JP2004181934A - Method for frp lining - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for FRP lining which is aimed at protecting a tank or the like made of concrete that is regarded as necessitating corrosion resistance and waterproofness and which uses a short-wavelength photosetting prepreg sheet. <P>SOLUTION: In this method for FRP lining, a fiber reinforcement is impregnated with a resin composition containing (A) a radical polymerizable resin such as an unsaturated polyester resin : 100 pts.wt., (B) two or more kinds of photopolymerization initiators obtained by combining a photopolymerization initiator being photosensitive in the region of a wavelength of 500 nm or above with a photopolymerization initiator photosensitive in the region below 500 nm : 0.01-10 pts.wt. and (C) a filler : 100 pts.wt. or below. Thereby a part of a radical polymerizable unsaturated group in the composition is preliminarily polymerized to be put in a B-stage and made a photosetting prepreg sheet. Then, the prepreg sheet is stuck on the ground which is prepared on the surface of concrete from a water emulsion resin primer and further coated with the primer, and the end part of the prepreg sheet and a gap between the prepreg sheets are sealed with a photosetting/thermosetting resin. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

Ｐｈ：ベンゼン核、Ｒ＝ＨまたはＣＨ_３、ｍ＋ｎ＝２〜３０
【００２５】
また市販品には、２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパン（新中村化学工業（株）製：ＢＰＥ−１００）、２，２−ビス［４−（メタクリロキシ・ジエトキシ）フェニル］プロパン（新中村化学工業（株）製：ＢＰＥ−２００）、２，２−ビス［４−（メタクリロキシ・ポリエトキシ）フェニル］プロパン（新中村化学工業（株）製：ＢＰＥ−５００）、２，２−ビス［４−（アクリロキシ・ジエトキシ）フェニル］プロパン（新中村化学工業（株）製：Ａ−ＢＰＥ−４）、２，２−ビス［４−（アクリロキシ・ポリエトキシ）フェニル］プロパン（新中村化学工業（株）製：Ａ−ＢＰＥ−１０）などが挙げられる。
【００２６】
本発明の樹脂等に配合されるラジカル重合性不飽和単量体は樹脂の粘度を下げ、硬度、強度、耐候性、耐水性、耐摩耗性等を向上させるために重要であり、不飽和ポリエステル、ビニルエステル、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート等の１００重量部に対して、１０〜２５０重量部、好ましくは２０〜１００重量部使用される。使用量が１０重量部未満では、高粘度のため作業性、含浸性が悪化し、２５０重量部を超える量では、充分な塗膜硬度が得られず、諸物性が不足しＦＲＰライニング用硬化性材料として好ましくない。
【００２７】
本発明で使用される熱重合開始剤として主に常温ラジカル重合開始剤が使用される。常温ラジカル重合開始剤としては、公知であるケトンパーオキサイドと還元剤の組み合わせ、ハイドロパーオキサイドと還元剤の組み合わせ、ジアシルパーオキサイドと還元剤の組み合わせが挙げられ、還元剤としての具体例としては、ナフテン酸コバルト、オクチル酸コバルト等のコバルト塩、五酸化バナジウム等のバナジウム化合物、ジメチルアニリン等のアミン類等が挙げられる。中でもポットライフ等の点でパーオキシエステルとコバルト塩の組み合わせが特に有効である。
【００２８】
その他、熱重合開始剤として公知のラジカル重合開始剤を使用してもよい。その例としては、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネートに分類されるものであり、またアゾ化合物も有効である。
【００２９】
具体例としては、例えばベンゾイルパーオキサイド、ジクミルパーオキサイド、ジイソプロピルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、２，５−ジメチルー２，５−ビス（ｔ−ブチルパーオキシ）ヘキシン−３、３−イソプロピルヒドロパーオキサイド、ｔ−ブチルヒドロパーオキサイド、ジクミルパーオキサイド、ジクミルヒドロパーオキサイド、アセチルパーオキサイド、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソブチルパーオキサイド、３，３，５−トリメチルヘキサノイルパーオキサイド、ラウリルパーオキサイド、アゾビスイソブチロニトリル、アゾビスカルボンアミドなどの使用できる。
【００３０】
常温ラジカル重合開始剤の使用量は、樹脂等１００重量部に対して０．０１〜１５重量部、好ましくは０．０５〜１０重量部である。有機過酸化物または還元剤と組合わせた常温硬化型のラジカル重合開始剤光重合開始剤の使用量が０．０１重量部未満では増粘反応や増粘後の重合が不十分になり易く、また１５重量部を越える量では硬化物の強度が不足する。
【００３１】
本発明で使用する光重合開始剤は、可視光領域及び／または紫外光領域に感光性を有するものが使用できる。
可視光領域に感光性を有する可視光重合開始剤としては、例えば非特許文献１，非特許文献２に記載の、カンファーキノン、ベンジルトリメチルベンゾイルジフェニルフォスフィンオキサイド、メチルチオキサントン、ジシクロペンタジエニルチタニウムージ（ペンタフルオロフェニル）等の単独の可視光重合開始剤の他、有機過酸化物／色素系、ジフェニルヨードニウム塩／色素、イミダゾール／ケト化合物、ヘキサアリールビイミダゾール化合物／水素供与性化合物、メルカプトベンゾチアゾール／チオピリリウム塩、金属アレーン／シアニン色素など（非特許文献１０参照）のヘキサアリールビイミダゾール／ラジカル発生剤等の公知の複合開始剤系などを挙げることができる。
【００３２】
また、紫外光から可視光領域まで感光性を有する開始剤として、アシルホスフィンオキサイド化合物が有効である。その具体例としては、ビス（２，６−ジクロルベンゾイル）−フェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−エトキシフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−ビフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−プロピルフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−２−ナフチルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−１−ナフチルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−クロルフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−２，２−ジメトキシフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−ドデシルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−オクチルフェニルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス（２，６−ジクロル−３，４，５−トリメトキシベンゾイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス（２，６−ジクロル−３，４，５−トリメトキシベンゾイル）−４−エトキシフェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−２，５−フェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−４−ビフェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−４−エトキシビフェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−２−ナフチルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−４−プロピルフェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス（２−メチル−１−ナフトイル）−４−メトキシフェニルホスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、２，６−ジフェニルベンゾイル−ジフェニルホスフィンオキサイド、２，６−ジメトキシベンゾイル−ジフェニルホスフィンオキサイド、２，３，５，６−テトラメチルベンゾイル−ジフェニルホスフィンオキサイド、２，６−ジクロルベンゾイル−ジフェニルホスフィンオキサイド、２，３，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、２−フェニル−６−メチルベンゾイル−ジフェニルホスフィンオキサイド、２，６−ジブロムベンゾイル−ジフェニルホスフィンオキサイド、２，８−ジメチルナフタリン−１−カルボニル−ジフェニルホスフィンオキサイド、１，３−ジメトキシナフタリン−２−カルボニル−ジフェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイル−フェニルホスフィン酸メチルエステル、２，６−ジメチルベンゾイル−フェニルホスフィン酸メチルエステル、２，６−ジクロルベンゾイル−フェニルホスフィン酸メチルエステル、等を挙げることができる。
【００３３】
具体的には、例えば２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（商品名：Ｄａｒｏｃｕｒ１１７３、チバスペシャルティーケミカルズ（株）製）とビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド（チバスペシャルティーケミカルズ（株）製）を７５％／２５％の割合で混合された商品名イルガキュア−１７００（チバスペシャルティーケミカルズ（株）製）、１−ヒドロキシ−シクロヘキシル−フェニルーケトン（商品名：イルガキュアー１８４、チバスペシャルティーケミカルズ（株）製）とビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド（チバスペシャルティーケミカルズ（株）製）を７５％／２５％の割合で混合された商品名イルガキュアー１８００（チバスペシャルティーケミカルズ（株）製）、５０％／５０％の割合で混合された商品名イルガキュアー１８５０（チバスペシャルティーケミカルズ（株）製）、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド（商品名：イルガキュアー８１９、チバスペシャルティーケミカルズ（株）製）、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド（商品名Ｌｕｃｉｒｉｎ ＴＰＯ、ＢＡＳＦ（株）製）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（商品名：Ｄａｒｏｃｕｒ１１７３、チバスペシャルティーケミカルズ（株）製）と２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド（商品名Ｌｕｃｉｒｉｎ ＴＰＯ、ＢＡＳＦ（株）製）を５０％／５０％の割合で混合された商品名Ｄａｒｏｃｕｒ４２６５などがある。可視光開始剤としては３８０ｎｍ〜７８０ｎｍの波長域に感光性を有する光重合開始剤であればよく、それらを組み合わせて使用してもよい。
【００３４】
また、紫外線重合開始剤としては、アセトフェノン系、ベンジルケタール系、（ビス）アシルホスフィンオキサイド系をはじめとする公知の重合開始剤を使用することができるが、短波長の紫外線ではＦＲＰ構成での光透過性が低いことから、比較的長波長、好ましくは３００ｎｍ以上の波長域に感光性を有する（ビス）アシルホスフィンオキサイド系等の紫外線重合開始剤を使用することが好ましい。
【００３５】
光重合開始の使用量は、樹脂等１００重量部に対して０．０１〜２０重量部、好ましくは０．０５〜１５重量部である。光重合開始剤の使用量が０．０１重量部未満では増粘反応や増粘後の重合が不十分になり易く、また２０重量部を越える量では硬化物の強度が不足する。
【００３６】
次にラジカル重合型以外のプライマーについて説明する。上述したラジカル重合型のプライマー以外のプライマーとしては、常温硬化型エポキシプライマーや湿気硬化型ウレタンプライマーなどを挙げることができる。
常温硬化型エポキシプライマーに使用されるエポキシ化合物としては、公知の方法により製造されるものでよく、１成分中に少なくとも２個以上のエポキシ基を有する熱硬化性エポキシ樹脂とエポキシ用硬化剤との組み合わせを意味する。
【００３７】
エポキシ樹脂としては、例えばエーテル型のビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリフェノール型エポキシ樹脂、脂肪族型エポキシ樹脂、エステル系の芳香族エポキシ樹脂、環状脂肪族エポキシ樹脂、エーテル・エステル型エポキシ樹脂等の公知のものがあり、これらの物は単独使用でも２種以上の併用でも良い。エポキシ樹脂硬化剤として一般的にアミン系硬化剤が用いられ、例えば脂肪族アミン、芳香族アミン、ポリアミド、複素環状アミン等が挙げられ、またこれら変性アミンなど公知のものの組み合わせでも使用できる。
【００３８】
本発明において水系エマルジョン樹脂プライマーとは、エポキシ樹脂、アクリル樹脂などのエマルジョンタイプで、例えば主剤がアクリル樹脂で、硬化剤がエポキシ樹脂である商品名ＭＦ４０／ＣＡＴ−ＥＰＫ（東洋モートン（株）製）も含めることができる。
また水系エマルジョン樹脂と粉体からなるモルタルは、水系エマルジョン樹脂と粉体を組合わせることで、セメントモルタル・コンクリートの欠点を補い更に特別の機能を付与したものである。水系エマルジョンには、アクリル樹脂、エポキシ樹脂、エチレン酢酸ビニル樹脂（ＥＶＡ）、スチレンブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）などが使用され、粉体にはセメント、骨材、顔料等が使用される。セメントの水和反応により硬化し、セメントの種類により速硬化型にもできる。具体例としては、商品名ショウゼットＳＡ−１（昭和電工建材（株）製）等がある。
【００３９】
湿気硬化型ウレタンプライマーに使用するウレタン樹脂は、ジイソシアネートと２個以上の活性水素原子を有する有機化合物（普通ジオール）とを反応させて得られるウレタン結合を主体とする重合体で、遊離イソシアネート基を含んでいるので、熱または触媒の作用を受けてイソシアネート基同士が反応するかまたはイソシアネート基と水、グリコールなどと反応して熱硬化樹脂となる「プラスチック工業辞典」（工業調査会、１９８５年発行）などに記載されている樹脂であり、公知のものが使用できる。
例えば、末端に２個以上の水酸基を有する化合物と水酸基のモル数よりも多いイソシアネート基を有する化合物とを反応させたものでよく、溶剤を含んでいてもよい。商品名を例示すれば、ＵＭ−５０Ｐ（昭和高分子（株）製）等がある。
【００４０】
光硬化性樹脂プライマーと常温硬化性樹脂プライマーはそれぞれ単独で使用してもよいが、光硬化の機能と常温硬化の機能の両方を併せ持たせて使用することも有効である。
【００４１】
プリプレグシートに使用する樹脂、５００ｎｍ未満の可視光及び／または紫外光領域に感光性を有する光重合開始剤及び熱重合開始剤は、上述の光硬化性及び／または熱硬化性のプライマーに使用する樹脂、光重合開始剤および熱重合開始剤と同様のものを使用する。
本発明で使用される５００ｎｍ以上の波長の可視光あるいは近赤外光領域に感光性を有する光重合開始剤としては、一般式（２）
Ｄ^＋ ・ Ａ⁻ ・・・・・・（２）
（式中、Ｄ^＋ は可視光あるいは近赤外光領域に感光性を有するメチン、ポリメチン、シアニン、キサンテン、オキサジン、チアジン、アリールメタン、ピリリウム系色素陽イオンであり、Ａ^ー は各種陰イオンを示す。）
で表される陽イオン染料と、
【００４２】
一般式（３）
【化２】

