JPWO2019049668A1 - 組成物及び難燃性樹脂組成物 - Google Patents
組成物及び難燃性樹脂組成物 Download PDFInfo
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- JPWO2019049668A1 JPWO2019049668A1 JP2019540874A JP2019540874A JPWO2019049668A1 JP WO2019049668 A1 JPWO2019049668 A1 JP WO2019049668A1 JP 2019540874 A JP2019540874 A JP 2019540874A JP 2019540874 A JP2019540874 A JP 2019540874A JP WO2019049668 A1 JPWO2019049668 A1 JP WO2019049668A1
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Classifications
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
Description
しかしながら、前述した従来の難燃剤は、加工成形性とドリップ防止効果とを両立させるという観点において、十分なものではなかった。
本発明は、前記の知見に基づくものであり、下記(A)成分、下記(B)成分及び下記(C)成分を含有する組成物を提供するものである。
(A)成分:オルトリン酸メラミン、ピロリン酸メラミン及びポリリン酸メラミンよりなる群から選択される少なくとも1種のメラミン塩。
(B)成分:オルトリン酸ピペラジン、ピロリン酸ピペラジン及びポリリン酸ピペラジンよりなる群から選択される少なくとも1種のピペラジン塩。
(C)成分:アルミナの一水和物。
更に本発明は、前記(A)成分、前記(B)成分及び前記(C)成分を含有する組成物の難燃剤としての使用を提供するものである。
なお、以下の説明において、難燃性とは、物質が着火しにくく、また着火して燃焼が持続してもその速度が非常に遅かったり、その後、自己消火したりする性質であること、好ましくは実施例に記載されているUL−94V規格に従った燃焼ランクのうち、少なくともV−2のランクを有することを意味し、より好ましくはV−1又はV−0のランクを有することを意味する。難燃剤組成物とは、難燃剤の1種以上を含有する組成物を意味する。難燃性樹脂組成物とは、前記の難燃性を有し、且つ合成樹脂を少なくとも1種含有する組成物を意味する。
これらリン酸とメラミンとの塩は、それぞれ対応するリン酸又はリン酸塩とメラミンを反応させることによって得ることができる。特に、本発明の(A)成分で使用されるメラミン塩は、オルトリン酸メラミンを加熱縮合させて得られたピロリン酸メラミン又はポリリン酸メラミンが好ましく、特にピロリン酸メラミンが好ましい。
本発明の組成物は(C)成分としてアルミナの一水和物を用いることに特徴の一つを有する。
従来、アルミナの一水和物は水酸化アルミニウムに比べて吸熱分解に要するエネルギーがかなり低いことが知られており、難燃作用は劣るとされていた。しかしながら、驚くべきことに、アルミナの一水和物を、上述した(A)成分及び(B)成分と併用することにより、樹脂に良好な難燃性能及び加工成形性を付与することができるという顕著な効果が奏されることが本発明者の検討の結果判明した。
これらの成分は本発明の組成物にあらかじめ配合することができ、合成樹脂に配合するときに合成樹脂に配合することができる。これらを配合することにより合成樹脂を安定化することが好ましい。
これらのフェノール系酸化防止剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.01〜1.0質量部がより好ましい。
これらのホスファイト系酸化防止剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.01〜1.0質量部がより好ましい。
これらのチオエーテル系酸化防止剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.01〜1.0質量部がより好ましい。
これらのその他の酸化防止剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.01〜1.0質量部がより好ましい。
これらの紫外線吸収剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.05〜0.5質量部がより好ましい。
これらの光安定剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.005〜0.5質量部がより好ましい。
これらの可塑剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.1〜500質量部が好ましく、1〜100質量部がより好ましい。
これらの充填剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、1〜100質量部が好ましく、3〜80質量部がより好ましい。
これらの脂肪酸金属塩の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.001〜5質量部が好ましく、0.05〜3質量部がより好ましい。
これらの帯電防止剤の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.01〜20質量部が好ましく、3〜10質量部がより好ましい。
これらの顔料の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.0001〜10質量部が好ましい。
これらの染料の使用量は、樹脂に配合したときに、難燃性樹脂組成物100質量部中、0.0001〜10質量部が好ましい。
これら樹脂は、1種でも2種以上を使用してもよい。また樹脂はアロイ化されていてもよい。
また、熱可塑性ポリウレタン樹脂は、その成形方法により、液状で型に注入・硬化反応させる注型タイプ、従来のゴムと同じくロール混練後プレス成形するタイプ及び一般熱可塑性樹脂と同様に加工できるタイプに大別できるが、本発明では、それらを区別するものではない。
