JP4196161B2 - Polyfunctional (meth) acrylate compound and cured product thereof - Google Patents

Description

【化５】

【０００６】
(式中、R1,R2,R3,R4,R5は水素原子またはメチル基を示す。-(O-X-O)-は構造式(2)で示され、R6,R7,R12,R13は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R8,R9,R10,R11は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Aは、炭素数20以下の直鎖状あるいは、分岐状あるいは、環状の炭化水素である。-(Y-O)-は構造式(3)で定義される1種類の構造、または構造式(3)で定義される2種類以上の構造がランダムに配列したものである。R14,R15は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R16,R17は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Zは、炭素数1以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。a,bは、少なくともいずれか一方が0でない、0〜300の整数を示す。c,dは、0または1の整数を示す。ｎは0から10の整数を示す。)
【０００７】
さらに本発明は前記（メタ）アクリレート化合物を含有する硬化性樹脂組成物に関し、さらには組成物を硬化してなる硬化物に関する。
【０００８】
【発明実施の形態】
以下、本発明を詳細に説明する。一般式（１）で表される化合物において、R1,R2,R3,R4,R5は水素原子またはメチル基である。-(O-X-O)-は構造式(２)で示され、R6,R7,R12,R13は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R8,R9,R10,R11は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Aは、炭素数20以下の直鎖状あるいは、分岐状あるいは、環状の炭化水素である。-(Y-O)-は構造式(３)で定義される1種類の構造、または構造式(３)で定義される2種類以上の構造がランダムに配列したものである。R14,R15は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R16,R17は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Zは、炭素数1以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。a,bは、少なくともいずれか一方が0でない、0〜300の整数を示す。c,dは、0または1の整数を示す。ｎは0〜10の整数を示す。これらのなかでも好ましくは、R6,R7, R12,R13は炭素数３以下のアルキル基、R8,R9,R10,R11は水素原子または炭素数３以下のアルキル基、R14,R15は炭素数３以下のアルキル基、R16,R17は水素原子または炭素数３以下のアルキル基であり、これらのなかでも、好ましくは、-(O-X-O)-の構造式（2）において、R6,R7,R12,R13がメチル基であり、-(Y-O)-が構造式(4)あるいは、構造式(5)で示されるものである。
【０００９】
【化６】

【００１０】
本発明の一般式（１）で示される（メタ）アクリレートの製法は、特に限定されず、如何なる方法で製造してもよい。例えば、一般式（６）で示される化合物に対して（メタ）アクリル酸または（メタ）アクリル酸誘導体を反応させることにより得ることができる。具体的には、始めに、一般式（６）でしめされる化合物と（メタ）アクリル酸を、例えば、トリエチルアミン、ジメチルブチルアミン、トリ-n-ブチルアミン等のアミン類、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、ベンジルトリエチルアンモニウム塩等の第4級アンモニウム塩、または第4級ホスホニウム塩、その他トリフェニルホスフィン等のホスフィン類や、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール等のイミダゾール類を触媒として反応させる。つづいて、得られた生成物に対して（メタ）アクリル酸を、例えば、p-トルエンスルホン酸、トリフルオロメタンスルホン酸または硫酸等のエステル化触媒の存在下に、好ましくはトルエン、キシレン、シクロヘキサン、n-ヘキサン、n-ヘプタンまたはこれらの混合物等の溶剤類の存在下に、好ましくは70℃〜150℃の温度で反応させることにより、あるいはその酸ハロゲン化物を例えば有機アミン、水酸化ナトリウムまたは炭酸ナトリウムの存在下に、好ましくはトルエン、キシレン、シクロヘキサン、n-ヘキサン、n-ヘプタン、塩化メチレン、クロロホルムまたはこれらの混合物等の溶剤類の存在下に、-20℃〜50℃の温度で反応させることにより目的の化合物を得ることができる。
【００１１】
【化７】

