TW470770B - A flame retardant, halogen-free polymer composition - Google Patents

A flame retardant, halogen-free polymer composition Download PDF

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TW470770B
TW470770B TW087114913A TW87114913A TW470770B TW 470770 B TW470770 B TW 470770B TW 087114913 A TW087114913 A TW 087114913A TW 87114913 A TW87114913 A TW 87114913A TW 470770 B TW470770 B TW 470770B
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weight
blend
vinyl acetate
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density polyethylene
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TW087114913A
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Duran Juan-Antonio Garcia
Loic Pierre Rolland
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Du Pont
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    • C08K5/00—Use of organic ingredients
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    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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    • C08L23/0853—Vinylacetate
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    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
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    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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Description

470770
五、發明說明（1) [發明背景] [發明範疇] 而更特定言之，係關 ’以及一種由其製成 本發明係關於一種聚稀烴組合物， 於不含i素且為阻燃性的那種組合物 之成形物件。 [背景討論] —聚氯乙烯（PVC)產品已上市多年，並且常常用於多種不 2的應用。由於不含氯之環境的傾向，所以某些市 ^，建造和電線電纜等工業）需要PVW替代物。數m =素之阻燃性化合物已在市場上供應，但需要困難的混人 方法。雖然這些化合物常常必須由專門的化合專家來 造，，但是電線電纜和地板瓷磚造者本身經常不具有專門 知識。 對電線電纜應用而言，不含鹵素之阻燃性物質係提供低 電壓電纜絕緣作用和護套作用二者所想要的，該低電壓電 纜係應用在著火時，必須避免產生有毒氣體之地方。此種 使用不含鹵素之低電壓電纜的地方包括旅館、醫院、學 校、劇院及其他此種公開場所。 護套物質之重要特徵為’其有高度阻燃性、 能和良好的物理性質。 ' 美國專利字號4, 948, 669、4, 430, 468、4, 434, 258、 4’673, 620、4, 701’359揭示一種不含pvc之組合物，其遁 合使用作為電纜之被覆物。這些組合物包含數種與本文說 明的那些類似之組份，但是缺少本文中說明過的^聚物。
