JP6856037B2 - シリコーン変性ポリベンゾオキサゾール樹脂及びその製造方法 - Google Patents
シリコーン変性ポリベンゾオキサゾール樹脂及びその製造方法 Download PDFInfo
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- JP6856037B2 JP6856037B2 JP2018012229A JP2018012229A JP6856037B2 JP 6856037 B2 JP6856037 B2 JP 6856037B2 JP 2018012229 A JP2018012229 A JP 2018012229A JP 2018012229 A JP2018012229 A JP 2018012229A JP 6856037 B2 JP6856037 B2 JP 6856037B2
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- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Description
1.下記式(1a)で表される繰り返し単位及び下記式(1b)で表される繰り返し単位を有するシリコーン変性ポリベンゾオキサゾール樹脂。
2.重量平均分子量が3,000〜500,000である1のシリコーン変性ポリベンゾオキサゾール樹脂。
3.X2が、下記式で表される基から選ばれる基である1又は2のシリコーン変性ポリベンゾオキサゾール樹脂。
4.1〜3のいずれかのシリコーン変性ポリベンゾオキサゾール樹脂を含む樹脂皮膜。
5.下記式(1−A)で表されるオルガノポリシロキサンと、下記式(1−B)で表される化合物と、下記式(2−A)で表されるベンゾオキサゾール化合物とを付加重合反応させる、1〜3のいずれかのシリコーン変性ポリベンゾオキサゾール樹脂の製造方法。
6.下記式(2−A)で表されるベンゾオキサゾール化合物。
7.下記式(2−B)で表される化合物と、下記式(2−C)で表される化合物と、下記式(2−D)で表される化合物とを反応させる、6のベンゾオキサゾール化合物の製造方法。
本発明のシリコーン変性ポリベンゾオキサゾール樹脂は、下記式(1−A)で表されるオルガノポリシロキサンと、下記式(1−B)で表される化合物と、下記式(2−A)で表されるベンゾオキサゾール化合物との付加重合反応によって製造することができる。
本発明のシリコーン変性ポリベンゾオキサゾール樹脂を、トルエン、テトラヒドロフラン、エチレングリコールブチルエーテルアセテート、メチルエチルケトン等の溶剤に溶解させてシリコーン変性ポリベンゾオキサゾール樹脂組成物を調製し、該樹脂組成物をガラス、鉄、銅、ニッケル、アルミニウム等の金属、ガラス等の基材からなる基板上に塗布し、溶剤を蒸発・除去して成膜した後に、好ましくは40〜400℃、より好ましくは80〜250℃の範囲の温度条件で、好ましくは0.01〜30時間、より好ましくは0.1〜20時間加熱することにより、表面が平滑で、アルコール類、ケトン類、トルエン系等に対する耐溶剤性に優れた良好な樹脂皮膜が得られる。前記樹脂皮膜は、形成方法にもよるが、好ましくは1μm〜1cm程度、より好ましくは10〜500μmの範囲内で任意なものとすることができる。また、得られた樹脂皮膜は、基材との接着性や密着性に優れたものである。なお、前記樹脂組成物においては、シリコーン変性ポリベンゾオキサゾール樹脂は、1種のみが含まれていてもよく、2種以上が含まれていてもよい。
[実施例1]ベンゾオキサゾール化合物S−1aの合成
窒素気流下、300mL4口フラスコに、化合物A−2を35.6g(0.20mol)仕込み、γ−ブチロラクトン50gに溶解させた。これに、ジシクロへキシルカルボジイミド41.2g(0.20mol)をγ−ブチロラクトン50gに溶解させた溶液を5℃で滴下した。その後、温度を5℃に保ったまま20分攪拌した後、γ−ブチロラクトン50gに化合物A−1を36.6g(0.10mol)溶解させた溶液を5℃で滴下した。その後、5℃で3時間攪拌し、更に室温で10時間攪拌した。攪拌終了後、系内を200℃まで昇温し、閉環脱水反応を20時間行った。なお、閉環脱水反応中は、ディーン・スタークトラップを用いて系内から水を取り除きながら反応を行った。副生成物の尿素を濾過で除去した後、イソプロピルアルコール中で再結晶を行い(純水を貧溶剤として添加した。)、最後に結晶を120℃×3時間乾燥させることで、ベンゾオキサゾール化合物S−1aを53.3g得た(収率82.0%)。1H−NMR及び13C−NMR(Bruker社製AV400M、溶剤:重トルエン、以下同じ。)の結果を、それぞれ表1及び2に示す。
窒素気流下、300mL4口フラスコに、化合物B−1を28.0g(0.10mol)及び化合物B−2を47.6g(0.20mol)仕込み、N−メチル−2−ピロリドン(NMP)100gに溶解させ、180℃まで加熱した。なお、反応中は、系中を減圧して副生成物として出たフェノールを取り除きながら行った。3時間加熱した後、常圧に戻し、系内を200℃まで昇温し、閉環脱水反応を20時間行った。なお、閉環脱水反応中は、ディーン・スタークトラップを用いて系内から水を取り除きながら反応を行った。反応溶液を水1,000mLに投入し再沈殿させ、結晶を取り出し、イオン交換水及びメタノールで洗浄し、最後に結晶を120℃×3時間乾燥させることで、ベンゾオキサゾール化合物S−1bを45.3g得た(収率85.2%)。1H−NMR及び13C−NMRの結果を、それぞれ表3及び4に示す。