【化８】

【００１２】
(式中、-(O-X-O)-は構造式(2)で示され、R6,R7,R12,R13は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R8,R9,R10,R11は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Aは、炭素数20以下の直鎖状あるいは、分岐状あるいは、環状の炭化水素である。-(Y-O)-は構造式(3)で定義される1種類の構造、または構造式(3)で定義される2種類以上の構造がランダムに配列したものである。R14,R15は、同一または異なってもよく、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。R16,R17は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数6以下のアルキル基またはフェニル基である。Zは、炭素数1以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。a,bは、少なくともいずれか一方が0でない、0〜300の整数を示す。c,dは、0または1の整数を示す。ｎは0から10の整数を示す。)
【００１３】
一般式（６）で示される化合物は、例えば、特願2002-018508に記載の２価フェノールと１価フェノールを酸化重合する方法で得た2官能PPEオリゴマーに対し、エピクロロヒドリンを反応させることで得ることができる。
【００１４】
次に、本発明の硬化性樹脂組成物について説明する。該硬化性樹脂組成物は、上述した本発明の（メタ）アクリレート化合物を含有することを特徴とするものであり、公知のエポキシ樹脂、オキセタン樹脂、重合可能な不飽和基を有する化合物、光および/または熱重合開始剤、光増感剤等を添加することも可能である。
【００１５】
エポキシ樹脂としては、一般に公知のものが使用できる。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、キシレンノボラック型エポキシ樹脂、トリグリシジルイソシアヌレート、脂環式エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、特願2001-353194、特願2002-018508に示されるPPE骨格を有するエポキシ樹脂等が挙げられる。これらのエポキシ樹脂は1種あるいは2種以上混合して用いられる。
【００１６】
オキセタン樹脂としては、一般に公知のものが使用できる。例えば、オキセタン、2-メチルオキセタン、2,2-ジメチルオキセタン、3-メチルオキセタン、3,3-ジメチルオキセタン、等のアルキルオキセタン、3-メチル-3-メトキシメチルオキセタン、3,3'-ジ（トリフルオロメチル）パーフルオキセタン、2-クロロメチルオキセタン、3,3-ビス（クロロメチル）オキセタン、OXT-101（東亞合成製商品名）、OXT-121（東亞合成製商品名）等が挙げられる。これらのオキセタン樹脂は1種あるいは2種以上混合して用いられる。
【００１７】
本発明の硬化性樹脂組成物にエポキシ樹脂および/またはオキセタン樹脂を使用する場合にはエポキシ樹脂硬化剤および/またはオキセタン樹脂硬化剤を使用することができる。該エポキシ樹脂硬化剤としては、一般に公知のものが使用でき、例えば、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、２−フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾール誘導体、ジシアンジアミド、ベンジルジメチルアミン、4-メチル-N,N-ジメチルベンジルアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン等のアミン化合物、ホスフィン系はホスホニウム系のリン化合物を挙げることができる。該オキセタン樹脂硬化剤としては公知のカチオン重合開始剤が使用できる。例えば、市販のものではサンエードSI-60L、サンエードSI-80L、サンエードSI-100L（三新化学工業製）、CI-2064（日本曹達製）、イルガキュア261（チバスペシャリティーケミカル製）、アデカオプトマーSP-170、アデカオプトマーSP-150（旭電化製）、サイラキュアーUVI-6990（UCC製）等が挙げられる。カチオン重合開始剤はエポキシ樹脂硬化剤としても使用できる。これらの硬化剤は1種あるいは2種以上組み合わせて使用される。
【００１８】
重合可能な不飽和基を有する化合物としては、一般に公知のものが使用できる。例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の1価または多価アルコールの（メタ）アクリレート類、ビスフェノールA型エポキシ（メタ）アクリレート、ビスフェノールF型エポキシ（メタ）アクリレート、特願2001-387968、特願2002-038156に示されるPPE骨格を有するエポキシ（メタ）アクリレート等のエポキシ（メタ）アクリレート類、特願2002-053653、特願2002-055765に示されるPPE骨格を有する（メタ）アクリレート、ベンゾシクロブテン樹脂等が挙げられる。これらのエチレン性不飽和基を有する化合物は1種あるいは2種以上混合して用いられる。
【００１９】
光重合開始剤としては、一般に公知のものが使用できる。例えば、ベンジル、ジアセチル等のα-ジケトン類、ベンゾイルエチルエーテル、ベンゾインイソプロピルエーテル等のアシロインエーテル類、チオキサントン、2,4-ジエチルチオキサントン、2-イソプロピルチオキサントンなどのチオキサントン類、ベンゾフェノン、4,4'-ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン類、アセトフェノン、2,2'-ジメトキシ-2-フェニルアセトフェノン、β-メトキシアセトフェノン等のアセトフェノン類、2-メチル-１-[4-（メチルチオ）フェニル]-2-モルフォリノプロパン-1-オン、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等のアミノアセトフェノン類が挙げられる。これらの光重合開始剤は1種あるいは2種以上組み合わせて使用される。
【００２０】
さらに、これらの光重合開始剤と公知の光増感剤の1種または2種以上を組み合わせて使用できる。該光増感剤としては、例えば、N,N-ジメチルアミノ安息香酸エチルエステル、N,N-ジメチルアミノ安息香酸イソアミルエステル、トリエタノールアミン、トリエチルアミン等を挙げることができる。
【００２１】
熱重合開始剤としては、一般に公知のものが使用できる。例えば、ベンゾイルパーオキサイド、p-クロロベンゾイルパーオキサイド、ジ-t-ブチルパーオキサイド、ジイソプロピルパーオキシカーボネート、ジ-2-エチルヘキシルパーオキシカーボネート等の過酸化物、およびアゾビスイソブチロニトリル等のアゾ化合等が挙げられる。
【００２２】
さらに本発明の硬化性樹脂組成物を製造する際には、必要に応じて、無機充填剤、着色顔料、消泡剤、表面調整剤、難燃剤、紫外線吸収剤、酸化防止剤、重合禁止剤、流動調整剤等の公知の添加剤を添加することができる。無機充填剤としては、例えば、天然シリカ、溶融シリカ、アモルファスシリカ等のシリカ類、ホワイトカーボン、チタンホワイト、アエロジル、アルミナ、タルク、天然マイカ、合成マイカ、カオリン、クレー、水酸化アルミニウム、硫酸バリウム、E-ガラス、A-ガラス、C-ガラス、L-ガラス、D-ガラス、S-ガラス、M-ガラスG20等が挙げられる。このようにして得られた硬化性樹脂組成物は、ソルダーレジスト組成物、ビルドアップ配線板材料、絶縁塗料、接着剤、印刷インキ、コーティング剤等の各種用途に有用である。
【００２３】
本発明の硬化物は、前述の方法で得られた本発明の硬化性樹脂組成物を、公知の方法、例えば、電子線、紫外線および熱による硬化方法に従って硬化することにより得られる。紫外線を用いて硬化を行う場合、紫外線の光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプあるいはメタルハライドランプ等が使用できる。
【００２４】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明は以下の実施例により特に限定されるものではない。なお、数平均分子量および重量平均分子量の測定にゲル・パーミエーション・クロマトグラフィー(GPC)法により求めた。
【００２５】
実施例１
(2官能PPEオリゴマー体の合成)
撹拌装置、温度計、空気導入管、じゃま板のついた2Ｌの縦長反応器にCuCl1.3 g(0.012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メチルエチルケトン 400ｇを仕込み、反応温度40℃にて撹拌を行い、あらかじめ800ｇのメチルエチルケトンに溶解させた2価のフェノール4,4'-(1-メチルエチリデン)ビス(2,6-ジメチルフェノール)45.4ｇ（0.16mol）と2,6-ジメチルフェノール58.6ｇ（0.48mol）を2 L/minの空気のバブリングを行いながら120分かけて滴下し、さらに滴下終了後60分間、2 L/minの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、樹脂イを98.8ｇ得た。樹脂イの数平均分子量は845、重量平均分子量1106、水酸基当量が451であった。
【００２６】
(エポキシ体の合成)
撹拌装置、温度計、滴下漏斗のついた反応器を100℃まで加熱し、樹脂イ49.6g(水酸基0.11mol)とエピクロロヒドリン292gを仕込んだ。その後、あらかじめエタノール30gにナトリウムエトキシド8.6g(0.13mol)を溶解した溶液を滴下漏斗から、60分かけて滴下し、さらに滴下終了後5時間の撹拌を行った。その後、0.1Nの塩酸水溶液で3回洗浄とイオン交換水での水洗さらにはろ過を行い、生成塩と不純物を除去した。得られた溶液から過剰のエピクロロヒドリンを留去し、さらに減圧乾燥を行い、上記一般式（６）で示される樹脂ロを53.6g得た。樹脂ロは、IRの分析によりフェノール性水酸基の吸収ピーク(3600cm-1)の消滅と、さらにNMRの分析によりグリシジルエーテル由来のピークの発現から、100%の官能基変換を確認した。樹脂ロの数平均分子量は998、重量平均分子量は1277、エポキシ当量は565であった。
【００２７】
(エポキシアクリレート体の合成)
攪拌装置、温度計、還流管のついた反応器に樹脂ロ26ｇ、アクリル酸3.3ｇ、トルエン20ｇ、トリフェニルホスフィン0.13ｇ、ハイドロキノンメチルエーテル13mｇを仕込んだ。これを120℃に加熱、攪拌しながら反応させた。反応中、酸価測定を行い、酸価２mgKOH/gとなるまで反応を行った。120℃での攪拌時間は5時間であった。反応液をトルエン40ｇで希釈し、メタノール中に滴下して再沈殿を行い、ろ過して固体を回収、減圧乾燥して樹脂ハを26.4ｇ得た。樹脂ハの数平均分子量は1388、重量平均分子量は1679であった。
【００２８】
(多官能アクリレート体の合成)
攪拌装置、温度計、滴下ロートのついた反応器に樹脂ハ25g、トリエチルアミン5.2g、塩化メチレン400ｇを反応器に、アクリル酸クロライド4.6ｇ、塩化メチレン100ｇを滴下ロートに仕込んだ。これを窒素下で0℃に冷却、攪拌状態で1時間かけてアクリル酸クロライドを滴下した後、室温に戻して攪拌を続けた。反応液をサンプリングしてNMR測定を行い反応を追跡した。2時間攪拌したところで反応が終了したため、0.1NHClaqおよび純水で分液洗浄を行った。有機層を濃縮し、メタノール中に滴下して再沈殿を行い、濾過して固体を回収、減圧乾燥して上記一般式（１）で示した樹脂ニを17.6g得た。樹脂ニの数平均分子量は1664、重量平均分子量は2205であった。
【００２９】
樹脂ニ10ｇを150℃で溶融、脱気、成形し、200℃6時間硬化を行い、硬化物ホを得た。
【００３０】
樹脂ニ6ｇをカルビトールアセテート4ｇに溶解し、ダロキュア1173（チバスペシャリティケミカルズ製、光重合開始剤）0.6gを添加した樹脂組成物ヘをスクリーン印刷機で銅張積層板上に塗布し、送風乾燥機で80℃30分乾燥した後、パターンフィルムを当て、UV照射装置（アイグラフィックス製：UB0151、光源：メタルハライドランプ）を用いて2000mJ露光した。露光後、メチルエチルケトンで現像したところ、未露光部のみがメチルエチルケトンに溶解し樹脂硬化物トの現像パターンが得られた。樹脂硬化物ヘの鉛筆引っかき値（JIS K5400）はHであった。
【００３１】
実施例２
(2官能PPEオリゴマー体の合成)
撹拌装置、温度計、空気導入管、じゃま板のついた2Ｌの縦長反応器にCuCl1.3 g(0.012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メチルエチルケトン 400ｇを仕込み、反応温度40℃にて撹拌を行い、あらかじめ800ｇのメチルエチルケトンに溶解させた2価のフェノール4,4'-シクロヘキシリデンビス(2,6-ジメチルフェノール)51.8ｇ（0.16mol）と2,6-ジメチルフェノール58.6ｇ（0.48mol）を2 L/minの空気のバブリングを行いながら120分かけて滴下し、さらに滴下終了後60分間、2 L/minの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、樹脂チを102.6ｇ得た。樹脂チの数平均分子量は877、重量平均分子量1183、水酸基当量が477であった。
【００３２】
(エポキシ体の合成)
撹拌装置、温度計、滴下漏斗のついた反応器を100℃まで加熱し、樹脂チ52.5g(水酸基0.11mol)とエピクロロヒドリン292gを仕込んだ。その後、あらかじめエタノール30gにナトリウムエトキシド8.6g(0.13mol)を溶解した溶液を滴下漏斗から、60分かけて滴下し、さらに滴下終了後5時間の撹拌を行った。その後、0.1Nの塩酸水溶液で3回洗浄とイオン交換水での水洗さらにはろ過を行い、生成塩と不純物を除去した。得られた溶液から過剰のエピクロロヒドリンを留去し、さらに減圧乾燥を行い、上記一般式（６）で示される樹脂リを54.1g得た。樹脂リは、IRの分析によりフェノール性水酸基の吸収ピーク(3600cm-1)の消滅と、さらにNMRの分析によりグリシジルエーテル由来のピークの発現から、100%の官能基変換を確認した。樹脂リの数平均分子量は1029、重量平均分子量は1301、エポキシ当量は576であった。
【００３３】
(エポキシアクリレート体の合成)
