 150 to 230 ° C. Heat treatment in a hot stove for 10 minutes The polyurethane precursor composition is converted into a flame retardant polyurethane resin (with respect to the flame retardant resin coating layer by the curing reaction between an isocyanate group that is regenerated by dissociating the blocking agent of the cyanate compound and the active hydrogen group. It can be obtained by a production method in which the flame retarder is contained in a flame retardant resin coating layer.
[0047]
2). In addition, the production of the mesh sheet of the present invention can be carried out by applying a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./10° C. 0.5 to 3 hours), 0.5 to 10 Pa · s (20 ° C./0.5 hours), particularly preferably 0.5 to 5 Pa · s (10 to 50 ° C./0.5 to 3 hours), 1 A flame retardant imparting agent-containing polyurethane precursor composition liquid composition of ˜5 Pa · s (20 ° C./0.5 hour) is applied to a knife coat, gravure transfer coat, rotary screen coat, clearance coat, spray coat, etc. After the polyurethane precursor composition is impregnated and adhered to at least the entire exposed outer peripheral surface of the fiber yarn constituting the coarse woven or knitted fabric, it is applied to the front and back surfaces by a construction method, and then at 100 ° C. or higher for 5 to 30 minutes, preferably 150 to 1-1 at 230 ° C The polyurethane precursor composition is made into a flame-retardant polyurethane resin by the curing reaction between an isocyanate group that is regenerated by dissociating and regenerating the blocking agent of the blocked isocyanate compound by performing a heat treatment in a hot air oven for 5 minutes. The flame retardant resin coating layer can be obtained by a manufacturing method in which the flame retardant imparting agent is converted to 10 to 50% by mass and this is used as the flame retardant resin coating layer.
[0048]
3). The production of the mesh sheet according to the present invention includes, in the production methods of the above 1) and 2), if necessary, the polyurethane precursor composition contains a diluent solvent and / or a plasticizer as a viscosity modifier, and the liquid viscosity is 0. 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours), 0.5 to 10 Pa · s (20 ° C./0.5 hour), particularly preferably 0.5 to 5 Pa · s (10 to 10 ° C.) 50 ° C./0.5 to 3 hours) and 1 to 5 pa · s (20 ° C./0.5 hours), and can also be produced using a flame retardant imparting agent-containing polyurethane precursor composition liquid. .
[0049]
In the production method according to the above 1 to 3), the liquid viscosity requirement of the flame retardant imparting agent-containing polyurethane precursor composition liquid, 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours) , 0.5 to 10 Pa · s (20 ° C./0.5 hour) means that the viscosity of the polyurethane precursor composition liquid containing the flame retardant imparting agent is within a temperature range of 10 to 50 ° C. is 0.1. 10 Pa · s, meaning that the liquid viscosity can be maintained for 0.5 to 3 hours. The viscosity can be measured using a Brookfield rotary viscometer (BL, BM, BH) used for measuring the viscosity of the vinyl chloride paste sol. In particular, the viscosity of the polyurethane precursor composition liquid containing the flame retardant imparting agent is determined by a numerical value after 60 seconds (× 500 cP) at 12 rpm using a BM type viscometer equipped with a No. 4 rotor. Or by using a BH viscometer equipped with a No. 6 rotor, a numerical value after 60 seconds at a rotation speed of 4 rpm (× 2500 cP). At this time, the relationship between cP and Pa · s is 1 Pa · s = 1000 cP. When the liquid viscosity of the polyurethane precursor composition is greater than 10 Pa · s (10 to 50 ° C./0.5 to 3 hours) and 10 Pa · s (20 ° C./0.5 hour), a flame retardancy imparting agent is contained. The fluidity of the polyurethane precursor composition to be deteriorated may make it difficult to produce the mesh sheet of the present invention. Further, when the liquid viscosity of the polyurethane precursor composition is less than 0.1 Pa · s (10 to 50 ° C./0.5 to 3 hours), the polyurethane precursor composition containing the flame retardant imparting agent is contained. In some cases, the absorption to the coarse woven or knitted fabric may be uneven and the flame retardant imparting agent may be separated, making it difficult to produce the mesh sheet of the present invention. The reason why the liquid viscosity of 50 ° C. is necessary is that the polyurethane precursor composition exceeding 5 Pa · s at room temperature is reduced in viscosity by heating up to 50 ° C., or the polyurethane precursor composition in a solid state at room temperature. It is because it is included in the manufacturable range of the mesh sheet of the present invention by liquefying. At this time, the polyurethane precursor composition once reduced in viscosity by heating with an upper limit of 50 ° C. increases the viscosity in a short time, or if it causes gelation, it becomes impossible to produce the mesh sheet of the present invention. The pot life in the processable range was set to 3 hours starting from 0.5 hours after the preparation of the polyurethane precursor composition. Moreover, when the heating of a polyurethane precursor composition exceeds 50 degreeC, the pot life of the liquid viscosity of the processable range may become short, and it may cause trouble in manufacture of the mesh sheet of this invention.
[0050]
Moreover, when manufacturing the mesh sheet of this invention normally, in order to clarify more the liquid viscosity of the polyurethane precursor composition to be used, the viscosity of 20 degreeC / 0.5 hour conditions was written together. Further, the heat treatment and curing conditions of the polyurethane precursor composition (at 100 ° C. or higher for 5 to 30 minutes, preferably 150 to 230 ° C. for 1 to 10 minutes) are the blocking agent dissociation temperature of the polyurethane precursor composition to be used, and the production It is a condition that can be arbitrarily set according to the heat capacity and furnace length of a hot stove attached to a processing machine such as a dipping machine or a coating machine used in the above. Moreover, the ratio of the flame-retardant resin coating layer to the mass of the mesh sheet obtained by the said manufacturing method is 10-60 mass%, Preferably it is 25-50 mass%. If the ratio of the flame retardant resin coating layer is less than 10% by mass, the resulting mesh sheet has insufficient washing resistance and flame resistance. Moreover, it becomes difficult to produce a mesh sheet in which the ratio of the flame-retardant resin coating layer exceeds 60% by mass while maintaining the void area ratio of 5 to 65%. As for the obtained mesh sheet, for example, 1 piece is 1.8 m wide x 3.4 m long, 1.8 m wide x 3.6 m long, 1.8 m wide x 5.1 m long, 1.8 m wide x 5.4 m long, Sewn in a standard such as 3.6m width x 5.4m length, and each edge is reinforced by folding back to prevent fraying, and if necessary, the edge has a sewing rope for connection, or in particular A slit support such as a urethane resin-coated sheet can be inserted and sewn into the folded portion, and the fixing strength of the eyelets provided at regular intervals over the entire edge portion can be used. The edge can be sewn by sewing or high-frequency welder sewing.
