JP2004339263A - Ultraviolet curing type epoxy resin composition and method for producing the same - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、優れた接着力を有し、アウトガス（高温条件下で揮発するガス）の発生が低く、低吸湿性で寸法安定性の高い紫外線硬化型の透明液状エポキシ樹脂組成物およびその製法に関するものであり、光部品やボールレンズ等のレンズの固定、光デバイスパッケージのシールやＶ溝基板への光ファイバーの固定等に好適な接着剤、すなわち、過酷な温湿度条件下であっても劣化しない接着性を有する光素子や光部品固定用に有用な接着剤である紫外線硬化型エポキシ樹脂組成物およびその製法に関するものである。
【０００２】
【従来の技術】
近年、精密な光ファイバーコネクタ部品の組立においては、接着剤を使用する方法が用いられるようになってきた。この組立の際には、ミクロンオーダーの固定精度が必要とされることから、低線膨張係数を有し成形収縮の小さい寸法安定性に優れた接着剤材料が要望されていた。また、石英ガラスや光ファイバーに対する優れた接着性、さらに長期信頼性の観点から高温高湿環境下に置かれても優れた接着性を保持していることが要望されていた。そして、光学部品が熱応力を嫌うため、紫外線硬化等の光硬化型接着剤が多く用いられている。特に、ファイバーアレイの組み立てにおけるファイバーやカバーガラスの固定やレンズの固定では光軸ずれが発生するため、特に寸法安定性の高い樹脂が要望されていた。
【０００３】
例えば、従来のエポキシ系樹脂を用いたカチオン重合型光硬化接着剤は、比較的接着性に優れているが、石英ガラスや光ファイバーに対する接着性において、特に高温高湿下での使用においては吸水率が高く、そのことにより接着力の低下が大きく、満足できるものではなかった。さらに、アクリル系樹脂を用いたラジカル重合型光硬化接着剤は、一般的には、接着力の安定性は高いが硬化収縮が大きいことやガラス転移温度が低いこと等から寸法安定性、耐熱性において満足できるものではなかった。
【０００４】
一方、無機質充填剤を添加することにより得られる樹脂硬化体の線膨張係数を下げるという手法が広く用いられている。上記無機質充填剤を含有した紫外線硬化型樹脂組成物の一例として、エポキシ化合物とともに、板状無機質充填剤や鱗片状無機質充填剤からなる無機質充填剤を必須成分として含有する樹脂組成物が提案されている（特許文献１参照）。
【０００５】
【特許文献１】
特開２０００−１９１７４５号公報
【０００６】
【発明が解決しようとする課題】
しかしながら、上記添加される無機質充填剤の粒径が細かくなりサブミクロン単位となってくると表面積が著しく増大して相互作用が強まるため、凝集して均一に分散できなかったり、増粘したりして液状樹脂として取り扱えなくなるため多量の無機質充填剤を添加することが困難となることが知られている。また、無機質充填剤を多量に添加すれば当然ながら光を通し難くなり紫外線硬化も困難となることが知られている。このように、無機質充填剤を含む従来の紫外線硬化型エポキシ樹脂組成物は、各種光学用接着剤としては充分な特性が得られず、未だ満足のいくものが得られていないのが実情である。
【０００７】
本発明は、このような事情に鑑みなされたもので、高温高湿条件下でも安定した接着力を有するとともに、低線膨張係数で寸法安定性が高い樹脂組成物からなる光学素子および光部品固定用接着剤等に用いられる紫外線硬化型エポキシ樹脂組成物およびその製法の提供をその目的とする。
【０００８】
【課題を解決するための手段】
上記の目的を達成するため、本発明は、下記の（Ａ）〜（Ｃ）を含有する紫外線硬化型エポキシ樹脂組成物を第１の要旨とする。
（Ａ）下記の（ａ１）および（ａ２）を含有するエポキシ樹脂。
（ａ１）下記の式（１）で表されるエポキシ樹脂。
【化３】
（Ｂ）光重合開始剤。
（Ｃ）平均粒径が０．３〜０．５μｍの範囲で、かつ粒径５μｍ以上のものを実質的に含有しない球状シリカ粉末。
【０００９】
また、本発明は、上記（Ａ）〜（Ｃ）を含有する紫外線硬化型エポキシ樹脂組成物の製法であって、予め上記球状シリカ粉末（Ｃ）を上記脂環式エポキシ樹脂（ａ２）に分散させた後、この分散物と上記式（１）で表されるエポキシ樹脂（ａ１）および光重合開始剤（Ｂ）を含む残りの成分を配合し混合する紫外線硬化型エポキシ樹脂組成物の製法を第２の要旨とする。
【００１０】
すなわち、本発明者らは、高温高湿条件下でも優れた接着性を有し、しかも線膨張係数が低く寸法安定性に優れた紫外線硬化型のエポキシ樹脂組成物を得るために鋭意検討を重ねた。その結果、エポキシ樹脂（Ａ）として、上記式（１）で表されるエポキシ樹脂（ａ１）および脂環式エポキシ樹脂（ａ２）の２つのエポキシ樹脂を併用するとともに、上記特定の平均粒径を有し、かつ特定の粒径以上の粒子を含有しない球状シリカ粉末（Ｃ）を用いると、式（１）で表されるエポキシ樹脂（ａ１）の屈折率が１．４７以下であることから、エポキシ樹脂成分全体の屈折率を下げ、シリカ粉末の屈折率に近づけることが可能となる。そのため、シリカ粉末を含有していながら光硬化性が良好となる。しかも、上記球状シリカ粉末（Ｃ）が均一分散され、光も通し易く紫外線硬化性も良好で、低線膨張係数化が実現して優れた寸法安定性が得られるようになり上記のような所期の目的が達成されることを突き止めた。そして、このようなエポキシ樹脂組成物としては、予め上記特定の球状シリカ粉末（Ｃ）を脂環式エポキシ樹脂（ａ２）に分散させた後、これに残りの成分を配合し混合することにより、上記特定の球状シリカ粉末（Ｃ）がエポキシ樹脂組成物中に均一に分散されたものが得られることを見出し本発明に到達した。
