JP4316101B2 - Process for producing cast cured products - Google Patents

Description

【００１５】
（式中、Ｚ⁺ は任意の陽イオンを示し、Ｒ¹ ，Ｒ² ，Ｒ³ 及びＲ⁴ 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，置換アルキニル基又は置換シリル基を示す。）
で表される有機ホウ素化合物からなる可視光領域あるいは近赤外光領域に感光性を有する光重合開始剤、
▲２▼一般式（３）
【００１６】
【化７】

【００１７】
（式中、Ｒ⁵ ，Ｒ⁶ 及びＲ⁷ はそれぞれ独立してアルキル基，アリール基，アラルキル基，アルケニル基，アルキニル基，複素環基，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，置換アルキニル基又は置換複素環基を示す）
で表されるビスアシルホスフィンオキサイド化合物からなる紫外光から可視光領域に感光性を有する重合開始剤、
▲３▼一般式（４）
【００１８】
【化８】

【００１９】
（式中、Ｒ⁸ ，Ｒ⁹ 及びＲ¹⁰はそれぞれ独立してアルキル基，アリール基，アラルキル基，アルケニル基，アルキニル基，複素環基，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，置換アルキニル基又は置換複素環基を示す。）
で表されるアシルホスフィンオキサイド化合物からなる紫外光から可視光領域に感光性を有する光重合開始剤、並びに
▲４▼ベンゾイン、ベンジル、アセトフェノン、ベンゾフェノンおよびこれらの誘導体から選ばれる紫外線重合開始剤
から選ばれる光重合開始剤が好ましい。
なお、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。
【００２０】
▲１▼可視光領域あるいは近赤外光領域波長に感光性を有する光重合開始剤を構成する、一般式（１）で表される陽イオン色素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（６）
【００２１】
【化９】

【００２２】
（式中、Ｒ¹¹，Ｒ¹²，Ｒ¹³及びＲ¹⁴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，置換シリル基又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。
【００２３】
一方。一般式（２）における陽イオン「Ｚ⁺ 」の例としては、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，、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。
本発明において、有機ホウ素化合物と近赤外光あるいは可視光吸収性陽イオン色素との組成比は、重量比で１／５〜１／0.０５（有機ホウ素化合物／陽イオン色素）が好ましく、特に好ましくは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。
【００２４】
一般式（２）で表される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陽イオン色素とを組み合わせることにより、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時点で容易に止めることができる。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、充填材や顔料などが添加された系においても容易に反応を進めることができるという特徴を有する。
【００２５】
上記陽イオン色素とホウ素系化合物との組み合わせの例は、特開平３−１１１４０２号公報、特開平３−１７９００３号公報、特開平４−１４６９０５号公報、特開平４−２６１４０５号公報、特開平４−２６１４０６号公報、特開平５−１９４６１９号公報などに詳細な記載がある。陽イオン色素における「Ｄ⁺ 」の具体例を第１表及び第２表に示す。これらの陽イオン色素の中でも好ましくはシアニン系、スチリル系陽イオン色素及びトリアリールメタン系色素である。シアニン系、スチリル系陽イオン色素は、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特に好ましい。
【００２６】
【表１】

【００２７】
【表２】

【００２８】
【表３】

【００２９】
【表４】

【００３０】
可視光重合開始剤としては、例えば山岡ら、「表面」，２７（７），５４８（１９８９）、佐藤ら、「第３回 ポリマー材料フォーラム要旨集」、１ＢＰ１８（１９９４）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シド、メチルチオキサントン、ビスペンタジエニルチタニウム−ジ（ペンタフルオロフェニル）等の単独での可視光重合開始剤の他、有機過酸化物触媒／色素系、ジフェニルヨ−ドニウム塩／色素、ビスイミダゾール／ケト化合物、ヘキサアリールビスミダゾール化合物／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／シアニン色素の他、特公昭４５−３７３７７号公報に記載のヘキサアリールビスイミダゾール／ラジカル発生剤等の公知の複合開始剤系を挙げることができる。
本発明においては、紫外光から可視光領域に感光性を有する光重合開始剤として、▲２▼一般式（３）
【００３１】
【化１０】

【００３２】
（式中、Ｒ⁵ ，Ｒ⁶ 及びＲ⁷ はそれぞれ独立してアルキル基，アリール基，アラルキル基，アルケニル基，アルキニル基，複素環基，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，置換アルキニル基又は置換複素環基を示す）
で表されるビスアシルホスフィンオキサイド化合物又は▲３▼一般式（４）
【００３３】
【化１１】

【００３４】
（式中、Ｒ⁸ ，Ｒ⁹ 及びＲ¹⁰はそれぞれ独立してアルキル基，アリール基，アラルキル基，アルケニル基，アルキニル基，複素環基，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，置換アルキニル基又は置換複素環基を示す。）
で表されるアシルホスフィンオキサイド化合物からなる光重合開始剤が使用される。
これらの開始剤は、従来用いられているＵＶ開始剤よりも長波長領域に感光性を有し（４００ｎｍ以上の可視光領域）、光の透過性に優れる上、光照射により開裂してアシルラジカルとホスフィノイルラジカルを発生するので、従来用いられているＵＶ開始剤よりも重合開始効率が高いとされている。これらは一種を単独で使用してもよく、二種以上を組み合わせて使用することもできる。
【００３５】
上記一般式（３）で表されるビスアシルホスフィンオキサイド化合物の具体例としては、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等を挙げることができる。
【００３６】
上記一般式（４）で表されるアシルホスフィンオキサイド化合物の具体例としては、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。
▲４▼の紫外線重合開始剤は、ベンゾイン、ベンジル、アセトフェノン、ベンゾフェノンおよびこれらの誘導体から選ばれるが、誘導体の例としては、ベンゾイン系のものとして、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、アセトフェノン系のものとして、ジエトキシアセトフェノン、2,2-ジメトキシ-1,2- ジフェニルエタン-1- オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-(4-( メチルチオ) フェニル)-2-モンフォリノプロパン-1、2-ベンジル-2- ジメチルアミノ-1-(4-モルフォリノフェニル) ブタノン-1、2-ヒドロキシ-2- メチル-1- フェニルプロパン-1- オン、1-(4-(2-ヒドロキシエトキシ)-フェニル)-2-ヒドロキシジ-2- メチル-1- プロパン-1- オン、ベンゾフェノン系のものとして、O-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4'-メチルジフェニルサルファイド、3,3',4,4'-テトラ(t- ブチルパーオキシカルボニル) ベンゾフェノン、2,4,6-トリメチルベンゾフェノン、4-ベンゾイル-N,N- ジメチル-N-[2-(1- オキシ-2- プロペニルオキシ) エチル] ベンゼンメタナミニウムブロミド、(4- ベンゾイルベンジル) トリメチルアンモニウムクロリド、4,4'- ジメチルアミノベンゾフェノン、4,4'- ジエチルアミノベンゾフェノン等が挙げられる。
（Ｃ）成分の紫外光から近赤外光領域の範囲内のいずれかに感光性を有する光重合開始剤の添加量は、（Ａ）成分の樹脂１００重量部に対して0.１〜１０重量部、好ましくは0.５〜５重量部であり、一種を単独で使用してもよく、二種以上を組み合わせて使用することもできる。光重合開始剤の添加量が0.１重量部より少なすぎる場合は、十分に硬化できず、また光重合開始剤の添加量が１０重量部を超えると、経済的に不利な上、硬化物の物性低下などが起こる。
【００３７】
本発明においては、（Ｃ）成分の紫外光から近赤外光領域の範囲内のいずれかに感光性を有する光重合開始剤に、上記一般式（２）で表される有機ホウ素化合物及び酸性化合物からなる重合開始剤、あるいは上記一般式（２）で表される有機ホウ素化合物、酸性化合物及び一般式（５）
【００３８】
【化１２】

