JP2015178592A - フルオレン骨格含有エポキシ樹脂の製造方法、エポキシ樹脂組成物、及び硬化物 - Google Patents
フルオレン骨格含有エポキシ樹脂の製造方法、エポキシ樹脂組成物、及び硬化物 Download PDFInfo
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- JP2015178592A JP2015178592A JP2014232494A JP2014232494A JP2015178592A JP 2015178592 A JP2015178592 A JP 2015178592A JP 2014232494 A JP2014232494 A JP 2014232494A JP 2014232494 A JP2014232494 A JP 2014232494A JP 2015178592 A JP2015178592 A JP 2015178592A
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- Prior art keywords
- epoxy resin
- fluorene skeleton
- resin composition
- cured product
- fluorene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 228
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 228
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 24
- 230000003287 optical effect Effects 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- -1 phenol compound Chemical class 0.000 claims description 83
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- 239000003795 chemical substances by application Substances 0.000 claims description 37
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
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Images
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Abstract
【解決手段】式(1)で表されるフルオレン骨格含有フェノール化合物を含むフェノール化合物と、2官能エポキシ樹脂とを反応させ、エポキシ当量が700〜1500g/eqであり、フルオレン骨格含有量が15〜70モル%であり、フルオレン骨格含有フェノール化合物が式(1)におけるnが0である化合物(a)を50質量%以上含み、nが1又は2である化合物(b)をHPLCで測定したとき0.01〜1.0面積%含み、触媒の存在下で、フェノール化合物の水酸基と2官能エポキシ樹脂のエポキシ基を反応させてフルオレン骨格含有エポキシ樹脂を製造する方法。
【選択図】なし
Description
(10×600/200+100×250/125)/(600/200+250/125)=46
しかし、ビスフェノールフルオレン類の通常の製造方法では、一般式(1)において、nが1以上である化合物が少量副生する。これは、精製工程で除去されていると考えられる。しかし、必要以上の精製は、環境に対する負荷を考えた場合好ましくない。
ビスフェノールフルオレン類をエポキシ樹脂とするために使用する用途では、化合物(b)を検出限界以下に低減してしまうことは、過剰品質でありばかりでなく、架橋密度を必要以上に低下させる。
2官能エポキシ樹脂Fのエポキシ当量は、230〜500g/eqであり、230〜400g/eqが好ましく、230〜350がより好ましい。そして、2官能エポキシ樹脂Fのエポキシ当量は、目的とするフルオレン骨格含有エポキシ樹脂のエポキシ当量より100g/eq以上低いこと、より好ましくは400g/eq以上低いことが望ましい。