【００１１】
【発明の実施の形態】
つぎに、本発明の実施の形態について詳しく説明する。
【００１２】
本発明の紫外線硬化型エポキシ樹脂組成物は、特定のエポキシ樹脂（ａ１）および脂環式エポキシ樹脂（ａ２）を含有するエポキシ樹脂（Ａ）と、光重合開始剤（Ｂ）と、特定の球状シリカ粉末（Ｃ）とを用いることにより得られる。
【００１３】
上記特定のエポキシ樹脂（ａ１）は、下記の式（１）で表されるものであり、非グリシジルエーテル型であり、エーテル結合を持たないため、エポキシ樹脂の高反応性を付与する。上記式（１）で表されるエポキシ樹脂（ａ１）は、例えば、つぎのようにして製造される。すなわち、オレフィンを、例えば、過酸化安息香酸等の有機過酸化物により酸化することで製造することができる。
【００１４】
【化４】
そして、上記式（１）で表されるエポキシ樹脂（ａ１）の含有量は、エポキシ樹脂（Ａ）全体中１５〜７０重量％を占めるように設定することが好ましい。特に好ましくは３０〜４０重量％である。すなわち、１５重量％未満では、光硬化性の低下や粘度の上昇が発生し易く、逆に７０重量％を超えると、光硬化性が悪くなり、作業性が著しく低下する傾向がみられるからである。
【００１６】
さらに、上記ａ１とともに用いられる脂環式エポキシ樹脂（ａ２）としては、特に限定するものではないが、反応性が高く透明なものを用いることが好ましく、しかも、低粘度であることが好ましい。また、反応性の点から、２官能以上であることが好ましく、波長５００〜１７００ｎｍでの光透過率が厚み１００ｍｍで９０％以上であることが好ましい。粘度は、５Ｐａ・ｓ（室温）以下であると、球状シリカ粉末混合後の取り扱い性の点から好ましい。具体的には、水添ビスフェノールＡ型エポキシ樹脂、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、３，４−エポキシシクロヘキシルエチル−３，４−エポキシシクロヘキサンカルボキシレート等が、透明性、粘性、反応性の観点から好ましい。これらは単独でもしくは２種以上併せて用いられる。なかでも、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートで低粘度であり特に好ましく用いられる。
【００１７】
本発明において、エポキシ樹脂（Ａ）としては、上記式（１）で表されるエポキシ樹脂（ａ１）および脂環式エポキシ樹脂（ａ２）を必須成分とし、これに従来公知のエポキシ樹脂を用いてもよい。具体的には、汎用のビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂等を用いることができる。なお、上記従来公知のエポキシ樹脂を用いる場合、その使用量は、エポキシ樹脂（Ａ）全体中の３０重量％以下に設定することが好ましい。
【００１８】
上記エポキシ樹脂（Ａ）とともに用いられる光重合開始剤（Ｂ）としては、特に限定するものではなく、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族スルホキソニウム塩、メタロセン化合物あるいは鉄アレーン系化合物等を用いることができる。その中でも、光硬化性の観点から、芳香族スルホニウム塩が好ましく、特に芳香族スルホニウム・ヘキサフロロホスホニウム化合物、芳香族スルホニウム・ヘキサフロロアンチモネート化合物、またはその両者の併用が、硬化性、接着性等の観点から好ましい。さらに、上記光重合開始剤（Ｂ）とともに、光増感剤や酸増殖剤等も必要に応じて添加することができる。
【００１９】
上記光重合開始剤（Ｂ）の含有量は、上記エポキシ樹脂（Ａ）および後述の特定の球状シリカ粉末（Ｃ）の合計量１００重量部（以下「部」と略す）に対して１〜１５部に設定することが好ましく、特に好ましくは２〜１０部である。
【００２０】
上記エポキシ樹脂（Ａ）および光重合開始剤（Ｂ）とともに用いられる特定の球状シリカ粉末（Ｃ）は、一般に略球状を有するシリカ粉末であれば特に限定するものではないが、真球度の高いものを用いることがより好ましい。そして、本発明においては、球状シリカ粉末（Ｃ）は、平均粒径０．３〜０．５μｍの範囲で、かつ粒径５μｍ以上のものを実質的に含有しないものである。上記範囲の平均粒径を有し、しかも粒径５μｍ以上の大きな粒径の粒子を含まない球状シリカ粉末を用いることにより、紫外線硬化性の低下と粘度の上昇が軽減されるのである。なお、上記平均粒径の測定は、例えば、レーザー回折散乱式粒度分布測定装置を用いて測定することができる。上記粒径５μｍ以上の球状シリカ粒子を実質的に含有しないものを得るための、粒径５μｍ以上の球状シリカ粒子の分別・除去方法としては、例えば、篩や遠心分離等により除去する方法があげられる。また、合成シリカであれば、ｐＨの調整により２次凝集を発生させないようにして取り扱うことにより、粒径と分布を精密に制御することが可能である。そして、粒径を制御して合成した後、表面処理によって凝集を防ぐ方法も、粒径５μｍ以上の粒子を発生させない方法として有効である。
【００２１】
上記特定の球状シリカ粉末（Ｃ）の含有量は、上記エポキシ樹脂（Ａ）および球状シリカ粉末（Ｃ）の合計量中５０〜８０重量％の範囲に設定することが好ましい。すなわち、特定の球状シリカ粉末（Ｃ）の含有量が５０重量％未満では、エポキシ樹脂組成物硬化体の線膨張係数が充分に下げられず、良好な寸法安定性が得られ難く、８０重量％を超えると、エポキシ樹脂組成物が非常に高粘度となり作業性が低下するばかりでなく、光硬化性の低下をも引き起こす傾向がみられるからである。
【００２２】
