JP5394836B2 - 難燃及び衝撃改質剤、その製造方法、並びにそれを含む熱可塑性樹脂組成物 - Google Patents
難燃及び衝撃改質剤、その製造方法、並びにそれを含む熱可塑性樹脂組成物 Download PDFInfo
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- JP5394836B2 JP5394836B2 JP2009159245A JP2009159245A JP5394836B2 JP 5394836 B2 JP5394836 B2 JP 5394836B2 JP 2009159245 A JP2009159245 A JP 2009159245A JP 2009159245 A JP2009159245 A JP 2009159245A JP 5394836 B2 JP5394836 B2 JP 5394836B2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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Description
これまでに、熱可塑性樹脂の難燃化のためにハロゲン系化合物とアンチモン系化合物を適用して難燃性を付与する方法がよく知られている。ハロゲン系化合物としては、ポリブロモジフェニルエーテル、テトラブロモビスフェノールA、臭素置換されたエポキシ化合物及び塩素化ポリエチレンなどがよく利用されている。アンチモン系化合物としては、三酸化アンチモンと五酸化アンチモンが主に用いられている。
本発明のホスフェート化合物は、下記化学式1で表されるように、トリフェノールホスフェートのひとつのフェニル基において、t−ブチル基が特定の位置に存在することを特徴とする。
本発明の他の形態においては、前記難燃及び衝撃改質剤を含む熱可塑性樹脂組成物を提供する。
オキシ塩化リン(767g、5.0mol)、2,4−ジ−tert−ブチルフェノール(206g、1mol)及びマグネシウムクロライド(1g、0.01mol)を容器に入れて、窒素雰囲気下、130℃で6時間攪拌した。容器温度を90℃に冷却し、減圧して残オキシ塩化リンを回収し、フェノール(188g、2mol)とトルエン(1L)を追加して窒素雰囲気下、130℃で5時間攪拌した。反応終了後、温度を室温まで冷却し、水(1L)を追加して攪拌し、有機層を取った後、減圧蒸留して純度98%以上、収率95%の2,4−ジ−tert−ブチルフェニルジフェニルホスフェートを得た。
ゴム変性スチレン樹脂(HIPS、HG−1760S、第一毛織(株)製造)75重量部と三菱エンジニアリングプラスチックス社製のポリ(2,6−ジメチル−フェニルエーテル)(PPE商品名:PX−100F)25重量部とからなるブレンドに、前記製造例で製造された2,4−ジ−tert−ブチルフェニルジフェニルホスフェートを下記表1の比率で投入し、通常の二軸押出器で200〜280℃の温度範囲で押出してペレットを製造した。製造されたペレットを80℃で2時間乾燥した後、射出器で成形温度180〜280℃、金型温度40〜80℃の条件で射出して難燃試片を製造した。製造した試片は、UL94VB難燃規定により1/8″の厚さで難燃度を測定し、衝撃強度は、アイゾット衝撃試験ASTM D256(1/8″ノッチ、kgf・cm/cm)に準じた。
<実施例2〜3>
基材樹脂をポリカーボネート樹脂(帝人化成(株)製のPanlite L−1225 Grade)を用いて、2,4−ジ−tert−ブチルフェニルジフェニルホスフェートの含量を下記表1に示す量に変更した以外は、前記実施例1と同様に行った。
基材樹脂をポリカーボネート樹脂(帝人化成(株)製のPanlite L−1225 Grade)とABS(g−ABS/SAN=3/7、g−ABSは第一毛織(株)製のCHT、SANは第一毛織(株)製のAP−70)を用いて、2,4−ジ−tert−ブチルフェニルジフェニルホスフェートの含量を下記表1に示す量に変更した以外は、前記実施例1と同様に行った。
下記表1に表した組成で、難燃剤としてトリフェニルホスフェート(大八化学工業株式会社製)を用いた以外は、前記実施例1と同様に行った。測定の結果を全て表1に示す。
難燃剤として2,4,6−トリメチルフェニルジフェニルホスフェートを用いた以外は、前記実施例1〜4と同様に行った。測定の結果を表2に示す。
Claims (11)
- 下記化学式1で表される、難燃及び衝撃改質剤。
- オキシ塩化リンと2,4−ジ−tert−ブチルフェノールとを反応させて2,4−ジ−tert−ブチルフェニルジクロロホスフェートを製造し;及び
前記2,4−ジ−tert−ブチルフェニルジクロロホスフェートにフェノールを反応させる;
段階を含んでなる下記化学式1で表される難燃及び衝撃改質剤の製造方法。
- 前記2,4−ジ−tert−ブチルフェノール1当量に対してオキシ塩化リン3〜6当量を反応させる、請求項2に記載の方法。
- 前記2,4−ジ−tert−ブチルフェニルジクロロホスフェート1当量に対してフェノール2〜4当量を反応させる、請求項2または3に記載の方法。
- 熱可塑性樹脂100重量部;及び
下記化学式1で表される難燃及び衝撃改質剤0.1〜30重量部;
を含んでなる、熱可塑性樹脂組成物。
- 前記熱可塑性樹脂は、ポリスチレン、スチレン−アクリロニトリル共重合体樹脂(SAN)、ゴム変性ポリスチレン樹脂(HIPS)、ゴム変性芳香族ビニル共重合体樹脂、ASA樹脂、MABS樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、ポリ(メタ)アクリル樹脂、ポリアミド樹脂及びポリビニルクロライド樹脂よりなる群から一つ以上選択される、請求項5に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂は、ゴム変性ポリスチレン樹脂70〜99重量%及びポリフェニレンエーテル樹脂1〜30重量%からなることを特徴とする、請求項6に記載の熱可塑性樹脂組成物。