窒素気流下、300mL4口フラスコに、化合物C−1を25.8g(0.10mol)及び化合物C−2を50.8g(0.20mol)仕込み、NMP100gに溶解させ、180℃まで加熱した。なお、反応中は、系中を減圧して副生成物として出たフェノールを取り除きながら行った。3時間加熱した後、常圧に戻し、系内を200℃まで昇温し、閉環脱水反応を20時間行った。なお、閉環脱水反応中は、ディーン・スタークトラップを用いて系内から水を取り除きながら反応を行った。反応溶液を水1,000mLに投入し再沈殿させ、結晶を取り出し、イオン交換水及びメタノールで洗浄し、最後に結晶を120℃×3時間乾燥させることで、ベンゾオキサゾール化合物S−1cを42.6g得た(収率78.7%)。1H−NMR及び13C−NMRの結果を、それぞれ表5及び6に示す。
[実施例4]樹脂Aの合成
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1a325.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=40、信越化学工業(株)製)755.0g(0.25mol)及び式(S−4)で表される化合物(信越化学工業(株)製)48.5g(0.25mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Aを得た。樹脂Aは、1H−NMR及び29Si−NMR(Bruker社製)により、式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂AのMwは42,000、シリコーン含有率は67.0質量%、式(1a)及び(1b)におけるa及びbは、a=0.5、b=0.5であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1b266.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=40、信越化学工業(株)製)151.0g(0.05mol)及び式(S−4)で表される化合物(信越化学工業(株)製)87.3g(0.45mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Bを得た。樹脂Bは、1H−NMR及び29Si−NMR(Bruker社製)により式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂BのMwは44,000、シリコーン含有率は30.0質量%、式(1a)及び(1b)におけるa及びbは、a=0.1、b=0.9であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1c271.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=40、信越化学工業(株)製)1057.0g(0.35mol)及び式(S−4)で表される化合物(信越化学工業(株)製)29.1g(0.15mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Cを得た。樹脂Cは、1H−NMR及び29Si−NMR(Bruker社製)により、式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂CのMwは45,000、シリコーン含有率は77.9質量%、式(1a)及び(1b)におけるa及びbは、a=0.7、b=0.3であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1a325.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=20、信越化学工業(株)製)396.3g(0.25mol)及び式(S−4)で表される化合物(信越化学工業(株)製)48.5g(0.25mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Dを得た。樹脂Dは、1H−NMR及び29Si−NMR(Bruker社製)により、式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂DのMwは40,000、シリコーン含有率は51.5質量%、式(1a)及び(1b)におけるa及びbは、a=0.5、b=0.5であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1b266.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=20、信越化学工業(株)製)396.3g(0.25mol)及び式(S−4)で表される化合物(信越化学工業(株)製)48.5g(0.25mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Eを得た。