また、本発明の紫外線硬化型エポキシ樹脂組成物には、上記（Ａ）〜（Ｃ）以外に、接着性を高めるためにシラン系あるいはチタン系のカップリング剤、合成ゴムやシリコーン化合物等の可撓性付与剤等の化合物、さらに酸化防止剤、消泡剤等の他の添加剤を必要に応じて適宜に配合することができる。
【００２３】
本発明の紫外線硬化型エポキシ樹脂組成物は、例えば、前記式（１）で表されるエポキシ樹脂（ａ１）および脂環式エポキシ樹脂（ａ２）と、光重合開始剤（Ｂ）、特定の球状シリカ粉末（Ｃ）さらに必要に応じて他の添加剤を用いて、つぎのようにして作製される。まず、予め、上記特定の球状シリカ粉末（Ｃ）を上記脂環式エポキシ樹脂（ａ２）に配合して分散させる。ついで、この分散物に、残りの配合成分を所定の割合で配合し溶融混合した後、室温に冷却することにより作製される。
【００２４】
上記特定の球状シリカ粉末（Ｃ）を上記脂環式エポキシ樹脂（ａ２）に配合して分散させる予備混合における条件としては、温度２５〜１００℃が好ましく、５０〜７０℃の範囲が特に好ましい。また、凝集を防ぐために、溶剤を加えて分散させた後に脱溶媒してもよい。また、上記分散物に残りの配合成分を配合して溶融混合する際の溶融条件としては、温度２５〜１００℃が好ましく、５０〜７０℃の範囲が特に好ましい。
【００２５】
このように、予め球状シリカ粉末（Ｃ）を脂環式エポキシ樹脂（ａ２）に配合して分散させることにより、球状シリカ粉末（Ｃ）のエポキシ樹脂組成物全体における均一分散が図られ、さらには球状シリカ粉末（Ｃ）の粒子とエポキシ樹脂との界面において濡れ性が向上して粘度の上昇が軽減できるようになる。また、上記濡れ性の一層の向上を図る目的で、先に述べたシランカップリング剤等のカップリング剤により球状シリカ粉末（Ｃ）の表面処理を行うことが好ましい。
【００２６】
そして、本発明の紫外線硬化型エポキシ樹脂組成物の粘度は、接着剤としての使用時における作業性等を考慮して、２５℃で１〜１００Ｐａ・ｓ程度であることが好ましい。
【００２７】
このようにして得られる紫外線硬化型エポキシ樹脂組成物は、例えば、ＵＶランプ等により紫外線を照射した後、所定の温度でのポストキュアを行うことにより硬化させることができる。
【００２８】
つぎに、実施例について比較例と併せて説明する。
【００２９】
まず、下記に示す各成分を準備した。
【００３０】
〔エポキシ樹脂１〕
下記の式（ａ）で表されるエポキシ樹脂
【化５】
〔エポキシ樹脂２〕
下記の式（ｂ）で表されるエポキシ樹脂
【化６】
〔エポキシ樹脂３〕
下記の式（ｃ）で表される脂環式エポキシ樹脂（ダイセル化学社製、セロキサイド２０２１Ｐ：３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート）
【化７】
〔球状シリカ粉末Ａ〕
平均粒径０．３μｍで粒径５μｍ以上の粒子を含まない球状シリカ粉末（アドマテックス社製、ＳＥ１０５０）
【００３４】
〔球状シリカ粉末Ｂ〕
平均粒径０．５μｍで粒径５μｍ以上の粒子を含まない球状シリカ粉末（アドマテックス社製、ＳＥ２０５０）
【００３５】
〔球状シリカ粉末Ｃ〕
平均粒径１．５μｍで粒径５μｍ以上の粒子を３重量％含有する球状シリカ粉末（アドマテックス社製、ＳＯ−Ｅ５）
【００３６】
〔光重合開始剤〕
スルホニウム・ヘキサフロロアンチモン系重合開始剤（旭電化社製、ＳＰ−１７０）
【００３７】
〔酸化防止剤〕
ＨＣＡ（三光化学社製）
【００３８】
〔カップリング剤〕
γ−グリシドキシプロピルトリメトキシシラン
【００３９】
【実施例１〜６、比較例１〜３】
まず、下記の表１〜表２に示す割合で、予め球状シリカ粉末をエポキシ樹脂２（脂環式エポキシ樹脂）に配合して分散させた（条件：５０℃×３０分）。ついで、この分散物に、同表に示す割合で残りの配合成分を配合し溶融混合（条件：５０℃×３０分）した後、室温に冷却することにより紫外線硬化型エポキシ樹脂組成物を作製した。なお、比較例１，２は球状シリカ粉末を配合しないため、予備分散を行わず、下記の表２に示す各成分を同表に示す割合で配合し混合した。
【００４０】
【表１】
【表２】
このようにして得られた実施例および比較例の各紫外線硬化型エポキシ樹脂組成物を用いて、２５℃でのエポキシ樹脂組成物の粘度、線膨張係数、硬化後の初期接着強度・耐湿接着強度、耐湿試験、吸水率を下記の方法に従ってそれぞれ測定・評価した。これらの結果を後記の表３〜表４に併せて示す。
【００４３】
〔エポキシ樹脂組成物の粘度〕
Ｅ型粘度計を用いて２５℃での粘度を測定した。
【００４４】
〔線膨張係数〕
５００ＷのＵＶランプ（高圧水銀ランプ）を用いて７２０ｍＪ／ｃｍ２ にて光照射した後、１００℃で１時間のポストキュアを行うことにより、厚み１００μｍのフィルムを作製した。そして、このフィルムを用い、ＴＭＡ（測定機器：リガク社製のＴｈｅｒｍｏｐｌｕｓ ８２１０ 、測定温度：３０〜２５０℃）により引張モードにて測定した。そして、３５℃での線膨張係数の数値を読み取った。
【００４５】
〔初期接着強度・耐湿接着強度〕
まず、柱状の石英ガラス板（縦３．３ｍｍ×横３．３ｍｍ×厚み５ｍｍ）に、紫外線硬化型エポキシ樹脂組成物を接着剤として塗布した後、石英ガラス板（縦２０ｍｍ×横３５ｍｍ×厚み２ｍｍ）に圧着して貼り合わせ、つぎの硬化条件で接着剤を硬化させることにより接着片を作製した。すなわち、上記硬化は、上記と同様、５００ＷのＵＶランプ（高圧水銀ランプ）を用いて７２０ｍＪ／ｃｍ２ にて光照射した後、１００℃で１時間のポストキュアを行うことにより硬化させた。
【００４６】
そして、初期接着強度は、上記接着片を用い、２５℃にてプッシュプルゲージを用いて、剪断の接着強度を測定した。