[0051]
【Example】
Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to the range of these examples. Test methods applied to the evaluation of mesh sheets obtained in the following examples and comparative examples are as follows.
(I). Viscosity measurement
Using a BM-type rotational viscometer equipped with a No. 4 rotor (manufactured by Tokimec Co., Ltd.), a polyurethane precursor composition (after a liquid temperature of 20 and 50 ° C., after 0.5 hours and after 3.0 hours, respectively) The viscosity of was determined by a numerical value after 60 seconds at a rotational speed of 12 rpm (× 500 cP). (Determined by a numerical value (× 2500 cP) after 60 seconds at a rotation speed of 4 rpm using a BH type rotational viscometer equipped with a No. 6 rotor as required (made by Tokimec Co., Ltd.)). And Pa · s is 1 Pa · s = 1000 cP.
[0052]
(II). Flameproof
The test was conducted according to JIS L-1091 and evaluated according to the following criteria. (Mass 450g / m² The following is Category 3 of Method A-1, mass 450 g / m² For those exceeding 1, Category 3 of the A-2 method was applied. )
○: Carbonization area 40cm² Hereinafter, the afterflame time is 5 seconds or less, the residual dust time is 20 seconds or less, and the carbonization distance is 20 cm or less.
X: One or more items of the carbonization area, the after flame time, the residual time, and the carbonization distance exceed the standard numerical values.
[0053]
(III). Penetration resistance test [Certified Industrial Association Certification Criteria]
Targeting the center part of the mesh sheet fixed to the 30 ° tilt test frame specified in JIS A8952, a steel pipe drop body (compliance with JIS A8952 standard) with a mass of 3m to 5kg is allowed to fall freely to prevent penetration of the mesh sheet. And the state of breakage (breakage) were observed.
○: No penetration of the steel pipe drop.
Δ: There is no penetration of the steel pipe drop, but the mesh sheet is severely cracked.
X: The steel pipe falling body breaks the mesh sheet and penetrates completely.
(IV). Wash resistance
Using an industrial rotary washing machine with a capacity of 450 L, the washing resistance of an unused mesh sheet sewing product (1.8 m width × 3.6 m length: lengthwise 8 folds × widthwise 4 folds) was evaluated. . Laundry is a mildly alkaline industrial detergent (Trademark: Genbunais: [Components] Sodium linear alkylbenzene sulfonate as surfactant, sulfate as process agent, silicate as alkali agent, carbonate, alumino as water conversion agent Use silicate and fluorescent whitening agent: Genbu Co., Ltd. (500 g) and sodium metasilicate 9 hydrate (Sanpo Chemical Industry Co., Ltd.) 100 g as an alkaline agent dissolved in 40 liters of warm water 300 L. The appearance immediately after washing for 30 minutes was observed.
○: No appearance abnormality such as dropping or swelling of the resin coating layer.
Δ: Swelling of the resin coating layer is observed.
X: The resin coating layer is swollen and partially dropped.
[0054]
(V). Flameproof after washing
The same flameproof test as in the above (II) was carried out by rinsing the mesh sheet tested in (IV) with industrial water for 5 minutes and drying it at room temperature for 24 hours.
(VI). Penetration resistance after washing
The mesh sheet tested in (IV) above was rinsed with industrial water for 5 minutes and dried at room temperature for 24 hours, and the same flameproof test as in the above (III) penetration resistance test was performed. .
[0055]
[Example 1]
i). Polyurethane precursor composition (1)
An active hydrogen group / isocyanate equivalent ratio of a uretdione group-containing HMDI (1,6-hexamethylene diisocyanate) derivative and a polytetramethylene ether polyol having a number average molecular weight of 500 and an average functional group number of 2.0 as an active hydrogen group-containing compound. 1.3, and 100 parts by mass of the polyurethane precursor having an uretdione group / active hydrogen group equivalent ratio in the polyurethane precursor of 0.72, 1,5-diazabicyclo (4 , 3, 0) 0.5 parts by weight of nonene-5 (DBN) and a composite additive of an antioxidant and a weathering stabilizer, trademark: Tinuvin B-75 (Ciba Spatialty Chemicals Co., Ltd.) 0 parts by weight, 4.0 parts by weight of a rutile titanium oxide pigment as a colorant, 0.8 parts by weight of a carbon black pigment, and flame retardant 30 parts by mass of melamine cyanurate (trademark: MC-610: average particle size 1 to 5 μm: Nissan Chemical Co., Ltd.) as an agent (nitrogen atom-containing compound (b-1)), flame retardant imparting agent (phosphorus atom-containing compound) b-2-1) is a basic composition comprising 10 parts by mass of a phosphonic acid compound (trademark: K-19A, a mixture of phosphonic acid compounds of the above chemical formula (1) or (2): Meisei Kasei Co., Ltd.). This was uniformly stirred with a blender to obtain a gray polyurethane precursor composition (1). The polyurethane precursor composition (1) has a liquid viscosity (measured by a BM type rotational viscometer) of 3.6 Pa · s (20 ° C./0.5 hours), 3.9 Pa · s (20 ° C./3. 0 Pa), 1.2 Pa · s (50 ° C./0.5 hr), and 1.8 Pa · s (50 ° C./3.0 hr).
