JP2021138826A - ポリエステル系樹脂およびその製造方法 - Google Patents
ポリエステル系樹脂およびその製造方法 Download PDFInfo
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- JP2021138826A JP2021138826A JP2020036926A JP2020036926A JP2021138826A JP 2021138826 A JP2021138826 A JP 2021138826A JP 2020036926 A JP2020036926 A JP 2020036926A JP 2020036926 A JP2020036926 A JP 2020036926A JP 2021138826 A JP2021138826 A JP 2021138826A
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Abstract
Description
Adはアダマンタン環を示し、R1は置換基を示し、kは0〜15の整数を示し、mは1または2を示し、
A1aおよびA1bはそれぞれ独立して直鎖状または分岐鎖状アルキレン基を示し、n1およびn2はそれぞれ独立して0以上の整数を示し、
R2は置換基を示し、pは0以上の整数を示す)。
R3は置換基を示し、rは0〜8の整数を示す)。
(第1のジオール単位(A1))
ポリエステル系樹脂は、少なくともジオール単位(A)を含んでおり、ジオール単位(A)は、少なくとも下記式(1)で表される第1のジオール単位(A1)を有している。第1のジオール単位(A1)を含むことにより、アッベ数を中間領域に容易に調整できる。また、低い複屈折を保持しつつ耐熱性(またはガラス転移温度Tg)を大きく向上できる。
Adはアダマンタン環を示し、R1は置換基を示し、kは0〜15の整数を示し、mは1または2を示し、
A1aおよびA1bはそれぞれ独立して直鎖状または分岐鎖状アルキレン基を示し、n1およびn2はそれぞれ独立して0以上の整数を示し、
R2は置換基を示し、pは0以上の整数を示す)。
ジオール単位(A)は、必要に応じて、さらに、下記式(2)で表される第2のジオール単位(A2)を含んでいてもよい。この構成単位に対応する第2のジオール成分(A2)を重合成分として含んでいると、重合反応性を高めて分子量の大きなポリエステル系樹脂を調製でき、成形性(生産性)や機械的特性を向上できる。また、第2のジオール単位(A2)を前記第1のジオール単位(A1)と組み合わせて含むことにより、アッベ数を中間領域内で低めに調整でき、ガラス転移温度Tgを調整して生産性(または成形性)を向上することもできる。
なお、ジオール単位(A)は、第1のジオール単位(A1)および第2のジオール単位(A2)とは異なるジオール単位(第3のジオール単位(A3))を必要に応じて含んでいてもよいが、含んでいなくてもよい。
ポリエステル系樹脂は、少なくともジオール単位(A)を含んでいればよいが、必要に応じてジカルボン酸単位(B)を含んでいてもよく、ジオール単位(A)とジカルボン酸単位(B)とで主鎖としてのエステル結合を形成してもよい。
ジカルボン酸単位(B)は、さらに、下記式(3)で表される第1のジカルボン酸単位(B1)を有していてもよい。第1のジカルボン酸単位(B1)を含んでいると、高い耐熱性を保持しつつ、複屈折を有効に低減できる。また、アッベ数を中間領域内で低めに調整することもできる。
R3は置換基を示し、rは0〜8の整数を示す)。
ジカルボン酸単位(B)は、必要に応じて、さらに、脂環族ジカルボン酸成分に由来する第2のジカルボン酸単位(B2)を含んでいてもよい。第2のジカルボン酸単位(B2)を含んでいると、複屈折を過度に上昇させることなく耐熱性を向上できる。また、アッベ数を中間領域の範囲内で高めるように調整することもできる。
A4aおよびA4bはそれぞれ独立して直鎖状または分岐鎖状アルキレン基を示し、s1およびs2は0または1を示し、
R4は置換基を示し、tは0以上の整数を示す)。
なお、ジカルボン酸単位(B)は、第1のジカルボン酸単位(B1)および第2のジカルボン酸単位(B2)とは異なるジカルボン酸単位(第3のジカルボン酸単位(B3))を必要に応じて含んでいてもよいが、含んでいなくてもよい。
なお、ポリエステル系樹脂は、ジオール単位(A)およびジカルボン酸単位(B)とは異なる他の構成単位(C)を必要に応じて含んでいてもよいが、含んでいなくてもよい。