【００４７】
また、耐湿接着強度は、上記接着片を、ＰＣＴ条件下（１２１℃×２０２．６ｋＰａ）に２４時間放置して吸湿させた後、２５℃にてプッシュプルゲージを用いて、剪断の接着強度を測定した。
【００４８】
〔耐湿試験〕
３０ｍｍ×２０ｍｍ×厚み２ｍｍの石英ガラス板を２枚準備し、両石英ガラス板を紫外線硬化型エポキシ樹脂組成物を用いて貼り合わせ、厚み１００μｍとなるよう硬化させた。ついで、これをＰＣＴ条件下（１２１℃×２０２．６ｋＰａ）に２４時間放置して吸湿させた後、石英ガラス板の剥離状況の有無を目視により観察した。上記硬化条件は、上記初期接着強度における試料の作製と同様に設定した。
【００４９】
〔吸水率〕
紫外線硬化型エポキシ樹脂組成物を用い、５００ＷのＵＶランプ（高圧水銀ランプ）を用いて７２０ｍＪ／ｃｍ２ にて光照射した後、１００℃で１時間のポストキュアを行うことにより、厚み１００μｍのフィルムを作製した。そして、このフィルムを用い、２５℃で水中に２４時間浸漬させ、その初期重量からの重量変化から吸水率を求めた。
【００５０】
【表３】
【表４】
上記結果から、実施例品は、シリカ粉末が含有されているにもかかわらず充分硬化し、初期接着強度はもちろん耐湿接着強度においても高い数値が得られ、耐湿試験における剥離の発生も見られなかった。しかも、吸水率も低く、さらに線膨張係数も低く低線膨張化が図られている。
【００５３】
これに対して、球状シリカ粉末を用いない比較例１，２品は、吸水率が高く、そして耐湿接着強度も低く、しかも耐湿試験において剥離が発生し、線膨張係数も６０ｐｐｍを超えて高いものであった。また、平均粒径が０．５μｍを超え、粒径５μｍ以上の粒子を含有する球状シリカ粉末を用いた比較例３品では、紫外線が樹脂組成物の内部に到達しにくいため、硬化性が悪く、その結果、耐湿接着強度が低く、耐湿試験において剥離が発生した。
【００５４】
【発明の効果】
以上のように、本発明は、前記式（１）で表されるエポキシ樹脂（ａ１）および脂環式エポキシ樹脂（ａ２）を含有するエポキシ樹脂（Ａ）とともに、前記特定の球状シリカ粉末（Ｃ）を用いた紫外線硬化型エポキシ樹脂組成物である。このため、紫外線が樹脂組成物の内部に到達し易く、光硬化性が良好であり、かつ高温高湿雰囲気下での吸水性が低く、初期および吸湿後の耐湿接着強度も高く優れた実用性を備えている。しかも、上記特定の球状シリカ粉末（Ｃ）を含有するため、低線膨張係数で優れた寸法安定性を備えている。そして、このような本発明の紫外線硬化型エポキシ樹脂組成物は、予め上記特定の球状シリカ粉末（Ｃ）を上記脂環式エポキシ樹脂（ａ２）に分散させた後、これに残りの成分を配合し混合することにより製造され、このような製造工程を経由することにより、上記特定の球状シリカ粉末（Ｃ）が樹脂組成物中に均一に分散される。したがって、本発明の紫外線硬化型エポキシ樹脂組成物を、光通信系における光導波路やＶグルーヴ等の精密光部品の接着およびファイバーアレイの接着用途、またレンズ等の小型部品の固定用等に適用すると、長期信頼性に優れた接着結合部が実現する。
【００５５】
そして、上記ａ１の含有量を、エポキシ樹脂（Ａ）全体の１５〜７０重量％の範囲に設定すると、耐湿接着性および流動性に一層優れるようになる。
【００５６】
また、上記特定の球状シリカ粉末（Ｃ）の含有量を、上記エポキシ樹脂（Ａ）および特定の球状シリカ粉末（Ｃ）の合計量中５０〜８０重量％の範囲に設定すると、低線膨張係数化が図られ寸法安定性に一層優れるようになり、しかも作業性に関してもより良好なものが得られるようになる。
【００５７】
さらに、上記ａ２である脂環式エポキシ樹脂として、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートを用いると、良好な透明性および反応性とともに低粘度であり、一層好ましいものとなる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an ultraviolet-curable transparent liquid epoxy resin composition having excellent adhesive strength, low outgassing (gas volatilized under high temperature conditions), low moisture absorption and high dimensional stability, and a method for producing the same. An adhesive suitable for fixing an optical component or a lens such as a ball lens, sealing an optical device package or fixing an optical fiber to a V-groove substrate, that is, does not deteriorate even under severe temperature and humidity conditions. The present invention relates to an ultraviolet-curable epoxy resin composition, which is an adhesive useful for fixing an optical element or an optical component having adhesiveness, and a method for producing the same.