下記表1及び2記載の成分のうち、樹脂以外の成分を当該成分表に記載の割合で配合し、ヘンシェルミキサーを用いて混合した。組成物に(E)成分(エポキシ系カップリング剤、滑剤及び/又はシリコーンオイル)を配合する場合には、(E)成分以外の成分を予備混合した後に、(E)成分を添加してヘンシェルミキサーを用いて混合し、組成物を得た。
・実施例1〜6及び比較例1〜6
熱可塑性ポリウレタン樹脂(BASF製 Elastollan 1185A)100質量部にステアリン酸カルシウム0.1質量部、グリセリンモノステアレート0.3質量部、テトラキス[3−(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオン酸メチル]メタン0.1質量部、2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)−2−エチルヘキシルホスファイト0.1質量部を配合し、ヘンシェルミキサーにて予備混合して熱可塑性ポリウレタン樹脂組成物を得た。得られた熱可塑性ポリウレタン樹脂組成物に対して、表1又は2に示す組成物を表に記載の質量部配合し、ヘンシェルミキサーで混合し樹脂組成物を得た。
ポリプロピレン(JIS K7210に準拠して測定された、荷重2.16kg、230℃におけるメルトフローレート=8g/10min)100質量部に、ステアリン酸カルシウム(高級脂肪酸金属塩)0.1質量部、テトラキス[3−(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオン酸メチル]メタン(フェノール系酸化防止剤)0.1質量部、トリス(2,4−ジ−第三ブチルフェニル)ホスファイト(リン系酸化防止剤)0.1質量部を配合し、ヘンシェルミキサーにて予備混合してポリプロピレン樹脂組成物を得た。得られたポリプロピレン樹脂組成物に対して、表1又は表2に示す組成物を表に記載の質量部配合し、ヘンシェルミキサーで混合し樹脂組成物を得た。
<難燃性評価>
熱可塑性ポリウレタン樹脂を含有する実施例1〜6の樹脂組成物及び比較例1〜6の樹脂組成物を、二軸押出成形機(株式会社日本製鋼所製;TEX−30α)を用いて、シリンダー温度190〜200℃、及びスクリュー速度150rpmの条件で溶融混練した。ダイスから吐出されたストランドを冷却バスにより冷却し、ペレタイザーにて切断することにより、樹脂組成物のペレットを作製した。
前記で得られた樹脂組成物のペレットを、日精樹脂工業社製;NEX−80を用いて射出成形を行い、長さ100mm×100mm、厚さ3mmの成形体を得た。この射出成形を30ショット行った後に、金型表面のモールドデポジットを目視観察し、下記の基準で評価した。実施例1〜6及び比較例1〜6については、スクリュー設定温度を180℃とし、金型温度を40℃とした。実施例7〜12及び比較例7〜12については、スクリュー設定温度を230℃とし、金型温度を40℃とした。
○:金型表面にモールドデポジットが全く観察されない
△:金型表面にモールドデポジットが若干観察される
×:金型表面に著しいモールドデポジットが観察される。
以上の結果から、本発明の組成物が、高い難燃性及び成形性を樹脂に付与でき、難燃剤として優れていることが判る。
Claims (9)
- 下記(A)成分、下記(B)成分及び下記(C)成分を含有する組成物。
(A)成分:オルトリン酸メラミン、ピロリン酸メラミン及びポリリン酸メラミンよりなる群から選択される少なくとも1種のメラミン塩。
(B)成分:オルトリン酸ピペラジン、ピロリン酸ピペラジン及びポリリン酸ピペラジンよりなる群から選択される少なくとも1種のピペラジン塩。
(C)成分:アルミナの一水和物。 - 前記(A)成分及び前記(B)成分の合計100質量部に対して、前記(C)成分を0.1〜20質量部含有する、請求項1記載の組成物。
- 更に(D)成分:酸化亜鉛を、前記(A)成分と前記(B)成分との合計100質量部に対して0.01〜10質量部含有する、請求項1又は2記載の組成物。
- 更に(E)成分:シリコーンオイル、エポキシ系カップリング剤、ハイドロタルサイト及び滑剤からなる群から選ばれる少なくとも1種を、前記(A)成分と前記(B)成分との合計100質量部に対して0.01〜5質量部含有し、樹脂に混合されて使用される、請求項1〜3の何れか1項に記載の組成物。
- 請求項1〜4の何れか1項に記載の組成物を含有する難燃剤。
- 樹脂100質量部に対して請求項5に記載の難燃剤を10〜400質量部含有する難燃性樹脂組成物。
- 請求項6記載の難燃性樹脂組成物の成形品。
- 下記(A)成分、下記(B)成分及び下記(C)成分を含有する組成物を、樹脂と混合する、樹脂の難燃化方法。
(A)成分:オルトリン酸メラミン、ピロリン酸メラミン及びポリリン酸メラミンよりなる群から選択される少なくとも1種のメラミン塩。
(B)成分:オルトリン酸ピペラジン、ピロリン酸ピペラジン及びポリリン酸ピペラジンよりなる群から選択される少なくとも1種のピペラジン塩。
(C)成分:アルミナの一水和物。 - 下記(A)成分、下記(B)成分及び下記(C)成分を含有する組成物の難燃剤としての使用。
(A)成分:オルトリン酸メラミン、ピロリン酸メラミン及びポリリン酸メラミンよりなる群から選択される少なくとも1種のメラミン塩。
(B)成分:オルトリン酸ピペラジン、ピロリン酸ピペラジン及びポリリン酸ピペラジンよりなる群から選択される少なくとも1種のピペラジン塩。
(C)成分:アルミナの一水和物。
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US11674037B2 (en) | 2023-06-13 |
CN111032829B (zh) | 2022-03-22 |
CN111032829A (zh) | 2020-04-17 |
KR102573165B1 (ko) | 2023-09-01 |
EP3680310A4 (en) | 2021-05-12 |
KR20200051592A (ko) | 2020-05-13 |
JP7158389B2 (ja) | 2022-10-21 |
WO2019049668A1 (ja) | 2019-03-14 |
US20200165448A1 (en) | 2020-05-28 |
TW201920634A (zh) | 2019-06-01 |
EP3680310B1 (en) | 2024-10-02 |
EP3680310A1 (en) | 2020-07-15 |
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