（式中、Ｚ^＋は任意の陽イオンを示し、Ｒ_１，Ｒ_２，Ｒ_３及びＲ_４はそれぞれ独立してアルキル基、アリール基、アシル基、アラルキル基、アルケニル基、アルキニル基、シリル基、複素環基、ハロゲン原子、置換アルキル基、置換アリール基、置換アシル基、置換アラルキル基、置換アルケニル基、置換アルキニル基、置換シリル基または置換複素環基を示す。）
で表されるホウ素系化合物を組み合わせた光重合開始剤が好ましい。
【００４３】
また一般式（２）における陽イオン「Ｚ^＋」の例としては、可視光あるいは近赤外光領域に感光性を有しない４級アンモニウム陽イオン、４級ピリジニウム陽イオン、４級キノリニウム陽イオン、ジアゾニウム陽イオン、テトラゾリウム陽イオン、スルホニウム陽イオン、オキソスルホニウム陽イオン、ナトリウム、カリウム、リチウム、マグネシウム、カルシウム等の金属陽イオン、フラビリウム、ピラニウム塩等の酸素原子上に陽イオン電荷を持つ（有機）化合物、トロピリウム、シクロプロピリウム等の炭素陽イオン、ヨードニウム等のハロゲニウム陽イオン、砒素、コバルト、パラジウム、クロム、チタン、スズ、アンチモン等の金属化合物の陽イオン等が挙げられる。
【００４４】
この有機ホウ素化合物と可視光あるいは近赤外光領域に感光波長を有するカチオン色素とを組み合わせることで、感光領域の波長の光照射を受けた色素が励起され、有機ホウ素化合物と電子授受を行うことで色素が消色すると共にラジカルが発生し、共存する重合性不飽和化合物の重合反応が起こる。この重合反応では、従来の紫外線重合反応などと異なり、発生ラジカルをコントロールしやすく、樹脂中の不飽和基の一部をラジカル重合したところで容易に止めることが出来る。また、可視光あるいは近赤外光領域の長波長を使用するため、充填材や顔料など添加された系でも容易に反応を進めることができるという特徴を持っている。
【００４５】
上記陽イオン染料とホウ素系化合物との組み合わせの例は、特許文献１１、特許文献１２、特許文献１３、特許文献１４、特許文献１５、特許文献１６などに詳細な記載がある。陽イオン染料の「Ｄ^＋ 」の具体例を表１乃至表４に示す。これらの陽イオン染料の中でも好ましくはシアニン系、スチリル系陽イオン染料及びトリアリールメタン系染料が使用される。シアニン系、スチリル系陽イオン染料は、一般に有機ホウ素系化合物との電子授受が起こりやすいので本発明の反応を容易に起こしやすいなどの点で好ましい。
【００４６】
【表１】

【００４７】
【表２】

【００４８】
【表３】

【００４９】
【表４】

【００５０】
一般式（２）で表される陽イオン染料のカウンターアニオンであるＡ⁻ は、ｐ−トルエンスルホネートイオン、有機カルボキシレートイオン、パークロレートイオン、ハライドイオン等の任意の陰イオンであるが、一般式（４）
【化３】