[0002]
[Prior art]
In recent years, in the assembly of precision optical fiber connector parts, a method using an adhesive has been used. At the time of this assembling, since fixing accuracy on the order of microns is required, an adhesive material having a low linear expansion coefficient, small molding shrinkage, and excellent dimensional stability has been demanded. In addition, from the viewpoint of long-term reliability, excellent adhesiveness to quartz glass and optical fibers, and excellent adhesiveness even when placed in a high-temperature and high-humidity environment have been demanded. Since optical components dislike thermal stress, photocurable adhesives such as ultraviolet curing are often used. In particular, when the fiber or cover glass is fixed or the lens is fixed in the assembly of the fiber array, an optical axis shift occurs. Therefore, a resin having particularly high dimensional stability has been demanded.
[0003]
For example, a cationically polymerizable photo-curing adhesive using a conventional epoxy resin has relatively excellent adhesiveness, but the adhesiveness to quartz glass and optical fibers, especially when used under high temperature and high humidity, has a high water absorption. And the adhesive strength was greatly reduced due to this, which was not satisfactory. Furthermore, a radical polymerization type photo-curing adhesive using an acrylic resin generally has high adhesive strength, but has high dimensional stability and heat resistance due to large curing shrinkage and low glass transition temperature. Was not satisfactory.
[0004]
On the other hand, a technique of lowering the linear expansion coefficient of a cured resin obtained by adding an inorganic filler is widely used. As an example of the ultraviolet-curable resin composition containing the above-mentioned inorganic filler, a resin composition containing, as an essential component, an inorganic filler composed of a plate-like inorganic filler or a flaky inorganic filler together with an epoxy compound has been proposed. (See Patent Document 1).
[0005]
[Patent Document 1]
JP 2000-191745 A
[Problems to be solved by the invention]
However, when the particle size of the added inorganic filler is reduced to a sub-micron unit, the surface area is remarkably increased and the interaction is strengthened, so that the filler cannot be uniformly dispersed or thickened. It is known that it becomes difficult to add a large amount of an inorganic filler because it cannot be handled as a liquid resin. Also, it is known that if a large amount of an inorganic filler is added, it is naturally difficult for light to pass through and ultraviolet curing is difficult. As described above, the conventional UV-curable epoxy resin composition containing an inorganic filler does not have sufficient properties as various optical adhesives, and it is a fact that satisfactory ones have not yet been obtained. .
[0007]
The present invention has been made in view of such circumstances, and has a stable adhesive force even under high temperature and high humidity conditions, and has an optical element and an optical component fixed from a resin composition having a low linear expansion coefficient and high dimensional stability. It is an object of the present invention to provide an ultraviolet-curable epoxy resin composition used for an adhesive or the like and a method for producing the same.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, a first aspect of the present invention is an ultraviolet-curable epoxy resin composition containing the following (A) to (C).
(A) An epoxy resin containing the following (a1) and (a2).
(A1) An epoxy resin represented by the following formula (1).
Embedded image
(B) a photopolymerization initiator.
(C) A spherical silica powder having an average particle size in the range of 0.3 to 0.5 μm and substantially not containing a particle size of 5 μm or more.
[0009]
The present invention also relates to a method for producing an ultraviolet-curable epoxy resin composition containing (A) to (C), wherein the spherical silica powder (C) is dispersed in the alicyclic epoxy resin (a2) in advance. After that, the dispersion is mixed with the epoxy resin (a1) represented by the above formula (1) and the remaining components including the photopolymerization initiator (B). This is the second point.
[0010]
That is, the present inventors have intensively studied to obtain an ultraviolet-curable epoxy resin composition having excellent adhesion even under high temperature and high humidity conditions, and having a low linear expansion coefficient and excellent dimensional stability. Was. As a result, two epoxy resins of the epoxy resin (a1) and the alicyclic epoxy resin (a2) represented by the above formula (1) are used in combination as the epoxy resin (A), and the specific average particle size is reduced. When the spherical silica powder (C) having no particles having a specific particle size or more is used, since the epoxy resin (a1) represented by the formula (1) has a refractive index of 1.47 or less, It is possible to lower the refractive index of the entire epoxy resin component and approach the refractive index of the silica powder. Therefore, the photocurability becomes good while containing the silica powder. In addition, the spherical silica powder (C) is uniformly dispersed, is easy to transmit light, has good ultraviolet curability, realizes a low linear expansion coefficient, and can obtain excellent dimensional stability. The goal of the period was achieved. As such an epoxy resin composition, the above-mentioned specific spherical silica powder (C) is dispersed in advance in the alicyclic epoxy resin (a2), and then the remaining components are blended and mixed. The present inventors have found that the above-mentioned specific spherical silica powder (C) can be uniformly dispersed in an epoxy resin composition, and have reached the present invention.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, embodiments of the present invention will be described in detail.
[0012]
The ultraviolet-curable epoxy resin composition of the present invention comprises: an epoxy resin (A) containing a specific epoxy resin (a1) and an alicyclic epoxy resin (a2); a photopolymerization initiator (B); It is obtained by using silica powder (C).
[0013]
The specific epoxy resin (a1) is represented by the following formula (1), is a non-glycidyl ether type, and does not have an ether bond, so that the epoxy resin has high reactivity. The epoxy resin (a1) represented by the above formula (1) is produced, for example, as follows. That is, it can be produced by oxidizing an olefin with, for example, an organic peroxide such as benzoic peroxide.
[0014]
Embedded image
The content of the epoxy resin (a1) represented by the above formula (1) is preferably set so as to account for 15 to 70% by weight of the entire epoxy resin (A). Particularly preferably, it is 30 to 40% by weight. That is, if the content is less than 15% by weight, the photocurability tends to decrease and the viscosity tends to increase. Conversely, if the content exceeds 70% by weight, the photocurability deteriorates and the workability tends to decrease significantly. is there.
[0016]
Further, the alicyclic epoxy resin (a2) used together with the above-mentioned a1 is not particularly limited, but it is preferable to use a highly reactive and transparent one, and it is preferable that it has a low viscosity. Further, from the viewpoint of reactivity, it is preferably bifunctional or more, and the light transmittance at a wavelength of 500 to 1700 nm is preferably 90% or more at a thickness of 100 mm. It is preferable that the viscosity is 5 Pa · s (room temperature) or less from the viewpoint of handleability after mixing the spherical silica powder. Specifically, hydrogenated bisphenol A type epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate and the like are transparent. It is preferable from the viewpoints of properties, viscosity and reactivity. These may be used alone or in combination of two or more. Among them, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate has a low viscosity and is particularly preferably used.