単独で使用しても2種類以上併用してもよい。
(2)フェノール性水酸基当量:試料に4%のメタノールを含むテトラヒドロフランを加えて完全に溶解した後、10%テトラブチルアンモニウムヒドロキシドを加えて、紫外可視分光光度計を用いて波長400nmから250nm間の吸光度を測定し、フェノール性水酸基を水酸基1当量当たりの試料のg数として求めた。
(3)エポキシ当量:JIS K−7236により測定した。
(4)軟化点:JIS K−7234に従い、環球法により測定した。
(5)色相:JIS K−0071−1により、ハーゼン単位色数を測定した。試料は樹脂をテトラヒドロフランに溶解した不揮発分50%の樹脂ワニスを使用した。
(7)硬化物色相:厚み1mmの試験片を、測色色差計(東京電色社製、TC−1500MC−88)を使用してYI値を測定した。熱履歴をかける前の試験片の測定値をブランクとして、所定温度で恒温を保っているオーブンに所定時間保管した後の試験片も測定した。なお、数値が小さいほど、色相が良いことを示す。また、熱履歴をかけた後の試験片の数値が小さいほど、耐熱黄変性が良いことを示す。
(8)耐湿性:JIS K−6911に準拠して吸水率を測定した。厚さ1mm、直径50mmの円盤状の硬化物を試験片として用いた。数値が小さいほど、耐湿性が良いことを示す。
(9)成形性:上記耐湿性試験片を目視で確認し、全く「欠け」や「割れ」がなかった場合を○とし、それ以外を×とした。
特許文献6の実施例に従って、9,9−ビス(4−ヒドロキシフェニル)フルオレンを合成し、BPFL(1)を得た。得られたBPFL(1)を再結晶によって精製した。具体的には、メタノールを加え、加温して溶解させた後、撹拌しながら室温でもしくは必要に応じて冷水で容器の回りを冷却しながら固体を析出させ、次いで、得られた固形物をろ過し、乾燥させ、BPFL(2)を得た。BPFL(2)を再度、再結晶を行い、BPFL(3)を得た。
(エポキシ樹脂)
・YD−128;2,2−ビス(4−ヒドロキシフェニル)プロパンのジグリシジルエーテル、エポキシ当量185g/eq、粘度12800mPs・s/25℃、新日鉄住金化学株式会社製、エポトートYD−128
・ESF−300;9,9‐ビス(4−ヒドロキシフェニル)−9H−フルオレンのジグリシジルエーテル、エポキシ当量250g/eq、軟化点87℃、新日鉄住金化学株式会社製
・ZX−1658GS;1,4‐シクロヘキサンジメタノールのジグリシジルエーテル、エポキシ当量134g/eq、粘度37mPs・s/25℃、新日鉄住金化学株式会社製、エポトートZX−1658GS
・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、エポキシ当量133g/eq、粘度240mPa・s/25℃、ダイセル化学工業株式会社製、セロキサイド2021P
・BPFL(1)〜(4);上記
・BPA;2,2−ビス(4−ヒドロキシフェニル)プロパン、水酸基当量=114g/eq、新日鉄住金化学株式会社製
・TPP−BB;n−ブチルトリフェニルホスホニウムブロマイド、北興化学株式会社製
・TPP;トリフェニルフォスフィン、北興化学株式会社製
・HH;ヘキサヒドロ無水フタル酸、新日本理化株式会社製、リカシッドHH
・MH;4‐メチルヘキサヒドロ無水フタル酸、新日本理化株式会社製、リカシッドMH
・PX−4ET;有機ホスホニウム塩化合物、日本化学工業株式会社製、ヒシコーリンPX−4ET
・HCA;9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド、三光株式会社製
撹拌機、温度計、窒素吹き込み管、及び冷却管を備えた反応装置に2官能エポキシ樹脂としてYD−128を370部とフェノール化合物としてBPFL(2)を121部とBPFL(3)を121部仕込み、130℃まで昇温し、触媒としてTPP−BBを0.242部仕込み、さらに165℃まで昇温し、4時間撹拌混合してエポキシ樹脂1を得た。
実施例1で使用した装置を用い、表1の配合に従って、実施例1と同様にしてエポキシ樹脂2〜8を得た。実施例1で得られたエポキシ樹脂を、エポキシ樹脂1とし、以下同様とする。