【００３９】
（式中、Ｌ¹ ，Ｌ² 及びＬ³ はそれぞれ独立にアリール基又は置換アリール基を示す。）
で表されるヘキサアリールビイミダゾール化合物からなる重合開始剤を組み合わせて使用することができる。ヘキサアリールビイミダゾール化合物の具体例としては、ビス（２，４，５−トリフェニル）イミダゾール，ビス（２−ｏ−クロロフェニル−４，５−ジフェニル）イミダゾール，ビス（２−ｏ，ｐ−ジクロロフェニル−４，５−ジフェニル）イミダゾール，ビス（２−ｏ−ブロモフェニル−４，５−ジフェニル）イミダゾール等が挙げられる。
【００４０】
酸性化合物の具体例としては、例えば一般にブレンステッド酸として知られている無機酸や有機酸が挙げられる。無機酸としては、例えば塩酸，硫酸，硝酸等が挙げられ、有機酸としては、例えば酢酸，プロピオン酸，マレイン酸，アジピン酸，（メタ）アクリル酸，安息香酸，フタル酸類などのカルボン酸類、ｐ−トルエンスルホン酸，メタンスルホン酸、トリフルオロメタンスルホン酸等のスルホン酸類等が挙げられる。また、フェノール、アルコール類などの水酸基含有化合物、各種チオール類などのメルカプト基を有する化合物、及びルイス酸として知られる電子対を受け取って共有結合を作り得る物質、例えば塩化アルミニウム、塩化第二スズ、三塩化ホウ素、三臭化ホウ素なども用いることができる。
また、これ以外にも酸性イオン交換樹脂、カーボンブラック、アルミナなど、固体表面に酸性の活性点を有する物質、あるいは塩化水素、亜硫酸ガスなどの酸性気体化合物も用いることができる。
これらの酸性化合物の中で、（無水）マレイン酸，フマル酸，あるいはそれらのハーフエステル、（メタ）アクリル酸，イタコン酸などの重合性不飽和基を有する酸性化合物あるいはそれらの官能基を有するオリゴマーあるいはポリマー類などが特に好ましい。さらにそのもの自体は酸性物質ではなく、加熱、空気中の水分、酸素などの作用により分解あるいは反応して酸性化合物を発生する化合物（潜在性酸性化合物）も用いることができる。また、光照射により分解して酸性化合物を発生する物質も知られており、例えば光カチオン重合開始剤と呼ばれてい化合物などの光潜在性酸性化合物も用いることができる。光カチオン開始剤としては、ジアゾニウム化合物、スルホニウム化合物、ヨードニウム化合物、金属錯体化合物金属錯体化合物など様々な化合物が知られており、「機能材料」１９８５年１０月号５項、「ＵＶ・ＥＢ硬化技術の応用と市場」、シーエムシー社１９８９年発行７８ページなどに詳細な記述がある。これらの潜在性酸性化合物と呼ぶべき化合物の中では、入手の容易性、経済性、組成物中の安定性、操作性などを勘案すると光あるいは熱によって酸を発生する化合物が望ましい。さらに好ましくは熱によっての酸発生であり、特に加熱により分解して酸を発生する有機スルホニウム化合物が好適である。
この有機スルホニウム化合物は一般に３個の置換基（アルキル基、アリール基など）を有するスルホニウム陽イオン部分と、対イオンである陰イオンとのイオン対から構成されるが、化合物の安定性、酸性化合物の発生能、発生する酸性化合物の酸強度などの観点からスルホニウム塩の置換基の、少なくとも１個が（置換）フェニル基、（置換）ナフチル基などのアリール基であることが望ましい。例えば好ましい化合物としてトリフェニルスルホニウム、ジフェニルスルホニウムなどの陽イオン部分を持つスルホニウム化合物が挙げられる。
重合開始剤が、上記一般式（２）で表される有機ホウ素化合物及び酸性化合物からなるものである場合、有機ホウ素化合物と酸性化合物との組成比は、重量比で0.１／５〜５／0.１（有機ホウ素化合物／酸性化合物）が好ましく、特に好ましくは0.５／５〜５／0.５である。また、この重合開始剤の使用量は、（Ａ）成分の樹脂１００重量部に対して0.０１〜２０重量部であることが好ましく、特に0.０５〜１５重量部が好ましい。重合開始剤が、上記一般式（２）で表される有機ホウ素化合物、酸性化合物及び上記一般式（５）で表されるヘキサアリールビイミダゾール化合物からなるものである場合、有機ホウ素化合物と酸性化合物との合計とヘキサアリールビイミダゾール化合物の組成比は、重量比で0.１／５〜５／0.５（有機ホウ素化合物＋酸性化合物／ヘキサアリールビイミダゾール化合物）が好ましく、特に好ましくは0.５／５〜５／0.５である。また、この重合開始剤の使用量は、（Ａ）成分の樹脂１００重量部に対して0.０１〜２０重量部であることが好ましく、特に0.０５〜１５重量部が好ましい。
【００４１】
本発明で用いる光重合開始剤として具体的には、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）とが７５重量％／２５重量％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）とが７５重量％／重量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）、同様に５０重量％／５０重量％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）とが５０重量％／重量５０％の割合で混合されたＤａｒｏｃｕｒ４２６５（商品名）などがある。本発明においてはこれらを組合わせて使用してもよい。
【００４２】
注型硬化物を得るには、上記（Ａ），（Ｂ）及び（Ｃ）成分に必要に応じて所望の成分を添加した光硬化性樹脂組成物を型枠などに注入し、これに２８０〜１２００ｎｍの波長領域の光を照射し、光硬化性樹脂組成物を硬化させればよい。また、本発明の製造方法においては、光硬化樹脂組成物とモルタル等の他の材料との混合物を注型硬化させることもでき、他の材料の使用量は、光硬化性樹脂組成物１００重量部に対して０〜５０重量部とすることが好ましく、０〜３０重量部が特に好ましい。
光硬化に使用できる光源としては、２８０〜１２００ｎｍの波長領域の光を出す光源であればよく、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、キセノンランプ、水銀灯、陽光ランプ、近赤外ランプ、ナトリウムランプ、ハロゲンランプ、太陽光などを用いることができる。
硬化のための光照射時間は、光源の有効波長域、出力、照射距離、組成物の厚さ等に応じて適宜選定され、一概に規定できないが、0.０１時間以上、好ましくは0.０５時間以上である。
【００４３】
【実施例】
以下、実施例及び比較例により本発明の内容を詳細にするが、本発明はこれらの例によってなんら限定されるものではない。なお、各例中の「部」は重量部を示す。
実施例１
ビスフェノールＡ型ビニルエステル樹脂リポキシＲ−８０６（昭和高分子（株）製）１００部に、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン２５重量％、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７５重量％からなる、紫外光から可視光領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重合開始剤（商品名：イルガキュア１８００，チバスペシャルティーケミカルズ（株）製、以下Ｉ−１８００と略す）2.５部を添加し、光硬化性樹脂組成物を得た。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ３ｍｍとなるように上記光硬化性樹脂組成物を注入し、可視光の光源である６００Ｗメタルハライドランプを使用し、４０ｃｍの距離（波長３８０〜４５０ｎｍの照度＝２０ｍＷ／ｃｍ² ）で２０分間光照射して注型板を得た。