（式中、Ｒ_５ ，Ｒ_６ ，Ｒ_７ 及びＲ_８ はそれぞれ独立してアルキル基、アリール基、アシル基、アラルキル基、アルケニル基、アルキニル基、シリル基、複素環基、ハロゲン原子、置換アルキル基、置換アリール基、置換アシル基、置換アラルキル基、置換アルケニル基、置換アルキニル基または置換シリル基または置換複素環基を示す。）
で表される４配位ホウ素陰イオンが特に好ましい。
本発明の［有機ホウ素化合物］／［近赤外光あるいは可視光吸収性陽イオン染料化合物］との組成比は、重量で１／５〜１／０．０５、好ましくは１／１〜１／０．１である。色素の消色反応及びラジカル発生効率の観点から、一般には有機ホウ素化合物を陽イオン染料よりも多く用いることが好ましい。
【００５１】
５００ｎｍ以上波長の可視光あるいは近赤外光領域に感光性を有する光重合開始剤と、５００ｎｍ未満の可視光及び／または紫外光領域に感光性を有する光重合開始剤の組み合わせである少なくとも２種の重合開始の使用量は、樹脂等１００重量部に対して０．０１〜２０重量部、好ましくは０．０５〜１５重量部である。光重合開始剤の使用量が０．０１重量部未満ではＢステージ化反応やＢステージ化後の重合が不十分になり易く、また２０重量部を越える量では硬化物の強度が不足する。
【００５２】
Ｂステージ状態にするための予備重合反応用の５００ｎｍ以上波長の可視光あるいは近赤外光領域に感光性を有する光重合開始剤と予備重合反応物を本硬化させる５００ｎｍ未満の可視光及び／または紫外光領域に感光性を有する光重合開始剤とを併用する場合、その組成比は、重量比で０．１／５〜５／０．１、好ましくは０．５／５〜５／０．５である。予備重合用光重合開始剤と本硬化用光重合開始剤の比が０．１／５未満では、Ｂステージ状態にするための予備重合用光重合開始剤の感光波長（５００〜１２００ｎｍ）の光照射をしても予備重合反応が進まない場合があり、一方前記比が５／０．１を越える量では予備重合反応が進みすぎてしまう場合がある。
【００５３】
予備重合したものを本硬化させるときの重合開始剤として、５００ｎｍ未満の可視光及び／または紫外光領域に感光性を有する光重合開始剤を使用するが、熱重合開始剤を組み合わせてもよい。熱重合開始剤を組み合わせて使用する場合、その組成比は、重量比で０．１／５〜５／０．１、好ましくは０．５／５〜５／０．５である。
【００５４】
本発明で使用する繊維強化材は、有機及び／または無機繊維、例えばガラス繊維、炭素繊維、アラミド繊維、ポリエチレンテレフタレート繊維、ビニロン繊維、ポリエステル繊維、アミド繊維、金属繊維、セラミック繊維などのクロス、マット、不織布などの公知のものが使用される。むろんこれらの繊維を二種以上組み合わせて使用してもよい。これらの強化材の中で、本発明は特にガラス繊維や有機繊維が望ましく、施工性などを考慮するとクロス、マットが好適である。
【００５５】
本発明のには充填材を添加してもよく、使用される充填材は、無機質フィラー、有機質フィラーまたはポリマーであり、無機質フィラーとしては、例えば水酸化アルミニウム、炭酸カルシウム、タルク、クレー、ガラス粉、シリカ、硫酸バリウム、酸化チタン、セメントなどの公知のものが使用されるが、硬化性プリプレグ組成物に難燃性を付与する場合は、水酸化アルミニウムが有効である。むろん、これらの無機質フィラーを組み合わせて使用することもでき、その使用量は、重合性不飽和化合物１００重量部に対して０〜２００重量部、好ましくは０〜１００重量部である。無機充填材が２００重量部より多い場合、粘度が高すぎて作業性が低下し、泡が残りやすく強度が低下する。
さらに本発明では、公知の方法で揺変性を付与してもよく、揺変剤としては、例えばシリカパウダー（エアロジルタイプ）、マイカパウダー、炭酸カウシウムパウダーなどを重合性不飽和化合物１００重量部に対して０．１〜５０重量部添加する方法などがある。
【００５６】
この他、本発明の組成物に配合できる有機充填材またはポリマーとしては、低収縮剤としても効果のある、例えば公知のポリスチレン、ポリ酢酸ビニル、ポリメチルメタクリレート、ポリエチレン、ポリ塩化ビニリデンマイクロバルーン、ポリアクリロニトリルマイクロバルーン等が使用できる。低収縮剤として使用する場合のその使用量は樹脂１００重量部に対して０〜２００重量部、好ましくは０〜５０重量部である。
本発明において顔料を使用することができる。その種類の制限は特になく、有機顔料及び無機顔料が使用可能である。その時の配合量としては、樹脂１００重量部に対し、多くとも２０重量部、好ましくは１０重量部までの量を使用することである。
【００５７】
本発明において、紫外光とは２８０〜３８０ｎｍ、可視光とは３８０〜７８０ｎｍ、 近赤外光とは、７８０〜１２００ｎｍの波長領域の光線を指す。
本発明のプリプレグ状のコンクリート剥落防止用硬化性材料を得るためのＢステージ化状態にするための予備重合反応に使用される光源としては、光重合開始剤の感光波長域に分光分布を有する光源であれば良く、例えば近赤外ランプ、ナトリウムランプ、ハロゲンランプ、蛍光灯、メタルハライドランプなどを使用することができる。またこれらのランプあるいは広い波長域の光を光源に波長カットフィルターを組み合わせて予備重合反応に必要な波長を選択して照射することもできる。
予備重合反応に使用する波長は、エネルギーレベルの低い長波長側の光が望ましく、特に近赤外光を使用するとＢステージ化反応を制御しやすい。
【００５８】
予備重合させてＢステージ化状態にするためのランプの照射時間としては、光源の有効波長域、出力、照射距離、組成物の厚さ等が異なるため一概に規定できないが、０．０１時間以上、好ましくは０．０５時間以上照射すればよい。
具体的な製造例を示す。例えば可視線開始剤と近赤外線開始剤を添加したビニルエステル樹脂を使用してビニロンメッシュ、ビニロンマットを積層し、フィルムで挟み込んだものに近赤外線を照射して近赤外線ラジカル重合にて予備重合を進めれば、可視光開始剤と重合性不飽和基が残存する可視光硬化性プリプレグシートとしてのコンクリート剥落防止用硬化性材料を作製することができる。
このようにして製造されたプリプレグ状のコンクリート剥落防止用硬化性材料は、残存する光重合開始剤により光照射で速やかに本硬化できる。
光照射の光源としては、残存する光重合開始剤の感光波長域に分光分布を有する光源であればよく、例えば太陽光、メタルハライドランプ、ハロゲンランプ、紫外線ランプ、蛍光灯などがある。
【００５９】
本発明において使用するプライマーとしては、ラジカル重合型樹脂やエポキシ樹脂光硬化性及び／または熱硬化性のプライマーであって良く、光硬化性プリプレグシートに用いる樹脂（Ａ）を、熱硬化型にしたものや光硬化性にしたものあるいは常温硬化性にしたもの、またはその両方の機能を持たせたものが使用できる。
また本発明で使用する光硬化性及び／または熱硬化性樹脂は、上述した光硬化性プリプレグシートに用いる樹脂（Ａ）、重合開始剤を組み合わせたものを使用する。
またパテ材としては光硬化性及び／または熱硬化性樹脂にさらに充填材を組み合わせて配合したものを使用するか、市販のパテ材を使用してもよい。市販のパテ材としてはエポキシ系、ウレタン系のものが使用できる。
【００６０】
本発明の硬化方法では、コンクリートの表面を処理し、プライマーを塗布後、プリプレグシートをラップ部が生じないように貼り付け、プリプレグシートの間の隙間をパテ材で埋めて光照射などして硬化させてもよいし、夫々の工程を独立して硬化させて次工程に進んでもよい。またプライマーを硬化後に、プリプレグシートをラップ部が生じないように貼り付け、プリプレグシートの間の隙間をパテ材で埋めて一括して硬化してもよいし、プライマーとプリプレグシートを一括して硬化後にプリプレグシートの間の隙間をパテ材で埋めて硬化させてもよい。
【００６１】
また、プリプレグシートの間の隙間をパテ材で埋めた上に、更にプリプレグシートを貼り付けて保護してもよい。その際、下側が硬化後にプリプレグシートを貼り付けるのであれば、サンディング処理、プライマー塗布後にプリプレグシートを貼り付けて硬化させることが望ましい。下側が未硬化であればそのままプリプレグシートを貼り付けて硬化させてもよい。
【００６２】
［実施例］
以下、実施例、比較例により本発明の内容を詳細にするが、各例中の「部」は重量基準を示す。本発明はこれらの実施例のみに限定されるものではない。
［原料の調製］
＜プライマーの調製＞
可視光硬化性プライマー用ビニルエステル樹脂リポキシＬＣ−７２０ＰＴ（昭和高分子（株）製用揺変性付与タイプ）：１００重量部に常温ラジカル硬化剤であるメチルエチルケトンパーオキサイド（商品名、パーメックＮ：日本油脂（株）製）：１．０部、ナフテン酸Ｃｏ：０．５部を添加し光、熱硬化性プライマー−１を得た。
【００６３】
＜プリプレグシートの調製＞
ビニルエステル樹脂リポキシＲ−８０６（昭和高分子（株）製）：１００重量部にトリエチルアミン：１．０部、表１の番号３に示す１，１，５，５−テトラキス（ｐ−ジエチルアミノフェニル）−２，４−ペンタジエニル・トリフェニル−ｎ−ブチルボレート（昭和電工（株）製：以下ＩＲＢと略す。近赤外光吸収性陽イオン染料）：０．０３部とテトラ−ｎ−ブチルアンモニウム・トリフェニル−ｎ−ブチルボレート（昭和電工（株）製、以下Ｐ３Ｂと略す。ホウ素化合物）：０．１５部を組み合わせたＢステージ化用近赤外光重合開始剤、Ｂステージ化物を本硬化のためのＩ−１８００：１．０部を添加し硬化性樹脂組成物を得た。
【００６４】
次に５０ｃｍ×５０ｃｍのビニロン三軸メッシュ（商品名：ＴＲＩＮＥＯ、ユニチカ（株）製）とポリエステル不織布（商品名：ソンタラ８００５Ｈ、デュポン（株）製）１枚を組み合わせたものに繊維含有率が１０Ｗｔ％となるように含浸させたものを透明ＰＥＴフィルムで被覆して３８０〜１２００ｎｍの波長域を含む光源であるＡＬ−スポットライト（ＡＬＦ−１０）１ＫＷに５００ｎｍ以下カットフィルターであるＳＣ−５０を併用して、２０ｃｍの距離で照射したところ２分でＢステージ化し、その後１分光照射を続けてもＢステージ状態は変わらなかった。そこで３分間光照射後のＢステージ状態のものをプリプレグシート−１とし、３０℃、暗所における保存安定性を調べたところ、６ヶ月以上プリプレグの硬さは変化なかった。
【００６５】
＜パテの調製＞
ビニルエステル樹脂リポキシＲ−８０２（昭和高分子（株）製）：１００重量部にタルク：８０重量部、炭酸カルシウム：３０重量部、Ｉ−１８００：１．０部、常温ラジカル硬化剤であるメチルエチルケトンパーオキサイド（商品名、パーメックＮ：日本油脂（株）製）：１．０部、ナフテン酸Ｃｏ：０．５部を添加し光、熱硬化性パテ−１を得た。
【００６６】
＜光硬化性及び／または熱硬化性の樹脂の調整＞
可視光硬化性プライマー用ビニルエステル樹脂リポキシＬＣ−７２０（昭和高分子（株）製）：１００重量部に常温ラジカル硬化剤であるメチルエチルケトンパーオキサイド（商品名、パーメックＮ：日本油脂（株）製）：１．０部、ナフテン酸Ｃｏ：０．５部を添加し光、熱硬化性樹脂−１を得た。
【００６７】
［試験体の製造］
実施例１（試験体−１の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、水系エマルジョン樹脂と粉体からなるモルタルである商品名ショウゼットＳＡ−１（昭和電工建材（株）製）を塗膜厚：１ｍｍに塗布して２日間養生後、光、熱硬化性プライマー−１を１５０ｇ／ｍ^２となるように塗布後、プリプレグシート−１の３０ｃｍ×３０ｃｍ２枚と３０ｃｍ×５ｃｍ４枚をラップさせずに出隅部分が１ｍｍ以内の隙間になるように表面にＰＥＴフィルムを付けたまま貼り付けたものを屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。表面のＰＥＴフィルムは硬化後に剥がした。
次にプリプレグシートの隙間を室内で光、熱硬化性パテ−１で埋め、再度屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、プライマー、プリプレグシートを一括硬化後パテを硬化した試験体−１を得た。
【００６８】
実施例２（試験体−２の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、水系エマルジョン樹脂と粉体からなるモルタルである商品名ショウゼットＳＡ−１（昭和電工建材（株）製）を塗膜厚：１ｍｍに塗布して２日間養生後、光、熱硬化性プライマー−１を１５０ｇ／ｍ^２となるように塗布後、プリプレグシート−１の３０ｃｍ×３０ｃｍ２枚と３０ｃｍ×５ｃｍ４枚をラップさせずに出隅部分が１ｍｍ以内の隙間になるように表面にＰＥＴフィルムを付けたまま貼り付けた。
次に、プライマー、プリプレグシートが未硬化のまま、プリプレグシートの隙間を室内で光、熱硬化性パテ−１で埋め、屋外に出して直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。表面のＰＥＴフィルムは硬化後に剥がした。 プライマー、プリプレグシート、パテの全てを一括硬化した試験体−２を得た。
【００６９】
実施例３（試験体−３の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、水系エマルジョン樹脂と粉体からなるモルタルである商品名ショウゼットＳＡ−１（昭和電工建材（株）製）を塗膜厚：１ｍｍに塗布して２日間養生後、水系エマルジョン系プライマーとして商品名：ＭＦ４０／ＣＡＴ−ＥＰＫ（東洋モートン（株）製）を１００ｇ／ｍ^２となるように塗布してさらに１日間養生後、その上に可視光硬化性プライマー用ビニルエステル樹脂リポキシＬＣ−７２０ＰＴを１００ｇ／ｍ^２となるように塗布後、その上に可視光硬化性プライマー用ビニルエステル樹脂リポキシＬＣ−７２０ＰＴを１００ｇ／ｍ^２となるように塗布後、屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。
【００７０】
次に、プリプレグシート−１の３０ｃｍ×３０ｃｍ２枚と３０ｃｍ×５ｃｍ４枚をラップさせずに出隅部分が１ｍｍ以内の隙間になるように表面にＰＥＴフィルムを付けたまま貼り付けたものを再度屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。表面のＰＥＴフィルムは硬化後に剥がした。
次にプリプレグシートの隙間を室内で光、熱硬化性パテ−１で埋め、再度屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、プライマー、プリプレグシート、パテを夫々別々に硬化した試験体−３を得た。
【００７１】
実施例４（試験体−４の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、水系エマルジョン樹脂と粉体からなるモルタルである商品名ショウゼットＳＡ−１（昭和電工建材（株）製）を塗膜厚：１ｍｍに塗布して２日間養生後、光、熱硬化性プライマー−１を１５０ｇ／ｍ^２となるように塗布後、屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。
次に、プリプレグシート−１の３０ｃｍ×３０ｃｍ２枚と３０ｃｍ×５ｃｍ４枚をラップさせずに出隅部分が１ｍｍ以内の隙間になるように表面にＰＥＴフィルムを付け、更にプリプレグシートが未硬化のまま、プリプレグシートの隙間を室内で光、熱硬化性パテ−１で埋め、更に屋外に出して直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。表面のＰＥＴフィルムは硬化後に剥がした。
【００７２】
以上のようにプライマーを硬化後、プリプレグシート、パテを一括硬化した試験体の長さ３０ｃｍの出隅部８ヶ所に、更に光、熱硬化性プライマー−１を１５０ｇ／ｍ^２となるように塗布して３０ｃｍ×５ｃｍのプリプレグシート−１を貼り、プリプレグシートの端部を光、熱硬化性プライマー−１で封止して屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。プリプレグシートとプリプレグシートの間のパテ材（出隅部）の上に更にプリプレグシートを貼り付けた部分が存在する試験体−４を得た。
【００７３】
比較例１（試験体の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、水系エマルジョン樹脂と粉体からなるモルタルである商品名ショウゼットＳＡ−１（昭和電工建材（株）製）を塗膜厚：１ｍｍに塗布して２日間養生後、光、熱硬化性プライマー−１を塗布後、屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。
次に、３０ｃｍ×７５ｃｍのプリプレグシート−１を巻きつけ、５ｃｍラップさせた状態で貼り付けた。ラップ部は片側のＰＥＴフィルムをその部分のみ剥がして切断して貼り合せ、表面は全てＰＥＴフィルムになるようにした。残された３０ｃｍ×５ｃｍの２面は、プリプレグシート−１を３０ｃｍ×５ｃｍのサイズにして貼り付け、更に出隅部の隙間を光、熱硬化性パテ−１で埋め、再度屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、ラップ部を含む試験体−５を得た。
【００７４】
（耐食試験）
試験体−１，２，３，４および５を水、５％硫酸、５％硝酸、５％苛性ソーダ水溶液の各薬液に浸漬し、常温で６ヶ月間放置し、外観観察、建研式コンクリート付着強度試験を行った結果、試験体−１，２，３，４は大きな外観変化、コンクリート付着強度の低下も無く良好な結果であった。
一方試験体−５はラップ部の端部から薬液の浸透が見られ、コンクリート付着強度が低下した。また、一部剥離も見られた。これらの結果を表５に示す。
【００７５】
【表５】

