JP7468015B2 - 高周波通信機器部品用熱可塑性ポリエステル樹脂組成物 - Google Patents
高周波通信機器部品用熱可塑性ポリエステル樹脂組成物 Download PDFInfo
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- JP7468015B2 JP7468015B2 JP2020045251A JP2020045251A JP7468015B2 JP 7468015 B2 JP7468015 B2 JP 7468015B2 JP 2020045251 A JP2020045251 A JP 2020045251A JP 2020045251 A JP2020045251 A JP 2020045251A JP 7468015 B2 JP7468015 B2 JP 7468015B2
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000011116 polymethylpentene Substances 0.000 description 1
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
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- 229910052895 riebeckite Inorganic materials 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
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- LOAWHQCNQSFKDK-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC.CC[Sn](CC)CC LOAWHQCNQSFKDK-UHFFFAOYSA-N 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Description
誘電損失=K×f×√εr×tanδ 式(1)
(K:定数、f:周波数、εr:比誘電率、tanδ:誘電正接)。
本発明で用いる(A)熱可塑性ポリエステル樹脂としては、ジカルボン酸(あるいは、そのエステル形成性誘導体)とジオール(あるいは、そのエステル形成性誘導体)とを主成分とする重縮合反応によって得られる重合体ないし共重合体などが使用できる。
本発明で言う(B)カーボンブラックは、その製法により、ファーネスブラック、チャネルブラック、サーマルブラック等に、また原料の違いにより、アセチレンブラック、ケッチェンブラック、オイルブラック、ガスブラック等に分類され、本発明においては、いずれも使用することができる。カーボンブラックの粒子径は、1次粒径として5nm以上、100nm以下が好ましく、より好ましくは10nm以上、80nm以下、更に好ましくは15nm以上、60nm以下である。1次粒径が5nm以上とすることで、凝集による分散不良を抑制でき意匠性が向上する。一方で1次粒径が100nm以下とすることで、機械的特性を維持することができる。
エポキシ化合物としては、ノボラックとエピクロロヒドリンとの反応から得られる、ノボラック型エポキシ化合物が好ましい。中でも下記一般式(2)で表されるノボラック型エポキシ化合物が、耐加水分解性の点から好ましい。
本発明の熱可塑性ポリエステル樹脂組成物は、(D)繊維状強化材を含んでもよい。本発明の熱可塑性ポリエステル樹脂組成物が(D)繊維状強化材を含むことは機械的特性向上の目的のためには好ましい。
本発明の熱可塑性ポリエステル樹脂組成物には、本発明の効果を損なわない範囲で、他の樹脂成分、(D)成分以外の無機充填材、離型剤、酸化防止剤、安定剤、相溶化剤、結晶核剤、着色剤、滑剤などの通常の添加剤を配合することができる。これらを二種以上配合してもよい。
本発明の熱可塑性ポリエステル樹脂組成物の製造方法としては、例えば、単軸あるいは二軸の押出機、バンバリーミキサー、ニーダーあるいはミキシングロールなどの公知の溶融混練機を用いて、各成分を溶融混練する方法を挙げることができる。各成分は、予め一括して混合しておき、それから溶融混練してもよい。なお、各成分に含まれる水分は少ない方がよく、必要により予め乾燥しておくことが望ましい。
本発明の高周波通信機器部品は、上記熱可塑性ポリエステル樹脂組成物を成形してなる。成形方法は特に限定されないが、公知の射出成形、押出成形、ブロー成形、プレス成形、紡糸などが挙げられる。例えば射出成形時の温度は、流動性をより向上させる観点から240℃以上が好ましく、機械特性を向上させる観点から280℃以下が好ましい。
(A)熱可塑性ポリエステル樹脂
A-1:ポリブチレンテレフタレート(カルボキシル基量:15eq/t)
(B)カーボンブラック
B-1:カーボンブラック(一次粒子径:25nm)
(C)エポキシ化合物
C-1:一般式(2)で表されるエポキシ当量:276g/eqのジシクロペンタジエンノボラック型エポキシ化合物:DIC(株)製“HP-7200H”を用いた。