[0017]
In the present invention, as the epoxy resin (A), an epoxy resin (a1) and an alicyclic epoxy resin (a2) represented by the above formula (1) are essential components, and a conventionally known epoxy resin is used as the essential component. Is also good. Specifically, a general-purpose bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, a novolak type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, or the like can be used. When the above-mentioned conventionally known epoxy resin is used, its amount is preferably set to 30% by weight or less based on the entire epoxy resin (A).
[0018]
The photopolymerization initiator (B) used together with the epoxy resin (A) is not particularly limited, and may be an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, an aromatic sulfoxonium salt, or a metallocene compound. Alternatively, an iron arene-based compound or the like can be used. Among them, from the viewpoint of photocurability, aromatic sulfonium salts are preferable, and in particular, aromatic sulfonium hexafluorophosphonium compounds, aromatic sulfonium hexafluoroantimonate compounds, or a combination of both thereof is curable, adhesive, etc. It is preferable from the viewpoint of. Further, together with the photopolymerization initiator (B), a photosensitizer, an acid multiplying agent and the like can be added as required.
[0019]
The content of the photopolymerization initiator (B) is 1 to 15 with respect to 100 parts by weight (hereinafter abbreviated as “parts”) of the total amount of the epoxy resin (A) and the specific spherical silica powder (C) described below. Is preferably set to 2 parts, particularly preferably 2 to 10 parts.
[0020]
The specific spherical silica powder (C) used together with the epoxy resin (A) and the photopolymerization initiator (B) is not particularly limited as long as it is generally a silica powder having a substantially spherical shape. It is more preferable to use one. In the present invention, the spherical silica powder (C) has an average particle size of 0.3 to 0.5 μm and does not substantially contain a particle size of 5 μm or more. By using a spherical silica powder having an average particle diameter in the above range and not containing particles having a large particle diameter of 5 μm or more, a decrease in ultraviolet curability and an increase in viscosity are reduced. The average particle size can be measured, for example, using a laser diffraction / scattering type particle size distribution analyzer. As a method for separating and removing the spherical silica particles having a particle diameter of 5 μm or more for obtaining a substance substantially not containing the above-mentioned spherical silica particles having a particle diameter of 5 μm or more, for example, a method of removing the particles by a sieve or centrifugal separation is used. Can be Further, in the case of synthetic silica, it is possible to precisely control the particle size and distribution by adjusting the pH so as not to cause secondary aggregation. Also, a method of preventing aggregation by surface treatment after controlling and synthesizing the particle size is also effective as a method of not generating particles having a particle size of 5 μm or more.
[0021]
The content of the specific spherical silica powder (C) is preferably set in the range of 50 to 80% by weight based on the total amount of the epoxy resin (A) and the spherical silica powder (C). That is, when the content of the specific spherical silica powder (C) is less than 50% by weight, the linear expansion coefficient of the cured epoxy resin composition cannot be sufficiently reduced, and it is difficult to obtain good dimensional stability. If it exceeds 3, the epoxy resin composition will have a very high viscosity and not only the workability will be reduced, but also the photocurability will tend to be reduced.
[0022]
In addition to the above (A) to (C), the ultraviolet-curable epoxy resin composition of the present invention may contain a silane-based or titanium-based coupling agent, a synthetic rubber, a silicone compound, or the like in order to enhance adhesiveness. Compounds such as a flexibility-imparting agent and other additives such as an antioxidant and an antifoaming agent can be appropriately compounded as required.
[0023]
The ultraviolet-curable epoxy resin composition of the present invention comprises, for example, an epoxy resin (a1) and an alicyclic epoxy resin (a2) represented by the above formula (1), a photopolymerization initiator (B), and a specific sphere. The silica powder (C) is produced as follows using, if necessary, other additives. First, the specific spherical silica powder (C) is previously mixed and dispersed in the alicyclic epoxy resin (a2). Next, this dispersion is mixed with the remaining components at a predetermined ratio, melt-mixed, and cooled to room temperature.
[0024]
The conditions for the premixing in which the specific spherical silica powder (C) is mixed and dispersed in the alicyclic epoxy resin (a2) are preferably a temperature of 25 to 100 ° C, and particularly preferably a temperature of 50 to 70 ° C. Further, in order to prevent aggregation, the solvent may be added and dispersed, and then the solvent may be removed. In addition, as a melting condition when the remaining compounding components are blended with the dispersion and melt-mixed, a temperature of 25 to 100 ° C is preferable, and a range of 50 to 70 ° C is particularly preferable.
[0025]
In this way, by previously mixing and dispersing the spherical silica powder (C) with the alicyclic epoxy resin (a2), uniform dispersion of the spherical silica powder (C) in the entire epoxy resin composition is achieved. The wettability is improved at the interface between the particles of the spherical silica powder (C) and the epoxy resin, and the increase in viscosity can be reduced. For the purpose of further improving the wettability, it is preferable to perform the surface treatment of the spherical silica powder (C) with a coupling agent such as the silane coupling agent described above.
[0026]
The viscosity of the ultraviolet-curable epoxy resin composition of the present invention is preferably about 1 to 100 Pa · s at 25 ° C. in consideration of workability when used as an adhesive.
[0027]
The ultraviolet-curable epoxy resin composition thus obtained can be cured by irradiating ultraviolet rays with a UV lamp or the like and then performing post-curing at a predetermined temperature.
[0028]
Next, examples will be described together with comparative examples.
[0029]
First, the following components were prepared.