得られた注型板について、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定を行った結果、比較例の過酸化物硬化による注型板とは異なる降伏値（降伏破断）を有し、且つ同じ引張強度において比較例の注型板よりも大きな伸び率（破断）を示した。また、ＤＭＡ法によるガラス転移温度Ｔｇの測定を行なった結果、比較例の過酸化物硬化による注型板と比べて約１０℃高い数値を示し、耐熱性も向上していることが確認された。結果を第３表に示す。。
【００４４】
比較例１
実施例１で用いた光重合開始剤Ｉ−１８００の代わりに常温硬化触媒であるメチエチルケトンパーオキサイド（日本油脂（株) 製, パーメックＮ）／ナフテン酸Ｃｏ（Ｃｏ：６重量％）＝1.０部／0.５部を添加した常温硬化性樹脂組成物を使用し、常温硬化１日＋１２０℃２時間の条件で硬化させた以外は、全て実施例１と同じ条件で注型板を作製し、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定及びＤＭＡ法によるガラス転移温度Ｔｇの測定を行った。結果を第３表に示す。
【００４５】
実施例２
ビスフェノールＡ型ビニルエステル樹脂リポキシＲ−８０６（昭和高分子（株）製）１００部に、紫外光から可視光領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重合開始剤であるフェニルビス（２，４，６−トリメチルベンゾイル）−ホスフィンオキサイド（商品名：イルガキュア８１９, チバスペシャルティーケミカルズ（株）製、以下Ｉ−８１９と略す）１．５部、及び１，１，５，５−テトラキス（ｐ−ジフェニルアミノフェニル）−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色素）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部からなる近赤外光重合開始剤を添加し、光硬化性樹脂組成物を調製した。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ３ｍｍとなるように上記光硬化性樹脂組成物を注入し、３８０〜１２００ｎｍの波長域を含む光源である１ｋＷハロゲンランプ（商品名：ＡＬ−スポットライトＡＬＦ−１０，アールディエス（株）製）と可視光の光源である１ｋＷメタルハライドランプを使用し、５０ｃｍ距離（波長３８０〜４５０ｎｍの照度＝４０ｍＷ／ｃｍ² ）で１０分間光照射して注型板を得た。
得られた注型板について、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定を行った結果、比較例の過酸化物硬化による注型板と比べて、同じ引張強度において大きな伸び率（破断）を示した。また、ＤＭＡ法によるＴｇの測定を行なった結果、比較例の過酸化物硬化による注型板と比べて約１０℃高い数値を示し、耐熱性も向上していることが確認された。結果を第３表に示す。
【００４６】
実施例３
フェノールノボラック型ビニルエステル樹脂リポキシＨ−６３０（昭和高分子（株）製）１００部に、可視光重合開始剤であるビス（２−ｏ−クロロフェニル−４，５−ジフェニル）イミダゾール及び２−メルカプトベンゾチアゾールを各々０．５部、Ｐ３Ｂを０．１５部及び光／熱潜在性酸発生剤（スルホニウム化合物、商品名：ＣＩ−２８５５，日本曹達（株）製）1.０部を添加し、光硬化性樹脂組成物を調製した。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ３ｍｍとなるように上記光硬化性樹脂組成物を注入し、３８０〜１２００ｎｍの波長域を含む光源である１ｋＷハロゲンランプ（商品名：ＡＬ−スポットライトＡＬＦ−１０，アールディエス（株）製）と可視光の光源である１ｋＷメタルハライドランプを使用し、５０ｃｍの距離（波長３８０〜４５０ｎｍの照度＝４０ｍＷ／ｃｍ² ）で１０分間光照射して注型板を得た。
得られた注型板について、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定を行った結果、比較例の過酸化物硬化による注型板と比べて、同じ引張強度において大きな伸び率（破断）を示した。また、ＤＭＡ法によるＴｇの測定を行なった結果、比較例の過酸化物硬化による注型板と比べて約１０℃高い数値を示し、耐熱性も向上していることが確認された。結果を第３表に示す。
【００４７】
比較例２
ビニルエステル樹脂リポキシＨ−６３０（昭和高分子（株）製）１００部に、常温硬化触媒であるパーメックＮ／ナフテン酸Ｃｏ（Ｃｏ：６％）＝1.０部／0.５部を添加した常温硬化性樹脂組成物を使用し、比較例１と同様の操作で注型板を作製し、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定及びＤＭＡ法によるＴｇの測定を行った。結果を第３表に示す。
【００４８】
実施例４
イソフタル酸系不飽和ポリエステル樹脂リゴラック１５５７（酸化：２５，昭和高分子（株) 製）１００部に、重合開始剤であるＰ３Ｂを1.５部、ビス（２−ｏ−クロロフェニル−４，５−ジフェニル）イミダゾール，（和光純薬工業（株）製）1.０部を混合し、光硬化性樹脂組成物を調製した。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ３ｍｍとなるように上記光硬化性樹脂組成物を注入し、樹脂が漏れない様にシールした後、３８０〜１２００ｎｍの波長域を含む光源である１ｋＷハロゲンランプ（商品名：ＡＬ−スポットライトＡＬＦ−１０，アールディエス（株）製）を使用し、５０ｃｍの距離で２０分間光照射して注型板を得た。
得られた注型板について、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定を行った結果、比較例の過酸化物硬化による注型板と比べて、同じ引張強度おいて大きな伸び率（破断）を示した。また、ＤＭＡ法によるＴｇ測定を行なった結果、比較の過酸化物硬化と比べ、約１０℃高い数値を示し、耐熱性も向上していることが確認された。結果を第３表に示す。
【００４９】
比較例３
不飽和ポリエステル樹脂リゴラック１５５７（昭和高分子( 株) 社製）１００部に、常温硬化触媒であるパーメックＮ／ナフテン酸Ｃｏ（Ｃｏ：６％）＝１．０部／０．５部を添加した常温硬化性樹脂組成物を使用し、比較例１と同様の操作で注型板を作製し、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定及びＤＭＡ法によるＴｇの測定を行った。結果を第３表に示す。
【００５０】
【表５】