[0056]
ii ). Mesh sheet manufacturing
Next, in a bath filled with a polyurethane precursor composition (1) at a liquid temperature of 50 ° C., a polyester coarse patterned fabric base fabric (1111 dtex / 3 multifilament yarn: warp driving density) subjected to the following pretreatment: 7 pieces / 2.54 cm × weft driving density 7 pieces / 2.54 cm: mass 185 g / m² : 34% porosity) is dipped (dipped), and the coarsely patterned fabric base fabric to which the polyurethane precursor composition (1) is attached is pulled up and simultaneously niped (pressed) with a mangle roll to obtain a polyurethane precursor composition. After impregnating and attaching (1) to the entire surface of the coarse patterned fabric base fabric, heat treatment was performed for 6 minutes in a hot air drying oven at 200 ° C., thickness 0.74 mm, mass 410 g / m.² A mesh sheet was obtained.
(Preparation of polyester coarse fabric base fabric)
Trademark: K-19A, phosphonic acid of formula (1) and (2)
Compound mixture: 5 parts by mass of Meisei Kasei Co., Ltd.
Diluent: 95 parts by weight of water
After dipping and pulling up the polyester coarse woven fabric base fabric in the above-mentioned pre-treatment agent bath, the excess pre-treatment agent is squeezed out with a nip roll of high hardness rubber and dried in a hot air drying oven at 120 ° C. for 1 minute. Then, heat treatment was performed in a hot air drying oven at 200 ° C. for 1 minute to fix the phosphonic acid compound to the fiber. (The fixing amount of the phosphonic acid compound to the base fabric is 2.5 g / m² Met. )
[0057]
[Example 2]
i). Polyurethane precursor composition (2)
The active hydrogen group-containing compound (polytetramethylene ether polyol) of the polyurethane precursor of Example 1 was changed to polybutylene adipate having a number average molecular weight of 2000 and an average functional group number of 2.0, and an active hydrogen group / isocyanate equivalent ratio of 1. 2 and 100 parts by mass of a polyurethane precursor having an uretdione group / active hydrogen group equivalent ratio of 0.59 in the polyurethane precursor was obtained. Other than this, a gray polyurethane precursor composition (2) was obtained in the same formulation as in Example 1. The polyurethane precursor composition (2) has a liquid viscosity (measured with a BM rotational viscometer) of 3.8 Pa · s (20 ° C./0.5 hours), 4.1 Pa · s (20 ° C./3. 0 Pa), 1.4 Pa · s (50 ° C./0.5 hr), 2.0 Pa · s (50 ° C./3.0 hr).
ii ). Mesh sheet manufacturing
Next, in a bath filled with a polyurethane precursor composition (2) having a liquid temperature of 50 ° C., a polyester coarse triaxial fabric base fabric (1111 dtex / 2 pieces of the same phosphonic acid compound pretreatment as in Example 1) was performed. Multifilament yarn: Warp yarn driving density 13 / 2.54 cm × Bias yarn driving density 13 / 2.54 cm: Mass 225 g / m² <Fixed amount of phosphonic acid compound 2.5 g / m² >: Porosity 22%) is dipped (immersed), and the coarse triaxial fabric base fabric to which the polyurethane precursor composition (2) is attached is pulled up and simultaneously niped (pressed) with a mangle roll to obtain a polyurethane precursor composition. The product (2) was impregnated and adhered to the entire surface of the coarse triaxial woven fabric, and then heat treated for 6 minutes in a hot air drying oven at 200 ° C., thickness 0.74 mm, mass 428 g / m.² A mesh sheet was obtained.
[0058]
[Example 3]
i). Polyurethane precursor composition (3)
The active hydrogen group-containing compound (polytetramethylene ether polyol) of the polyurethane precursor of Example 1 was changed to a polypropylene ether polyol having a number average molecular weight of 1000 and an average functional group number of 2.0, and an active hydrogen group / isocyanate equivalent ratio of 1. 4 and 100 parts by mass of a polyurethane precursor having an uretdione group / active hydrogen group equivalent ratio of 0.49 in the polyurethane precursor was obtained. Other than this, a gray polyurethane precursor composition (3) was obtained in the same formulation as in Example 1. The polyurethane precursor composition (3) has a liquid viscosity (measured by a BM type rotational viscometer) of 3.5 Pa · s (20 ° C./0.5 hours), 3.8 Pa · s (20 ° C./3. 0 Pa), 1.5 Pa · s (50 ° C./0.5 hr), 2.1 Pa · s (50 ° C./3.0 hr).
ii ). Mesh sheet manufacturing
Next, in a bath filled with a polyurethane precursor composition (3) at a liquid temperature of 50 ° C., a polyester coarse pattern fabric base fabric (833 dtex / 3 pieces of the same phosphonic acid compound pretreatment as in Example 1 was applied. Multifilament yarn: Warp yarn driving density 11 / 2.54 cm × Bias yarn driving density 11 / 2.54 cm: Mass 225 g / m² <Fixed amount of phosphonic acid compound 2.5 g / m² >: Dip (dipping) 14%), pull up the coarse patterned fabric base fabric to which the polyurethane precursor composition (3) is attached, and simultaneously nip (press) it with a mangle roll to obtain a polyurethane precursor composition. The product (3) was impregnated and adhered to the entire surface of the coarse patterned fabric base fabric, and then heat treated for 6 minutes in a hot air drying oven at 200 ° C., thickness 0.74 mm, mass 436 g / m.² A mesh sheet was obtained.