C-2:一般式(5)で表されるエポキシ当量:920g/eqのビスフェノール型エポキシ化合物:三菱ケミカル(株)製“jER1004K”を用いた。
C-3:一般式(5)で表されるエポキシ当量:2850g/eqのビスフェノール型エポキシ化合物:三菱ケミカル(株)製“jER1009”を用いた。
D-1:ガラス繊維(平均繊維径13μmチョップドストランド)、表面処理剤:ビスフェノール型エポキシ化合物。
本実施例、比較例においては以下に記載する測定方法によって、その特性を評価した。なお、射出成形機にて成形品を得る過程においては、得られた熱可塑性ポリエステル樹脂組成物のペレットは130℃の熱風乾燥機で3時間以上乾燥してから用いた。
各実施例および比較例により得られた樹脂組成物を用いて、シリンダ温度260℃、金型温度80℃でISO527-1,2:2012年に準拠して試験片を成形し、ISO527-1,2:2012年に準拠した条件で、引張強度を測定した。
各実施例および比較例により得られた樹脂組成物を用いて、シリンダ温度260℃、金型温度80℃で上記(1)に記載の方法と同様の方法で成形した試験片を(株)TABAI ESPEC製HAST CHAMBER EHS-221Mを用いて、121℃、100%RHの加水分解処理を50時間行った。加水分解処理を行った試験片の引張強度を(1)と同様の手法で測定し、以下の算出式より引張強度保持率を求め、耐加水分解性の評価を行った。
引張強度保持率(%)=(引張強度(加水分解処理後)(MPa)/引張強度(加水分解処理前)(MPa))×100
成形品の耐加水分解性は、引張強度保持率が70%以上であれば良好、引張強度保持率が80%以上であれば非常に良好と判断できる。
各実施例及び比較例により得られた樹脂組成物を用いて、住友重機械工業(株)社製SE50D型射出成形機にて、シリンダ温度260℃、金型温度80℃で、縦80mm、横80mm、厚み1mmであるフィルムゲートの角板を成形した。次に、得られた角板状成形品の中心部から、樹脂の流れ方向に1mm幅の角柱状成形品を切削した。初期の誘電特性は、当該角柱状成形品を23℃、50%RHで3日間調湿した状態にて測定した。PCT処理50時間後の吸水時の誘電特性は、上記(2)と同様の手法でPCT処理を50時間実施し、その後、85℃、85%RHで3日間吸水させた状態を経た後に測定した。誘電特性は、アジレント・テクノロジー(株)製ネットワークアナライザE5071Cおよび(株)関東電子応用開発製空洞共振器CP521を用いた空洞共振摂動法によって5.8GHzにおける比誘電率および誘電正接を求めた。各状態のサンプルの誘電特性を測定し、誘電率の平方根と誘電正接の積を求めた。PCT処理前とPCT処理50時間後の吸水時との差が小さいほど使用環境における誘電特性が安定していると判断できる。PCT処理前とPCT処理50時間後の吸水時との√εr×tanδの差が、0.0055以下なら〇、0.0055より大きい場合は×と判定した。ここで、εrは比誘電率、tanδは誘電正接を示す。
表1に示す配合組成に従い、(A)、(B)、(C)成分、ならびにその他添加剤全てを二軸押出機の元込め部から供給し、(D)成分を主投入口と押出機先端の間に設置した副投入口から供給してシリンダ温度250℃に設定したスクリュー径37mmφの二軸押出機(東芝機械(株)社製TEM37SS(商品名))で溶融混練を行った。ダイスから吐出されたストランドを冷却バス内で冷却した後、ストランドカッターにてペレット化し、樹脂組成物を得た。得られた樹脂組成物について、上記方法で評価した結果を表1に記した。なお、実施例5および実施例6は参考例である。
Claims (9)
- (A)熱可塑性ポリエステル樹脂100重量部に対し、(B)カーボンブラックを0.05~1重量部、ならびに(C)エポキシ化合物を0.1~5重量部配合してなり、前記(C)エポキシ化合物が、ノボラック型エポキシ化合物である高周波通信機器部品用熱可塑性ポリエステル樹脂組成物。
- (A)熱可塑性ポリエステル樹脂100重量部に対し、更に(D)繊維状強化材を15~100重量部配合してなる、請求項1に記載の高周波通信機器部品用熱可塑性ポリエステル樹脂組成物。
- 前記(C)エポキシ化合物のエポキシ当量が800g/eq以下である、請求項1または2に記載の高周波通信機器部品用熱可塑性ポリエステル樹脂組成物。
- 前記(C)エポキシ化合物が、一般式(2)で表されるノボラック型エポキシ化合物である請求項1~3のいずれかに記載の高周波通信機器部品用熱可塑性ポリエステル樹脂組成物。
- 請求項1~4のいずれかに記載の高周波通信機器部品用熱可塑性ポリエステル樹脂組成物からなる高周波通信機器部品。
- 高周波通信機器のコネクタである、請求項5に記載の高周波通信機器部品。
- 高周波通信機器の筐体である、請求項5に記載の高周波通信機器部品。
- 高周波通信機器のアンテナカバーである、請求項5に記載の高周波通信機器部品。
- 前記高周波通信機器部品が車載通信機器の部品である、請求項5に記載の高周波通信機器部品。
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