【００７６】
実施例５（試験体−６の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板を表面処理を施した後、光、熱硬化性プライマー−１を１５０ｇ／ｍ^２となるように塗布後、プリプレグシート−１（３０ｃｍ×４５ｃｍ）２枚を使用し、上下のＰＥＴフィルムを剥がして３０ｃｍ×３０ｃｍの面の中央にラップ部が来るようにラップさせて貼り付け、且つプライマーで端部の隙間を埋めながら貼り付けた。次に、プリプレグシート−１（３０ｃｍ×１５ｃｍ）２枚を上下のＰＥＴフィルムを剥がして側面に貼り付け３０ｃｍ×３０ｃｍの面でラップさせた。更にプリプレグシート−１（１０ｃｍ×５ｃｍ）４枚を上下のＰＥＴフィルムを剥がして側面のコーナー部に貼り付けた。
最後に光、トップコートとして光、熱硬化性樹脂−１を端部処理を含め全面に塗布して、屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、 プライマー、プリプレグシート、トップコートを一括硬化した試験体−６を得た。
【００７７】
実施例６（試験体−７の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板を表面処理を施した後、エポキシ樹脂プライマーとして商品名：クリートコートＥＸ２００１プライマー（主剤：３００部／変性脂環式ポリアミン硬化剤：１００部の混合物、大日本色材工業（株）製）を１００ｇ／ｍ^２となるように塗布し、その上に可視光硬化性プライマー用ビニルエステル樹脂リポキシＬＣ−７２０ＰＴを１００ｇ／ｍ^２となるように塗布後、プリプレグシート−１（３０ｃｍ×４５ｃｍ）２枚を使用し、下側のＰＥＴフィルムを剥がして３０ｃｍ×３０ｃｍの面の中央にラップ部が来るように貼り付けた。ラップ部は下側に来るプリプレグシートラップ部の上側のＰＥＴフィルムを一時剥がしてラップして剥がしていたＰＥＴフィルムを上側のプリプレグシートのＰＥＴ面の上から重ねた。このときプライマーで下側のプリプレグシート端部とコンクリート面側の隙間を埋め、上側に来たプリプレグシート端部も埋めた。この状態で屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、表面のＰＥＴフィルムを剥がした。
【００７８】
次に、残った側面（光、熱硬化性プライマー−１の硬化面）に、プリプレグシート−１（３０ｃｍ×１５ｃｍ）２枚を下側のＰＥＴフィルムを剥がして貼り付け３０ｃｍ×３０ｃｍの面でラップさせた。シートの端部、隙間はプライマーで埋め、この状態で屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、表面のＰＥＴフィルムを剥がした。
最後にプリプレグシート−１（１０ｃｍ×５ｃｍ）４枚を下側のＰＥＴフィルムを剥がして側面のコーナー部に貼り付けた。シートの端部、隙間はプライマーで埋め、この状態で屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、表面のＰＥＴフィルムを剥がして試験体−７を得た。
【００７９】
比較例２（試験体−８の作製）
室内で３０ｃｍ×３０ｃｍ×５ｃｍの大きさのコンクリート板の表面処理を施した後、光、熱硬化性プライマー−１を塗布後、屋外に出し、直射日光下で２０分間直射日光面に放置し硬化した（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）。
次に、３０ｃｍ×７５ｃｍのプリプレグシート−１を巻きつけ、５ｃｍラップさせた状態で貼り付けた。ラップ部は片側のＰＥＴフィルムをその部分のみ剥がして切断して貼り合せ、表面は全てＰＥＴフィルムになるようにした。残された３０ｃｍ×５ｃｍの２面は、プリプレグシート−１を３０ｃｍ×５ｃｍのサイズにして貼り付け、更に出隅部の隙間を光、熱硬化性樹脂−１で埋め、再度屋外に出して直射日光下で２０分間直射日光面に放置し硬化して（３０ｃｍ×３０ｃｍの面を上に１０分間づつ放置して硬化）、ラップ部を含む試験体−８を得た。
【００８０】
（耐食試験）
また前記の耐食試験と同様に、試験体−６，７及び８を水、５％硫酸、５％硝酸、５％苛性ソーダ水溶液の各薬液に浸漬し、常温で６ヶ月管放置し、外観観察、建研式コンクリート付着強度試験を行った結果、試験体−６，７は大きな外観変化、コンクリート付着強度の低下も無く良好な結果であった。結果は表６にまとめた。
一方、試験体−８は、ラップ部の端部から薬液の浸透が見られ、コンクリート付着強度が低下した。また、一部剥離も見られた。結果は表６に示す。
【００８１】
【表６】