[0059]
[Example 4]
i). Polyurethane precursor composition (4)
1,6-hexamethylene diisocyanate (HMDI) isocyanurate-modified polyisocyanate (Trademark: Takenate D-170N: isocyanate group content 20.7% by mass, solid content 100% by mass: Takeda Pharmaceutical Co., Ltd.) 100 parts by mass A block isocyanate compound (1) having a solid content of 60% by mass obtained by adding 35 parts by mass of methyl ethyl ketoxime to (a free methyl ethyl ketoxime equivalent ratio is 0.03 equivalents per equivalent of blocked isocyanate: xylene solvent), 44 parts by mass, As an active hydrogen group-containing resin, 148 parts by mass of acrylic polyol (trade name: ACRYDEC A-801: hydroxyl value 100 mg KOH / g, solid content 50% by mass: toluene / butyl acetate solvent: Dainippon Ink & Chemicals, Inc.) Polyurethane precursor having an equivalent ratio of 0.15 92 parts by mass (solid content: 52.2% by mass), 5 parts by mass of a tin-based compound (trademark: Formate K: solid content: 10% by mass: Takeda Pharmaceutical Co., Ltd.) as a blocking agent dissociation catalyst, crosslinking agent As a carbodiimide compound (trade name: Carbodilite T-02, carbodiimide equivalent 277: Nisshinbo Co., Ltd.), 1 part by weight as a composite additive of an antioxidant and a weathering stabilizer: Trade name: Tinuvin B-75 (Ciba Specialty Chemicals ( Co., Ltd.) 1.0 parts by weight, 4.0 parts by weight of a rutile titanium oxide pigment as a colorant and 0.8 parts by weight of a carbon black pigment, and melamine cyanurate (trademark) as a flame retardant imparting agent (nitrogen atom-containing compound) : MC-610: average particle size 1-5 μm: Nissan Chemical Co., Ltd.) 20 parts by mass, as flame retardant imparting agent, phosphorus atom-containing compound-1): phosphonic acid compound Trademark: K-19A, mixture of phosphonic acid compound of chemical formula (1) or (2): 10 parts by mass of Meisei Kasei Co., Ltd., and phosphorus atom-containing compound-2: melamine-coated ammonium polyphosphate (degree of polymerization n = 1000) ) (Trademark: Exorit AP462: Clariant Japan Co., Ltd.) 10 parts by mass was used as a basic composition, and this was uniformly stirred with a blender to obtain a gray polyurethane precursor composition (4). The polyurethane precursor composition (4) has a liquid viscosity (measured with a BM type rotational viscometer) of 4.0 Pa · s (20 ° C./0.5 hours), 4.4 Pa · s (20 ° C./3. 0 Pa), 2.1 Pa · s (50 ° C./0.5 hr), 3.2 Pa · s (50 ° C./3.0 hr).
[0060]
ii ). Mesh sheet manufacturing
Next, in the bath filled with the polyurethane precursor composition (4) at a liquid temperature of 20 ° C., the same polyester coarse textured textile base fabric as in Example 1 (preparation of phosphonic acid compound) was dipped (immersed), The coarse pattern fabric base fabric to which the polyurethane precursor composition (4) is attached is pulled up and simultaneously niped (pressed) with a mangle roll, and the polyurethane precursor composition (4) is applied to the entire surface of the coarse pattern fabric base fabric. After impregnating and adhering and heat-treating in a hot air drying oven at 180 ° C. for 3 minutes, this mesh sheet was again dipped in the polyurethane precursor composition (4) filling bath, and the same procedure as the first dipping-heat treatment was performed. Thickness 0.74mm, mass 422g / m² A mesh sheet was obtained.
[0061]
[Example 5]
i). Polyurethane precursor composition (5)
44 mass parts of blocked isocyanate compound (1) of Example 4 was changed into 44 mass parts of the following blocked isocyanate compound (2). This blocked isocyanate compound (2) is a 1,6-hexamethylene diisocyanate (HMDI) biuret-modified polyisocyanate (trademark: Takenate D-165N90PX: isocyanate group content 21.0% by mass, solid content 90% by mass: Takeda Pharmaceutical) This was a xylene solution having a solid content of 60% by mass obtained by adding 35 parts by mass of methyl ethyl ketoxime to 100 parts by mass of Kogyo Co., Ltd. (* Equivalent ratio of free methyl ethyl ketoxime is 0.03 equivalent per equivalent of blocked isocyanate) Otherwise, the liquid viscosity (BM type rotational viscosity) of the gray polyurethane precursor composition (5) obtained in the same manner as in Example 4 The measured value is 4.2 Pa · s (20 ° C / 0.5 hours), 4.8 Pa · s (20 ° C / 3.0 hours), 2.6 Pa · s (50 ° C / 0.5 hours). ) 3.6 Pa · s (50 ° C./3.0 hours).
ii ). Mesh sheet manufacturing
Next, in the bath filled with the polyurethane precursor composition (5) having a liquid temperature of 20 ° C., the same polyester coarse triaxial fabric base fabric (preparation of phosphonic acid compound) as in Example 2 was dipped (dipped), The coarse triaxial fabric base fabric to which the polyurethane precursor composition (5) is attached is pulled up and simultaneously niped (pressed) with a mangle roll, and the polyurethane precursor composition (5) is applied to the entire surface of the coarse triaxial fabric base fabric. After impregnating and heat-treating in a hot air drying furnace at 180 ° C. for 3 minutes, the mesh sheet was dipped again in the polyurethane precursor composition (5) filling bath, and the same procedure as the first dip-heat treatment was performed. , Thickness 0.74mm, mass 435g / m² A mesh sheet was obtained.