470770 案號 87114913 J.1 : 修 *^，-ϊ上，.;·· ./ 補尤 ---- 平 《 五、發明說明（2) [發明概述] 根據本發明，所提供的係一種阻燃性、不含齒素之組合 物，其包含由下列各物所組成之掺合物： (1) 乙烯乙酸乙烯酯一氧化碳三聚物，其包含30-90重量 %乙烯、1 0 - 7 0重量％乙酸乙烯酯和1 - 4 0重量％ —氧化碳； (2) 選自下列各物之乙烯乙酸乙烯酯或聚烯烴：（a)包含 25-90重量％乙烯和10-75重量％乙酸乙烯酯之乙烯乙酸乙烯 酯，（b)線性低密度聚乙烯，（c)低密度聚乙烯，（d)非常 低密度聚乙烯和（e )高密度聚乙烯；及其混合物； (3) 選自下列各物之乙烯乙酸乙烯酯或聚烯烴：（a)包含 2 5 - 9 0重量％乙烯和1 0 - 7 5重量％乙酸乙烯酯之乙烯乙酸乙烯 酯，（b)線性低密度聚乙烯，（c)低密度聚乙烯，（d)非常 低密度聚乙烯和（e)高密度聚乙烯；及其混合物；其之每 一種皆以0 . 0 5 - 3重量％的其羧酸或酸酐接枝；和 (4 )無機填料。 可包含在本發明之組合物中的普通添加劑，包括抗氧化 劑，二氧化鈦（抗U V劑並使產物成為白色），加工助劑 (像，硬醋酸鋅）和U V安定劑。 [發明之詳細說明]
本發明係關於一種阻燃性、不含i素之熱塑性聚合物摻 合物，其可用為電線電纜被覆物或以薄片形狀使用，例 如，用在地板瓷磚。這些摻合物一般係，由使下列各物化 合而形成：乙烯乙酸乙烯酯一氧化碳（EVACO)三聚物；選 自下列各物之乙烯乙酸乙烯酯（E V A)共聚物或聚烯烴：EV A
O:\54\54236.ptc 第6頁 2000.11.06.006 470770 五、發明說明（3) ' 共聚物、線性低密度聚乙烯、低密度聚乙烯、非常低密声 聚乙烯、高密度聚乙烯及其混合物；選自下列各物之己^ 乙酸乙烯酯（EVA)共聚物或聚烯烴·· EVA共聚物、線性低密 度聚乙烯、低密度聚乙烯、非常低密度聚乙烯、高密度聚 乙烯及其混合物，其之每一種皆以其羧酸或酸酐接枝；和 無機填料。 根據本發明之聚合物摻合物可形成電線電纜被覆物或 供，例如，地板瓷磚使用之薄片形狀，並且具有許多比夺曰 上包含聚氣乙烯（PVC)之#合物的性質，但是不含_素。子 除另有說明外，本發明之組合物中的每一種組份之重息 百分比範圍的計算皆不含可存在的任何添加物。 本發明中使用的EVAC0三聚场飞組份（1))較佳係包含 30-90重量％乙烯、10-70重量％乙酸乙烯酯和1-2〇重量。/q — 氧化碳，更隹係55-65重量％乙烯和20-30重量％乙酸乙歸妒 及5-15重量％ —氧化碳。一般，這些EVAC〇的溶化流動指^ (MFI)在1-50克/10分鐘範圍内，較佳係在1〇一4〇克/1〇分铲 範圍内，其係由ASTM D- 123 8 (在2, 16公斤和190 °C下測里 量）來測定並且係此藝中悉知的。 組份（1)較佳係組成本發明之組合物的丨_ 6 〇重量％，更佳 係5 —25重量％，還要佳係5-1 5重量％。 當在本發明中使用作為組份（2)時，EVA共聚物較佳包含 25-90重量％乙烯和1〇 —75重量％乙酸乙烯酯，更佳係5卜^ 重量％乙烯和15_30重量％乙酸乙烯酯。一般，這些eva的、、容 化流動指數（MFI)在0.05_100克/1〇分鐘範圍内，較佳係少
D:\Y87\54236. ptd 第 7 頁一·~~------
470770 五'發明說明（4) 於50克/10分鐘，其係由ASTM d- 1 23 8 (在2, 16公斤和190 °C下測量）來測定並且係此藝中悉知的。 當使用作為組份（2)時，聚烯烴之溶化流動指數（MFI ) — 般將在0.05- 100克/1〇分鐘範圍内，較佳係少於50克/1〇分 鐘’其係由ASTM D-1 238 (在2，16公斤和19(TC下測量）來 測定並且係此藝中悉知的。 組份（2)較佳係組成本發明之組合物的卜“重量％，更佳 係5-25重量％，還要佳係1〇_2〇重量％。 ’ 組份（3 )和組份（2 )之定義相同，但是還要以〇 · 〇 5 - 3重量 %的其羧酸或酸酐（較佳係順-丁烯二酸酐）接枝。一般，組 份（3)之溶化流動指數（mfi)將在0.05-100克/10分鐘範圍 内，較佳係少於20克/1〇分鐘7其係由ASTM d-1 238 (在2, 1 6公斤和1 9 0 °C下測量）來測定。 組份（3 )較佳係組成本發明之組合物的卜4 〇重量％，更佳 係1 -1 5重量％，還要佳係3 — 1 〇童量％。 組份（4)係無機填料。適合的無機填料為此藝中習知 的；較佳係亦具有阻燃性質的那種。特定言之，較佳的無 機填料包含鋁二水合物、氫氧化鎂、碳酸鈣、焙燒過黏 土、滑石、雲母、删酸鋅及其混合物。 組份（4)杈佳係組成本發明之組合物的2 〇 _ 8 5重量％，更 佳係50-75重量％，還要佳係6〇_7〇重量％。 組份（3)之接枝過部份傾向於與無機填料組份反應. (c.f. K.賀斯曼（Hausmann)，v.弗來爾（FlaHs)，聚合物 和聚合物組合物（polyiners & p〇lynier c⑽叩“1；^)第5冊