【００８２】
【発明の効果】
本発明は、短波長の光重合開始剤と長波長の光重合開始剤を含む樹脂組成物を繊維強化材に含浸し、予備重合せしめることにより、短波長の光に感光性を有する光重合開始剤を残存させた、Ｂステージ化の光硬化性プリプレグシートとし、該プリプレグシートを使用した工法で、従来問題とされてきた完全硬化までに長時間を必要とされ、このために揮発性の反応性モノマーの揮発を防止することにより、配合比率の変化による樹脂性能の低下、樹脂量の損失、臭気の発生、作業環境の汚染を防止するとともに、非熟練者によっても施工可能とすることに成功したものである。そして得られた硬化体は機械的強度が大であり、プリプレグシート同士を非熟練者であっても容易に完全に接着でき防水工法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for applying an FRP lining using a short-wavelength light-curable prepreg sheet for the purpose of protecting concrete tanks, pipes, floors, rooftops, verandas, etc., which require corrosion resistance and waterproofness.
[0002]
[Prior art]
In the field of anticorrosion, corrosion-resistant FRP has been widely used because of its excellent corrosion resistance, inexpensiveness, room-temperature curability and easy moldability. Examples of the resin used as the matrix of the corrosion-resistant FRP include each of unsaturated polyester resins such as isophthalic acid type, bisphenol type, and heptonic acid type, vinyl ester resin, epoxy resin, and phenol resin. However, due to its superiority in corrosion resistance, it has been used in fields of application that are not applicable to unsaturated polyester resins, and its application is expanding.
In the field of waterproofing, the characteristics required of waterproofing materials used as a waterproof covering on concrete or mortar of civil engineering buildings such as rooftops, verandas, parking lots, corridors, pools, etc. It is necessary to withstand the impact of cracks in base concrete and mortar, to have alkali resistance, and to have high adhesiveness to the base, so that it can replace conventional asphalt and urethane resin. In recent years, the FRP method using a flexible unsaturated polyester resin or vinyl ester resin combined with a fiber reinforcing material is often used.
The thermosetting resin used in the FRP method has been particularly advanced in recent years,
There are proposals such as a type having both flexibility and chemical resistance, a type having a large elongation at low temperatures, and an air-drying type. (See Patent Documents 1 to 7)
[0003]
However, when lining is performed using an unsaturated polyester resin or a vinyl ester resin, normal temperature curing is usually performed using a peroxide catalyst, and a long time is required until complete curing. If the curing takes too much time, not only does the work efficiency decrease, but also the volatile reactive monomer (styrene monomer, etc.) contained in these resins volatilizes, resulting in a change in the resin composition due to a change in the mixing ratio of the resin composition. Not only decrease, loss of resin amount, but also generation of odor, air pollution at the work site, and danger of ignition. In addition, from the technical point of view, when performing lining work, defoaming work on site is required, and the work requires skill, and it is difficult to work so that air bubbles do not completely enter.
[0004]
As one means of solving these drawbacks, attempts have been made to take measures against air pollution and odor at the site by replacing volatile monomers such as styrene in the resin with other high-boiling unsaturated compounds. However, the corrosion-resistant layer used in applications requiring high corrosion resistance was insufficient in corrosion resistance performance, and could not be completely defoamed during lining construction.
Therefore, a method has been proposed in which a fiber reinforced material is impregnated with an unsaturated polyester resin or vinyl ester resin in advance and a B-staged sheet is used. In this method, by attaching a prepreg sheet without any air bubbles, it is possible to perform FRP lining work without defoaming work, but a gap is easily formed where the sheet is wrapped, and the problem in the work has not been solved .
[0005]
As one of these measures, an unsaturated polyester resin syrup obtained by esterifying an unsaturated polybasic acid and a saturated polybasic acid together with a glycol and dissolving it in a copolymerizable monomer is impregnated and molded into glass fiber, A method has been proposed in which the thus obtained flexible glass fiber reinforced resin molded sheet is coated on a substrate surface via a synthetic resin adhesive having high elasticity of 100% to 300% (see Patent Document 8). ).
According to this method, since the cured FRP sheet has flexibility, even if the base material has a complicated shape, there is an advantage that coating can be performed according to the shape. Has the effect of minimizing the formation of the coating, but the sheet used for coating requires flexibility, and thus has a fatal defect that the mechanical strength of the coating material is insufficient.
[0006]
Also, after coating the prepreg sheet impregnated with the photocurable resin composition on the waterproof base, curing the prepreg sheet by light irradiation, and between the prepreg sheets impregnated with the photocurable resin composition. As a bonding method, a waterproofing method has been proposed in which a part of the prepreg sheet is overlapped and temporarily bonded, and then the sheet is cured by light irradiation so that the prepreg sheets are completely bonded to each other.
When this method is used, the prepreg sheet impregnated with the photocurable resin composition is coated on the waterproof substrate, and then cured by light irradiation. In the case of coating, since it is necessary to partially cure the prepreg sheets and temporarily bond them, and then to cure the whole by light irradiation, there is a disadvantage that the coating operation itself requires a high degree of technical skill. (See Patent Document 9)
[0007]
[Patent Document 1]
JP-A-8-319328
[Patent Document 2]
JP-A-1-2013362
[Patent Document 3]
JP-A-8-31805
[Patent Document 4]
JP-A-5-295860
[Patent Document 5]
JP-A-1-96079
[Patent Document 6]
JP-A-4-253717
[Patent Document 7]
JP-A-4-142323
[Patent Document 8]
JP-A-9-11376
[Patent Document 9]
JP-A-10-331345
[Patent Document 10]
JP-B-45-37377
[Patent Document 11]
JP-A-3-111402
[Patent Document 12]
JP-A-3-179003
[Patent Document 13]
JP-A-4-146905
[Patent Document 14]
JP-A-4-261405
[Patent Document 15]
JP-A-4-261406
[Patent Document 16]
JP-A-5-194609
[Non-patent document 1]
Yamaoka et al., “Surface”, 27 (7), 548 (1989)
[Non-patent document 2]
Sato et al., "Abstracts of the 3rd Polymer Material Forum", IBP18 (1994)
[0008]
[Problems to be solved by the present invention]
In view of this situation, the present invention impregnates a resin composition containing a short-wavelength photopolymerization initiator and a long-wavelength photopolymerization initiator into a fiber reinforcing material, and prepolymerizes the resin composition, thereby increasing the sensitivity to short-wavelength light. It is an object of the present invention to provide a B-staged photocurable prepreg sheet having a photopolymerization initiator remaining therein, and to solve the above-mentioned problems in construction by a method using the prepreg sheet.
[0009]
[Means for Solving the Problems]
The present invention
[1] (A) One or more radical polymerizable resins selected from unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins: 100 parts by weight,
(B) A combination of a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region with a wavelength of 500 nm or more and a photopolymerization initiator having photosensitivity in the visible light and / or ultraviolet region of less than 500 nm. At least two photopolymerization initiators: 0.01 to 10 parts by weight and
(C) Inorganic or organic filler: 100 parts by weight or less
By impregnating the fiber reinforcing material with a resin composition containing the compound, and pre-polymerizing a part of the radically polymerizable unsaturated groups in the composition, so that photopolymerization sensitive to light having a wavelength of at least less than 500 nm is obtained. After leaving a part of the initiator and radically polymerizable unsaturated groups and performing B-stage to obtain a photocurable prepreg sheet, the prepreg sheet is laid on a concrete surface with a mortar composed of an aqueous emulsion resin and powder. Made and then applied to a substrate coated with a photo-curing and / or thermo-setting primer, and sealing the edges of the prepreg sheet and the gap between the prepreg sheets with a photo-curing and / or thermo-setting resin. An FRP lining method, characterized by:
[0010]
[2] After applying a photo-curable and / or thermo-curable primer to the base, a B-staged photo-curable prepreg sheet that is impregnated with a fiber-reinforced material with a curable resin and adhered so as not to generate a wrap portion. The FRP lining method according to the above [1], wherein a gap between the end portion of the prepreg sheet and the prepreg sheet is sealed with a photocurable and / or thermosetting resin;
[3] After applying a photo-curable and / or thermo-curable primer to the substrate, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material with a curable resin and attached so that a wrap does not occur. After sealing the gap between the prepreg sheets with a photocurable and / or thermosetting resin, further covering the upper portion of the gap with a prepreg sheet, and then curing the end of the prepreg sheet with a photocurable and / or thermosetting resin. The FRP lining method according to the above [1], wherein the FRP lining is cured by sealing with a resin,
[4] After applying a photocurable and / or thermosetting primer to the base, a photocurable prepreg sheet impregnated with a curable resin into a fiber reinforced material and B-staged is adhered and wrapped on the prepreg sheet. The FRP lining method according to the above [1], wherein after coating with another photocurable prepreg sheet, the end of the prepreg sheet is sealed with a photocurable and / or thermosetting resin and cured.
[0011]
[5] The method according to any one of [1] to [4], wherein the photocurable and / or thermosetting resin used for sealing the end portion of the prepreg sheet and the gap between the prepreg sheets is a putty material. FRP lining method,
[6] Any of the above-mentioned [1] to [5], wherein, when a photo-curable and / or thermosetting primer is applied to the base, a water-based emulsion resin primer is applied to the base and then a photo-curable primer is applied. The FRP lining method described in Crab,
[7] The radical polymerization type resin as the component (A) is subjected to radical polymerization with respect to 100 parts by weight of at least one polymer selected from unsaturated polyesters, vinyl esters, urethane (meth) acrylates, and polyester (meth) acrylates. The FRP lining method according to the above [1], which is a resin component containing 10 to 250 parts by weight of a unsaturated monomer.
[0012]
[8] The photopolymerization initiator of the component (B) comprises (b1) a photopolymerization initiator having photosensitivity in the visible light or near infrared light region having a wavelength of 500 nm or more, and (b2) a visible light having a wavelength of less than 500 nm and / or Or the compounding ratio of a photopolymerization initiator which is a combination of at least two types of photopolymerization initiators having photosensitivity in the ultraviolet region is b1: b2 = 1: 50 to 50: 1. FRP lining method,
[9] As the photopolymerization initiator, (b1) a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more, and (b2) a photopolymerization initiator having a visible light and / or ultraviolet light region of less than 500 nm. The FRP lining method according to the above [8], wherein a combination of the photopolymerization initiator having photosensitivity and 0.02 to 50 parts by weight of a thermal polymerization initiator per 1 part by weight of the photopolymerization initiator is further blended;
[0013]
[10] After applying a photocurable and / or thermosetting primer to the substrate, a B-staged photocurable prepreg sheet obtained by impregnating a curable resin with a fiber reinforced material is attached, Alternatively, in the FRP lining method of burying and curing with a thermosetting putty material, the work was performed in an uncured state of the curable resin in each step of applying a primer, attaching a photocurable prepreg sheet, and filling with a putty material. The FRP lining method according to any one of the above [1] to [4], wherein the FRP lining is hardened later at once.
[11] After applying a photocurable and / or thermosetting primer to the substrate, a B-staged photocurable prepreg sheet obtained by impregnating a curable resin with a fiber reinforcing material is applied, and the photocurable and / or Alternatively, in the FRP lining method of embedding and curing with a thermosetting putty material, each step of applying a primer, attaching a photocurable prepreg sheet and filling with a putty material is performed by curing the curable resin for each step, and The above object has been solved by developing the FRP lining method according to any one of the above [1] to [4] for performing the process.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention provides a radical based on an unsaturated polyester resin or the like containing at least two types of photopolymerization initiators, a photopolymerization initiator having photosensitivity at a long wavelength and a photopolymerization initiator having photosensitivity at a short wavelength. The polymerizable resin is impregnated into the fiber reinforcement, and the generated radicals are easily controlled, and some of the unsaturated groups in the resin can be easily stopped by radical polymerization, and the fiber reinforcement, filler, pigment, etc. By irradiating with a long wavelength light that can easily promote the reaction even in a system to which is added, a photopolymerization initiator having short wavelength sensitivity and some radical polymerizable unsaturated groups in the base resin (Some unsaturated groups and some radically polymerizable unsaturated monomers in the polymer in the radically polymerizable resin) are left to form a B-stage prepreg, and a primer treatment is performed using the prepreg sheet. It was there to be pasted by providing a joint in the base.
[0015]
For this reason, the content of the radical polymerizable unsaturated monomer in the B-staged prepreg sheet is significantly reduced as compared with the impregnated resin composition, and the radical polymerizable unsaturated monomer is volatilized. This greatly reduces the properties of the resin composition, thereby preventing the composition of the resin composition from being changed and preventing the working environment from being contaminated by radically polymerizable unsaturated monomers. In addition, the prepreg sheet in the B stage has an advantage that it can be easily stored and handled at a construction site. In addition, since it is in a B-stage state, the prepreg sheet adhered to the photopolymerization initiator having photosensitivity at the short wavelength remaining by irradiating light of the short wavelength and the radical polymerizable in the base resin. It can be easily cured by the unsaturated group to form a coating having high hardness.
[0016]
The B-staged photocurable prepreg sheet in which the curable resin used in the present invention is impregnated with a fiber reinforcing material and is B-staged is obtained by (A) unsaturated polyester resin, vinyl ester resin, urethane (meth) acrylate resin, polyester (meth) ) At least one resin selected from acrylate resins: 100 parts by weight and (B) a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more, and visible light having a wavelength of less than 500 nm and / or At least two photopolymerization initiators which are a combination of photopolymerization initiators having photosensitivity in the ultraviolet region: 0.01 to 10 parts by weight and (C) an inorganic or organic filler: 100 parts by weight or less (filler Impregnated into a fiber reinforced material, and irradiated with a light having a wavelength of 500 nm or more to obtain a radical polymerizable compound in the composition. Some with allowed to prepolymerization saturated group, in which is left photopolymerization initiator having photosensitivity to light having a wavelength less than at least 500 nm, and a part of the radical polymerizable unsaturated group.
[0017]
The component (A) as the resin used in the prepreg sheet of the present invention is selected from unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins.
First, as the unsaturated polyester, those manufactured by a known method may be used.Specifically, polymerizable unsaturated bonds such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid are used. Unsaturated polybasic acid or its anhydride and fumaric acid, maleic anhydride, maleic acid, unsaturated polybasic acid having an active unsaturated bond such as itaconic acid or its anhydride as an acid component, This and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediole, 1,6- Hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol Bisphenol - ethylene oxide adducts of Le A, bisphenol - multivalent or propylene oxide adduct of Le A alcohol - Le alcohol - are those prepared by reacting a Le component.
[0018]
The vinyl ester is produced by a known method, and is obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid, or epoxy (meth) acrylate, or saturated dicarboxylic acid and / or Saturated polyester or unsaturated polyester obtained by using a saturated polyester or unsaturated polyester having a terminal carboxyl group obtained from an unsaturated dicarboxylic acid and a polyhydric alcohol and an epoxy compound containing an α, β-unsaturated carboxylic ester group as a component Is a polyester (meth) acrylate.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high-molecular-weight homologues, and novolak-type polyglycidyl ethers.
As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group used in the production of vinyl ester, glycidyl methacrylate is a typical example.
[0019]
The urethane (meth) acrylate used in the present invention is not particularly limited. For example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and a A radically polymerizable unsaturated group-containing oligomer which can be obtained by reacting a hydroxyl group-containing allyl ether compound accordingly. Further, after the hydroxyl group-containing (meth) acrylic compound is reacted with a polyhydroxy compound or a polyhydric alcohol, a polyisocyanate may be further reacted.
[0020]
The polyester (meth) acrylate used in the present invention includes (1) a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol, and an α, β-unsaturated carboxylic acid. (Meth) acrylate obtained by reacting an epoxy compound having an ester group, (2) a hydroxyl group-containing acrylate to a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol; (Meth) acrylic acid is reacted with (meth) acrylate obtained by reacting (meth) acrylate, (3) polyester having a terminal hydroxyl group obtained from saturated polybasic acid and / or unsaturated polybasic acid and polyhydric alcohol. ) Acrylate.
[0021]
The radical-curable resin used in the present invention may be any of the above-mentioned unsaturated polyesters, vinyl esters, urethane (meth) acrylates, polyester (meth) acrylates and radical polymerizable resins such as styrene monomer and methyl (meth) acrylate. It contains a saturated monomer.
[0022]
Specific examples of the radically polymerizable unsaturated monomer other than styrene monomer and methyl (meth) acrylate include α-, o-, mp-alkyl, nitro, cyano, amide, ester derivatives of styrene, and chlorostyrene. Styrene monomers such as vinyl toluene and divinylbenzene, butenes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acryl Acid i-propyl, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, ter-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2- (meth) acrylate Lehexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) Isobornyl acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, (meth) acryl Anthraninonyl acid, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, (meth) ) Benzyl acrylate Phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro (meth) acrylate n-propyl, perfluoro-i-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, ( (Meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N, N-dimethylamide (meth) acrylate, ( (Meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N- -(Meth) acrylic amides such as i-propylamide, (meth) acrylic anthracenylamide, (meth) acrylic anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, fluorine Vinyl compounds such as vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate and diethyl itaconate; N-phenylmaleimide; N-cyclohexylmaleimide , N-laurylmaleimide, monomaleimide compounds such as N- (4-hydroxyphenyl) maleimide, and N- (meth) acryloylphthalimide.
[0023]
In the present invention, a (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule may be used, and a known compound may be used. Specific examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl Examples include (meth) acrylates of various glycols such as (meth) acrylate and trimethylolpropane tri (meth) acrylate, and those represented by the general formula (1).
[0024]
Embedded image