[0062]
[Example 6]
i). Polyurethane precursor composition (6)
44 parts by mass of the blocked isocyanate compound (1) of Example 4 was changed to 70 parts by mass of the following blocked isocyanate compound (3), and the acrylic polyol of Example 4 (trademark: ACRYDEC A-801: solid content 50% by mass) : Dainippon Ink & Chemicals, Inc.) 148 parts by mass was changed to 117 parts by mass. The blocked isocyanate compound (3) is an isophorone diisocyanate (IPDI) -based trimethylolpropane / adduct-modified polyisocyanate (trademark: Takenate D-140N: isocyanate group content 10.5% by mass, solid content 75% by mass: Takeda Pharmaceutical Co., Ltd. ( Co.)) xylene solution having a solid content of 60% by mass obtained by adding 35 parts by mass of methyl ethyl ketoxime to 100 parts by mass. (* Equivalent ratio of free methyl ethyl ketoxime is 0.03 equivalent per equivalent of blocked isocyanate) Based on 187 parts by mass of this polyurethane precursor (solid content 53.6% by mass), the same composition as in Example 4 (blocking agent) The liquid viscosity (measured by a BM type rotational viscometer) of the gray polyurethane precursor composition (6) obtained by carrying out the dissociation catalyst, composite additive, colorant, flame retardancy imparting agent) is 4. 4 Pa · s (20 ° C./0.5 hours), 4.9 Pa · s (20 ° C./3.0 hours), 2.5 Pa · s (50 ° C./0.5 hours), 3.9 Pa · s (50 ° C / 3.0 hours).
ii ). Mesh sheet manufacturing
Next, in the bath filled with the polyurethane precursor composition (6) having a liquid temperature of 20 ° C., the same polyester coarse textured textile base fabric as that in Example 3 (preparation of phosphonic acid compound) was dipped (dipped), The coarse pattern fabric base fabric to which the polyurethane precursor composition (6) is attached is pulled up and simultaneously niped (pressed) with a mangle roll, and the polyurethane precursor composition (6) is applied to the entire surface of the coarse pattern fabric base fabric. After impregnating and heat-treating in a hot air drying furnace at 180 ° C. for 3 minutes, the mesh sheet was again dipped in the polyurethane precursor composition (6) filling bath, and the same procedure as in the first dipping-heat treatment was performed. 0.74mm, mass 442g / m² A mesh sheet was obtained.
[0063]
[Example 7]
i). Polyurethane precursor composition (7)
1,3-bis (isocyanatomethyl) cyclohexane (H₆ XDI) trimer-based (methylethylketoxime) blocked isocyanate compound (4) (Trademark: Takenate B-842N, effective isocyanate group content 9.7% by mass, solid content 70% by mass, Solvents # 100 / butyl acetate solvent : Takeda Pharmaceutical Co., Ltd.) 40 parts by mass, and as an active hydrogen group-containing resin, acrylic polyol (trademark: Takelac UA-702: hydroxyl value 50 mg KOH / g, solid content 50% by mass: toluene / butyl acetate solvent: Takeda Pharmaceutical Co., Ltd. Co., Ltd.) 185 parts by mass of a polyurethane precursor having an equivalent ratio of 0.15 (solid content: 54.3% by mass) and a tin-based compound (trademark: Trademark: Formate K: solid content 10% by mass: Takeda Pharmaceutical Co., Ltd.) 5 parts by mass, a composite additive of an antioxidant and a weathering stabilizer Trademark: Tinuvin B-75 (Ciba Specialty Chemicals Co., Ltd.) 1.0 part by weight, 4.0 parts by weight of rutile titanium oxide pigment as a colorant and 0.8 part by weight of carbon black pigment, flame retardant As a property imparting agent (nitrogen atom-containing compound), 30 parts by mass of melamine cyanurate (trademark: MC-610: average particle size 1-5 μm: Nissan Chemical Co., Ltd.), flame retardancy imparting agent (phosphorus atom-containing compound-1) As a basic composition, blended with 10 parts by mass of a phosphonic acid compound (trademark: K-19A, a mixture of phosphonic acid compounds of chemical formulas (1) and (2): Meisei Kasei Co., Ltd.) The mixture was stirred to obtain a gray polyurethane precursor composition (7). The polyurethane precursor composition (7) has a liquid viscosity (measured by a BM rotational viscometer) of 3.7 Pa · s (20 ° C./0.5 hours), 4.2 Pa · s (20 ° C./3. 0 Pa), 3.0 Pa · s (35 ° C./0.5 hr), 3.6 Pa · s (35 ° C./3.0 hr), 2.2 Pa · s (50 ° C./0.5 hr), 2 0.7 Pa · s (50 ° C./3.0 hours).
ii ). Mesh sheet manufacturing
Next, in the bath filled with the polyurethane precursor composition (7) having a liquid temperature of 35 ° C., the same polyester coarse textured textile base fabric (preparation of phosphonic acid compound) as in Example 1 was dipped (dipped), The coarse pattern fabric base fabric to which the polyurethane precursor composition (7) is attached is pulled up and simultaneously niped (pressed) with a mangle roll, and the polyurethane precursor composition (7) is applied to the entire surface of the coarse pattern fabric base fabric. After impregnating and applying heat treatment in a hot air drying oven at 180 ° C. for 3 minutes, this mesh sheet was again dipped in the polyurethane precursor composition (7) filling bath, and the same procedure as in the first dip-heat treatment was performed. Thickness 0.74mm, mass 425g / m² A mesh sheet was obtained.
[0064]
[Example 8]
i). Polyurethane precursor composition (8)
The blocked isocyanate compound (1) used in Example 4 and a polytetramethylene ether polyol having a number average molecular weight of 500 and an average functional group number of 2.0 as an active hydrogen group-containing compound are combined with an active hydrogen group / isocyanate equivalent ratio of 1. 3 and a tin-based compound (trademark: formate) as a blocking agent dissociation catalyst with respect to 100 parts by mass of the polyurethane precursor having a blocked isocyanate group / active hydrogen group equivalent ratio of 0.72 in the polyurethane precursor. K: solid content 10% by mass: Takeda Pharmaceutical Co., Ltd.) 5 parts by mass and trademark: Tinuvin B-75 (Ciba Specialty Chemicals Co., Ltd.) as a combined additive of antioxidant and weathering stabilizer 1.0 part by mass, 4.0 parts by mass of a lithyl-type titanium oxide pigment and 0.8 part by mass of a carbon black pigment as a colorant, a flame retardant imparting agent ( Melamine cyanurate (trademark: MC-610: average particle diameter 1-5 μm: Nissan Chemical Co., Ltd.) 30 parts by mass as flame atom imparting agent (phosphorus atom-containing compound-1) A blend of 10 parts by weight of a compound (trademark: K-19A, a mixture of phosphonic acid compounds of chemical formulas (1) and (2): Meisei Kasei Co., Ltd.) is used as a basic composition, and this is uniformly stirred with a blender to give a gray A colored polyurethane precursor composition (8) was obtained. The polyurethane precursor composition (8) has a liquid viscosity (measured with a BM type rotational viscometer) of 3.3 Pa · s (20 ° C./0.5 hours), 3.6 Pa · s (20 ° C./3. 0 Pa), 2.6 Pa · s (35 ° C./0.5 hr), 3.1 Pa · s (35 ° C./3.0 hr), 2.1 Pa · s (50 ° C./0.5 hr), 2 It was 5 Pa · s (50 ° C./3.0 hours).