攪拌装置、温度計、還流管のついた反応器に樹脂リ26.5ｇ、アクリル酸3.3ｇ、トルエン20ｇ、トリフェニルホスフィン0.13ｇ、ハイドロキノンメチルエーテル13mｇを仕込んだ。これを120℃に加熱、攪拌しながら反応させた。反応中、酸価測定を行い、酸価２mgKOH/gとなるまで反応を行った。120℃での攪拌時間は5時間であった。反応液をトルエン40ｇで希釈し、メタノール中に滴下して再沈殿を行い、ろ過して固体を回収、減圧乾燥して樹脂ヌを26.5ｇ得た。樹脂ヌの数平均分子量は1411、重量平均分子量は1721であった。
【００３４】
(多官能アクリレート体の合成)
攪拌装置、温度計、滴下ロートのついた反応器に樹脂ハ25g、トリエチルアミン5.1g、塩化メチレン400ｇを反応器に、アクリル酸クロライド4.5ｇ、塩化メチレン100ｇを滴下ロートに仕込んだ。これを窒素下で0℃に冷却、攪拌状態で1時間かけてアクリル酸クロライドを滴下した後、室温に戻して攪拌を続けた。反応液をサンプリングしてNMR測定を行い反応を追跡した。2時間攪拌したところで反応が終了したため、0.1NHClaqおよび純水で分液洗浄を行った。有機層を濃縮し、メタノール中に滴下して再沈殿を行い、濾過して固体を回収、減圧乾燥して上記一般式（１）で示される樹脂ルを18.3g得た。樹脂ルの数平均分子量は1710、重量平均分子量は2341であった。
【００３５】
樹脂ル10ｇを150℃で溶融、脱気、成形し、200℃6時間硬化を行い、硬化物ヲを得た。
【００３６】
樹脂ル6ｇをカルビトールアセテート4ｇに溶解し、ダロキュア1173（チバスペシャリティケミカルズ製、光重合開始剤）0.6gを添加した樹脂組成物ワをスクリーン印刷機で銅張積層板上に塗布し、送風乾燥機で80℃30分乾燥した後、パターンフィルムを当て、UV照射装置（アイグラフィックス製：UB0151、光源：メタルハライドランプ）を用いて2000mJ露光した。露光後、メチルエチルケトンで現像したところ、未露光部のみがメチルエチルケトンに溶解し樹脂硬化物カの現像パターンが得られた。樹脂硬化物ワの鉛筆引っかき値（JIS K5400）はHであった。
【００３７】
実施例３
(2官能PPEオリゴマー体の合成)
撹拌装置、温度計、空気導入管、じゃま板のついた2Ｌの縦長反応器にCuCl1.3 g(0.012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メチルエチルケトン 400ｇを仕込み、反応温度40℃にて撹拌を行い、あらかじめ800ｇのメチルエチルケトンに溶解させた2価のフェノール4,4'-メチリデンビス(2,3,6-トリメチルフェノール)45.4ｇ（0.16mol）と2,6-ジメチルフェノール58.6ｇ（0.48mol）を2 L/minの空気のバブリングを行いながら120分かけて滴下し、さらに滴下終了後60分間、2 L/minの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、樹脂ヨを97.4ｇ得た。樹脂ヨの数平均分子量は852、重量平均分子量1133、水酸基当量が460であった。
【００３８】
(エポキシ体の合成)
撹拌装置、温度計、滴下漏斗のついた反応器を100℃まで加熱し、樹脂ヨ50.6g(水酸基0.11mol)とエピクロロヒドリン292gを仕込んだ。その後、あらかじめエタノール30gにナトリウムエトキシド8.6g(0.13mol)を溶解した溶液を滴下漏斗から、60分かけて滴下し、さらに滴下終了後5時間の撹拌を行った。その後、0.1Nの塩酸水溶液で3回洗浄とイオン交換水での水洗さらにはろ過を行い、生成塩と不純物を除去した。得られた溶液から過剰のエピクロロヒドリンを留去し、さらに減圧乾燥を行い、上記一般式（６）で示される樹脂タを53.8g得た。樹脂タは、IRの分析によりフェノール性水酸基の吸収ピーク(3600cm-1)の消滅と、さらにNMRの分析によりグリシジルエーテル由来のピークの発現から、100%の官能基変換を確認した。樹脂タの数平均分子量は1005、重量平均分子量は1275、エポキシ当量は566であった。
【００３９】
(エポキシアクリレート体の合成)
攪拌装置、温度計、還流管のついた反応器に樹脂タ26ｇ、アクリル酸3.3ｇ、トルエン20ｇ、トリフェニルホスフィン0.13ｇ、ハイドロキノンメチルエーテル13mｇを仕込んだ。これを120℃に加熱、攪拌しながら反応させた。反応中、酸価測定を行い、酸価２mgKOH/gとなるまで反応を行った。120℃での攪拌時間は5時間であった。反応液をトルエン40ｇで希釈し、メタノール中に滴下して再沈殿を行い、ろ過して固体を回収、減圧乾燥して樹脂レを26.7g得た。樹脂レの数平均分子量は1395、重量平均分子量は1687であった。
【００４０】
(多官能アクリレート体の合成)
攪拌装置、温度計、滴下ロートのついた反応器に樹脂レ25g、トリエチルアミン5.2g、塩化メチレン400ｇを反応器に、アクリル酸クロライド4.6ｇ、塩化メチレン100ｇを滴下ロートに仕込んだ。これを窒素下で0℃に冷却、攪拌状態で1時間かけてアクリル酸クロライドを滴下した後、室温に戻して攪拌を続けた。反応液をサンプリングしてNMR測定を行い反応を追跡した。2時間攪拌したところで反応が終了したため、0.1NHClaqおよび純水で分液洗浄を行った。有機層を濃縮し、メタノール中に滴下して再沈殿を行い、濾過して固体を回収、減圧乾燥して上記一般式（１）で示される樹脂ソを16.5g得た。樹脂ソの数平均分子量は1705、重量平均分子量は2298であった。
【００４１】
樹脂ソ10ｇを150℃で溶融、脱気、成形し、200℃6時間硬化を行い、硬化物ツを得た。
【００４２】
樹脂ソ6ｇをカルビトールアセテート4ｇに溶解し、ダロキュア1173（チバスペシャリティケミカルズ製、光重合開始剤）0.6gを添加した樹脂組成物ネをスクリーン印刷機で銅張積層板上に塗布し、送風乾燥機で80℃30分乾燥した後、パターンフィルムを当て、UV照射装置（アイグラフィックス製：UB0151、光源：メタルハライドランプ）を用いて2000mJ露光した。露光後、メチルエチルケトンで現像したところ、未露光部のみがメチルエチルケトンに溶解し樹脂硬化物ナの現像パターンが得られた。樹脂硬化物ナの鉛筆引っかき値（JIS K5400）はHであった。
【００４３】
実施例４
(2官能PPEオリゴマー体の合成)
撹拌装置、温度計、空気導入管、じゃま板のついた2Ｌの縦長反応器にCuCl1.3 g(0.012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メチルエチルケトン 400ｇを仕込み、反応温度40℃にて撹拌を行い、あらかじめ800ｇのメチルエチルケトンに溶解させた2価のフェノール4,4'-[1,4-フェニレンビス(1-メチルエチリデン)]ビス(2,3,6-トリメチルフェノール)68.8ｇ（0.16mol）と2,6-ジメチルフェノール58.6ｇ（0.48mol）を2 L/minの空気のバブリングを行いながら120分かけて滴下し、さらに滴下終了後60分間、2 L/minの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、樹脂ラを114.6ｇ得た。樹脂ラの数平均分子量は934、重量平均分子量1223、水酸基当量が496であった。
【００４４】
(エポキシ体の合成)
撹拌装置、温度計、滴下漏斗のついた反応器を100℃まで加熱し、樹脂ラ54.6g(水酸基0.11mol)とエピクロロヒドリン292gを仕込んだ。その後、あらかじめエタノール30gにナトリウムエトキシド8.6g(0.13mol)を溶解した溶液を滴下漏斗から、60分かけて滴下し、さらに滴下終了後5時間の撹拌を行った。その後、0.1Nの塩酸水溶液で3回洗浄とイオン交換水での水洗さらにはろ過を行い、生成塩と不純物を除去した。得られた溶液から過剰のエピクロロヒドリンを留去し、さらに減圧乾燥を行い、上記一般式（６）で示される樹脂ムを56.9g得た。樹脂ムは、IRの分析によりフェノール性水酸基の吸収ピーク(3600cm-1)の消滅と、さらにNMRの分析によりグリシジルエーテル由来のピークの発現から、100%の官能基変換を確認した。樹脂ムの数平均分子量は1092、重量平均分子量は1408、エポキシ当量は612であった。
【００４５】
(エポキシアクリレート体の合成)
攪拌装置、温度計、還流管のついた反応器に樹脂ム28.1ｇ、アクリル酸3.3ｇ、トルエン20ｇ、トリフェニルホスフィン0.13ｇ、ハイドロキノンメチルエーテル13mｇを仕込んだ。これを120℃に加熱、攪拌しながら反応させた。反応中、酸価測定を行い、酸価２mgKOH/gとなるまで反応を行った。120℃での攪拌時間は5時間であった。反応液をトルエン40ｇで希釈し、メタノール中に滴下して再沈殿を行い、ろ過して固体を回収、減圧乾燥して樹脂ウを28.3ｇ得た。樹脂ウの数平均分子量は1497、重量平均分子量は1841であった。
【００４６】
(多官能アクリレート体の合成)
攪拌装置、温度計、滴下ロートのついた反応器に樹脂ウ25g、トリエチルアミン4.8g、塩化メチレン400ｇを反応器に、アクリル酸クロライド4.3ｇ、塩化メチレン100ｇを滴下ロートに仕込んだ。これを窒素下で0℃に冷却、攪拌状態で1時間かけてアクリル酸クロライドを滴下した後、室温に戻して攪拌を続けた。反応液をサンプリングしてNMR測定を行い反応を追跡した。2時間攪拌したところで反応が終了したため、0.1NHClaqおよび純水で分液洗浄を行った。有機層を濃縮し、メタノール中に滴下して再沈殿を行い、濾過して固体を回収、減圧乾燥して上記一般式（１）で示される樹脂ノを17.6g得た。樹脂ノの数平均分子量は1788、重量平均分子量は2407であった。
【００４７】
樹脂ノ10ｇを150℃で溶融、脱気、成形し、200℃6時間硬化を行い、硬化物オを得た。
【００４８】
樹脂ノ6ｇをカルビトールアセテート4ｇに溶解し、ダロキュア1173（チバスペシャリティケミカルズ製、光重合開始剤）0.6gを添加した樹脂組成物クをスクリーン印刷機で銅張積層板上に塗布し、送風乾燥機で80℃30分乾燥した後、パターンフィルムを当て、UV照射装置（アイグラフィックス製：UB0151、光源：メタルハライドランプ）を用いて2000mJ露光した。露光後、メチルエチルケトンで現像したところ、未露光部のみがメチルエチルケトンに溶解し樹脂硬化物ヤの現像パターンが得られた。樹脂硬化物ヤの鉛筆引っかき値（JIS K5400）はHであった。
【００４９】
実施例５
(2官能PPEオリゴマー体の合成)
撹拌装置、温度計、空気導入管、じゃま板のついた2Ｌの縦長反応器にCuCl1.3 g(0.012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メチルエチルケトン 400ｇを仕込み、反応温度40℃にて撹拌を行い、あらかじめ800ｇのメチルエチルケトンに溶解させた2価のフェノール4,4'-メチレンビス(2,6-ジメチルフェノール)41.0ｇ（0.16mol）と2,6-ジメチルフェノール58.6ｇ（0.48mol）を2 L/minの空気のバブリングを行いながら120分かけて滴下し、さらに滴下終了後60分間、2 L/minの空気のバブリングを続けながら撹拌を行った。これにエチレンジアミン四酢酸二水素二ナトリウム水溶液を加え、反応を停止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交換水で洗浄を行った。得られた溶液をエバポレイタ−で濃縮し、さらに減圧乾燥を行い、樹脂マを94.6ｇ得た。樹脂マの数平均分子量は801、重量平均分子量1081、水酸基当量が455であった。
【００５０】
(エポキシ体の合成)
撹拌装置、温度計、滴下漏斗のついた反応器を100℃まで加熱し、樹脂マ50.1g(水酸基0.11mol)とエピクロロヒドリン292gを仕込んだ。その後、あらかじめエタノール30gにナトリウムエトキシド8.6g(0.13mol)を溶解した溶液を滴下漏斗から、60分かけて滴下し、さらに滴下終了後5時間の撹拌を行った。その後、0.1Nの塩酸水溶液で3回洗浄とイオン交換水での水洗さらにはろ過を行い、生成塩と不純物を除去した。得られた溶液から過剰のエピクロロヒドリンを留去し、さらに減圧乾燥を行い、上記一般式（６）で示される樹脂ケを50.2g得た。樹脂フは、IRの分析によりフェノール性水酸基の吸収ピーク(3600cm-1)の消滅と、さらにNMRの分析によりグリシジルエーテル由来のピークの発現から、100%の官能基変換を確認した。樹脂ケの数平均分子量は956、重量平均分子量は1204、エポキシ当量は545であった。
【００５１】
(エポキシアクリレート体の合成)
攪拌装置、温度計、還流管のついた反応器に樹脂ケ25.1ｇ、アクリル酸3.3ｇ、トルエン20ｇ、トリフェニルホスフィン0.13ｇ、ハイドロキノンメチルエーテル13mｇを仕込んだ。これを120℃に加熱、攪拌しながら反応させた。反応中、酸価測定を行い、酸価２mgKOH/gとなるまで反応を行った。120℃での攪拌時間は5時間であった。反応液をトルエン40ｇで希釈し、メタノール中に滴下して再沈殿を行い、ろ過して固体を回収、減圧乾燥して樹脂フを25.4ｇ得た。樹脂フの数平均分子量は1359、重量平均分子量は1657であった。
【００５２】
(多官能アクリレート体の合成)
攪拌装置、温度計、滴下ロートのついた反応器に樹脂フ25g、トリエチルアミン5.3g、塩化メチレン400ｇを反応器に、アクリル酸クロライド4.8ｇ、塩化メチレン100ｇを滴下ロートに仕込んだ。これを窒素下で0℃に冷却、攪拌状態で1時間かけてアクリル酸クロライドを滴下した後、室温に戻して攪拌を続けた。反応液をサンプリングしてNMR測定を行い反応を追跡した。2時間攪拌したところで反応が終了したため、0.1NHClaqおよび純水で分液洗浄を行った。有機層を濃縮し、メタノール中に滴下して再沈殿を行い、濾過して固体を回収、減圧乾燥して上記一般式（１）で示される樹脂コを16.6g得た。樹脂コの数平均分子量は1623、重量平均分子量は2278であった。
【００５３】
樹脂コ10ｇを150℃で溶融、脱気、成形し、200℃6時間硬化を行い、硬化物エを得た。
【００５４】
樹脂コ6ｇをカルビトールアセテート4ｇに溶解し、ダロキュア1173（チバスペシャリティケミカルズ製、光重合開始剤）0.6gを添加した樹脂組成物テをスクリーン印刷機で銅張積層板上に塗布し、送風乾燥機で80℃30分乾燥した後、パターンフィルムを当て、UV照射装置（アイグラフィックス製：UB0151、光源：メタルハライドランプ）を用いて2000mJ露光した。露光後、メチルエチルケトンで現像したところ、未露光部のみがメチルエチルケトンに溶解し樹脂硬化物アの現像パターンが得られた。樹脂硬化物アの鉛筆引っかき値（JIS K5400）はHであった。
【００５５】
比較例１
実施例１で得られた樹脂ハ10gを150℃で脱気、成形し、200℃6時間熱硬化を行い、硬化物サを得た。
【００５６】
実施例１、２、３、４、５、比較例１で得られた硬化物の特性を以下の方法により評価した。
ガラス転移温度（Tg）：動的粘弾性測定（DMA）により求めた。振動周波数10Hzで測定を行った。
誘電率、誘電正接：空洞共振摂動法により求めた。
【００５７】
以上の物性の評価結果を表１に示す。
【表１】