Ph: benzene nucleus, R = H or CH ₃ , M + n = 2-30
[0025]
Commercially available products include 2,2-bis [4- (methacryloxyethoxy) phenyl] propane (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2,2-bis [4- (methacryloxy diethoxy). Phenyl] propane (Shin-Nakamura Chemical Co., Ltd .: BPE-200), 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (Shin-Nakamura Chemical Co., Ltd .: BPE-500), 2 2,2-bis [4- (acryloxydiethoxy) phenyl] propane (A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane (new A-BPE-10, manufactured by Nakamura Chemical Industry Co., Ltd.).
[0026]
The radically polymerizable unsaturated monomer blended in the resin of the present invention is important for lowering the viscosity of the resin and improving hardness, strength, weather resistance, water resistance, abrasion resistance, etc. It is used in an amount of 10 to 250 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of vinyl ester, urethane (meth) acrylate, polyester (meth) acrylate and the like. If the amount is less than 10 parts by weight, workability and impregnation deteriorate due to high viscosity. If the amount is more than 250 parts by weight, sufficient coating film hardness cannot be obtained, various physical properties are insufficient, and curability for FRP lining is low. It is not preferable as a material.
[0027]
A room temperature radical polymerization initiator is mainly used as the thermal polymerization initiator used in the present invention. Examples of the room temperature radical polymerization initiator include a known combination of a ketone peroxide and a reducing agent, a combination of a hydroperoxide and a reducing agent, and a combination of a diacyl peroxide and a reducing agent.Specific examples of the reducing agent include: Cobalt salts such as cobalt naphthenate and cobalt octylate; vanadium compounds such as vanadium pentoxide; amines such as dimethylaniline; Among them, a combination of a peroxyester and a cobalt salt is particularly effective in terms of pot life and the like.
[0028]
In addition, a known radical polymerization initiator may be used as the thermal polymerization initiator. Examples thereof are ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate, and azo compounds are also effective.
[0029]
Specific examples include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3. , 5-Trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroper Oxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, azobi Isobutyronitrile, available such as azobis carbonamido.
[0030]
The amount of the room-temperature radical polymerization initiator used is 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the resin or the like. When the amount of the room-temperature curing type radical polymerization initiator photopolymerization initiator combined with the organic peroxide or the reducing agent is less than 0.01 part by weight, the thickening reaction or the polymerization after the thickening is likely to be insufficient, If the amount exceeds 15 parts by weight, the strength of the cured product is insufficient.
[0031]
As the photopolymerization initiator used in the present invention, those having photosensitivity in a visible light region and / or an ultraviolet light region can be used.
Examples of visible light polymerization initiators having photosensitivity in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, and dicyclopentadienyltitanium described in Non-Patent Documents 1 and 2. Di (pentafluorophenyl) or other single visible light polymerization initiator, organic peroxide / dye system, diphenyliodonium salt / dye, imidazole / keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercapto Known complex initiator systems such as benzothiazole / thiopyrylium salts and hexaarylbiimidazole / radical generators such as metal arenes / cyanine dyes (see Non-Patent Document 10) can be mentioned.
[0032]
Further, an acylphosphine oxide compound is effective as an initiator having photosensitivity from ultraviolet light to visible light. Specific examples thereof include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl). ) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2 6-dichlorobenzoyl) -2,2-dimethoxy Phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2 , 5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5- Trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis ( 2-methyl-1-naphthoyl) -4-ethoxy Biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl)- 2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2, 4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphene Nylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl- Diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester, and the like.
[0033]
Specifically, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2, Irgacure-1700 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed with 4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 75% / 25%, 1-hydroxy- Cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Specialty Chemicals, Inc.) )) At a ratio of 75% / 25% Trade name Irgacure 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade names Irgacure 1850 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 50% / 50%, screws (2, 4 , 6-Trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO, BASF Corporation) 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name) Lucirin TP O, BASF Corp.) in a ratio of 50% / 50%, such as Darocur4265 (trade name). The visible light initiator may be any photopolymerization initiator having photosensitivity in the wavelength range of 380 nm to 780 nm, and may be used in combination.
[0034]
As the UV polymerization initiator, known polymerization initiators such as acetophenone-based, benzyl ketal-based, and (bis) acylphosphine oxide-based can be used. Because of low transmittance, it is preferable to use an ultraviolet polymerization initiator such as a (bis) acylphosphine oxide-based compound having photosensitivity in a relatively long wavelength region, preferably in a wavelength region of 300 nm or more.
[0035]
The amount of photopolymerization to be used is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the resin or the like. If the amount of the photopolymerization initiator is less than 0.01 part by weight, the thickening reaction and polymerization after the thickening tend to be insufficient, and if the amount exceeds 20 parts by weight, the strength of the cured product is insufficient.
[0036]
Next, primers other than the radical polymerization type will be described. Examples of primers other than the radical polymerization type primer include a room temperature curing type epoxy primer and a moisture curing type urethane primer.
The epoxy compound used for the cold-setting epoxy primer may be one produced by a known method, and may be a thermosetting epoxy resin having at least two or more epoxy groups in one component and a curing agent for epoxy. Means a combination.
[0037]
Examples of the epoxy resin include an ether type bisphenol type epoxy resin, a novolak type epoxy resin, a polyphenol type epoxy resin, an aliphatic type epoxy resin, an ester type aromatic epoxy resin, a cyclic aliphatic epoxy resin, and an ether / ester type epoxy resin. And these may be used alone or in combination of two or more. An amine-based curing agent is generally used as the epoxy resin curing agent, and examples thereof include aliphatic amines, aromatic amines, polyamides, and heterocyclic amines, and a combination of known ones such as modified amines can also be used.
[0038]
In the present invention, the water-based emulsion resin primer is an emulsion type such as an epoxy resin or an acrylic resin. For example, trade name MF40 / CAT-EPK (manufactured by Toyo Morton Co., Ltd.) in which the main agent is an acrylic resin and the curing agent is an epoxy resin. Can also be included.
The mortar composed of the water-based emulsion resin and the powder is a combination of the water-based emulsion resin and the powder, which compensates for the disadvantages of the cement mortar / concrete and further provides a special function. Acrylic resin, epoxy resin, ethylene vinyl acetate resin (EVA), styrene butadiene rubber (SBR), chloroprene rubber (CR), etc. are used for the aqueous emulsion, and cement, aggregate, pigment, etc. are used for the powder. You. It hardens due to the hydration reaction of cement, and can be made into a quick-setting type depending on the type of cement. Specific examples include Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.).
[0039]
The urethane resin used for the moisture-curable urethane primer is a polymer mainly composed of urethane bonds obtained by reacting a diisocyanate with an organic compound having two or more active hydrogen atoms (usually a diol). "Plastic Industry Dictionary" (industry research committee, published in 1985) that isocyanate groups react with each other under the action of heat or a catalyst or react with isocyanate groups and water, glycol, etc. to become a thermosetting resin. ), And known resins can be used.
For example, a compound obtained by reacting a compound having two or more hydroxyl groups at a terminal with a compound having an isocyanate group larger than the number of moles of hydroxyl groups may be used, and may contain a solvent. An example of a trade name is UM-50P (manufactured by Showa Polymer Co., Ltd.).
[0040]
The photocurable resin primer and the room temperature curable resin primer may be used alone, but it is also effective to use both the photocuring function and the room temperature curing function.
[0041]
The resin used for the prepreg sheet, the photopolymerization initiator and the thermopolymerization initiator having photosensitivity in the visible light region and / or ultraviolet region of less than 500 nm are used for the above-mentioned photocurable and / or thermosetting primer. The same resin, photopolymerization initiator and thermal polymerization initiator are used.
The photopolymerization initiator having photosensitivity in the visible or near-infrared light region having a wavelength of 500 nm or more used in the present invention is represented by the general formula (2):
D ⁺ ・ A ⁻ ・ ・ ・ ・ ・ ・ (2)
(Where D ⁺ Are methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, and pyrylium dye cations having a sensitivity to visible light or near infrared light. ^ー Represents various anions. )
And a cationic dye represented by
[0042]
General formula (3)
Embedded image

(Where Z ⁺ Represents any cation, and R ₁ , R ₂ , R ₃ And R ₄ Each independently represents an alkyl group, an aryl group, an acyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, It represents an alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. )
The photopolymerization initiator which combined the boron compound represented by these is preferable.
[0043]
The cation “Z” in the general formula (2) ⁺ Examples of the quaternary ammonium cation, quaternary pyridinium cation, quaternary quinolinium cation, diazonium cation, tetrazolium cation, sulfonium cation, which is not sensitive to visible light or near infrared light Oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium, (organic) compounds having a cation charge on oxygen atoms such as flavylium and pyrium salts, and carbon cations such as tropylium and cyclopropylium And cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin, and antimony.
[0044]
By combining this organic boron compound with a cationic dye having a photosensitive wavelength in the visible light or near-infrared light region, the dye irradiated with light having a wavelength in the photosensitive region is excited to exchange electrons with the organic boron compound. As a result, the dye is decolorized and radicals are generated, and a polymerization reaction of the coexisting polymerizable unsaturated compound occurs. In this polymerization reaction, unlike the conventional ultraviolet polymerization reaction and the like, the generated radicals are easily controlled, and the radicals can be easily stopped when a part of the unsaturated groups in the resin is radically polymerized. Further, since a long wavelength in the visible light or near infrared region is used, the reaction can be easily promoted even in a system to which a filler or a pigment is added.
[0045]
Examples of the combination of the cationic dye and the boron-based compound are described in detail in Patent Literature 11, Patent Literature 12, Patent Literature 13, Patent Literature 14, Patent Literature 15, Patent Literature 16, and the like. The cationic dye “D ⁺ Are shown in Tables 1 to 4. Among these cationic dyes, cyanine-based, styryl-based cationic dyes and triarylmethane-based dyes are preferably used. Cyanine-based and styryl-based cationic dyes are preferred in that the electron transfer with an organic boron-based compound generally occurs easily and the reaction of the present invention is easily caused.
[0046]
[Table 1]

[0047]
[Table 2]

[0048]
[Table 3]

[0049]
[Table 4]

[0050]
A which is a counter anion of the cationic dye represented by the general formula (2) ⁻ Is any anion such as p-toluenesulfonate ion, organic carboxylate ion, perchlorate ion and halide ion, and is represented by the general formula (4)
Embedded image