【００５１】
【表６】

【００５２】
実施例５
ビニルエステル樹脂リポキシＲＦ−３００（昭和高分子（株）製）１００部に、Ｉ−８１９を１．５部、ＩＲＢを０．０３部及びＰ３Ｂを０．１５部を添加し、光硬化性樹脂組成物を調製した。この光硬化性樹脂組成物１００部に水酸化アルミニウムハイジライトＨＢＴ−３２０（昭和電工（株）製）１８０重量部を混合し光硬化性モルタル配合組成物を得た。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ１５ｍｍとなるように上記光硬化性モルタル配合組成物を注入し、３８０〜１２００ｎｍの波長域を含む光源である１ｋＷハロゲンランプ（商品名：ＡＬ−スポットライトＡＬＦ−１０，アールディエス（株）製）と可視光の光源である１ｋＷメタルハライドランプを使用し、５０ｃｍの距離（波長３８０〜４５０ｎｍの照度＝４０ｍＷ／ｃｍ² ）で２０分間光照射して注型板を得た。
得られた注型板を所定のサイズに切り出し、ＪＩＳ Ｋ６９１１によるシャルピー衝撃強度、熱変形温度の測定を行った結果、比較例の過酸化物硬化による注型板と比べて高い値を示した。結果を第４表に示す。
【００５３】
実施例６
不飽和ポリエステル樹脂リゴラック１５５７（昭和高分子（株）製）１００部に、紫外線重合開始剤である２，３−ジメトキシ−１，２−ジフェニルエタン−１−オン（商品名：イルガキュア６５１，チバスペシャルティーケミカルズ（株）製）を１．５部を添加し、光硬化性樹脂組成物を調製した。
次に、厚さ５ｍｍのガラス板で作製した枠の中に、厚さ３ｍｍとなるように上記光硬化性樹脂組成物を注入し、樹脂が漏れないようにシールした後、紫外線の光源であるベルト式１ｋＷ高圧水銀灯（１ｐａｓｓ＝６０ｍＪ／ｃｍ² ）でＵＶ照射したところ３０ｐａｓｓで裏面まで硬化し、注型板を得た。
得られた注型板について、ＪＩＳ Ｋ６９１１による曲げ強度、引張強度、伸び率の測定を行った結果、比較例３の過酸化物硬化による注型板と、同様の引張強度で大きな伸び率（破断）を示した。また、ＤＭＡ法によるＴｇ測定を行なった結果、比較例３の過酸化物硬化による注型板と比べ、約１０℃高い数値を示し、耐熱性も向上していることが確認された。結果を第３表に示す。
【００５４】
比較例４
ビニルエステル樹脂リポキシＲＦ−３００（昭和高分子（株）製）１００部に、常温硬化触媒であるパーメックＮ／ナフテン酸Ｃｏ（Ｃｏ：６重量％）＝１．０部／０．５部を添加した常温硬化性樹脂組成物を調製した。この樹脂組成物１００部に水酸化アルミニウムハイジラントＨＢＴ−３２０（昭和電工（株）製）１８０部を混合して得たモルタル配合組成物を、実施例４と同様のガラス板枠中に注入し、常温硬化１日＋１２０℃２時間の条件で硬化した以外は、全て実施例４と同じ条件で注型板を作製し、ＪＩＳ Ｋ６９１１によるシャルピー衝撃強度、熱変形温度の測定を行った。結果を第４表に示す。
【００５５】
【表７】

【００５６】
【発明の効果】
本発明によれば、耐熱性があり、伸び率が大きく、靭性の高い注型硬化物を製造することができる。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a method for producing a cast cured product, and more particularly, to light an unsaturated polyester resin and / or vinyl ester resin composition having a heat resistance, a large elongation rate, and a cast cured product having high toughness. The present invention relates to a method for producing a cast cured product by curing.
[0002]
[Prior art]
Conventional uses of cast cured products obtained by cast-curing resin compositions include artificial marble casting and encapsulation of electrical components. Thermosetting resins such as unsaturated polyester resins, vinyl ester resins, and epoxy resins are used as resin components to obtain these cast cured products. There has been a problem that cracks are generated in the cooling and heating cycle when the object is used. For this reason, a formulation for improving the toughness of the cast cured product has been taken by devising the composition of the resin composition, but no attempt has been made to fundamentally improve the toughness other than the composition of the resin composition.
In addition, in the field of artificial marble casting, an artificial marble casting method that does not use a gel coat was developed in place of the conventional gel coat method, and the molding cycle was improved. Since it is carried out by thermal curing, the usable time is limited, and after-curing is also necessary. Therefore, it takes a long time for curing, and it is close to the limit in terms of improving the molding cycle.
In addition, when the cast cured product is used for applications that require heat resistance, toughness is reduced when trying to improve the heat resistance of the cast cured product, so cracking is unavoidable. There has been a demand for a production method capable of obtaining a cast-cured product having both toughness characteristics.
[0003]
[Problems to be solved by the invention]
It is an object of the present invention to provide a method for producing a cast cured product that uses an unsaturated polyester resin and / or vinyl ester resin composition as a resin component, has heat resistance, has a high elongation rate, and has high toughness. To do.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a specific photopolymerization initiator. The present invention has been completed based on such findings.
  That is, the present invention includes (A) 100 parts by weight of unsaturated polyester resin and / or vinyl ester resin, (B) 0 to 300 parts by weight of powdery filler, and (C)In the visible light regionA photocurable resin composition containing 0.1 to 10 parts by weight of one or more photopolymerization initiators having photosensitivityIlluminance is 10 mW / cm using a visible light lamp that emits light in the wavelength region of 380 to 450 nm as a light source. ² more thanIt is intended to provide a method for producing a cast-cured product, which is cast-cured by irradiating the light.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing a cast cured product of the present invention, as the component (A), at least one of unsaturated polyester resin or vinyl ester resin (hereinafter, both resins may be collectively referred to as resins) is used. To do.
Unsaturated polyester resin refers to a condensation product (unsaturated polyester) obtained by esterification reaction of polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid if necessary), polymerizable monomer such as styrene. This is a resin described in “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) and “Paint Glossary of Terms” (edited by Color Material Association, published in 1993).
Vinyl ester resin, also called epoxy acrylate resin, is generally formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound with a polymerizable unsaturated bond (vinyl ester) is dissolved in a polymerizable monomer such as styrene, and the “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) and “Paint Glossary” "(Color Material Association, published in 1993).
[0006]
As the unsaturated polyester used as a raw material for the unsaturated polyester resin, those produced by a known method can be used. Specifically, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and other polybasic acids having no polymerizable unsaturated bond or anhydrides thereof and fumaric acid, maleic acid, itaconic acid A polymerizable unsaturated polybasic acid or an anhydride thereof such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A Polyhydric alcohol such as propylene oxide adduct of bisphenol A It is those prepared by reacting a minute.
[0007]
Moreover, as vinyl ester used as a raw material of vinyl ester resin (epoxy acrylate resin), what is manufactured by a well-known method can be used, and unsaturated monobasic acid, for example, acrylic acid or methacrylic acid, can be used for epoxy resin. Α, β-unsaturated epoxy having an epoxy (meth) acrylate obtained by reacting with a saturated polyester or unsaturated polyester of a terminal carboxyl group obtained from a saturated dicarboxylic acid and / or unsaturated dicarboxylic acid and a polyhydric alcohol. Examples thereof include polyester (meth) acrylates of saturated polyesters or unsaturated polyesters obtained by reacting saturated carboxylic acid ester groups.
Examples of the raw material epoxy resin include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolac type polyglycidyl ethers, and the like, but preferably bisphenol type typified by bisphenol A, bisphenol F, bisphenol S and the like. Diglycidyl ether and high molecular weight homologues thereof.
[0008]
Saturated dicarboxylic acids used for the production of terminal carboxyl polyesters (vinyl ester raw materials) include dicarboxylic acids having no active unsaturated groups, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Is mentioned. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Multivalents such as methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Examples include alcohol.
A typical example of the α, β-unsaturated carboxylic acid ester having an epoxy group used for the production of polyester (meth) acrylate is glycidyl methacrylate.
[0009]
The unsaturated polyester or vinyl ester as the component (A) preferably has a relatively high degree of unsaturation, and preferably has an unsaturated group equivalent (molecular weight per unsaturated group) of about 100 to 800. Those having an unsaturated group equivalent of less than 100 cannot be synthesized, and if the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained.
The unsaturated polyester resin or vinyl ester resin as component (A) is usually a compound (reactive diluent) having an unsaturated group represented by a styrene monomer in the unsaturated polyester or vinyl ester. . Monomers having unsaturated groups are important for improving the kneadability and impregnation properties of fiber reinforcements and fillers in the production of composite materials, and improving the hardness, strength, chemical resistance, weather resistance, etc. of molded products. In order to improve the corrosion resistance, styrene monomer is particularly effective. The addition amount of the monomer having an unsaturated group is 10 to 250 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester or vinyl ester. If the amount used is less than 10 parts by weight, the workability, impregnation and corrosion resistance deteriorate due to high viscosity. If the amount used exceeds 250 parts by weight, sufficient strength and heat resistance cannot be obtained, and the matrix of corrosion resistant FRP. It is not preferable.
When a styrene monomer is used as a monomer having an unsaturated group, a part or all of the styrene monomer is converted into a styrene monomer such as chlorostyrene, vinyltoluene, divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, Other polymerizable monomers such as ethylene glycol di (meth) acrylate can be substituted and used as long as the gist of the present invention is not impaired.
[0010]
(B) As a powdery filler of a component, an inorganic filler, an organic filler, or a polymer is mentioned, An inorganic filler is preferable. As the powdery inorganic filler, known fillers such as glass flakes, glass powders, glass beads, silica, calcium carbonate, talc, clay, aluminum hydroxide, barium sulfate, and titanium oxide can be used. These inorganic fillers may be used individually by 1 type, and can also be used in combination of 2 or more type. The amount of the inorganic filler used is 0 to 300 parts by weight, preferably 0 to 200 parts by weight, based on 100 parts by weight of the resin (A). When the blending amount of the inorganic filler is more than 300 parts by weight, the viscosity of the resin composition becomes high, impairing impregnation property, and bubbles are likely to remain in the resin, and the quality is also high. descend.
[0011]
When using an organic filler or polymer as the powder filler, it is also effective as a low shrinkage agent, such as polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, polyvinylidene chloride microballoon, polyacrylonitrile microballoon, etc. It is preferable to use it. When these are used for the purpose of obtaining the effect of a low shrinkage agent, the amount used is preferably 0 to 40 parts by weight, particularly preferably 0 to 40 parts by weight with respect to 100 parts by weight of the resin of component (A). 30 parts by weight. If the amount of the low shrinkage agent used exceeds 40 parts by weight, the viscosity becomes too high and the casting workability is impaired, and the physical properties such as mechanical strength may be lowered.
[0012]
Further, in the present invention, a pigment can be used. There is no particular limitation on the type, and organic pigments or inorganic pigments can be used. The amount of the pigment blended is at most 20 parts by weight, preferably up to 10 parts by weight, per 100 parts by weight of the resin of component (A).
[0013]
As the photopolymerization initiator having photosensitivity in any of the components in the range from the ultraviolet light to the near infrared light region of the component (C), conventionally known ones can be used.
(1) General formula (1)
D⁺・ A^-                          ... (1)
(Where D⁺Is a methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane or pyrylium dye cation having photosensitivity in the visible light region or near infrared light region, and A^-Indicates various anions. )
A cationic dye having photosensitivity in the visible light region or near infrared light region represented by the formula (2)
[0014]
[Chemical 6]