【００５８】
【発明の効果】
本発明の多官能（メタ）アクリレート化合物は、高いガラス転移温度を有し、低誘電率、低誘電正接であることから高機能性高分子材料として極めて有用であり、熱的、電気的に優れた材料として各種コーティング剤、UV塗料、接着剤、レジスト、ビルドアップ配線板材料などの幅広い用途に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel (meth) acrylate compound having a PPE skeleton and a cured product thereof, and further relates to a curable resin composition containing the compound and a cured product thereof. The (meth) acrylate compound of the present invention can obtain a polymer material excellent in heat resistance and dielectric properties by polymerizing itself or copolymerizing with another unsaturated compound. In addition, the (meth) acrylate compound of the present invention can also be made into a photosensitive resin composition by combining with a photopolymerization initiator. Such a photosensitive resin composition includes a resin for resist and a resin for build-up wiring board. It can be used for a wide range of applications such as liquid crystal display panel sealing resins, liquid crystal color filter resins, UV paints, various coating agents, and adhesives.
[0002]
[Prior art]
Conventionally, (meth) acrylate compounds have been widely used as raw materials for various functional polymer materials such as photosensitive materials, optical materials, dental materials, electronic materials, and various polymer crosslinking agents. However, in recent years, with the sophistication of required performance in these application fields, the physical properties required as a functional polymer material have become increasingly severe. As such physical properties, for example, heat resistance, weather resistance, low water absorption, high refractive index, high fracture toughness, low dielectric constant, low dielectric loss tangent, etc. are required. I have not been satisfied.
[0003]
[Problems to be solved by the present invention]
An object of the present invention is to provide a novel (meth) acrylate compound and a curable resin composition having excellent heat resistance, low dielectric constant and low dielectric loss tangent.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have used epoxy (meth) acrylate (Japanese Patent Application No. 2002-038156), (meth) acrylate (patent application) as a radical polymerization type bifunctional PPE oligomer that inherited the excellent dielectric properties and heat resistance of PPE. 2002-055765) was synthesized. As a result of intensive studies aimed at further increasing the heat resistance, oligomers of bifunctional PPE (-(OXO)-is structural formula (2) and-(YO)-is defined by structural formula (3). In order to complete the present invention, it is found that the object can be met by making the (meth) acrylate group capable of radical polymerization into four or more functional groups (one type or two or more types of structures arranged randomly). It came. That is, this invention relates to the (meth) acrylate compound represented by General formula (1).
[0005]
[Formula 4]