(Where R ₅ , R ₆ , R ₇ And R ₈ Each independently represents an alkyl group, an aryl group, an acyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, It represents an alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. )
Is particularly preferred.
The composition ratio of [organic boron compound] / [near-infrared light or visible light-absorbing cationic dye compound] of the present invention is 1/5 to 1 / 0.05, preferably 1/1 to 1/1/1 by weight. 0.1. In general, it is preferable to use a larger amount of the organic boron compound than the cationic dye from the viewpoints of the decoloring reaction of the dye and the radical generation efficiency.
[0051]
At least two kinds of photopolymerization initiators having photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more and photopolymerization initiators having photosensitivity in the visible light and / or ultraviolet light region having a wavelength of less than 500 nm. Is used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the resin or the like. When the amount of the photopolymerization initiator is less than 0.01 part by weight, the B-stage reaction and the polymerization after the B-stage are apt to be insufficient, and when the amount exceeds 20 parts by weight, the strength of the cured product is insufficient.
[0052]
A photopolymerization initiator having a photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more for a prepolymerization reaction for bringing into a B-stage state, and visible light of less than 500 nm for fully curing the prepolymerized reaction product and / or When a photopolymerization initiator having photosensitivity in the ultraviolet region is used in combination, the composition ratio is 0.1 / 5 to 5 / 0.1, preferably 0.5 / 5 to 5/0. 5 When the ratio of the photopolymerization initiator for prepolymerization to the photopolymerization initiator for main curing is less than 0.1 / 5, the light of the photosensitive wavelength (500 to 1200 nm) of the photopolymerization initiator for prepolymerization for bringing into the B-stage state. Even if irradiation is performed, the prepolymerization reaction may not proceed, while if the ratio exceeds 5 / 0.1, the prepolymerization reaction may proceed too much.
[0053]
A photopolymerization initiator having photosensitivity in the visible light region and / or ultraviolet region of less than 500 nm is used as a polymerization initiator when the prepolymerized product is fully cured, but may be combined with a thermal polymerization initiator. When a thermal polymerization initiator is used in combination, the composition ratio is 0.1 / 5 to 5 / 0.1, preferably 0.5 / 5 to 5 / 0.5 by weight.
[0054]
The fiber reinforcing material used in the present invention is a cloth or mat such as an organic and / or inorganic fiber such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, and ceramic fiber. A known material such as a nonwoven fabric is used. Of course, two or more of these fibers may be used in combination. Among these reinforcing materials, glass fibers and organic fibers are particularly desirable in the present invention, and cloths and mats are preferred in view of workability and the like.
[0055]
In the present invention, a filler may be added, and the filler used is an inorganic filler, an organic filler or a polymer. Examples of the inorganic filler include aluminum hydroxide, calcium carbonate, talc, clay, and glass powder. Known materials such as silica, barium sulfate, titanium oxide, and cement are used, but aluminum hydroxide is effective for imparting flame retardancy to the curable prepreg composition. Of course, these inorganic fillers can also be used in combination, and the amount used is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the polymerizable unsaturated compound. When the amount of the inorganic filler is more than 200 parts by weight, the viscosity is too high, the workability is reduced, and the foam is likely to remain, and the strength is reduced.
Further, in the present invention, thixotropic may be imparted by a known method. As the thixotropic agent, for example, silica powder (aerosil type), mica powder, casium carbonate powder and the like can be used in an amount of 100 parts by weight of a polymerizable unsaturated compound. 0.1 to 50 parts by weight based on the weight of the mixture.
[0056]
In addition, as the organic filler or polymer that can be added to the composition of the present invention, for example, known polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, polyvinylidene chloride microballoon, and polystyrene which are also effective as a low shrinkage agent Acrylonitrile microballoons and the like can be used. When used as a low shrinkage agent, the amount used is 0 to 200 parts by weight, preferably 0 to 50 parts by weight, per 100 parts by weight of the resin.
Pigments can be used in the present invention. There is no particular limitation on the type, and organic pigments and inorganic pigments can be used. At that time, the compounding amount is at most 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the resin.
[0057]
In the present invention, ultraviolet light refers to light rays in a wavelength range of 280 to 380 nm, visible light refers to light rays in a wavelength range of 380 to 780 nm, and near infrared light refers to light rays in a wavelength range of 780 to 1200 nm.
As a light source used in the prepolymerization reaction for obtaining the prepreg-like curable material for preventing concrete from falling off in the B-stage state of the present invention, a light source having a spectral distribution in a photosensitive wavelength region of a photopolymerization initiator is used. For example, a near-infrared lamp, a sodium lamp, a halogen lamp, a fluorescent lamp, a metal halide lamp, or the like can be used. In addition, it is also possible to select and irradiate a wavelength necessary for the prepolymerization reaction by combining these lamps or light in a wide wavelength range with a light source and a wavelength cut filter.
The wavelength used for the prepolymerization reaction is preferably light on the long wavelength side having a low energy level. In particular, when near infrared light is used, the B-stage reaction can be easily controlled.
[0058]
The irradiation time of the lamp for pre-polymerizing to be in the B-stage state cannot be defined unconditionally because the effective wavelength range of the light source, the output, the irradiation distance, the thickness of the composition, etc. are different, but 0.01 hours or more. Irradiation is preferably performed for 0.05 hours or more.
A specific production example will be described. For example, vinylon mesh and vinylon mat are laminated using a vinyl ester resin to which a visible ray initiator and a near-infrared initiator are added, and those sandwiched between films are irradiated with near-infrared rays to perform prepolymerization by near-infrared radical polymerization. By proceeding, it is possible to produce a curable material for concrete exfoliation prevention as a visible light curable prepreg sheet in which a visible light initiator and a polymerizable unsaturated group remain.
The prepreg-shaped curable material for concrete exfoliation prevention manufactured in this way can be quickly and completely cured by light irradiation with the remaining photopolymerization initiator.
The light source for light irradiation may be any light source having a spectral distribution in the photosensitive wavelength region of the remaining photopolymerization initiator, such as sunlight, a metal halide lamp, a halogen lamp, an ultraviolet lamp, and a fluorescent lamp.
[0059]
The primer used in the present invention may be a radical polymerizable resin or an epoxy resin photo-curable and / or thermo-curable primer. The resin (A) used for the photo-curable prepreg sheet is a thermo-curable resin. One that has been made to be light curable, one that has been cured at room temperature, or one that has both functions can be used.
As the photo-curable and / or thermo-curable resin used in the present invention, a combination of the resin (A) used for the above-described photo-curable prepreg sheet and a polymerization initiator is used.
Further, as the putty material, a material prepared by further combining a filler with a photocurable and / or thermosetting resin may be used, or a commercially available putty material may be used. Epoxy-based and urethane-based putty materials can be used.
[0060]
In the curing method of the present invention, the surface of concrete is treated, a primer is applied, a prepreg sheet is attached so that a wrap portion is not generated, and a gap between the prepreg sheets is filled with a putty material and cured by light irradiation or the like. Alternatively, each step may be independently cured to proceed to the next step. After the primer is cured, the prepreg sheet may be adhered so that no wrap is formed, and the gap between the prepreg sheets may be filled with putty material and cured together, or the primer and prepreg sheet may be cured together. Later, the gap between the prepreg sheets may be filled with a putty material and cured.
[0061]
Alternatively, the gap between the prepreg sheets may be filled with a putty material, and then the prepreg sheet may be further attached and protected. At this time, if the prepreg sheet is to be pasted after the lower side is cured, it is desirable that the prepreg sheet be pasted and cured after sanding and primer application. If the lower side is not cured, a prepreg sheet may be pasted and cured as it is.
[0062]
[Example]
Hereinafter, the content of the present invention will be described in detail with reference to Examples and Comparative Examples, where “parts” in each example is based on weight. The present invention is not limited to only these examples.
[Preparation of raw materials]
<Preparation of primer>
Vinyl ester resin lipoxy LC-720PT for visible light curable primer (thixotropic modification type manufactured by Showa Polymer Co., Ltd.): 100 parts by weight of a normal temperature radical curing agent methyl ethyl ketone peroxide (trade name, Permec N: Nippon Oil & Fats) (Co., Ltd.): 1.0 part and Co: naphthenate: 0.5 part were added to obtain a light- and thermosetting primer-1.
[0063]
<Preparation of prepreg sheet>
Vinyl ester resin Lipoxy R-806 (manufactured by Showa Polymer Co., Ltd.): 100 parts by weight, triethylamine: 1.0 part, 1,1,5,5-tetrakis (p-diethylaminophenyl) shown in No. 3 of Table 1 -2,4-pentadienyl triphenyl-n-butyl borate (manufactured by Showa Denko KK; hereinafter abbreviated as IRB; near-infrared light absorbing cationic dye): 0.03 part and tetra-n-butylammonium. Triphenyl-n-butyl borate (manufactured by Showa Denko KK, hereinafter abbreviated as P3B. Boron compound): Near-infrared photopolymerization initiator for B-stage combining 0.15 parts, I-1800: 1.0 part was added to obtain a curable resin composition.
[0064]
Next, a 50 cm × 50 cm vinylon triaxial mesh (trade name: TRINEO, manufactured by Unitika Ltd.) and a polyester nonwoven fabric (trade name: Sontara 8005H, manufactured by Dupont) are combined with a fiber content of 10 Wt. % Is covered with a transparent PET film, and AL-Spotlight (ALF-10) 1KW which is a light source including a wavelength range of 380 to 1200 nm is used in combination with SC-50 which is a cut filter of 500 nm or less. Then, when irradiation was performed at a distance of 20 cm, the B-stage was formed in 2 minutes, and the B-stage state was not changed even after one spectral irradiation was continued. Therefore, the B-stage state after light irradiation for 3 minutes was designated as prepreg sheet-1, and the storage stability in a dark place at 30 ° C. was examined. As a result, the hardness of the prepreg did not change for 6 months or more.
[0065]
<Preparation of putty>
Vinyl ester resin Lipoxy R-802 (manufactured by Showa Polymer Co., Ltd.): 100 parts by weight, talc: 80 parts by weight, calcium carbonate: 30 parts by weight, I-1800: 1.0 part, methyl ethyl ketone as a room temperature radical curing agent 1.0 part of peroxide (trade name, Permec N: manufactured by NOF CORPORATION) and 0.5 part of naphthenic acid Co were added to obtain a light- and thermosetting putty-1.
[0066]
<Adjustment of photocurable and / or thermosetting resin>
Vinyl ester resin Lipoxy LC-720 for visible light curable primer (manufactured by Showa Polymer Co., Ltd.): 100 parts by weight of a methyl ethyl ketone peroxide as a room temperature radical curing agent (trade name, Permec N: manufactured by NOF Corporation) : 1.0 part and Co: 0.5 part of naphthenate were added to obtain a light- and thermosetting resin-1.
[0067]
[Production of test specimen]
Example 1 (Production of Specimen-1)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm in a room, a mortar composed of water-based emulsion resin and powder, Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.) is applied. Thickness: applied to 1 mm, cured for 2 days, then coated with light and thermosetting primer-1 at 150 g / m ² After the application, the prepreg sheet-1 was affixed with the PET film attached to the surface so that the protruding corner portion became a gap of 1 mm or less without wrapping the 30 cm × 30 cm2 sheet and the 30 cm × 5 cm4 sheet. Was placed outdoors in direct sunlight for 20 minutes to cure on the surface exposed to direct sunlight (curing by leaving the 30 cm × 30 cm surface on top for 10 minutes each). The PET film on the surface was peeled off after curing.
Next, the gap between the prepreg sheets is filled with light and thermosetting putty-1 in a room, and then put out again and left under direct sunlight for 20 minutes in a direct sunlight surface to be cured (10 cm on a 30 cm × 30 cm surface up). After curing the primer and the prepreg sheet at one time, a putty was cured to obtain a test body-1.
[0068]
Example 2 (production of test body-2)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm in a room, a mortar composed of water-based emulsion resin and powder, Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.) is applied. Thickness: applied to 1 mm, cured for 2 days, then coated with light and thermosetting primer-1 at 150 g / m ² After application, the prepreg sheet-1 was affixed with a PET film attached to the surface so that the protruding corner portion was a gap of 1 mm or less without wrapping 30 cm × 30 cm2 and 30 cm × 5 cm4.
Next, while the primer and the prepreg sheet remain uncured, the gap between the prepreg sheets is filled with light and thermosetting putty-1 indoors, put out of the room, and left for 20 minutes under direct sunlight to cure. (A 30 cm × 30 cm surface is left on each for 10 minutes to cure). The PET film on the surface was peeled off after curing. Specimen-2 in which all of the primer, prepreg sheet and putty were cured at one time was obtained.
[0069]
Example 3 (Production of test body-3)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm in a room, a mortar composed of an aqueous emulsion resin and powder, Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.) is applied. Film thickness: applied to 1 mm and cured for 2 days, then 100 g / m of MF40 / CAT-EPK (manufactured by Toyo Morton Co., Ltd.) as an aqueous emulsion primer ² After curing for an additional day, 100 g / m of lipoxy LC-720PT, a vinyl ester resin for visible light curable primer, was applied thereon. ² After coating, a vinyl ester resin for visible light curable primer, Lipoxy LC-720PT, was coated thereon at 100 g / m2. ² After the application, the film was put outdoors and left for 20 minutes under direct sunlight to cure on the surface exposed to direct sunlight (curing by leaving the 30 cm × 30 cm surface on each side for 10 minutes).
[0070]
Next, 30 cm × 30 cm 2 sheets and 30 cm × 5 cm 4 sheets of the prepreg sheet-1 were stuck together with the PET film attached on the surface so that the protruding corner portion was a gap of 1 mm or less without being wrapped, and then outdoors. It was then left in direct sunlight for 20 minutes in direct sunlight to cure (hardening by leaving the 30 cm × 30 cm surface on top for 10 minutes each). The PET film on the surface was peeled off after curing.
Next, the gap between the prepreg sheets is filled with light and thermosetting putty-1 in a room, and then put out again and left under direct sunlight for 20 minutes in a direct sunlight surface to be cured (10 cm on a 30 cm × 30 cm surface up). The cured product was allowed to stand for each minute, and a primer-3, a prepreg sheet, and a putty were separately cured to obtain a test sample-3.
[0071]
Example 4 (production of test body-4)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm in a room, a mortar composed of water-based emulsion resin and powder, Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.) is applied. Thickness: applied to 1 mm, cured for 2 days, then coated with light and thermosetting primer-1 at 150 g / m ² After the application, the film was put outdoors and left for 20 minutes under direct sunlight to cure on the surface exposed to direct sunlight (curing by leaving the 30 cm × 30 cm surface on each side for 10 minutes).
Next, without wrapping 30 cm x 30 cm2 and 30 cm x 5 cm4 of the prepreg sheet-1, a PET film is attached to the surface so that the protruding corner portion is a gap within 1 mm, and further, the prepreg sheet remains uncured. Fill the gap of the prepreg sheet with light and thermosetting putty-1 indoors, and then put it outdoors and leave it in direct sunlight for 20 minutes under direct sunlight and cure (left side of 30cm x 30cm surface for 10 minutes) And cured). The PET film on the surface was peeled off after curing.
[0072]
After curing the primer as described above, the prepreg sheet and the putty were cured at one time. ² And prepreg sheet-1 of 30 cm × 5 cm is adhered, and the end of the prepreg sheet is sealed with light and thermosetting primer-1 and put out, and exposed to direct sunlight for 20 minutes under direct sunlight (30 cm × 30 cm surface was cured by leaving it on each side for 10 minutes). Specimen-4 was obtained in which a prepreg sheet was further stuck on the putty material (protruding corner) between the prepreg sheets.
[0073]
Comparative Example 1 (Preparation of test piece)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm in a room, a mortar composed of water-based emulsion resin and powder, Showet SA-1 (trade name, manufactured by Showa Denko Kenzai Co., Ltd.) is applied. Thickness: applied to 1 mm, cured for 2 days, coated with light and thermosetting primer-1, put out, left to stand in direct sunlight for 20 minutes under direct sunlight, and cured (30 cm × 30 cm surface Leave on top for 10 minutes to cure).
Next, prepreg sheet-1 of 30 cm × 75 cm was wound around and pasted in a state of 5 cm wrap. The wrap portion was obtained by peeling off only one side of the PET film and cutting and bonding the whole, so that the entire surface became a PET film. The remaining two sides of 30 cm × 5 cm are pasted on a prepreg sheet-1 having a size of 30 cm × 5 cm, and the gaps at the corners are filled with light and thermosetting putty-1. The specimen was cured by leaving it on a direct sunlight surface for 20 minutes in the sunlight (30 cm × 30 cm surface was left standing for 10 minutes each) to obtain a test body-5 including a wrap portion.
[0074]
(Corrosion resistance test)
Specimens-1, 2, 3, 4, and 5 were immersed in water, 5% sulfuric acid, 5% nitric acid, and 5% aqueous caustic soda solution, allowed to stand at room temperature for 6 months, observed for appearance, and adhered to Kenken-type concrete As a result of the strength test, the specimens 1, 2, 3, and 4 showed good results without a large change in appearance and a decrease in concrete adhesion strength.
On the other hand, in the test body-5, the penetration of the chemical solution was observed from the end of the lap portion, and the concrete adhesion strength was reduced. Partial peeling was also observed. Table 5 shows the results.
[0075]
[Table 5]