ii ). Mesh sheet manufacturing
Next, in the bath filled with the polyurethane precursor composition (8) at a liquid temperature of 35 ° C., the polyester coarse patterned fabric base fabric subjected to the same phosphonic acid compound pretreatment as in Example 3 was dipped (immersed). Then, the coarse pattern fabric base fabric to which the polyurethane precursor composition (8) was adhered was pulled up and simultaneously niped (pressed) with a mangle roll, so that the polyurethane precursor composition (8) was applied to the entire surface of the coarse pattern fabric base fabric. After impregnating and adhering to the film, it was heat-treated in a hot air drying furnace at 200 ° C. for 6 minutes, thickness 0.74 mm, mass 444 g / m.² A mesh sheet was obtained.
[0065]
The test results of Examples 1 to 8 are shown in Table 1.
[Table 1]

[0066]
[Comparative Example 1]
The polyurethane precursor (1) of Example 1 was changed to the water-based polyurethane resin (1), and a part of the flame retardant imparting agent was further changed and increased. That is, with respect to 200 parts by mass (100 parts by mass in terms of solids) of polyurethane resin (1) (trademark: Adekabon titer HUX-290N: ester polyurethane resin emulsion: solid content 50% by mass: Asahi Denka Kogyo Co., Ltd.) Trademark: 1.0 part by weight of Tinuvin B-75 (Ciba Specialty Chemicals Co., Ltd.) as a composite additive of an antioxidant and a weathering stabilizer, and 4.0 parts by weight of a rutile titanium oxide pigment as a colorant 0.8 parts by mass of carbon black pigment, 100 parts by mass of melamine cyanurate (trademark: MC-610: average particle size 1-5 μm: Nissan Chemical Co., Ltd.) as a flame retardant imparting agent (nitrogen atom-containing compound), flame retardant Aromatic condensed phosphate ester (trademark CR-747: viscosity 3900 cP / 40 ° C .: Daihachi Chemical Co., Ltd.) A blend of 30 parts by mass was used as a basic composition, and this was uniformly stirred with a blender to obtain a gray polyurethane (1) composition. The liquid viscosity (measured by a BM type rotational viscometer) of this polyurethane (1) composition is 3.2 Pa · s (20 ° C./0.5 hours), 3.5 Pa · s (20 ° C./3.0 hours). ) 2.8 Pa · s (50 ° C./0.5 hours), 3.3 Pa · s (50 ° C./3.0 hours). Next, using the pretreated polyester coarse woven fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 412 g / m.² A mesh sheet was obtained.
[0067]
[Comparative Example 2]
Addition of 10 parts by mass (4 parts by mass in terms of solid content) of carbodiimide-based crosslinking agent (trademark: Carbodilite V-02, 40% by mass of active ingredient: Nisshinbo Co., Ltd.) in the polyurethane (1) composition of Comparative Example 1 The composition was the same as in Comparative Example 1 except that. The polyurethane (1) composition has a liquid viscosity (measured by a BM type rotational viscometer) of 3.0 Pa · s (20 ° C./0.5 hours), 4.4 Pa · s (20 ° C./3.0 hours). ) 2.7 Pa · s (50 ° C./0.5 hours) and 7.6 Pa · s (50 ° C./3.0 hours). Next, by using the pretreated polyester coarse patterned fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 415 g / m.² A mesh sheet was obtained.
[0068]
[Comparative Example 3]
The polyurethane precursor (1) of Example 1 was changed to an aqueous vinyl acetate-ethylene copolymer resin, and a part of the flame retardant imparting agent was further changed and increased. That is, the same as Comparative Example 1 with respect to 182 parts by mass (100 parts by mass in terms of solids) of vinyl acetate-ethylene copolymer resin (trademark: Sumikaflex S-500: solid content 55% by mass: Sumitomo Chemical Co., Ltd.) The same amount of the composite additive, the colorant, and the flame retardant imparting agent was used as a basic composition, and this was uniformly stirred with a blender to obtain a gray vinyl acetate-ethylene copolymer resin composition. . The liquid viscosity of the vinyl acetate-ethylene copolymer resin composition (measured by a BM type rotational viscometer) is 2.7 Pa · s (20 ° C./0.5 hours), 3.1 Pa · s (20 ° C./20° C.). 3.0 Pa), 2.5 Pa · s (50 ° C./0.5 hour), and 2.8 Pa · s (50 ° C./3.0 hour). Next, by using the pretreated polyester coarse woven fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 410 g / m.² A mesh sheet was obtained.
