JP2021521287A - ワイヤおよびケーブルコーティング用発泡ポリオレフィン組成物 - Google Patents
ワイヤおよびケーブルコーティング用発泡ポリオレフィン組成物 Download PDFInfo
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Abstract
Description
(A)55〜94.98重量%の熱可塑性ポリマーと、
(B)5〜44.98重量%の湿気硬化性ポリマーと、
(C)0.01〜5重量%の湿気縮合触媒と、
(D)0.01〜5重量%の発泡剤と、を含む、溶融ブレンド組成物である。
米国特許実務を目的として、いかなる参照される特許、特許出願、または刊行物の内容も、特に定義の開示(本開示に具体的に提供されるいかなる定義にも矛盾しない範囲で)、および当該技術分野における一般的知識に関して、それらの全体において参照により組み込まれる(または、その同等の米国版が参照によりそのように組み込まれる)。
加熱すると軟化する任意のポリマーは、本発明の実施に使用され得る熱可塑性ポリマーである。そのようなポリマーには、ポリオレフィン、ポリエステル、ポリアミド、ポリ塩化ビニル(PVC)、ポリスチレン、ポリテトラフルオロエチレン(PTFE)などが含まれる。
本発明の実施において使用される湿気硬化性ポリオレフィンは、シラン官能基を有するポリオレフィンである。シラン官能基は、共重合および/またはグラフト化によってポリオレフィンの中または上に導入することができる。
湿気縮合触媒、または単に架橋触媒には、ルイスおよびブレンステッド酸および塩基が含まれる。ルイス酸は、ルイス塩基からの電子対を受け入れることができる化学種である。ルイス塩基は、電子対をルイス酸に供与することができる化学種である。本発明の実施において使用され得るルイス酸には、ジブチルスズジラウレート(DBTDL)などのカルボン酸スズ、ジメチルヒドロキシスズオレエート、ジオクチルスズマレエート、ジ−n−ブチルスズマレエート、ジブチルスズジアセテート、ジブチルスズジオクトエート、酢酸第一スズ、オクタン酸第一スズ、ならびにナフテン酸鉛、カプリル酸亜鉛、およびナフテン酸コバルトなどの様々な他の有機金属化合物が含まれる。DBTDLは、好ましいルイス酸である。本発明の実施において使用され得るルイス塩基には、これらに限定されないが、第一級、第二級、および第三級アミンが含まれる。
本発明の実施において使用される発泡剤は、典型的には膨張剤である。好適な膨張剤には、様々な低沸点クロロフルオロカーボン、フルオロカーボン、および炭化水素、ならびに二酸化炭素、窒素などのような物理膨張剤が含まれる。低いまたはゼロの地球温暖化およびオゾン破壊係数を有するフルオロカーボンおよび炭化水素は、物理膨張剤の中でも好ましい。熱可塑性ポリマーおよび湿気硬化性ポリオレフィンが溶融ブレンドされる条件下で分解または反応しない化学膨張剤もまた有用である。そのような化学膨張剤は、発泡ステップの間に分解する(溶融ブレンドステップの後に続く)。一般的な化学膨張剤は、アゾジカルボンアミド(ADC)である。化学膨張剤はまた、1つ以上の物理発泡剤、例えば、二酸化炭素、空気、窒素、またはアルゴンと組み合わせて使用され得る。
本発明の組成物は、1つ以上の充填剤および/または添加剤を含むことができる。存在する充填剤の量は、好ましくは、湿気硬化性組成物の機械的および/または化学的特性の許容不能に大きな劣化を引き起こすであろう量を超えるべきではない。典型的には、存在する充填剤の量は、組成物の重量に基づいて、2〜35、好ましくは5〜20重量パーセント(重量%)である。代表的な充填剤には、補強剤としてまたはUV安定化のためのいずれかで、カオリン粘土、水酸化マグネシウム、シリカ、炭酸カルシウム、およびカーボンブラックが挙げられる。充填剤は、難燃特性を有していても、または有していなくてもよい。充填剤が存在する場合の本発明の好ましい一実施形態では、充填剤は、充填剤がさもないとシラン硬化反応を妨げかねない可能性があるいかなる傾向も防止または遅延させる材料でコーティングされる。ステアリン酸は、そのような充填剤コーティングの例示である。充填剤および触媒は、あらゆる望ましくない相互作用および反応も回避するように選択され、この選択は、当該技術の範囲内で良好である。
熱可塑性ポリマー、湿気硬化性ポリマー、縮合触媒、発泡剤、ならびに最適な充填剤および添加剤の化合は、当業者に既知の標準的な手段によって実施することができる。化合機器の例は、BANBURY(商標)またはBOLLING(商標)内部ミキサーなどの内部バッチミキサーである。代替として、FARREL(商標)連続ミキサー、WERNER AND PFLEIDERER(商標)二軸スクリューミキサー、またはBUSS(商標)混練連続押出機などの、連続一軸もしくは二軸スクリューミキサーまたは押出機が使用され得る。使用するミキサーのタイプ、およびミキサーの動作条件は、粘度、発泡密度、体積抵抗率、押出表面平滑性などの組成物の特性に影響を与える。
一実施形態では、本発明の発泡組成物は、既知の量および既知の方法によって(例えば、USP5,246,783および4,144,202に記載される機器および方法を用いて)、保護ジャケットまたは絶縁層としてケーブルに適用することができる。典型的には、組成物は、ケーブルコーティング用ダイを備える反応器−押出機内で調製され、組成物の構成成分が配合された後、ケーブルがダイから引き出される際に、組成物は、ケーブル上に押出される。硬化は、反応器−押出機中で開始することができる。