実施例1で使用した装置を用い、表2の配合に従って、実施例1と同様にしてエポキシ樹脂9〜15を得た。比較例1で得られたエポキシ樹脂を、エポキシ樹脂9とし、以下比較例番号+8を、エポキシ樹脂番号とする。なお、比較例3、及び比較例5については、反応終了時点で粘度が高くなり取り出せなかったため、温度を200℃まで上げて取り出した。
エポキシ樹脂として実施例1で得られたエポキシ樹脂1を100部と、硬化剤としてリカシッドMHを16.2部とを、温度100℃で均一になるまで混合した後、硬化促進剤としてPX−4ETを0.25部添加し、撹拌、溶解してエポキシ樹脂組成物を得た。この組成物を減圧下で脱泡した後、型の中に流し込み、オーブン中にて120℃で3時間、次いで、150℃で10時間硬化させて、試験片を得た。
エポキシ樹脂として実施例2〜8で得られたエポキシ樹脂2〜8を100部と、表5に示す硬化剤を使用して、実施例9と同様にして試験片を作成し、評価を行った。
エポキシ樹脂、硬化剤の種類と、硬化剤の使用量を表5に示す。硬化物について、Tg、硬化物色相、耐水性、及び成形性を評価した結果を表6に示す。
エポキシ樹脂として比較例1〜7で得られた樹脂9〜15を100部と、表7に示す硬化剤を使用して、実施例9と同様にして試験片を作成し、評価を行った。
エポキシ樹脂、硬化剤の種類と、硬化剤の使用量を表7に示す。評価結果を表8に示す。
エポキシ樹脂、硬化剤、硬化促進剤、及び酸化防止剤を、表9の配合表に従って、配合し、これらを温度100℃で均一になるまで混合した後、硬化促進剤を添加し、撹拌、溶解してエポキシ樹脂組成物を得た。この組成物を減圧下で脱泡した後、金型の中に流し込み、オーブン中にて120℃で3時間、次いで、150℃で10時間硬化し硬化物を得た。この硬化物の物性値を表9に示す。
Claims (13)
- 下記一般式(1)で表されるフルオレン骨格含有フェノール化合物を含むフェノール化合物と2官能エポキシ樹脂とを反応させて得られ、エポキシ当量が700〜1500g/eqであり、フルオレン骨格含有量が15〜70モル%であるフルオレン骨格含有エポキシ樹脂の製造方法であって、フルオレン骨格含有フェノール化合物が一般式(1)におけるnが0である化合物(a)を50質量%以上含み、nが1または2である化合物(b)を高速液体クロマトグラフィーで測定したとき0.01〜1.0面積%含むものであり、フェノール性水酸基とエポキシ基の付加反応を促進する触媒の存在下で、フェノール化合物の水酸基と2官能エポキシ樹脂のエポキシ基を反応させることを特徴とするフルオレン骨格含有エポキシ樹脂の製造方法。
- フルオレン骨格含有フェノール化合物が、9,9−ビス(4−ヒドロキシフェニル)フルオレンを90質量%以上含有するものである請求項1に記載のフルオレン骨格含有エポキシ樹脂の製造方法。
- 2官能エポキシ樹脂が、ビスフェノールA型エポキシ樹脂である請求項1または2に記載のフルオレン骨格含有エポキシ樹脂の製造方法。
- 2官能エポキシ樹脂の少なくとも一部が、フルオレン骨格を有し、エポキシ当量が230〜500g/eqである請求項1または2に記載のフルオレン骨格含有エポキシ樹脂の製造方法。
- 触媒が、ホスフィン類または第4級ホスホニウム塩である請求項1〜4のいずれか1項に記載のフルオレン骨格含有エポキシ樹脂の製造方法。
- 請求項1〜5のいずれか1項に記載の製造方法により製造されたフルオレン骨格含有エポキシ樹脂。
- エポキシ樹脂(A)及びエポキシ樹脂硬化剤(B)を必須成分として含有してなるエポキシ樹脂組成物であって、(A)成分として請求項6に記載のフルオレン骨格含有エポキシ樹脂を含有することを特徴とするエポキシ樹脂組成物。
- (B)成分が、酸無水物である請求項7記載のエポキシ樹脂組成物。
- 請求項7または8に記載のエポキシ樹脂組成物からなる光学素子用エポキシ樹脂組成物。
- 請求項9に記載の光学素子用エポキシ樹脂組成物を用いて得られる光学素子用封止剤。
- 請求項9に記載の光学素子用エポキシ樹脂組成物を用いて得られる光学素子用基板。
- 請求項7または8に記載のエポキシ樹脂組成物を硬化させて得られる硬化物。
- 硬化物が、厚さ1mmで、180℃の環境下、100時間の条件での熱処理後のYI値が20以下である請求項12に記載の硬化物。
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