樹脂Eは、1H−NMR及び29Si−NMR(Bruker社製)により、式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂EのMwは39,000、シリコーン含有率は55.8質量%、式(1a)及び(1b)におけるa及びbは、a=0.5、b=0.5であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、ベンゾオキサゾール化合物S−1c271.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=20、信越化学工業(株)製)396.3g(0.25mol)及び式(S−4)で表される化合物(信越化学工業(株)製)48.5g(0.25mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Fを得た。樹脂Fは、1H−NMR及び29Si−NMR(Bruker社製)により、式(1a)で表される繰り返し単位及び式(1b)で表される繰り返し単位を有することを確認した。樹脂FのMwは41,000、シリコーン含有率は55.4質量%、式(1a)及び(1b)におけるa及びbは、a=0.5、b=0.5であった。
[比較例1]樹脂Gの合成
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、式(S−3a)で表される化合物285.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=40、信越化学工業(株)製)906.0g(0.30mol)及び式(S−4)で表される化合物(信越化学工業(株)製)38.8g(0.20mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Gを得た。樹脂GのMwは44,000、シリコーン含有率は73.7質量%であった。
攪拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコに、式(S−3b)で表される化合物286.0g(0.5mol)を加えた後、トルエン2,000gを加え、70℃になるまで加熱した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、式(S−2)で表される化合物(d=20、信越化学工業(株)製)317.0g(0.20mol)及び式(S−4)で表される化合物(信越化学工業(株)製)58.2g(0.30mol)を1時間かけて滴下した(ヒドロシリル基の合計/アルケニル基の合計=1/1(モル比))。滴下終了後、100℃になるまで加熱し、6時間熟成した後、反応溶液からトルエンを減圧留去し、樹脂Hを得た。樹脂HのMwは41,000、シリコーン含有率は47.9質量%であった。
[実施例10〜15、比較例3〜4]
樹脂A〜Hを、それぞれ、メチルエチルケトン(MEK)に濃度が30質量%になるように溶解し、樹脂組成物を調製した。得られた各樹脂組成物を用いて、以下のとおり樹脂皮膜を形成し、その評価を行った。
各樹脂溶液を、それぞれ、ガラス基板上に塗布し、60℃の温度で30分間、更に230℃の温度で2時間加熱し、樹脂皮膜(厚さ:120μm)を形成させた。
得られたガラス基板上に密着した状態の各樹脂皮膜を、25℃のMEKに5分間浸漬した後、皮膜の表面の変化の有無を光学顕微鏡によって観察した。結果を表7に示す。なお、「表面平滑」との表示は、樹脂皮膜表面がMEKにより膨潤して、前記表面に変形、凹凸等が生じていないことを示す。
各樹脂溶液を、それぞれ、銅基板、ガラス基板、シリコンウェハー、SiNウェハー、及びSiO2ウェハー、アクリル系プラスチック、エポキシ系プラスチック上に塗布し、60℃の温度で30分間、更に230℃の温度で2時間加熱し、樹脂皮膜(厚さ:25μm)を各基板上に形成させた。次いで、2.1気圧の飽和水蒸気中に72時間放置した後、各基板上の前記各樹脂皮膜について、碁盤目剥離テスト(JIS K 5400)を行い、高湿条件放置後の接着性を評価した。結果を表7に示す。なお、表7中の数値は、分画数100当たり、剥離しなかった分画数を表す。すなわち、100の場合は全く剥離せず、0の場合はすべて剥離したことを示す。
各樹脂溶液を、それぞれ、銅基板上に塗布し、60℃の温度で30分間、更に230℃の温度で2時間加熱し、樹脂皮膜(厚さ:25μm)を形成させた。これを試験片として、2mmφのマンドレルによりJIS K 5600に準拠し、屈曲追従性を調べた。結果を表7に示す。なお、「○」は、屈曲追従性が良好であり、樹脂皮膜の基板からの剥離又は破断が生じていないことを示す。また、「×」は、樹脂皮膜の基板からの剥離又は破断を示す。
Claims (6)
- 下記式(1a)で表される繰り返し単位及び下記式(1b)で表される繰り返し単位を有するシリコーン変性ポリベンゾオキサゾール樹脂。
- 重量平均分子量が3,000〜500,000である請求項1記載のシリコーン変性ポリベンゾオキサゾール樹脂。
- 請求項1又は2記載のシリコーン変性ポリベンゾオキサゾール樹脂を含む樹脂皮膜。
- 下記式(2−A)で表されるベンゾオキサゾール化合物。
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