密度について測定される試料を、ASTM D1928に従って調製する。試料を、374°F(190℃)および30,000psiで3分間、次いで70°F(21℃)および30,000psiで1分間圧縮する。ASTM D792、方法Bを使用して、1時間以内の試料加圧で密度測定を行う。
DFH2065は、0.920g/cm3の密度および0.65g/10分のメルトインデックス(190℃/2.16kg)を有する粒状の線状低密度ポリエチレン(LLDPE)である。
過酸化物修飾LLDPE溶融混合/溶融化合:樹脂バッチを、Cam Bladesを備えた250ccのBRABENDER(商標)モデルPrep Mixer/Measuring Head実験室電気バッチミキサーを使用して調製した。BRABENDER(商標)Mixer/Measuring Headは、ミキサーブレード構造に依存して250ミリリットル(ml)の容量を有する2つの加熱ゾーンからなる3点設計である。バッチごとに混合された配合物は、280グラム(g)の樹脂、0.15gの過酸化物(TRIGONOX(商標)101)、および1.5gの膨張剤マスターバッチ(MB)である。ブレードを1分当たり20回転(rpm)で回転させながら、各混合の実行を、最初にLLDPE樹脂を混合ボウルに添加することによって開始した。両方のゾーンのプロセス温度設定点は、130℃であった。過酸化物を活性化するために、温度を200℃に上昇させた。トルク読取りが、全ての過酸化物が反応したことを示す安定になった後、温度を130℃に低下させ、一旦達成されると、膨張剤を添加した。混合サイクルの持続期間は、25分であった。次いで、溶融材料を回収して、2つのMYLAR(商標)ポリエステルシートの間に配置し、室温で平坦なパンケーキに圧縮成型し、次いで、ワイヤライン押出のために小片に切断した。
1秒当たり100ラジアン(rad/秒)で表2ならびに図1および2に示されるように、本発明のブレンドは、組成物全体の均一な過酸化物処理を介して達成されるものよりも高い溶融強度の増加を示す、より低い剪断速度でより高い粘度を呈する。対照的に、加工性のためにより低い粘度が望ましい高剪断速度で、本発明の化合物の粘度は、500ppmのそのような低い過酸化物レベルでも著しく影響されず、過酸化物処理組成物よりも低くない。過酸化物の量を増加させることは、実質的に粘度を増加させる。溶融強度を増加させることに対するこのアプローチは、とりわけ、HDPEおよびポリプロピレン(PP)などのより低い溶融強度材料を発泡することにおいて有用であり得る。本発明の方法はまた、化学膨張剤の分解に直面する一方で、過酸化物分解を確実にし、したがって2段階化合プロセスを必要とするため、それが高溶融温度を達成する必要性に関連する問題を排除するために、過酸化物アプローチよりも利点を有する。本発明の方法は、対照的に、本質的に制限されず、硬化ステップがペレット化された材料で開始するため、すなわち、化合後であるため、良好な溶融混合に好都合な温度、および膨張剤の分解温度をはるかに下回る温度での化合を可能にする。
CE−4は、完全に架橋された非発泡システムであり、典型的な湿気硬化性シランコポリマーを表す。注釈2aのように、化合後に材料をペレット化し、次いで、硬化させた。この化合物は、CE−5での使用のために調製し、熱可塑性ではないため、それ自体では押出可能ではない。
Claims (13)
- 溶融ブレンド組成物であって、前記組成物の重量に基づく重量パーセント(重量%)で、
(A)55〜94.98重量%の熱可塑性ポリマーと、
(B)5〜44.98重量%の湿気硬化性ポリマーと、
(C)0.01〜5重量%の湿気縮合触媒と、
(D)0.01〜5重量%の発泡剤と、を含む、溶融ブレンド組成物。 - 前記熱可塑性ポリマーが、ポリオレフィンである、請求項1に記載の組成物。
- 前記熱可塑性ポリマーが、ポリエチレンである、請求項1に記載の組成物。
- 前記湿気硬化性ポリマーが、シラン官能化ポリオレフィンである、請求項1〜3のいずれかに記載の組成物。
- 前記縮合触媒が、ルイス酸またはルイス塩基である、請求項1〜4のいずれかに記載の組成物。
- 前記縮合触媒が、ジブチルスズジラウレートである、請求項1〜5のいずれかに記載の組成物。
- 前記縮合触媒が、スルホン酸である、請求項1〜6のいずれかに記載の組成物。
- 前記発泡剤が、化学発泡剤である、請求項1〜7のいずれかに記載の組成物。
- 前記発泡剤が、物理発泡剤である、請求項1〜8のいずれかに記載の組成物。
- 前記発泡剤が、二酸化炭素または窒素を含む、請求項1〜9のいずれかに記載の組成物。
- 請求項1〜10のいずれかに記載の架橋組成物。
- 請求項1〜11のいずれかに記載の組成物を含む、ワイヤまたはケーブルシース。
- 請求項8に記載のシースを含む、ワイヤまたはケーブル。
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PCT/US2019/027031 WO2019209547A1 (en) | 2018-04-27 | 2019-04-11 | Foamed polyolefin compositions for wire and cable coating |
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WO2024031618A1 (en) * | 2022-08-12 | 2024-02-15 | Dow Global Technologies Llc | Ethylene/alpha-olefin interpolymer compositions for extrusion applications |
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