ポリエステル系樹脂の製造方法は、前記第1のジオール成分(A1)を含むジオール成分(A)を重合成分として用いること以外は特に制限されず、樹脂の種類または他の重合成分(共重合成分)などに応じて、慣用の方法が利用できる。例えば、ジオール単位(A)とジカルボン酸単位(B)とを含むポリエステル系樹脂である場合、前述の各構成単位に対応する成分を含む重合成分を反応(重合)させて製造すればよく、例えば、エステル交換法(エステル交換反応)、直接重合法などの溶融重合法、溶液重合法、界面重合法などの慣用の方法で調製でき、溶融重合法が好ましい。なお、反応は、重合方法に応じて、溶媒の存在下または非存在下で行ってもよい。
(特性)
ポリエステル系樹脂は、前記第1のジオール単位(A1)を含むため、アッベ数を中間領域に容易に調整できる。高い屈折率および高い耐熱性を有している。また、中間領域のアッベ数と、高い耐熱性と、低い複屈折の絶対値とを高度にバランスよく充足することもできる。
本発明の成形体は、少なくとも前記ポリエステル系樹脂を含み、優れた光学的特性などを示すため、光学フィルム(または光学シート)、光学レンズなどの光学部材として利用でき、中間領域のアッベ数や低い複屈折などの光学的特性に優れる点から、光学レンズとして有効に利用できる。
(ガラス転移温度(Tg))
示差走査熱量計(セイコーインスツル(株)製、DSC 6220)を用い、アルミパンに試料を入れ、窒素ガス雰囲気下、10℃/分の昇温速度の条件下30〜220℃の範囲でTgを測定した。
試料をクロロホルムに溶解し、ゲル浸透クロマトグラフィー(東ソー(株)製「HLC−8120GPC」)を用いて、ポリスチレン換算の重量平均分子量(Mw)を求めた。
多波長アッベ屈折計((株)アタゴ製「DR−M2/1550」)を用いて、接触液に1−ブロモナフタレンを使用して、測定温度20℃、測定波長486nm(F線)、589nm(D線)、656nm(C線)における屈折率nF、nD、nCをそれぞれ測定した。なお、アッベ数は以下の式によって算出した。
試験片をTg+10℃の温度条件下、25mm/分で延伸倍率が3倍となるように一軸延伸し、位相差フィルム・光学材料検査装置(大塚電子(株)製「RETS−100」)を用いて、測定温度20℃、測定波長600nmの条件下、回転検光子法にてリタデーションを測定し、その絶対値を測定部位の厚みで除することで算出した。
試料を、内部標準物質としてテトラメチルシランを含む重クロロホルムに溶解し、核磁気共鳴装置(BRUKER社製「AVANCE III HD」)を用いて、1H−NMRスペクトルを測定した。得られたスペクトルについて、重合に用いた各々のモノマーに由来するピークの積分値を求め、ポリマー中に導入された各モノマー成分(構成単位)の割合を算出した。
BARE:4,6−ビス(1−アダマンチル)−1,3−ビス(2−ヒドロキシエトキシ)ベンゼン、後述する合成例1に従って合成したもの
EG:エチレングリコール
CHDA−m:1,4−シクロヘキサンジカルボン酸のジメチルエステル、トランス比率98モル%(trans/cis(モル比)=98/2)
FDP−m:9,9−ビス(2−メトキシカルボニルエチル)フルオレン[すなわち、フルオレン−9,9−プロピオン酸のジメチルエステル]、特開2005−89422号公報の実施例1のアクリル酸t−ブチルをアクリル酸メチル37.9g(0.44モル)に変更した以外は同様にして合成したもの。
還流冷却管、攪拌機、温度計および窒素導入管を備え付けた1Lの4つ口フラスコに、1−アダマンタノール54.8g(0.36mol)、p−トルエンスルホン酸一水和物31.0g(0.18mol)およびヘプタン600mLを仕込み、窒素置換した。そこにレゾルシノール19.8g(0.18mol)を加えた後、100℃のオイルバスに入れ、1時間加熱攪拌した。反応液を冷却後、ろ過して集めた固形分を減圧乾燥し、メタノール水溶液で再結晶して、4,6−ビス(1−アダマンチル)−1,3−ジヒドロキシベンゼン50.0gを得た。
ジオール成分としてBARE 0.60molおよびEG 2.40mol、ジカルボン酸成分としてCHDA−m 0.75molおよびFDP−m 0.25mol、エステル交換触媒として酢酸マンガン・4水和物2×10−4molおよび酢酸カルシウム・1水和物8×10−4molを加え撹拌しながら徐々に加熱溶融し、230℃まで昇温した後、トリメチルホスフェート14×10−4mol、酸化ゲルマニウム20×10−4molを加え、270℃、0.13kPa以下に到達するまで徐々に昇温、減圧しながらEGを除去した。所定の撹拌トルクに到達後、内容物を反応器から取り出し、ポリエステル樹脂のペレットを得た。得られたペレットをNMRにより分析したところ、ポリエステル樹脂に導入されたジオール単位の60モル%がBARE由来、40モル%がEG由来であり、ポリエステル樹脂に導入されたジカルボン酸単位の75モル%がCHDA−m由来、25モル%がFDP−m由来であった。得られたポリエステル樹脂のガラス転移温度Tgは142℃、重量平均分子量Mwは66900、屈折率nDは1.5516、アッベ数は39.5、3倍複屈折は17×10−4であった。