[Chemical formula 5]

[0006]
(In the formula, R1, R2, R3, R4, and R5 represent a hydrogen atom or a methyl group.-(OXO)-is represented by the structural formula (2), and R6, R7, R12, and R13 are the same or different. Or a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R8, R9, R10, and R11 may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or phenyl A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms,-(YO)-is one type of structure or structure defined by structural formula (3) Two or more types of structures defined by the formula (3) are randomly arranged, R14 and R15 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R16 and R17 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a fluorine atom. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, and at least one of them is not 0, 0 to Represents an integer of 300. c and d represent an integer of 0 or 1. n represents an integer of 0 to 10.)
[0007]
Furthermore, this invention relates to the curable resin composition containing the said (meth) acrylate compound, Furthermore, it relates to the hardened | cured material formed by hardening | curing a composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (1), R1, R2, R3, R4, and R5 are a hydrogen atom or a methyl group. -(OXO)-is represented by the structural formula (2), and R6, R7, R12, and R13 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R8, R9, R10, and R11 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms. -(YO)-is one type of structure defined by structural formula (3) or two or more types of structures defined by structural formula (3) arranged at random. R14 and R15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R16 and R17 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b represent an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. n shows the integer of 0-10. Among these, R6, R7, R12 and R13 are preferably alkyl groups having 3 or less carbon atoms, R8, R9, R10 and R11 are hydrogen atoms or alkyl groups having 3 or less carbon atoms, and R14 and R15 are 3 or less carbon atoms. R16 and R17 are a hydrogen atom or an alkyl group having 3 or less carbon atoms. Among these, R6, R7, R12, and R13 are preferably represented by the structural formula (2) of-(OXO)-. A methyl group, and-(YO)-is represented by Structural Formula (4) or Structural Formula (5).
[0009]
[Chemical 6]

[0010]
The method for producing the (meth) acrylate represented by the general formula (1) of the present invention is not particularly limited and may be produced by any method. For example, it can be obtained by reacting the compound represented by the general formula (6) with (meth) acrylic acid or a (meth) acrylic acid derivative. Specifically, first, the compound represented by the general formula (6) and (meth) acrylic acid are mixed with amines such as triethylamine, dimethylbutylamine, tri-n-butylamine, tetramethylammonium salt, tetraethylammonium. Salts, tetrabutylammonium salts, quaternary ammonium salts such as benzyltriethylammonium salts, or quaternary phosphonium salts, other phosphines such as triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. The imidazoles are reacted as catalysts. Subsequently, (meth) acrylic acid is added to the obtained product in the presence of an esterification catalyst such as p-toluenesulfonic acid, trifluoromethanesulfonic acid or sulfuric acid, preferably toluene, xylene, cyclohexane, By reacting in the presence of solvents such as n-hexane, n-heptane or mixtures thereof, preferably at a temperature of 70 ° C. to 150 ° C., or the acid halide, for example organic amine, sodium hydroxide or carbonate The reaction is carried out in the presence of sodium, preferably in the presence of solvents such as toluene, xylene, cyclohexane, n-hexane, n-heptane, methylene chloride, chloroform or mixtures thereof at a temperature of -20 ° C to 50 ° C. Thus, the target compound can be obtained.
[0011]
[Chemical 7]

[Chemical 8]