- UL94難燃度(1/8″)がV−1またはV−0であり、ASTM D256により測定した衝撃強度(1/8″ノッチ)が10〜50kgf・cm/cmである、請求項7に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂は、ポリカーボネート樹脂であり、樹脂組成物のUL94難燃度(1/8″)がV−0であり、ASTM D256により測定した衝撃強度(1/8″ノッチ)が58〜80kgf・cm/cmであることを特徴とする、請求項6に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂は、ポリカーボネート樹脂55〜90重量%及びゴム変性芳香族ビニル共重合体樹脂10〜45重量%からなり、樹脂組成物のUL94難燃度(1/8″)がV−1またはV−0であり、ASTM D256により測定した衝撃強度(1/8″ノッチ)が55〜70kgf・cm/cmであることを特徴とする、請求項6に記載の熱可塑性樹脂組成物。
- 熱安定剤、滑剤、離型剤、可塑剤、帯電防止剤、難燃補助剤、滴下防止剤、酸化防止剤、相溶化剤、光安定剤、顔料、染料及び無機物充填剤よりなる群から選択される少なくとも一つ以上の添加剤をさらに含むことを特徴とする、請求項6〜10のいずれか1項に記載の熱可塑性樹脂組成物。
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US20130081850A1 (en) | 2011-09-30 | 2013-04-04 | Ticona Llc | Fire-Resisting Thermoplastic Composition for Plenum Raceways and Other Conduits |
US9260602B2 (en) | 2012-10-11 | 2016-02-16 | Sabic Global Technologies B.V. | Antistatic flame retardant resin compositions and methods and uses thereof |
US20150004402A1 (en) * | 2013-06-28 | 2015-01-01 | Sabic Innovative Plastics Ip B.V. | Intumescent coating composition comprising particulate poly(phenylene ether) |
US20150028247A1 (en) | 2013-07-23 | 2015-01-29 | Sabic Innovative Plastics Ip B.V. | Rigid foam and associated article and method |
US9447227B2 (en) | 2013-10-03 | 2016-09-20 | Sabic Global Technologies B.V. | Flexible polyurethane foam and associated method and article |
CN109280286A (zh) * | 2018-09-21 | 2019-01-29 | 浙江宏博新型建材有限公司 | 一种高韧性中流动流延膜用asa粒料 |
CN110698864A (zh) * | 2019-11-01 | 2020-01-17 | 兰飞 | 一种5g pps薄膜及其制备方法 |
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JPS6270380A (ja) * | 1985-09-24 | 1987-03-31 | Mitsubishi Kasei Vinyl Co | アルキルジアリ−ルホスフエ−トの合成方法 |
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JPH0940867A (ja) * | 1995-07-31 | 1997-02-10 | Ajinomoto Co Inc | 難燃性シリコーン組成物 |
JPH107690A (ja) * | 1996-06-20 | 1998-01-13 | Teijin Chem Ltd | 芳香族モノ置換ジクロロホスフェイト類の製造方法 |
GB9802181D0 (en) | 1998-02-03 | 1998-04-01 | Fmc Corp Uk Ltd | Polymer compositions |
KR20010009104A (ko) | 1998-07-10 | 2001-02-05 | 유현식 | 난연성 열가소성 수지조성물 |
JP2000344939A (ja) * | 1999-06-02 | 2000-12-12 | Polyplastics Co | 難燃性樹脂組成物 |
JP2001247583A (ja) * | 2000-03-09 | 2001-09-11 | Teijin Chem Ltd | 芳香族モノ置換ジクロロホスフェート類の製造方法 |
EP1403272B1 (en) * | 2001-06-08 | 2006-05-24 | Daihachi Chemical Industry Co., Ltd. | Process for preparation of phosphoric esters |
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KR100767428B1 (ko) * | 2006-04-14 | 2007-10-17 | 제일모직주식회사 | 내스크래치성을 갖는 난연성 열가소성 수지 조성물 |
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CA2672342A1 (en) * | 2006-12-11 | 2008-06-19 | The Governors Of The University Of Alberta | Mercury adsorption using chabazite supported metallic nanodots |
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