ジオール成分としてBARE 0.60molおよびEG 2.40mol、ジカルボン酸成分としてCHDA−m 0.50molおよびFDP−m 0.50molを用いた以外は、実施例1と同様にしてポリエステル樹脂のペレットを得た。得られたペレットをNMRにより分析したところ、ポリエステル樹脂に導入されたジオール単位の60モル%がBARE由来、40モル%がEG由来であり、ポリエステル樹脂に導入されたジカルボン酸単位の50モル%がCHDA−m由来、50モル%がFDP−m由来であった。得られたポリエステル樹脂のガラス転移温度Tgは132℃、重量平均分子量Mwは61700、屈折率nDは1.5581、アッベ数は37.5、3倍複屈折は15×10−4であった。
ジオール成分としてBARE 0.60molおよびEG 2.40mol、ジカルボン酸成分としてFDP−m 1.00molを用いた以外は、実施例1と同様にしてポリエステル樹脂のペレットを得た。得られたペレットをNMRにより分析したところ、ポリエステル樹脂に導入されたジオール単位の60モル%がBARE由来、40モル%がEG由来であり、ポリエステル樹脂に導入されたジカルボン酸単位の100モル%がFDP−m由来であった。得られたポリエステル樹脂のガラス転移温度Tgは134℃、重量平均分子量Mwは72000、屈折率nDは1.5852、アッベ数は31.8、3倍複屈折は−7×10−4であった。
ジオール成分としてBARE 0.40molおよびEG 2.60mol、ジカルボン酸成分としてFDP−m 1.00molを用いた以外は、実施例1と同様にしてポリエステル樹脂のペレットを得た。得られたペレットをNMRにより分析したところ、ポリエステル樹脂に導入されたジオール単位の40モル%がBARE由来、60モル%がEG由来であり、ポリエステル樹脂に導入されたジカルボン酸単位の100モル%がFDP−m由来であった。得られたポリエステル樹脂のガラス転移温度Tgは113℃、重量平均分子量Mwは46900、屈折率nDは1.5882、アッベ数は31.0、3倍複屈折は−3×10−4であった。
ジオール成分としてBARE 0.20molおよびEG 2.80mol、ジカルボン酸成分としてFDP−m 1.00molを用いた以外は、実施例1と同様にしてポリエステル樹脂のペレットを得た。得られたペレットをNMRにより分析したところ、ポリエステル樹脂に導入されたジオール単位の20モル%がBARE由来、80モル%がEG由来であり、ポリエステル樹脂に導入されたジカルボン酸単位の100モル%がFDP−m由来であった。得られたポリエステル樹脂のガラス転移温度Tgは93.6℃、重量平均分子量Mwは80300、屈折率nDは1.5992、アッベ数は27.7、3倍複屈折は−9×10−4であった。
Claims (12)
- 前記式(1)において、Z1がC6−12アレーン環であり、mが2であり、A1aおよびA1bが直鎖状または分岐鎖状C2−6アルキレン基であり、n1およびn2が0〜10の整数である請求項1記載のポリエステル系樹脂。
- 前記第1のジオール単位(A1)と前記第2のジオール単位(A2)との割合が、A1/A2(モル比)=40/60〜80/20である請求項3記載のポリエステル系樹脂。
- さらに、脂環族ジカルボン酸成分に由来する第2のジカルボン酸単位(B2)を有する請求項1〜5のいずれか一項に記載のポリエステル系樹脂。
- 前記第1のジカルボン酸単位(B1)と前記第2のジカルボン酸単位(B2)とを、B1/B2(モル比)=10/90〜60/40の割合で有する請求項6記載のポリエステル系樹脂。
- アッベ数が28〜55である請求項1〜7のいずれか一項に記載のポリエステル系樹脂。
- 請求項1〜8のいずれか一項に記載のポリエステル系樹脂を含む成形体。
- 光学フィルムである請求項10記載の成形体。
- 光学レンズである請求項10記載の成形体。
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JOURNAL OF APPLIED POLYMER SCIENCE, vol. 92, no. 4, JPN6023051660, 2004, pages 2486 - 2493, ISSN: 0005221209 * |
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