[0030]
[Epoxy resin 1]
An epoxy resin represented by the following formula (a):
[Epoxy resin 2]
An epoxy resin represented by the following formula (b):
[Epoxy resin 3]
An alicyclic epoxy resin represented by the following formula (c) (manufactured by Daicel Chemical Industries, Ltd., Celloxide 2021P: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate)
Embedded image
[Spherical silica powder A]
Spherical silica powder having an average particle diameter of 0.3 μm and containing no particles having a particle diameter of 5 μm or more (manufactured by Admatechs, SE1050)
[0034]
[Spherical silica powder B]
Spherical silica powder having an average particle diameter of 0.5 μm and containing no particles having a particle diameter of 5 μm or more (manufactured by Admatechs, SE2050)
[0035]
[Spherical silica powder C]
Spherical silica powder containing 3% by weight of particles having an average particle size of 1.5 μm and a particle size of 5 μm or more (manufactured by Admatechs, SO-E5)
[0036]
(Photopolymerization initiator)
Sulfonium hexafluoroantimony polymerization initiator (SP-170, manufactured by Asahi Denka Co., Ltd.)
[0037]
〔Antioxidant〕
HCA (manufactured by Sanko Chemical)
[0038]
(Coupling agent)
γ-glycidoxypropyltrimethoxysilane
Examples 1 to 6, Comparative Examples 1 to 3
First, spherical silica powder was previously mixed and dispersed in epoxy resin 2 (alicyclic epoxy resin) at the ratios shown in Tables 1 and 2 below (conditions: 50 ° C. × 30 minutes). Then, the remaining components were mixed with the dispersion at the ratios shown in the same table, melt-mixed (conditions: 50 ° C. × 30 minutes), and then cooled to room temperature to prepare an ultraviolet-curable epoxy resin composition. . In Comparative Examples 1 and 2, no spherical silica powder was blended, and thus the components shown in Table 2 below were blended and mixed at the ratios shown in Table 2 without preliminary dispersion.
[0040]
[Table 1]
[Table 2]
Using the ultraviolet-curable epoxy resin compositions of Examples and Comparative Examples obtained in this way, the viscosity of the epoxy resin composition at 25 ° C., the coefficient of linear expansion, the initial adhesive strength after curing and the moisture-resistant adhesive strength , Moisture resistance test and water absorption were measured and evaluated according to the following methods. The results are shown in Tables 3 and 4 below.
[0043]
(Viscosity of epoxy resin composition)
The viscosity at 25 ° C. was measured using an E-type viscometer.
[0044]
(Linear expansion coefficient)
After irradiation with light at 720 mJ / cm 2 using a 500 W UV lamp (high pressure mercury lamp), a 100 μm thick film was prepared by performing post-curing at 100 ° C. for 1 hour. The film was measured in a tensile mode by TMA (measurement instrument: Thermoplus 8210 manufactured by Rigaku Corporation, measurement temperature: 30 to 250 ° C.). Then, the numerical value of the linear expansion coefficient at 35 ° C. was read.
[0045]
[Initial adhesive strength / moisture resistant adhesive strength]
First, an ultraviolet-curable epoxy resin composition is applied as an adhesive to a columnar quartz glass plate (3.3 mm long × 3.3 mm wide × 5 mm thick), and then the quartz glass plate (20 mm long × 35 mm wide × 2 mm thick) is applied. ) Was bonded by pressure bonding, and the adhesive was cured under the following curing conditions to produce an adhesive piece. That is, similarly to the above, curing was performed by irradiating light at 720 mJ / cm 2 using a 500 W UV lamp (high pressure mercury lamp) and then performing post-curing at 100 ° C. for 1 hour.
[0046]
And the initial adhesive strength measured the adhesive strength of shearing using the said adhesive piece and the push-pull gauge at 25 degreeC.
[0047]
Further, the moisture-resistant adhesive strength was determined by measuring the shear strength of the above-mentioned adhesive piece by using a push-pull gauge at 25 ° C. after leaving the adhesive piece under PCT conditions (121 ° C. × 202.6 kPa) for 24 hours to absorb moisture. It was measured.
[0048]
(Moisture resistance test)
Two quartz glass plates of 30 mm × 20 mm × 2 mm thickness were prepared, and both quartz glass plates were bonded using an ultraviolet-curable epoxy resin composition and cured to a thickness of 100 μm. Then, after leaving it under PCT conditions (121 ° C. × 202.6 kPa) for 24 hours to absorb moisture, the presence or absence of peeling state of the quartz glass plate was visually observed. The curing conditions were set in the same manner as in the preparation of the sample with the initial adhesive strength.
[0049]
(Water absorption)
Using a UV-curable epoxy resin composition, irradiating light at 720 mJ / cm 2 using a 500 W UV lamp (high-pressure mercury lamp), and performing post-curing at 100 ° C. for 1 hour to obtain a 100 μm thick film Was prepared. Using this film, the film was immersed in water at 25 ° C. for 24 hours, and the water absorption was determined from the weight change from its initial weight.
[0050]
[Table 3]
[Table 4]
From the above results, the product of the example is sufficiently cured in spite of containing silica powder, a high value is obtained not only in the initial adhesive strength but also in the moisture resistant adhesive strength, and no occurrence of peeling in the moisture resistant test is observed. Was. In addition, the water absorption is low, the linear expansion coefficient is low, and low linear expansion is achieved.
[0053]
On the other hand, Comparative Examples 1 and 2 which did not use spherical silica powder had high water absorption, low moisture-resistant adhesive strength, peeled off in the moisture resistance test, and had a high linear expansion coefficient exceeding 60 ppm. Met. In Comparative Example 3 using spherical silica powder containing particles having an average particle size of more than 0.5 μm and having a particle size of 5 μm or more, the ultraviolet light hardly reaches the inside of the resin composition, and thus the curability is poor. As a result, the moisture-resistant adhesive strength was low, and peeling occurred in the moisture resistance test.