[0069]
[Comparative Example 4]
The polyurethane precursor (1) of Example 1 was changed to the water-based polyurethane resin (2), and a part of the flame retardant imparting agent was further changed and increased. That is, for polyurethane resin (2) (trademark: Permusen RU-40-350: polycarbonate polyurethane resin emulsion: solid content 40% by mass: Star Japan Co., Ltd.) 250 parts by mass (100% by mass in terms of solids), 1.0 part by mass of trademark: Tinuvin B-75 (Ciba Specialty Chemicals Co., Ltd.) as a composite additive of an antioxidant and a weathering stabilizer, and 4.0 parts by mass of a lithyl-type titanium oxide pigment as a colorant Carbon black pigment 0.8 parts by mass, flame retardant imparting agent (nitrogen atom-containing compound) melamine cyanurate (trademark: MC-610: average particle size 1-5 μm: Nissan Chemical Co., Ltd.) 60 parts by mass, flame retardant As a property imparting agent, phosphorus atom-containing compound-3): aromatic condensed phosphate ester (trademark CR-747: viscosity 3900 cP / 40 ° C .: Daihachi Science Co., Ltd.) 20 parts by mass and phosphorus atom-containing compound-4): red phosphorus (trademark: Hishiguard White CP, titanium oxide coated decolored product with red phosphorus content of 33% by mass: Nippon Chemical Co., Ltd.) 15 What mixed the mass part was made into the basic composition, and this was uniformly stirred with the blender, and the gray polyurethane (2) composition was obtained. The liquid viscosity (measured by a BM type rotational viscometer) of this polyurethane (2) composition is 1.8 Pa · s (20 ° C./0.5 hours), 2.1 Pa · s (20 ° C./3.0 hours). ), 1.5 Pa · s (50 ° C./0.5 hours), and 1.9 Pa · s (50 ° C./3.0 hours). Next, by using the pretreated polyester coarse woven fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 410 g / m.² A mesh sheet was obtained.
[0070]
[Comparative Example 5]
Addition of 10 parts by mass (4 parts by mass in terms of solid content) of carbodiimide-based crosslinking agent (trademark: Carbodilite V-02, 40% by mass of active ingredient: Nisshinbo Co., Ltd.) in the polyurethane (2) composition of Comparative Example 4 The composition was the same as in Comparative Example 4 except that. The polyurethane (2) composition has a liquid viscosity (measured by a BM rotational viscometer) of 1.7 Pa · s (20 ° C./0.5 hours) and 2.0 Pa · s (20 ° C./3.0 hours). ), 2.2 Pa · s (50 ° C./0.5 hours), and 7.4 Pa · s (50 ° C./3.0 hours). Next, using the pre-treated polyester coarse woven fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 417 g / m.² A mesh sheet was obtained.
[0071]
[Comparative Example 6]
The polyurethane precursor (1) of Example 1 was changed to a water-based acrylic resin, and a part of the flame retardant imparting agent was changed and increased. That is, the same and same amount of composite addition as in Comparative Example 4 with respect to 182 parts by mass (100 parts by mass in terms of solids) of acrylic resin (trademark: Ultrazol B-800: solid content 55% by mass: Gantz Kasei Co., Ltd.) A basic composition was obtained by paying out an agent, a colorant, and a flame retardant, and this was uniformly stirred with a blender to obtain a gray acrylic resin composition. The liquid viscosity of this acrylic resin composition (measured by a BM type rotational viscometer) is 1.6 Pa · s (20 ° C./0.5 hours), 1.8 Pa · s (20 ° C./3.0 hours). 1.3 Pa · s (50 ° C./0.5 hours) and 1.8 Pa · s (50 ° C./3.0 hours). Next, using the pretreated polyester coarse woven fabric base fabric used in Example 1, according to the same method and procedure as in Example 4, the thickness was 0.74 mm and the mass was 412 g / m.² A mesh sheet was obtained.
[0072]
* The mesh sheets obtained in Comparative Examples 1 to 6 are stipulated in the fire prevention performance of Article 4 (JIS L1091A method) of the Fire Service Act and JIS A8952 and the Temporary Industry Association Certification Standard when not in use. However, since all were processed using a water-based resin emulsion, the water resistance is not fundamentally excellent, The resin coating layer swollen by washing rubs and drops and deteriorates, so that the penetration test due to dropping of the steel pipe is rejected.Further, the flame retardant is not included in the system due to swelling of the resin coating layer during washing. As a result, it was impossible to obtain flameproofing properties. Therefore, in these mesh sheets, the flameproofing effect and penetration resistance are easily lost by one wash, and therefore cannot be used repeatedly.
[0073]
[Comparative Example 7]
It was set as the composition system which excluded the flocculant of the block isocyanate compound (1) used for the polyurethane precursor of Example 4. That is, 1,6-hexamethylene diisocyanate (HMDI) -based isocyanurate-modified polyisocyanate (trademark: Takenate D-170N: isocyanate group content 20.7% by mass, solid content 100% by mass: Takeda Pharmaceutical Co., Ltd.) Using. A gray polyurethane precursor composition (9) was obtained in the same manner as in Example 4 except for the change of the isocyanate compound. The polyurethane precursor composition (9) has a liquid viscosity (measured by a BM rotational viscometer) of 4.4 Pa · s (20 ° C./0.5 hours), 7.1 Pa · s (20 ° C./3. 0 hours), 5.3 Pa · s (35 ° C./0.5 hours), 12.8 Pa · s (35 ° C./3.0 hours), 18.5 Pa · s (50 ° C./0.5 hours), gel Measurement was impossible (50 ° C./3.0 hours). Next, an attempt was made to obtain a mesh sheet by the same method and procedure as in Example 7 using the pretreated polyester coarse woven fabric base fabric used in Example 1, but the liquid viscosity increased immediately after processing, and polyurethane was obtained. The fluidity of the precursor composition (9) was remarkably lowered, and as a result, processing became difficult, and a mesh sheet with normal resin adhesion and normal appearance could not be obtained.