[0012]
(In the formula,-(OXO)-is represented by the structural formula (2), and R6, R7, R12, and R13 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R8, R9, R10, and R11 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a linear or branched group having 20 or less carbon atoms. -(YO)-is one type of structure defined by structural formula (3) or two or more types of structures defined by structural formula (3) randomly arranged R14 and R15 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R16 and R17 may be the same or different, and may be a hydrogen atom, a halogen atom or An alkyl group having 6 or less carbon atoms or a phenyl group, and Z is an organic group having 1 or more carbon atoms. And may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, a and b represent an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1 (N represents an integer of 0 to 10)
[0013]
For example, the compound represented by the general formula (6) reacts epichlorohydrin with a bifunctional PPE oligomer obtained by the oxidative polymerization of dihydric phenol and monohydric phenol described in Japanese Patent Application No. 2002-018508. Can be obtained.
[0014]
Next, the curable resin composition of the present invention will be described. The curable resin composition is characterized by containing the (meth) acrylate compound of the present invention described above, a known epoxy resin, oxetane resin, compound having a polymerizable unsaturated group, light and It is also possible to add a thermal polymerization initiator, a photosensitizer or the like.
[0015]
As the epoxy resin, generally known epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, triglycidyl isocyanurate, alicyclic epoxy resin, dicyclo Examples thereof include pentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, and epoxy resins having a PPE skeleton as shown in Japanese Patent Application Nos. 2001-353194 and 2002-018508. These epoxy resins are used alone or in combination.
[0016]
As the oxetane resin, generally known oxetane resins can be used. For example, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3′-di ( Trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, OXT-101 (trade name, manufactured by Toagosei), OXT-121 (trade name, manufactured by Toagosei) . These oxetane resins are used alone or in combination.
[0017]
When using an epoxy resin and / or an oxetane resin in the curable resin composition of the present invention, an epoxy resin curing agent and / or an oxetane resin curing agent can be used. As the epoxy resin curing agent, generally known ones can be used. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- Imidazole derivatives such as 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, dicyandiamide, benzyldimethylamine, 4-methyl-N , N-dimethylbenzylamine, amine compounds such as diaminodiphenylmethane and diaminodiphenylsulfone, and phosphine compounds include phosphonium phosphorus compounds. A known cationic polymerization initiator can be used as the oxetane resin curing agent. For example, Sanedo SI-60L, Sanedo SI-80L, Sanedo SI-100L (manufactured by Sanshin Chemical Industry), CI-2064 (manufactured by Nippon Soda), Irgacure 261 (manufactured by Ciba Specialty Chemical), Adeka optomer SP-170, Adekaoptomer SP-150 (Asahi Denka), Syracure UVI-6990 (UCC), and the like. The cationic polymerization initiator can also be used as an epoxy resin curing agent. These curing agents are used alone or in combination of two or more.
[0018]
As the compound having a polymerizable unsaturated group, generally known compounds can be used. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylates, (meth) acrylates of monohydric or polyhydric alcohols such as dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, Japanese Patent Application 2001-387968 , Epoxy (meth) acrylates such as epoxy (meth) acrylate having PPE skeleton shown in Japanese Patent Application No. 2002-038156, (meth) acrylate having PPE skeleton shown in Japanese Patent Application No. 2002-053653, Japanese Patent Application No. 2002-055765, Ben Cyclobutene resins. These compounds having an ethylenically unsaturated group are used alone or in combination.
[0019]
As the photopolymerization initiator, generally known photopolymerization initiators can be used. For example, α-diketones such as benzyl and diacetyl, acyloin ethers such as benzoylethyl ether and benzoin isopropyl ether, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, and 2-isopropylthioxanthone, benzophenone, 4,4 ′ Benzophenones such as -bis (dimethylamino) benzophenone, acetophenones such as acetophenone, 2,2'-dimethoxy-2-phenylacetophenone, β-methoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl]- And aminoacetophenones such as 2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(-4-morpholinophenyl) -butanone-1. These photopolymerization initiators are used alone or in combination.
[0020]
Furthermore, these photopolymerization initiators and known photosensitizers can be used alone or in combination. Examples of the photosensitizer include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine.
[0021]
As the thermal polymerization initiator, generally known ones can be used. For example, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and azo such as azobisisobutyronitrile Compound etc. are mentioned.
[0022]
Furthermore, when producing the curable resin composition of the present invention, if necessary, an inorganic filler, a color pigment, an antifoaming agent, a surface conditioner, a flame retardant, an ultraviolet absorber, an antioxidant, a polymerization inhibitor. Well-known additives such as a flow regulator can be added. Examples of inorganic fillers include silicas such as natural silica, fused silica, amorphous silica, white carbon, titanium white, aerosil, alumina, talc, natural mica, synthetic mica, kaolin, clay, aluminum hydroxide, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20 and the like. The curable resin composition thus obtained is useful for various applications such as a solder resist composition, a build-up wiring board material, an insulating paint, an adhesive, a printing ink, and a coating agent.
[0023]
The cured product of the present invention is obtained by curing the curable resin composition of the present invention obtained by the above-described method according to a known method, for example, a curing method using an electron beam, ultraviolet rays, and heat. When curing is performed using ultraviolet rays, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used as the ultraviolet light source.
[0024]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not particularly limited to the following examples. The number average molecular weight and the weight average molecular weight were determined by gel permeation chromatography (GPC) method.
[0025]
Example 1
(Synthesis of bifunctional PPE oligomer)
CuL 1.3 g (0.012 mol), di-n-butylamine 70.7 g (0.55 mol), and methyl ethyl ketone 400 g were charged in a 2 liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and reaction temperature 40 The mixture was stirred at ℃, and 45.4 g (0.16 mol) of divalent phenol 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol) dissolved in 800 g of methyl ethyl ketone and 2,6- Dimethylphenol (58.6 g, 0.48 mol) was added dropwise over 120 minutes while bubbling 2 L / min of air, and stirring was continued for 60 minutes after the completion of dropping while continuing bubbling of 2 L / min of air. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Then, after washing 3 times with 1M hydrochloric acid aqueous solution, it was washed with ion-exchanged water. The obtained solution was concentrated by an evaporator and further dried under reduced pressure to obtain 98.8 g of Resin A. Resin A had a number average molecular weight of 845, a weight average molecular weight of 1106, and a hydroxyl group equivalent of 451.
[0026]
(Synthesis of epoxy body)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 49.6 g of resin (hydroxyl 0.11 mol) and 292 g of epichlorohydrin were charged. Thereafter, a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in 30 g of ethanol in advance was dropped from the dropping funnel over 60 minutes, and further stirred for 5 hours after the completion of the dropping. Thereafter, the resulting salt and impurities were removed by washing with 0.1N aqueous hydrochloric acid solution three times, with ion-exchanged water and filtration. Excess epichlorohydrin was distilled off from the resulting solution, followed by drying under reduced pressure to obtain 53.6 g of resin B represented by the above general formula (6). Resin B confirmed 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis. The number average molecular weight of Resin B was 998, the weight average molecular weight was 1277, and the epoxy equivalent was 565.
[0027]
(Synthesis of epoxy acrylate)
A reactor equipped with a stirrer, a thermometer, and a reflux tube was charged with 26 g of resin, 3.3 g of acrylic acid, 20 g of toluene, 0.13 g of triphenylphosphine, and 13 mg of hydroquinone methyl ether. This was reacted while heating to 120 ° C. and stirring. During the reaction, the acid value was measured and the reaction was continued until the acid value reached 2 mgKOH / g. The stirring time at 120 ° C. was 5 hours. The reaction solution was diluted with 40 g of toluene and added dropwise to methanol to perform reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 26.4 g of resin C. The number average molecular weight of Resin C was 1388, and the weight average molecular weight was 1679.
[0028]
(Synthesis of polyfunctional acrylate)
A reactor equipped with a stirrer, a thermometer and a dropping funnel was charged with 25 g of resin, 5.2 g of triethylamine, and 400 g of methylene chloride in the reactor, and 4.6 g of acrylic acid chloride and 100 g of methylene chloride were charged into the dropping funnel. This was cooled to 0 ° C. under nitrogen, and acrylic acid chloride was added dropwise over 1 hour with stirring, and then returned to room temperature and stirring was continued. The reaction solution was sampled and subjected to NMR measurement to monitor the reaction. Since the reaction was completed after stirring for 2 hours, liquid separation washing was performed with 0.1 N HClaq and pure water. The organic layer was concentrated and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 17.6 g of resin D represented by the above general formula (1). The number average molecular weight of Resin D was 1664, and the weight average molecular weight was 2205.
[0029]
10 g of resin was melted, degassed and molded at 150 ° C. and cured at 200 ° C. for 6 hours to obtain a cured product.
[0030]
Dissolve 6 g of resin d in 4 g of carbitol acetate, apply 0.6 g of Darocur 1173 (manufactured by Ciba Specialty Chemicals, photopolymerization initiator) to a copper-clad laminate with a screen printer, and blow dry. After drying at 80 ° C. for 30 minutes, a pattern film was applied and exposed to 2000 mJ using a UV irradiation device (made by Eye Graphics: UB0151, light source: metal halide lamp). After exposure, development with methyl ethyl ketone revealed that only the unexposed area was dissolved in methyl ethyl ketone and a development pattern of the cured resin product was obtained. The pencil scratch value (JIS K5400) on the cured resin was H.
[0031]
Example 2
(Synthesis of bifunctional PPE oligomer)
CuL 1.3 g (0.012 mol), di-n-butylamine 70.7 g (0.55 mol), and methyl ethyl ketone 400 g were charged in a 2 liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and reaction temperature 40 The mixture was stirred at ℃, and 51.8 g (0.16 mol) of divalent phenol 4,4'-cyclohexylidenebis (2,6-dimethylphenol) and 2,6-dimethylphenol 58.6 dissolved in 800 g of methyl ethyl ketone in advance. g (0.48 mol) was added dropwise over 120 minutes while bubbling 2 L / min of air, and stirring was continued for 60 minutes after the completion of the dripping while continuing bubbling of 2 L / min of air. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Then, after washing 3 times with 1M hydrochloric acid aqueous solution, it was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 102.6 g of resin h. The resin H had a number average molecular weight of 877, a weight average molecular weight of 1183, and a hydroxyl group equivalent of 477.
[0032]
(Synthesis of epoxy body)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 52.5 g of resin (hydroxyl 0.11 mol) and 292 g of epichlorohydrin were charged. Thereafter, a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in 30 g of ethanol in advance was dropped from the dropping funnel over 60 minutes, and further stirred for 5 hours after the completion of the dropping. Thereafter, the resulting salt and impurities were removed by washing with 0.1N aqueous hydrochloric acid solution three times, with ion-exchanged water and filtration. Excess epichlorohydrin was distilled off from the resulting solution, followed by drying under reduced pressure to obtain 54.1 g of a resin represented by the above general formula (6). Resin was confirmed to have 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis. The number average molecular weight of the resin was 1029, the weight average molecular weight was 1301, and the epoxy equivalent was 576.
[0033]
(Synthesis of epoxy acrylate)
A reactor equipped with a stirrer, a thermometer, and a reflux tube was charged with 26.5 g of resin, 3.3 g of acrylic acid, 20 g of toluene, 0.13 g of triphenylphosphine, and 13 mg of hydroquinone methyl ether. This was reacted while heating to 120 ° C. and stirring. During the reaction, the acid value was measured and the reaction was continued until the acid value reached 2 mgKOH / g. The stirring time at 120 ° C. was 5 hours. The reaction solution was diluted with 40 g of toluene and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 26.5 g of resin. The number average molecular weight of the resin was 1411, and the weight average molecular weight was 1721.
[0034]
(Synthesis of polyfunctional acrylate)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 25 g of resin, 5.1 g of triethylamine and 400 g of methylene chloride in the reactor, and 4.5 g of acrylic acid chloride and 100 g of methylene chloride were charged into the dropping funnel. This was cooled to 0 ° C. under nitrogen, and acrylic acid chloride was added dropwise over 1 hour with stirring, and then returned to room temperature and stirring was continued. The reaction solution was sampled and subjected to NMR measurement to monitor the reaction. Since the reaction was completed after stirring for 2 hours, liquid separation washing was performed with 0.1 N HClaq and pure water. The organic layer was concentrated, dropped into methanol and reprecipitated, filtered to recover the solid, and dried under reduced pressure to obtain 18.3 g of resin represented by the above general formula (1). The number average molecular weight of the resin was 1710, and the weight average molecular weight was 2341.