[0015]
(Where Z⁺Represents any cation, R¹, R², R^ThreeAnd R^FourEach independently represents an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted An alkenyl group, a substituted alkynyl group or a substituted silyl group is shown. )
A photopolymerization initiator having photosensitivity in the visible light region or near-infrared light region comprising an organic boron compound represented by
(2) General formula (3)
[0016]
[Chemical 7]

[0017]
(Wherein R^Five, R⁶And R⁷Each independently represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted complex. Represents a cyclic group)
A polymerization initiator having photosensitivity from ultraviolet light to visible light region, comprising a bisacylphosphine oxide compound represented by:
(3) General formula (4)
[0018]
[Chemical 8]

[0019]
(Wherein R⁸, R⁹And R^TenEach independently represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted complex. A ring group is shown. )
A photopolymerization initiator having photosensitivity from ultraviolet light to visible light region, comprising an acylphosphine oxide compound represented by:
(4) UV polymerization initiator selected from benzoin, benzyl, acetophenone, benzophenone and derivatives thereof
A photopolymerization initiator selected from is preferred.
In the present invention, ultraviolet light is 280 to 380 nm, visible light is 380 to 780 nm, and near infrared light is light in the wavelength range of 780 to 1200 nm.
[0020]
(1) A which is a counter anion of a cationic dye represented by the general formula (1), which constitutes a photopolymerization initiator having photosensitivity in the visible light region or near infrared light region wavelength.^-Is an arbitrary anion such as p-toluenesulfonate ion, organic carboxylate ion, perchlorate ion, halide ion, etc.
[0021]
[Chemical 9]

[0022]
(Wherein R¹¹, R¹², R¹³And R¹⁴Each independently represents an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted An alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group is shown. )
A tetracoordinate boron anion represented by the formula is particularly preferred.
[0023]
on the other hand. The cation “Z” in the general formula (2)⁺Examples of quaternary ammonium cation, quaternary pyridinium cation, quaternary quinolinium cation, diazonium cation, tetrazolium cation, sulfonium cation, oxosulfonium cation, sodium, potassium, lithium, magnesium, calcium Metal cations such as flavylium, pyranium salts (organic) compounds having a cation charge on the oxygen atom, carbon cations such as tropylium and cyclopropylium, halogenium cations such as iodonium, arsenic, cobalt, palladium , Cations of metal compounds such as chromium, titanium, tin, and antimony.
In the present invention, the composition ratio between the organic boron compound and the near-infrared light or visible light absorbing cation dye is preferably 1/5 to 1 / 0.05 (organoboron compound / cation dye) by weight, Particularly preferred is 1/1 to 1 / 0.1. In general, it is preferable to use more organoboron compounds than cationic dyes from the viewpoint of decolorization reaction of the dye and radical generation efficiency.
[0024]
By combining the organoboron compound represented by the general formula (2) with a cation 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. When the electron is transferred to and from the organic boron compound, the dye is decolored and a radical is generated, and a polymerization reaction of the coexisting polymerizable unsaturated compound occurs. In this polymerization reaction, unlike the conventional ultraviolet polymerization reaction, the generated radicals can be easily controlled, and can be easily stopped when a part of unsaturated groups in the resin is radically polymerized. In addition, since a long wavelength in the visible light or near-infrared light region is used, the reaction can be easily advanced even in a system to which a filler or a pigment is added.
[0025]
Examples of combinations of the above cationic dyes and boron compounds are disclosed in JP-A-3-111402, JP-A-3-179003, JP-A-4-146905, JP-A-4-261405, and JP-A-4. -261406, JP-A-5-194619, and the like. “D in cationic dyes⁺Specific examples of "are shown in Tables 1 and 2. Among these cationic dyes, cyanine-based, styryl-based cationic dyes, and triarylmethane-based dyes are preferable. Cyanine-based and styryl-based cation dyes are particularly preferable in that they tend to easily cause the reaction of the present invention because they generally tend to exchange electrons with organic boron compounds.
[0026]
[Table 1]

[0027]
[Table 2]

[0028]
[Table 3]

[0029]
[Table 4]