[0074]
[Comparative Example 8]
It was set as the composition system which excluded the flocculant of the block isocyanate compound (1) used for the polyurethane precursor of Example 4. That is, 1,6-hexamethylene diisocyanate (HMDI) -based isocyanurate-modified polyisocyanate (trademark: Takenate D-170N: isocyanate group content 20.7% by mass, solid content 100% by mass: Takeda Pharmaceutical Co., Ltd.) Using. A gray polyurethane precursor composition (10) was obtained in the same manner as in Example 4 except for the change of the isocyanate compound. The polyurethane precursor composition (10) has a liquid viscosity (measured by a BM type rotational viscometer) of 4.6 Pa · s (20 ° C./0.5 hours) and 7.3 Pa · s (20 ° C./3. 0 hours), 5.5 Pa · s (35 ° C./0.5 hours), 11.3 Pa · s (35 ° C./3.0 hours), 15.4 Pa · s (50 ° C./0.5 hours), gel Measurement was impossible (50 ° C./3.0 hours). Next, an attempt was made to obtain a mesh sheet by the same method and procedure as in Example 8 using the pretreated polyester coarse woven fabric base fabric used in Example 3, but the liquid viscosity increased immediately after processing and the polyurethane sheet was polyurethane. The fluidity of the precursor composition (10) was remarkably lowered, and as a result, processing became difficult, and a mesh sheet with normal resin adhesion and normal appearance could not be obtained.
[0075]
The test results of Comparative Examples 1 to 8 are shown in Table 2.
[Table 2]

[0076]
【The invention's effect】
As is clear from the above-mentioned Examples and Comparative Examples, the building curing mesh sheet obtained by the present invention has air permeability and daylighting properties, and also has a flameproof performance according to Article 4 of the Fire Service Construction Rules (JIS L1091A method). And the performance defined by JIS A8952 and the temporary industry association certification standard (penetration resistance test by dropping a steel pipe). In particular, the building curing mesh sheet obtained by the present invention has sufficient resistance to severe washing, and the coating layer made of the flame-retardant polyurethane resin swells and falls off due to washing, or the flame-retardant imparting agent is outside the system. No inconveniences such as reduced extraction were observed. In addition, the mesh sheet of the present invention does not easily lose the flameproofing effect after a single wash, or does not easily fail the penetration test due to steel pipe dropping. It can be washed and reused repeatedly. Therefore, the architectural curing mesh sheet of the present invention can be used in the same manner as a conventional mesh sheet using a polyvinyl chloride resin, and there is no fear of generating toxic hydrogen halide gas in the event of a fire. is there.

Claims (10)

A coarse woven knitted fabric composed of fiber yarns and having inter-yarn gaps formed by the crossing thereof, and at least the entire exposed surface of the fiber yarns of the coarse woven knitted fabric is formed by impregnation or coating. A flame retardant resin coating layer, wherein the flame retardant resin coating layer is formed by a thermosetting reaction of a composition of a polyurethane precursor and a flame retardant imparting agent,
(A) The polyurethane precursor is at least one selected from (a) a polyol monomer compound (a-1) having active hydrogen and a polyol polymer (a-2), and (b) a blocked isocyanate group. A liquid mixture ((a) + (b)) containing at least one selected from the compound (b-1) having a uretdione group and the compound (b-2) having a uretdione group,
(B) The flame retardant imparting agent includes at least one selected from an organic compound (c-1) containing a nitrogen atom and an organic compound (c-2) having a phosphorus atom,
(C) The composition of the polyurethane precursor and the flame retardant imparting agent has a liquid viscosity of 0.1 to 10 Pa · s (10 to 50 ° C./0.5 to 3 hours),
(D) Content of the said flame-retardant imparting agent with respect to the total mass of the said flame-retardant resin coating layer is 10-50 mass%, The building curing mesh sheet characterized by the above-mentioned.   The organic compound (c-1) containing the nitrogen atom is selected from (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivative compounds thereof. The architectural curing mesh sheet described.   The architectural curing mesh sheet according to claim 1, wherein the organic compound (c-2) containing phosphorus atom is selected from red phosphorus, (metal) (organic) phosphate, phosphoric acid derivative, and ammonium polyphosphate. . The coarse woven or knitted fabric, said the textile by 2-4 direction of crossing the fiber yarns, 2 Jikuo knit, 3 Jikuo knitted, selected from 4 Jikuo knitted fabric, any of claims 1-3 1 The flame-retardant mesh sheet according to Item. The flame-retardant mesh sheet according to any one of claims 1 to 4 , wherein the coarse woven fabric has a total void area of 5 to 65% with respect to a surface area of the coarse woven fabric. The flame retardant mesh sheet according to any one of claims 1 to 5 , wherein the coarse woven or knitted fabric is subjected to a flame retardant treatment with a phosphonic acid compound. A coarse knitted fabric consisting of fiber yarns and having yarn gaps formed by crossing them ,
(A) (a) at least one selected from polyol monomer compound (a-1) having active hydrogen and polyol polymer (a-2), and (b) compound having a blocked isocyanate group (b- 1) and a polyurethane precursor comprising a liquid mixture ((a) + (b)) containing at least one selected from the compound (b-2) having a uretdione group, and (B) an organic compound containing a nitrogen atom (C-1) and the flame retardant imparting agent containing at least 1 sort (s) chosen from the organic compound (c-2) which has a phosphorus atom, and (C) 0.1-10Pa * s (10-50 degreeC) having a liquid viscosity of /0.5～3 hours), and facilities impregnation or coating treatment with flame-retardant polyurethane precursor composition, then the surface that is at least exposed of the fiber thread of the coarse woven or knitted fabric Impregnating or covering the entire surface of The flame retardant polyurethane precursor composition is subjected to a heat treatment to transform it into a flame retardant polyurethane resin composition to form a flame retardant resin coating layer. At this time, all of the flame retardant resin coating layer is formed. The manufacturing method of the architectural curing mesh sheet | seat characterized by adjusting content of the said flame retardance provision agent with respect to mass to 10-50 mass%.   The manufacturing method of the architectural curing mesh sheet | seat of Claim 7 in which the said flame-retardant polyurethane precursor composition does not contain a dilution solvent.   The manufacturing method of the architectural curing mesh sheet | seat of Claim 7 in which the said flame-retardant polyurethane precursor composition contains a dilution solvent.   The building curing according to any one of claims 7 to 9, wherein the impregnation or coating of the flame retardant polyurethane precursor composition is performed at 10 to 50 ° C, and the heat treatment is performed at a temperature of 100 ° C or higher. A method for producing a mesh sheet.