[0054]
【The invention's effect】
As described above, the present invention provides the specific spherical silica powder (C) together with the epoxy resin (A) containing the epoxy resin (a1) and the alicyclic epoxy resin (a2) represented by the formula (1). ) Is an ultraviolet-curable epoxy resin composition. For this reason, the ultraviolet light easily reaches the inside of the resin composition, the photocurability is good, and the water absorption under a high-temperature and high-humidity atmosphere is low, and the moisture resistance adhesive strength at the initial stage and after the moisture absorption is high and excellent practicability. It has. In addition, since it contains the specific spherical silica powder (C), it has a low linear expansion coefficient and excellent dimensional stability. In the ultraviolet-curable epoxy resin composition of the present invention, after the specific spherical silica powder (C) is dispersed in the alicyclic epoxy resin (a2) in advance, the remaining components are blended. The specific spherical silica powder (C) is uniformly dispersed in the resin composition by passing through such a manufacturing process. Therefore, when the ultraviolet curable epoxy resin composition of the present invention is applied to bonding of precision optical components such as optical waveguides and V-grooves in optical communication systems and bonding of fiber arrays, and fixing of small components such as lenses, etc. As a result, an adhesive joint having excellent long-term reliability is realized.
[0055]
When the content of a1 is set in the range of 15 to 70% by weight of the entire epoxy resin (A), the moisture resistance and the fluidity are further improved.
[0056]
When the content of the specific spherical silica powder (C) is set in the range of 50 to 80% by weight based on the total amount of the epoxy resin (A) and the specific spherical silica powder (C), a low linear expansion coefficient is obtained. As a result, the dimensional stability can be further improved, and the workability can be improved.
[0057]
Further, when 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is used as the alicyclic epoxy resin of the above a2, low viscosity is obtained together with good transparency and reactivity, which is more preferable. Become.
Claims (5)
（Ａ）下記の（ａ１）および（ａ２）を含有するエポキシ樹脂。
（ａ１）下記の式（１）で表されるエポキシ樹脂。
（Ｂ）光重合開始剤。
（Ｃ）平均粒径が０．３〜０．５μｍの範囲で、かつ粒径５μｍ以上のものを実質的に含有しない球状シリカ粉末。An ultraviolet-curable epoxy resin composition comprising the following (A) to (C).
(A) An epoxy resin containing the following (a1) and (a2).
(A1) An epoxy resin represented by the following formula (1).
(B) a photopolymerization initiator.
(C) A spherical silica powder having an average particle size in the range of 0.3 to 0.5 μm and substantially not containing a particle size of 5 μm or more.
（Ａ）下記の（ａ１）および（ａ２）を含有するエポキシ樹脂。
（ａ１）下記の式（１）で表されるエポキシ樹脂。
（Ｂ）光重合開始剤。
（Ｃ）平均粒径が０．３〜０．５μｍの範囲で、かつ粒径５μｍ以上のものを実質的に含有しない球状シリカ粉末。It is a manufacturing method of the ultraviolet curing epoxy resin composition containing the following (A)-(C) as described in any one of Claims 1-4, Comprising: The said spherical silica powder (C) is made into the said alicyclic in advance. After dispersing in the formula epoxy resin (a2), the dispersion is mixed with the epoxy resin (a1) represented by the formula (1) and the remaining components including the photopolymerization initiator (B). A method for producing a UV-curable epoxy resin composition, which is a feature.
(A) An epoxy resin containing the following (a1) and (a2).
(A1) An epoxy resin represented by the following formula (1).
(B) a photopolymerization initiator.
(C) A spherical silica powder having an average particle size in the range of 0.3 to 0.5 μm and substantially not containing a particle size of 5 μm or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006299254A (en) * | 2005-03-24 | 2006-11-02 | Toray Ind Inc | Film comprising liquid crystalline resin composition and manufacturing method thereof |
| JP2007284500A (en) * | 2006-04-13 | 2007-11-01 | Sekisui Chem Co Ltd | Adhesive for optical part |
| WO2010047386A1 (en) * | 2008-10-24 | 2010-04-29 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member |
| JP2011063679A (en) * | 2009-09-16 | 2011-03-31 | Denki Kagaku Kogyo Kk | Synthetic resin sheet, substrate, circuit board and method for manufacturing the same |
| JP2012116935A (en) * | 2010-11-30 | 2012-06-21 | Daicel Corp | Curable epoxy resin composition |
| CN115011074A (en) * | 2021-08-20 | 2022-09-06 | 广东四会互感器厂有限公司 | Epoxy resin composition, preparation method and application thereof |
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2003
- 2003-05-13 JP JP2003133985A patent/JP4142981B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006299254A (en) * | 2005-03-24 | 2006-11-02 | Toray Ind Inc | Film comprising liquid crystalline resin composition and manufacturing method thereof |
| JP2007284500A (en) * | 2006-04-13 | 2007-11-01 | Sekisui Chem Co Ltd | Adhesive for optical part |
| WO2010047386A1 (en) * | 2008-10-24 | 2010-04-29 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member |
| US20110195249A1 (en) * | 2008-10-24 | 2011-08-11 | Cheong Hun Song | Adhesive composition and optical member |
| CN102197101A (en) * | 2008-10-24 | 2011-09-21 | 第一毛织株式会社 | Adhesive composition and optical member |
| US8236872B2 (en) | 2008-10-24 | 2012-08-07 | Cheil Industries, Inc. | Adhesive composition and optical member |
| KR101340553B1 (en) * | 2008-10-24 | 2013-12-11 | 제일모직주식회사 | Adhesive composition and optical member |
| JP2011063679A (en) * | 2009-09-16 | 2011-03-31 | Denki Kagaku Kogyo Kk | Synthetic resin sheet, substrate, circuit board and method for manufacturing the same |
| JP2012116935A (en) * | 2010-11-30 | 2012-06-21 | Daicel Corp | Curable epoxy resin composition |
| US9200133B2 (en) | 2010-11-30 | 2015-12-01 | Daicel Corporation | Curable epoxy resin composition |
| CN115011074A (en) * | 2021-08-20 | 2022-09-06 | 广东四会互感器厂有限公司 | Epoxy resin composition, preparation method and application thereof |
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