[0030]
As the visible light polymerization initiator, for example, Yamaoka et al., “Surface”, 27 (7), 548 (1989), Sato et al., “3rd Polymer Material Forum Abstract”, 1BP18 (1994), In addition to visible light polymerization initiators such as benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bispentadienyltitanium-di (pentafluorophenyl) alone, organic peroxide catalysts / dye systems, diphenyliodonium salts / Dye, bisimidazole / keto compound, hexaarylbismidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, hexaarylbisimidazole described in JP-B-45-37377 / Publicly known radical generators, etc. Mention may be made of a composite initiator system.
In the present invention, as a photopolymerization initiator having photosensitivity from ultraviolet light to visible light, (2) General formula (3)
[0031]
[Chemical Formula 10]

[0032]
(Wherein R^Five, R⁶And R⁷Each independently represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted complex. Represents a cyclic group)
Or a bisacylphosphine oxide compound represented by the general formula (4)
[0033]
Embedded image

[0034]
(Wherein R⁸, R⁹And R^TenEach independently represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted complex. A ring group is shown. )
The photoinitiator which consists of an acylphosphine oxide compound represented by these is used.
These initiators have photosensitivity in a longer wavelength region than that of conventionally used UV initiators (visible light region of 400 nm or more), have excellent light transmittance, and are cleaved by irradiation with acyl radicals. And phosphinoyl radicals are generated, so that the polymerization initiation efficiency is higher than that of conventionally used UV initiators. These may be used individually by 1 type and can also be used in combination of 2 or more type.
[0035]
Specific examples of the bisacylphosphine oxide compound represented by the general formula (3) include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5. -Dimethylphenylphosphine oxide, 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-di) Chlorbenzoyl) -4-chlorophenylphosphine oxa Bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine 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-dimethyl Phenylphosphine 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-biphenylphosphi Oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine 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-dimethoxy) And benzoyl) -2,4,4-trimethylpentylphosphine oxide.
[0036]
Specific examples of the acylphosphine oxide compound represented by the general formula (4) include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, and 2,6-dimethoxybenzoyl. -Diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine 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, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl -Phenylphosphinic acid methyl ester can be mentioned.
The ultraviolet polymerization initiator (4) is selected from benzoin, benzyl, acetophenone, benzophenone and derivatives thereof. Examples of the derivatives include benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, acetophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) Phenyl) -2-monfolinopropane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxydi-2-methyl-1-propan-1-one, Non-based ones include methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxy-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Examples include chloride, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, and the like.
The addition amount of the photopolymerization initiator having photosensitivity in any of the components from the ultraviolet light to the near infrared light region of the component (C) is 0.1 to 10 with respect to 100 parts by weight of the resin of the component (A). Part by weight, preferably 0.5 to 5 parts by weight, and one kind may be used alone, or two or more kinds may be used in combination. When the addition amount of the photopolymerization initiator is less than 0.1 parts by weight, it cannot be cured sufficiently, and when the addition amount of the photopolymerization initiator exceeds 10 parts by weight, it is economically disadvantageous and is also a cured product. Degradation of physical properties occurs.
[0037]
In the present invention, the organoboron compound represented by the above general formula (2) and an acidic compound are used as a photopolymerization initiator having photosensitivity in the range from the ultraviolet light to the near infrared light region of the component (C). A polymerization initiator comprising a compound, or an organic boron compound, an acidic compound and a general formula (5) represented by the general formula (2);
[0038]
Embedded image