[0035]
10 g of resin was melted, degassed and molded at 150 ° C. and cured at 200 ° C. for 6 hours to obtain a cured product.
[0036]
Resin 6g was dissolved in carbitol acetate 4g and Darocur 1173 (manufactured by Ciba Specialty Chemicals, photopolymerization initiator) 0.6g was added on a copper-clad laminate with a screen printer and dried by air blowing. After drying at 80 ° C. for 30 minutes, a pattern film was applied and exposed to 2000 mJ using a UV irradiation device (made by Eye Graphics: UB0151, light source: metal halide lamp). After exposure, development with methyl ethyl ketone revealed that only the unexposed area was dissolved in methyl ethyl ketone and a development pattern of the cured resin product was obtained. The pencil scratch value (JIS K5400) of the cured resin product was H.
[0037]
Example 3
(Synthesis of bifunctional PPE oligomer)
CuL 1.3 g (0.012 mol), di-n-butylamine 70.7 g (0.55 mol), and methyl ethyl ketone 400 g were charged in a 2 liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and reaction temperature 40 The mixture was stirred at ℃, and 45.4 g (0.16 mol) of divalent phenol 4,4'-methylidenebis (2,3,6-trimethylphenol) dissolved in 800 g of methyl ethyl ketone in advance and 58.6 g of 2,6-dimethylphenol (0.48 mol) was added dropwise over a period of 120 minutes while bubbling 2 L / min of air, and stirring was continued for 60 minutes after the completion of the dripping while continuing bubbling of 2 L / min of air. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Then, after washing 3 times with 1M hydrochloric acid aqueous solution, it was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 97.4 g of resin yo. The resin Y had a number average molecular weight of 852, a weight average molecular weight of 1133, and a hydroxyl group equivalent of 460.
[0038]
(Synthesis of epoxy body)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 50.6 g of resin (hydroxyl 0.11 mol) and 292 g of epichlorohydrin were charged. Thereafter, a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in 30 g of ethanol in advance was dropped from the dropping funnel over 60 minutes, and further stirred for 5 hours after the completion of the dropping. Thereafter, the resulting salt and impurities were removed by washing with 0.1N aqueous hydrochloric acid solution three times, with ion-exchanged water and filtration. Excess epichlorohydrin was distilled off from the resulting solution, followed by drying under reduced pressure, to obtain 53.8 g of the resin represented by the above general formula (6). The resin layer was confirmed to have 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis. The number average molecular weight of the resin layer was 1005, the weight average molecular weight was 1275, and the epoxy equivalent was 566.
[0039]
(Synthesis of epoxy acrylate)
A reactor equipped with a stirrer, a thermometer, and a reflux tube was charged with 26 g of resin, 3.3 g of acrylic acid, 20 g of toluene, 0.13 g of triphenylphosphine, and 13 mg of hydroquinone methyl ether. This was reacted while heating to 120 ° C. and stirring. During the reaction, the acid value was measured and the reaction was continued until the acid value reached 2 mgKOH / g. The stirring time at 120 ° C. was 5 hours. The reaction solution was diluted with 40 g of toluene and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 26.7 g of resin. The resin resin had a number average molecular weight of 1395 and a weight average molecular weight of 1687.
[0040]
(Synthesis of polyfunctional acrylate)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 25 g of resin, 5.2 g of triethylamine, and 400 g of methylene chloride, and 4.6 g of acrylic acid chloride and 100 g of methylene chloride were charged into the dropping funnel. This was cooled to 0 ° C. under nitrogen, and acrylic acid chloride was added dropwise over 1 hour with stirring, and then returned to room temperature and stirring was continued. The reaction solution was sampled and subjected to NMR measurement to monitor the reaction. Since the reaction was completed after stirring for 2 hours, liquid separation washing was performed with 0.1 N HClaq and pure water. The organic layer was concentrated and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 16.5 g of resin so represented by the general formula (1). The number average molecular weight of Resin So was 1705, and the weight average molecular weight was 2298.
[0041]
10 g of resin saw was melted, degassed and molded at 150 ° C. and cured at 200 ° C. for 6 hours to obtain a cured product.
[0042]
6g of resin soda is dissolved in 4g of carbitol acetate, and a resin composition with 0.6g of Darocur 1173 (manufactured by Ciba Specialty Chemicals, photopolymerization initiator) is applied on the copper-clad laminate with a screen printer, and dried by air blowing. After drying at 80 ° C. for 30 minutes, a pattern film was applied and exposed to 2000 mJ using a UV irradiation device (made by Eye Graphics: UB0151, light source: metal halide lamp). After exposure, development with methyl ethyl ketone revealed that only the unexposed area was dissolved in methyl ethyl ketone and a development pattern of a resin cured product was obtained. The pencil scratch value (JIS K5400) of the cured resin na was H.
[0043]
Example 4
(Synthesis of bifunctional PPE oligomer)
CuL 1.3 g (0.012 mol), di-n-butylamine 70.7 g (0.55 mol), and methyl ethyl ketone 400 g were charged in a 2 liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and reaction temperature 40 The divalent phenol 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis (2,3,6-trimethylphenol), dissolved in 800 g of methyl ethyl ketone, was stirred at ℃ 68.8 g (0.16 mol) and 2,6-dimethylphenol 58.6 g (0.48 mol) were added dropwise over a period of 120 minutes while bubbling 2 L / min of air. Stirring was continued while bubbling was continued. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Then, after washing 3 times with 1M hydrochloric acid aqueous solution, it was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 114.6 g of Resin LA. Resin Ra had a number average molecular weight of 934, a weight average molecular weight of 1223, and a hydroxyl group equivalent of 496.
[0044]
(Synthesis of epoxy body)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 54.6 g (hydroxyl group 0.11 mol) of resin ra and 292 g of epichlorohydrin were charged. Thereafter, a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in 30 g of ethanol in advance was dropped from the dropping funnel over 60 minutes, and further stirred for 5 hours after the completion of the dropping. Thereafter, the resulting salt and impurities were removed by washing with 0.1N aqueous hydrochloric acid solution three times, with ion-exchanged water and filtration. Excess epichlorohydrin was distilled off from the resulting solution, followed by drying under reduced pressure to obtain 56.9 g of a resin represented by the above general formula (6). Resinmu confirmed 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of a peak derived from glycidyl ether by NMR analysis. The number average molecular weight of the resin was 1092, the weight average molecular weight was 1408, and the epoxy equivalent was 612.
[0045]
(Synthesis of epoxy acrylate)
A reactor equipped with a stirrer, a thermometer, and a reflux tube was charged with 28.1 g of resin, 3.3 g of acrylic acid, 20 g of toluene, 0.13 g of triphenylphosphine, and 13 mg of hydroquinone methyl ether. This was reacted while heating to 120 ° C. and stirring. During the reaction, the acid value was measured and the reaction was continued until the acid value reached 2 mgKOH / g. The stirring time at 120 ° C. was 5 hours. The reaction solution was diluted with 40 g of toluene and added dropwise to methanol to perform reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 28.3 g of resin. The number average molecular weight of Resin C was 1497, and the weight average molecular weight was 1841.
[0046]
(Synthesis of polyfunctional acrylate)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 25 g of resin, 4.8 g of triethylamine, and 400 g of methylene chloride in the reactor, and 4.3 g of acrylic acid chloride and 100 g of methylene chloride were charged into the dropping funnel. This was cooled to 0 ° C. under nitrogen, and acrylic acid chloride was added dropwise over 1 hour with stirring, and then returned to room temperature and stirring was continued. The reaction solution was sampled and subjected to NMR measurement to monitor the reaction. Since the reaction was completed after stirring for 2 hours, liquid separation washing was performed with 0.1 N HClaq and pure water. The organic layer was concentrated and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 17.6 g of resin represented by the above general formula (1). The number average molecular weight of the resin was 1788, and the weight average molecular weight was 2407.
[0047]
Resin 10g was melted, degassed and molded at 150 ° C. and cured at 200 ° C. for 6 hours to obtain a cured product o.
[0048]
Resin composition 6g dissolved in 4g carbitol acetate and 0.6g of Darocur 1173 (manufactured by Ciba Specialty Chemicals, photopolymerization initiator) was applied on a copper-clad laminate with a screen printer and dried by air blowing. After drying at 80 ° C. for 30 minutes, a pattern film was applied and exposed to 2000 mJ using a UV irradiation device (made by Eye Graphics: UB0151, light source: metal halide lamp). After exposure, development with methyl ethyl ketone revealed that only the unexposed area was dissolved in methyl ethyl ketone, and a development pattern of a cured resin product was obtained. The pencil scratch value (JIS K5400) of the cured resin was H.
[0049]
Example 5
(Synthesis of bifunctional PPE oligomer)
CuL 1.3 g (0.012 mol), di-n-butylamine 70.7 g (0.55 mol), and methyl ethyl ketone 400 g were charged in a 2 liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and reaction temperature 40 The mixture was stirred at ℃, and 41.0 g (0.16 mol) of divalent phenol 4,4′-methylenebis (2,6-dimethylphenol) and 58.6 g (0.48) of 2,6-dimethylphenol previously dissolved in 800 g of methyl ethyl ketone. mol) was added dropwise over 120 minutes while bubbling 2 L / min of air, and stirring was continued for 60 minutes after bubbling of 2 L / min. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Then, after washing 3 times with 1M hydrochloric acid aqueous solution, it was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator, and further dried under reduced pressure to obtain 94.6 g of resin matrix. The number average molecular weight of the resin polymer was 801, the weight average molecular weight was 1081, and the hydroxyl group equivalent was 455.
[0050]
(Synthesis of epoxy body)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 50.1 g of resin resin (0.11 mol of hydroxyl group) and 292 g of epichlorohydrin were charged. Thereafter, a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in 30 g of ethanol in advance was dropped from the dropping funnel over 60 minutes, and further stirred for 5 hours after the completion of the dropping. Thereafter, the resulting salt and impurities were removed by washing with 0.1N aqueous hydrochloric acid solution three times, with ion-exchanged water and filtration. Excess epichlorohydrin was distilled off from the resulting solution, followed by drying under reduced pressure, to obtain 50.2 g of resin resin represented by the above general formula (6). Resin was confirmed to have 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis. The number average molecular weight of Resinke was 956, the weight average molecular weight was 1204, and the epoxy equivalent was 545.
[0051]
(Synthesis of epoxy acrylate)
A reactor equipped with a stirrer, a thermometer, and a reflux tube was charged with 25.1 g of resin, 3.3 g of acrylic acid, 20 g of toluene, 0.13 g of triphenylphosphine, and 13 mg of hydroquinone methyl ether. This was reacted while heating to 120 ° C. and stirring. During the reaction, the acid value was measured and the reaction was continued until the acid value reached 2 mgKOH / g. The stirring time at 120 ° C. was 5 hours. The reaction solution was diluted with 40 g of toluene and added dropwise to methanol for reprecipitation, and the solid was collected by filtration and dried under reduced pressure to obtain 25.4 g of resin. The resin resin had a number average molecular weight of 1359 and a weight average molecular weight of 1657.
[0052]
(Synthesis of polyfunctional acrylate)
A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 25 g of resin, 5.3 g of triethylamine, and 400 g of methylene chloride, and 4.8 g of acrylic acid chloride and 100 g of methylene chloride were charged into the dropping funnel. This was cooled to 0 ° C. under nitrogen, and acrylic acid chloride was added dropwise over 1 hour with stirring, and then returned to room temperature and stirring was continued. The reaction solution was sampled and subjected to NMR measurement to monitor the reaction. Since the reaction was completed after stirring for 2 hours, liquid separation washing was performed with 0.1 N HClaq and pure water. The organic layer was concentrated, dropped into methanol and reprecipitated, filtered to collect the solid, and dried under reduced pressure to obtain 16.6 g of the resin represented by the above general formula (1). The number average molecular weight of Resin Co was 1623, and the weight average molecular weight was 2278.
[0053]
10 g of resin resin was melted, degassed and molded at 150 ° C. and cured at 200 ° C. for 6 hours to obtain a cured product.
[0054]
Resin co 6g was dissolved in carbitol acetate 4g, and 0.6g of Darocur 1173 (manufactured by Ciba Specialty Chemicals, photopolymerization initiator) was added onto the copper clad laminate with a screen printer, and dried by air blowing. After drying at 80 ° C. for 30 minutes, a pattern film was applied and exposed to 2000 mJ using a UV irradiation device (made by Eye Graphics: UB0151, light source: metal halide lamp). After exposure, development with methyl ethyl ketone revealed that only the unexposed area was dissolved in methyl ethyl ketone and a development pattern of a cured resin product was obtained. The pencil scratch value (JIS K5400) of the cured resin product was H.
[0055]
Comparative Example 1
10 g of the resin obtained in Example 1 was degassed and molded at 150 ° C., and cured at 200 ° C. for 6 hours to obtain a cured product.
[0056]
The characteristics of the cured products obtained in Examples 1, 2, 3, 4, 5, and Comparative Example 1 were evaluated by the following methods.
Glass transition temperature (Tg): determined by dynamic viscoelasticity measurement (DMA). Measurement was performed at a vibration frequency of 10 Hz.
Dielectric constant, dielectric loss tangent: determined by cavity resonance perturbation method.
[0057]
The evaluation results of the above physical properties are shown in Table 1.
[Table 1]