[0076]
Example 5 (Production of test body-6)
After performing a surface treatment on a concrete plate having a size of 30 cm × 30 cm × 5 cm indoors, 150 g / m of light and thermosetting primer-1 is applied. ² After applying so that two sheets of prepreg sheet-1 (30 cm × 45 cm) are used, the upper and lower PET films are peeled off and wrapped so that the wrap portion comes to the center of the 30 cm × 30 cm surface, and adhered, and It was affixed while filling the gap at the end with a primer. Next, two sheets of prepreg sheet-1 (30 cm × 15 cm) were peeled off the upper and lower PET films, stuck on side surfaces, and wrapped on a 30 cm × 30 cm surface. Further, four prepreg sheets-1 (10 cm × 5 cm) were peeled off from the upper and lower PET films and attached to the corners on the side surfaces.
Finally, light and thermosetting resin-1 are applied to the entire surface including the edge treatment as a top coat, and then put out and left under direct sunlight for 20 minutes under direct sunlight to cure (30 cm × 30 cm). Was left standing for 10 minutes each side to cure), to obtain a test body-6 in which the primer, the prepreg sheet, and the top coat were collectively cured.
[0077]
Example 6 (Preparation of test body-7)
After a concrete plate having a size of 30 cm × 30 cm × 5 cm is subjected to a surface treatment in a room, a mixture of trade name: Cleatcoat EX2001 primer (main agent: 300 parts / modified alicyclic polyamine curing agent: 100 parts) is used as an epoxy resin primer. 100 g / m from Dainippon Color Material Co., Ltd. ² Is applied so that the vinyl ester resin for visible light curable primer Lipoxy LC-720PT is 100 g / m2. ² After the application, two prepreg sheets-1 (30 cm × 45 cm) were used, the lower PET film was peeled off, and the sheet was affixed so that the lap portion came to the center of the 30 cm × 30 cm surface. As for the wrap portion, the PET film on the upper side of the prepreg sheet wrap portion coming down was temporarily peeled off, and the PET film which had been wrapped and peeled was overlaid on the PET surface of the upper prepreg sheet. At this time, the gap between the lower end of the prepreg sheet and the concrete surface side was filled with the primer, and the end of the prepreg sheet coming above was also filled. In this state, the film was taken out of the room and left under direct sunlight for 20 minutes under direct sunlight to be cured (the surface of 30 cm × 30 cm was cured by leaving it up for 10 minutes), and the PET film on the surface was peeled off.
[0078]
Next, on the remaining side surface (cured surface of the light and thermosetting primer-1), two prepreg sheets-1 (30 cm × 15 cm) were peeled off and the lower PET film was peeled off and wrapped with a 30 cm × 30 cm surface. I let it. The edges and gaps of the sheet are filled with a primer, put out in this state, and left under direct sunlight for 20 minutes under direct sunlight, and cured (cured by leaving a 30 cm × 30 cm surface on each side for 10 minutes). Then, the PET film on the surface was peeled off.
Lastly, four prepreg sheets-1 (10 cm × 5 cm) were peeled off from the lower PET film and attached to the side corners. The edges and gaps of the sheet are filled with a primer, put out in this state, and left under direct sunlight for 20 minutes under direct sunlight, and cured (cured by leaving a 30 cm × 30 cm surface on each side for 10 minutes). Then, the PET film on the surface was peeled off to obtain a test body-7.
[0079]
Comparative Example 2 (Production of Specimen-8)
After applying a surface treatment of a concrete board of 30 cm x 30 cm x 5 cm indoors, apply a light and thermosetting primer-1 and then put it outdoors and leave it in direct sunlight for 20 minutes under direct sunlight to cure (Hardened by leaving the 30 cm × 30 cm surface on each side for 10 minutes).
Next, prepreg sheet-1 of 30 cm × 75 cm was wound around and pasted in a state of 5 cm wrap. The wrap portion was obtained by peeling off only one side of the PET film and cutting and bonding the whole, so that the entire surface became a PET film. The remaining two sides of 30 cm × 5 cm are pasted on a prepreg sheet-1 having a size of 30 cm × 5 cm, and the gaps at the protruding corners are filled with light and thermosetting resin-1. The specimen was cured by leaving it on a direct sunlight surface for 20 minutes in the sunlight (30 cm × 30 cm surface was left standing for 10 minutes each) to obtain a test piece-8 including a wrap portion.
[0080]
(Corrosion resistance test)
In the same manner as in the above-described corrosion resistance test, test specimens -6, 7, and 8 were immersed in water, 5% sulfuric acid, 5% nitric acid, and 5% aqueous solution of caustic soda, left in a tube at room temperature for 6 months, and observed for appearance. As a result of the Kenken-type concrete adhesion strength test, the test specimens -6 and 7 showed good results without a large change in appearance and a decrease in concrete adhesion strength. The results are summarized in Table 6.
On the other hand, in the test body-8, the penetration of the chemical solution was observed from the end of the lap portion, and the concrete adhesion strength was reduced. Partial peeling was also observed. The results are shown in Table 6.
[0081]
[Table 6]

[0082]
【The invention's effect】
The present invention impregnates a resin composition containing a short-wavelength photopolymerization initiator and a long-wavelength photopolymerization initiator into a fiber reinforcing material, and prepolymerizes the resin composition to initiate photopolymerization having photosensitivity to short-wavelength light. A B-staged photocurable prepreg sheet with the agent remaining is required, and the method using the prepreg sheet requires a long time to complete curing, which has been a problem in the past, and therefore, volatile reaction By preventing the volatilization of the reactive monomer, it is possible to prevent the deterioration of the resin performance due to the change of the mixing ratio, the loss of the resin amount, the generation of odor and the pollution of the working environment, and also to make it possible for unskilled workers to work It was done. The obtained cured product has high mechanical strength, and is a waterproofing method that enables even non-experts to easily and completely adhere prepreg sheets to each other.

Claims (11)

(A) at least one radical polymerizable resin selected from unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins: 100 parts by weight;
(B) A combination of a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region with a wavelength of 500 nm or more and a photopolymerization initiator having photosensitivity in the visible light and / or ultraviolet region of less than 500 nm. A resin composition containing at least two kinds of photopolymerization initiators:... 0.01 to 10 parts by weight and (C) an inorganic or organic filler:. A photopolymerization initiator and a radically polymerizable unsaturated group that are photosensitive to light having a wavelength of at least less than 500 nm by impregnating the material and prepolymerizing a part of the radically polymerizable unsaturated group in the composition. After leaving a part of the prepreg sheet and making it into the B stage to form a photocurable prepreg sheet, the prepreg sheet is formed on a concrete surface with a mortar composed of an aqueous emulsion resin and powder. Further, the photo-curable and / or thermo-curable primer is applied to the base, and the end of the prepreg sheet and the gap between the prepreg sheets are sealed with a photo-curable and / or thermo-curable resin. A featured FRP lining method. After applying a photo-curable and / or thermo-curable primer to the base, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material and then affixed so that a wrap portion is not generated. The FRP lining method according to claim 1, wherein a gap between the end portion of the prepreg sheet and the prepreg sheet is sealed with a photocurable and / or thermosetting resin. After applying a photo-curable and / or thermo-curable primer to the base, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material and then affixed so that a wrap portion is not generated. Is sealed with a photo-curing and / or thermosetting resin, and then the top of the gap is covered with a prepreg sheet, and then the end of the prepreg sheet is sealed with a photo-curing and / or thermosetting resin. The FRP lining method according to claim 1, wherein the FRP lining is stopped and cured. After applying a photo-curable and / or thermo-curable primer to the substrate, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material with a curable resin, and the prepreg sheet is wrapped with another prepreg sheet. The FRP lining method according to claim 1, wherein after coating with the photocurable prepreg sheet, the end of the prepreg sheet is sealed with a photocurable and / or thermosetting resin and cured. The FRP lining method according to any one of claims 1 to 4, wherein the photocurable and / or thermosetting resin used for sealing an end portion of the prepreg sheet and a gap between the prepreg sheets is a putty material. The photocurable primer according to any one of claims 1 to 5, wherein when applying a photocurable and / or thermosetting primer to the base, a water-based emulsion resin primer is applied to the base and then the photocurable primer is applied. FRP lining method. The radical-curable resin (A) is a radical-polymerizable unsaturated resin based on 100 parts by weight of at least one polymer selected from unsaturated polyesters, vinyl esters, urethane (meth) acrylates, and polyester (meth) acrylates. The FRP lining method according to claim 1, which is a resin component containing 10 to 250 parts by weight of a monomer. The photopolymerization initiator of the component (B) is (b1) a photopolymerization initiator having photosensitivity in the visible light or near infrared light region having a wavelength of 500 nm or more, and (b2) a visible light and / or ultraviolet light having a wavelength of less than 500 nm. The FRP lining method according to claim 1, wherein the blending ratio of the photopolymerization initiator, which is a combination of at least two photopolymerization initiators having photosensitivity in the region, is b1: b2 = 1: 50 to 50: 1. As the photopolymerization initiator, (b1) a photopolymerization initiator having photosensitivity in a visible light or near-infrared light region having a wavelength of 500 nm or more, and (b2) a photopolymerization initiator having photosensitivity in a visible light and / or ultraviolet light region of less than 500 nm. The FRP lining method according to claim 8, wherein 0.02 to 50 parts by weight of a thermal polymerization initiator is further blended with respect to 1 part by weight of the photopolymerization initiator based on the combination of the photopolymerization initiators. After applying a photo-curable and / or thermo-curable primer to the substrate, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material with a curable resin, and the photo-curable and / or thermo-curable In the FRP lining method of burying and curing with a putty material, after applying the primer, applying a photo-curable prepreg sheet and burying with the putty material, the curable resin in each process is performed in an uncured state. The FRP lining method according to any one of claims 1 to 4, wherein the FRP lining is cured all at once. After applying a photo-curable and / or thermo-curable primer to the substrate, a B-staged photo-curable prepreg sheet is impregnated with a fiber-reinforced material with a curable resin, and the photo-curable and / or thermo-curable In the FRP lining method of filling and curing with a putty material, the steps of applying a primer, attaching a photocurable prepreg sheet, and filling with a putty material are performed. The FRP lining method according to any one of claims 1 to 4.