[0039]
(Where L¹, L²And L^ThreeEach independently represents an aryl group or a substituted aryl group. )
A polymerization initiator composed of a hexaarylbiimidazole compound represented by the formula can be used in combination. Specific examples of the hexaarylbiimidazole compound include bis (2,4,5-triphenyl) imidazole, bis (2-o-chlorophenyl-4,5-diphenyl) imidazole, bis (2-o, p-dichlorophenyl- 4,5-diphenyl) imidazole, bis (2-o-bromophenyl-4,5-diphenyl) imidazole and the like.
[0040]
Specific examples of the acidic compound include inorganic acids and organic acids generally known as Bronsted acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and nitric acid. Examples of the organic acid include carboxylic acids such as acetic acid, propionic acid, maleic acid, adipic acid, (meth) acrylic acid, benzoic acid, and phthalic acids, p. -Sulfonic acids such as toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like. In addition, hydroxyl group-containing compounds such as phenol and alcohols, compounds having mercapto groups such as various thiols, and substances capable of receiving an electron pair known as Lewis acid to form a covalent bond, such as aluminum chloride, stannic chloride, Boron trichloride, boron tribromide and the like can also be used.
In addition, substances having an acidic active site on the solid surface such as acidic ion exchange resin, carbon black, and alumina, or acidic gaseous compounds such as hydrogen chloride and sulfurous acid gas can be used.
Among these acidic compounds, acidic compounds having a polymerizable unsaturated group such as (anhydrous) maleic acid, fumaric acid, or half esters thereof, (meth) acrylic acid, itaconic acid, or oligomers having functional groups thereof Or polymers are particularly preferred. Further, the compound itself is not an acidic substance, and a compound that generates an acidic compound by decomposition or reaction by the action of heat, moisture in the air, oxygen, or the like (latent acidic compound) can also be used. In addition, substances that decompose by light irradiation to generate acidic compounds are also known. For example, photolatent acidic compounds such as compounds called photocationic polymerization initiators can also be used. As the photocation initiator, various compounds such as diazonium compounds, sulfonium compounds, iodonium compounds, metal complex compounds and metal complex compounds are known. “Functional Materials”, October, 1985, Section 5, “UV / EB Curing Technology” Application and Market ", page 78, published by CMMC 1989. Among these compounds that should be called latent acidic compounds, compounds that generate an acid by light or heat are desirable in consideration of availability, economy, stability in the composition, operability, and the like. More preferably, the acid is generated by heat, and an organic sulfonium compound that decomposes by heating to generate an acid is particularly preferable.
This organic sulfonium compound is generally composed of an ion pair of a sulfonium cation moiety having three substituents (alkyl group, aryl group, etc.) and an anion which is a counter ion. From the viewpoints of the ability to generate the acid and the acid strength of the generated acidic compound, at least one of the substituents of the sulfonium salt is preferably an aryl group such as a (substituted) phenyl group or a (substituted) naphthyl group. For example, preferred compounds include sulfonium compounds having a cationic moiety such as triphenylsulfonium and diphenylsulfonium.
When the polymerization initiator is composed of an organic boron compound and an acidic compound represented by the general formula (2), the composition ratio of the organic boron compound and the acidic compound is 0.1 / 5 to 5 by weight. /0.1 (organic boron compound / acidic compound) is preferable, and 0.5 / 5 to 5 / 0.5 is particularly preferable. The amount of the polymerization initiator used is preferably 0.01 to 20 parts by weight, particularly 0.05 to 15 parts by weight, based on 100 parts by weight of the component (A) resin. When the polymerization initiator is composed of an organic boron compound represented by the general formula (2), an acidic compound and a hexaarylbiimidazole compound represented by the general formula (5), the organic boron compound and the acidic compound The composition ratio of the total and the hexaarylbiimidazole compound is preferably 0.1 / 5 to 5 / 0.5 (organoboron compound + acidic compound / hexaarylbiimidazole compound) in weight ratio, particularly preferably 0.5. 5/5 to 5 / 0.5. The amount of the polymerization initiator used is preferably 0.01 to 20 parts by weight, particularly 0.05 to 15 parts by weight, based on 100 parts by weight of the component (A) resin.
[0041]
Specific examples of the photopolymerization initiator used in the present invention include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) and bis (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 75 wt% / 25 wt%, trade name Irgacure-1700 (Ciba Special) Tea Chemicals), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: Irgacure 184, Ciba Specialty Chemicals) and bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethylpentylphosphine oxide (Ciba Special Tea Chemi) Trade name Irgacure 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.), mixed at a ratio of 75% by weight / 25% by weight, and similarly mixed at a ratio of 50% by weight / 50% by weight Trade name: Irgacure 1850 (manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals) ), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade names: Darocur 1173, Ciba) Specialty Chemicals Co., Ltd.) and 2,4,6-trimethyl There is Darocur 4265 (trade name) in which benzoyl-diphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corp.) is mixed at a ratio of 50% by weight / 50% by weight. In the present invention, these may be used in combination.
[0042]
In order to obtain a cast cured product, a photocurable resin composition in which a desired component is added to the components (A), (B) and (C) as necessary is poured into a mold or the like, and 280 is added thereto. The light curable resin composition may be cured by irradiating light in a wavelength region of ˜1200 nm. In the production method of the present invention, a mixture of the photocurable resin composition and another material such as mortar can be cast-cured, and the amount of the other material used is 100 wt% of the photocurable resin composition. It is preferable to set it as 0-50 weight part with respect to a part, and 0-30 weight part is especially preferable.
As a light source that can be used for photocuring, any light source that emits light in a wavelength region of 280 to 1200 nm may be used. A high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a mercury lamp, a sunlight lamp, a near-infrared lamp, A sodium lamp, a halogen lamp, sunlight, etc. can be used.
The light irradiation time for curing is appropriately selected according to the effective wavelength range of the light source, the output, the irradiation distance, the thickness of the composition, etc., and cannot be generally specified, but is 0.01 hours or more, preferably 0.05. It's over time.
[0043]
【Example】
Hereinafter, although the contents of the present invention will be described in detail by examples and comparative examples, the present invention is not limited to these examples. In addition, "part" in each example shows a weight part.
Example 1
100 parts of bisphenol A type vinyl ester resin Lipoxy R-806 (manufactured by Showa High Polymer Co., Ltd.), 25% by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, bis (2,6-dimethoxybenzoyl) -2,4, A bisacylphosphine oxide-based polymerization initiator (trade name: Irgacure 1800, manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as I-) consisting of 75% by weight of 4-trimethylpentylphosphine oxide and having photosensitivity in the ultraviolet to visible light region. 2.5 parts) was added to obtain a photocurable resin composition.
Next, the photocurable resin composition is injected into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 3 mm, and a 600 W metal halide lamp that is a visible light source is used. Distance (illuminance at a wavelength of 380 to 450 nm = 20 mW / cm²) For 20 minutes to obtain a cast plate.
As a result of measuring the bending strength, tensile strength and elongation rate of the obtained cast plate according to JIS K6911, it has a yield value (yield fracture) different from that of the cast plate by peroxide curing in the comparative example, And the elongation rate (break) larger than the cast plate of the comparative example was shown at the same tensile strength. In addition, as a result of measuring the glass transition temperature Tg by the DMA method, it was confirmed that the value was about 10 ° C. higher than the cast plate obtained by curing the peroxide in the comparative example, and the heat resistance was also improved. . The results are shown in Table 3. .
[0044]
Comparative Example 1
Methyl ethyl ketone peroxide (manufactured by NOF Corporation, Permec N) / Co-naphthenic acid (Co: 6 wt%) = 1 instead of the photopolymerization initiator I-1800 used in Example 1 The cast plate was used under the same conditions as in Example 1 except that a room temperature curable resin composition added with 0.0 part / 0.5 part was used and cured under the conditions of room temperature curing 1 day + 120 ° C. for 2 hours. It produced and measured the bending strength, the tensile strength, and the elongation rate by JISK6911, and measured the glass transition temperature Tg by DMA method. The results are shown in Table 3.
[0045]
Example 2
100 parts of bisphenol A-type vinyl ester resin Lipoxy R-806 (manufactured by Showa High Polymer Co., Ltd.), phenylbis (2,4) which is a bisacylphosphine oxide polymerization initiator having photosensitivity from ultraviolet light to visible light region. , 6-trimethylbenzoyl) -phosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals, hereinafter abbreviated as I-819), and 1,1,5,5-tetrakis (p- Diphenylaminophenyl) -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) 0.1 It was added a near infrared photopolymerization initiator consisting of parts, and the photo-curable resin composition was prepared.
Next, the photocurable resin composition was injected into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 3 mm, and a 1 kW halogen lamp (light source including a wavelength range of 380 to 1200 nm) ( Product name: AL-Spotlight ALF-10, manufactured by RDS Co., Ltd.) and a 1kW metal halide lamp that is a visible light source, 50 cm distance (illuminance at a wavelength of 380 to 450 nm = 40 mW / cm)²) For 10 minutes to obtain a cast plate.
As a result of measuring the bending strength, tensile strength, and elongation rate of the obtained cast plate according to JIS K6911, the elongation rate (breakage at break) was larger at the same tensile strength than the cast plate formed by peroxide curing in the comparative example. )showed that. Further, as a result of measuring Tg by the DMA method, it was confirmed that the value was about 10 ° C. higher than that of the cast plate obtained by peroxide curing in the comparative example, and the heat resistance was also improved. The results are shown in Table 3.
[0046]
Example 3
Visible light polymerization initiators bis (2-o-chlorophenyl-4,5-diphenyl) imidazole and 2-mercaptobenzo are added to 100 parts of phenol novolac-type vinyl ester resin Lipoxy H-630 (manufactured by Showa High Polymer Co., Ltd.). 0.5 parts each of thiazole, 0.15 parts of P3B, and 1.0 part of a light / thermal latent acid generator (sulfonium compound, trade name: CI-2855, manufactured by Nippon Soda Co., Ltd.) A curable resin composition was prepared.
Next, the photocurable resin composition was injected into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 3 mm, and a 1 kW halogen lamp (light source including a wavelength range of 380 to 1200 nm) ( Product name: AL-Spotlight ALF-10, manufactured by RDS Co., Ltd.) and a 1kW metal halide lamp that is a visible light source, and a distance of 50 cm (illuminance at a wavelength of 380 to 450 nm = 40 mW / cm)²) For 10 minutes to obtain a cast plate.
As a result of measuring the bending strength, tensile strength, and elongation rate of the obtained cast plate according to JIS K6911, the elongation rate (breakage at break) was larger at the same tensile strength than the cast plate formed by peroxide curing in the comparative example. )showed that. Further, as a result of measuring Tg by the DMA method, it was confirmed that the value was about 10 ° C. higher than that of the cast plate obtained by peroxide curing in the comparative example, and the heat resistance was also improved. The results are shown in Table 3.
[0047]
Comparative Example 2
To 100 parts of vinyl ester resin Lipoxy H-630 (manufactured by Showa Polymer Co., Ltd.) was added Permec N / Co-naphthenic acid (Co: 6%) = 1.0 part / 0.5 part as a room temperature curing catalyst. Using a room temperature curable resin composition, a cast plate was prepared in the same manner as in Comparative Example 1, and the bending strength, tensile strength, and elongation rate were measured according to JIS K6911, and Tg was measured according to the DMA method. The results are shown in Table 3.
[0048]
Example 4
100 parts of isophthalic acid unsaturated polyester resin Rigolac 1557 (oxidation: 25, manufactured by Showa Polymer Co., Ltd.), 1.5 parts of P3B as a polymerization initiator, bis (2-o-chlorophenyl-4,5- 1.0 part of diphenyl) imidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a photocurable resin composition.
Next, after injecting the photocurable resin composition into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 3 mm and sealing the resin so that it does not leak, a wavelength of 380 to 1200 nm is obtained. A cast plate was obtained by using a 1 kW halogen lamp (trade name: AL-Spotlight ALF-10, manufactured by RDS Co., Ltd.), which is a light source including a region, for 20 minutes at a distance of 50 cm.
As a result of measuring the bending strength, tensile strength, and elongation rate of the obtained cast plate according to JIS K6911, compared to the cast plate formed by peroxide curing in the comparative example, a large elongation rate at the same tensile strength ( Fracture). Further, as a result of Tg measurement by the DMA method, it was confirmed that the value was about 10 ° C. higher than the comparative peroxide curing, and the heat resistance was also improved. The results are shown in Table 3.
[0049]
Comparative Example 3
Permec N / Co-naphthenic acid (Co: 6%) = 1.0 part / 0.5 part as a room temperature curing catalyst was added to 100 parts of unsaturated polyester resin Rigolac 1557 (manufactured by Showa Polymer Co., Ltd.). Using a room temperature curable resin composition, a cast plate was prepared in the same manner as in Comparative Example 1, and the bending strength, tensile strength, and elongation rate were measured according to JIS K6911, and Tg was measured according to the DMA method. The results are shown in Table 3.
[0050]
[Table 5]