[0058]
【The invention's effect】
The polyfunctional (meth) acrylate compound of the present invention has a high glass transition temperature, a low dielectric constant, and a low dielectric loss tangent, so that it is extremely useful as a high-functional polymer material, and is excellent in thermal and electrical properties. It can be used in a wide range of applications such as various coating agents, UV paints, adhesives, resists, and build-up wiring board materials.

Claims (4)

(Meth) acrylate compound represented by general formula (1)

(Wherein, R1, R2, R3, R4, R5 are .- represents a hydrogen atom or a methyl group (OXO) - is represented by structural formula (2), R6, R7, R12, R13 are the same number of carbon atoms 6 is a an alkyl group .R8, R9, R10, R11 are the same or different, hydrogen atoms frame other is an alkyl group having 6 or less carbon atoms .A, the number 20 following the straight chain carbon Jo Alternatively, branched or are cyclic hydrocarbon .- (YO) - is one type of structure defined by the structural formula (3) .R14, R15, the same carbon number 6 an alkyl is a group .R16, R17 is the same hydrogen atoms frame other is an alkyl group having 6 or less carbon atoms .Z is a number 1 or more organic groups carbon, oxygen atom, nitrogen atom, sulfur atom, halogen also .a, b include atoms, at least one is not 0, .c represents an integer of 0 to 300, d is .n indicating 0 is an integer of 0 to 10.)

- (OXO) - in the structural formula (2), R6, R7, R12, R13 is a methyl group, - (YO) - is characterized by having a structure structural formula (5) has sequence The (meth) acrylate compound according to claim 1 Curable resin composition containing the (meth) acrylate compound according to claim 1 or 2. Hardened | cured material formed by hardening | curing curable resin composition of Claim 3