[0051]
[Table 6]

[0052]
Example 5
To 100 parts of vinyl ester resin Lipoxy RF-300 (manufactured by Showa Polymer Co., Ltd.), 1.5 parts of I-819, 0.03 parts of IRB and 0.15 parts of P3B are added, and a photo-curing resin. A composition was prepared. 180 parts by weight of aluminum hydroxide Heidilite HBT-320 (manufactured by Showa Denko KK) was mixed with 100 parts of this photocurable resin composition to obtain a photocurable mortar blended composition.
Next, the photocurable mortar composition is injected into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 15 mm, and a 1 kW halogen lamp which is a light source including a wavelength range of 380 to 1200 nm. (Product name: AL-Spotlight ALF-10, manufactured by RDS Co., Ltd.) and a 1 kW metal halide lamp which is a visible light source, and a distance of 50 cm (illuminance at a wavelength of 380 to 450 nm = 40 mW / cm)²) For 20 minutes to obtain a cast plate.
The obtained cast plate was cut into a predetermined size and measured for Charpy impact strength and heat distortion temperature according to JIS K6911. As a result, it showed a higher value than the cast plate formed by peroxide curing in the comparative example. The results are shown in Table 4.
[0053]
Example 6
100 parts of an unsaturated polyester resin Rigolac 1557 (manufactured by Showa Polymer Co., Ltd.) was added to 2,3-dimethoxy-1,2-diphenylethane-1-one (trade name: Irgacure 651, Ciba Special) which is an ultraviolet polymerization initiator. 1.5 parts of Tea Chemicals Co., Ltd. was added to prepare a photocurable resin composition.
Next, the photocurable resin composition is injected into a frame made of a glass plate having a thickness of 5 mm so as to have a thickness of 3 mm, and the resin is sealed so as not to leak, and then an ultraviolet light source. Belt type 1kW high pressure mercury lamp (1pass = 60mJ / cm²) Was cured with UV at 30 pass to obtain a cast plate.
As a result of measuring the bending strength, tensile strength, and elongation rate of the resulting cast plate according to JIS K6911, the cast plate obtained by curing the peroxide of Comparative Example 3 and a large elongation rate (breakage) at the same tensile strength. )showed that. Further, as a result of Tg measurement by the DMA method, it was confirmed that the value was about 10 ° C. higher than the cast plate obtained by peroxide curing in Comparative Example 3, and the heat resistance was also improved. The results are shown in Table 3.
[0054]
Comparative Example 4
To 100 parts of vinyl ester resin Lipoxy RF-300 (manufactured by Showa Polymer Co., Ltd.), Permec N / Co-naphthenic acid (Co: 6% by weight) = 1.0 part / 0.5 part as a room temperature curing catalyst was added. A room temperature curable resin composition was prepared. A mortar blended composition obtained by mixing 180 parts of aluminum hydroxide hygirant HBT-320 (manufactured by Showa Denko KK) with 100 parts of this resin composition was poured into the same glass plate frame as in Example 4. A cast plate was prepared under the same conditions as in Example 4 except that it was cured at room temperature for 1 day + 120 ° C. for 2 hours, and Charpy impact strength and heat distortion temperature were measured according to JIS K6911. The results are shown in Table 4.
[0055]
[Table 7]

[0056]
【The invention's effect】
According to the present invention, it is possible to produce a cast cured product having heat resistance, a high elongation rate, and high toughness.

Claims (4)

(A) 100 parts by weight of unsaturated polyester resin and / or vinyl ester resin,
(B) Photocurable resin containing 0 to 300 parts by weight of powdery filler and (C) one or more photopolymerization initiators having photosensitivity in the visible light region. A method for producing a cast cured product, characterized in that cast curing is performed by irradiating light having an illuminance of 10 mW / cm ² or more using a visible light lamp that irradiates light in a wavelength region of 380 to 450 nm as a light source . (C) A photopolymerization initiator having photosensitivity in the visible light region is: (i) General formula (1)
^{D + · A - ··· (1} )
In ^- (the shows the various anions wherein, D ⁺ is a methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, or pyrylium dye cation having photosensitivity in a visible light area, A) and a cationic dye having photosensitivity to visible light area represented by the general formula (2)

(In the formula, Z ⁺ represents an arbitrary cation, and R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group. , a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, substituted alkenyl group, a visible light comprising an organic boron compound represented by shown to) a substituted alkynyl group or substituted silyl group photopolymerization initiators having photosensitivity to realm, (ii) the general formula (3)

(Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group) group, a substituted alkenyl group, a polymerization initiator having photosensitivity in the visible light region ing from bisacylphosphine oxide compound represented by a substituted alkynyl group or substituted heterocyclic group), and (iii) the general formula (4 )

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group. group, a substituted alkenyl group, substituted alkynyl group or substituted heterocyclic group and indicates to) photopolymerization initiator or al photopolymerization initiator selected having photosensitivity to ing the visible light region from acylphosphine oxide compound represented by The manufacturing method according to claim 1.   The method according to claim 1 or 2, wherein the vinyl ester resin is of a bisphenol type. (C) A photopolymerization initiator having photosensitivity in the visible light region is represented by the general formula (2)

(In the formula, Z ⁺ represents an arbitrary cation, and R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group. , a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, substituted alkenyl group, an organic boron compound represented by shown to) a substituted alkynyl group or substituted silyl group and an acid compound Or an organic boron compound represented by the above general formula (2), an acidic compound and the general formula (5)

(Wherein, L ^1, L ² and L ³ each independently represents an aryl group or a substituted aryl group a to indicate) a hexaarylbiimidazole compound represented by the polymerization initiator combinations Ru of 請 Motomeko 1-3 The manufacturing method in any one.