D:\Y87\54236.ptd 第8頁 發明說明（5) ___ (v〇l 5)，第2 版（No. 2) ,1 997 1 1 3 頁 ff)。人 有更多互適性。且有古声貝。八使組合物 又，，、可有咼含量的無機填料，並 2強 阻燃性。 j «物具有較高 =其之聚合物和阻燃性無機填料外，本發
安定劑1 = ^ MU# ’抗氧化劑、UV
^ ^ ⑺h1(例如，油酸醯胺）、抗阻塞劑、抗靜I 物、蠟 '顏料、二ϋ各# ,a 机靜電 知的其他加工助叫（例如’：石、和聚合物化合技藝中習 合物的別。重硬醋酸鋅）。添加劑可高達總組 I # h h k I。 h漶組合物係以聚合物組份、阻Μ性 琪科加上添加劑為準。 ，概庇 本發明之摻合α 拼料。阻燃性填用之捏和設備’將聚合性 捏和設備包括，如‘需選用之添加劑混合而製備，該 (計abender Mix^f Μ '布拉班得混合器 斯寇（BUSs-ko)捏和哭伯利混合器（Banbury Mixer)、布 雙螺旋連續性混入^ 法瑞爾（Farrei)連續性混合器或 和順-丁嫌-缺XX 〇 展σ時間應為足以獲得均勻摻合物 反應通常人軒旋群/阻燃性填料（、组份⑷）之間的適當 麼為1 R (1 滿心的';tc*合時間為約5分鐘’而混合溫 混i作用。 果聚合物摻合物不均勻，那麼需要額外的 本發明可藉由下列杳η 分比皆係以重旦實例而被更加了解，其中的組份和—百 而溫度為攝氏度^ 每一百份像膠（Phr)中的份數計，
470770 五、發明說明（6) [實例1-4] [說明] MF I =溶化流動指數 EVAC0=乙烯乙酸乙烯酯一氧化碳 EVA=乙烯乙酸乙烯酯 EVA + MAH=以順-丁烯二酸酐接枝的乙烯乙酸乙烯酯 HDPE+MAH=以順-丁烯二酸酐接枝的高密度聚乙烯 ATH=鋁三水合物 MAH =順-丁烯二酸酐 [步驟] 摻合物係由將下列之組份，按列在後文表丨中的比例溶 化摻合而製備。 — .EVAC0 (71. 5%乙烯、20. 5%乙酸乙烯酯和8% 一氧化碳）， 其之MFI (190°C/2.16 公斤）為15 .EVA (72%乙稀和28%乙酸乙烯酯），其之mfi (190°C /2. 16公斤）為3. 0 • EVA+MAH (以1. 5% ΜΑΗ接枝的72%乙烯和28%乙酸乙烯 酯），其之MFI (190°C/2.16 公斤）為 1.4 .HDPE + MAH (以0.9% ΜΑΗ接枝），其之密度為0.9 5 5克/立 方公分而MFI (190°C/2.16公斤）為2 • VLDPE之密度為0.902克/立方公分而MFI (19CTC/2.16公 斤）為1. 0 ' •抗氧化劑-由喜巴專業化學品（Ciba Specialty Chemicals)以商品名艾根諾克斯（IRGANOX) 1010供應的酚
D:\Y87\54236. ptd 第10頁 470770 五、發明說明co 系型 溶化化合作用係在1 5 0 -1 7 0 X：下，以每批1 〇 0克，在雙乳 製機内進行約5分鐘。礙磨產物在150-170 °C的水壓機内5 分鍾，以形成試驗板。之後，進行應力應變試驗（ASTM D -412)。極限氧指數（Limited Oxygen Index)，即，L0I (ASTM D 286 3)和 80 及 90 °C 下的刀式刺入度（ICE 54 0 1 0.1 項）。結果示在表1。 [表1] [實驗編號] [1] [2] EVAC0 10 10 EVA 16 13 EVA+MAH 9 4 hdpe+mah — 4 VLDPE - 4 ATH 64. 7 64.7 抗氧化劑 0.3 0.3 抗張強度（MPa) 14. 6 15.7 伸展長度（％) 150 140 8〇 °C的刀式刺入度（％) 80 0 °C的刀式刺入度（％) 100 0 L〇I(%) 38 35 可發現’包含HDPE + MAH和VLDPE之配方較不包含其之配； 方顯示特別低的刀式刺入度值（較佳的熱性能），但是也有 低的阻燃性。雖然在其他應用中，阻燃性為最重要的標
470770
D:\Y87\54236.ptd 第12頁

Claims (1)

  1. 470770 案號 8Π14913 t //月厶曰 修正七 年月曰 89.117 六、申請專利範圍 1 · 一種不含—之-租—燃 各物所組成之摻合物： (1 )乙烯乙酸乙烯酯一氧化碳三聚物，其包含5 5 - 6 5重 量％乙稀、20-30重量％乙酸乙稀酯和5-15重量％ —氧化碳； (2 )選自下列各物之乙烯乙酸乙稀酯或聚烯烴：（a)包 含25-90重量％乙烯和10-75重量％乙酸乙烯酯之乙烯乙酸乙 烯酯，（b)線性低密度聚乙烯，（c)低密度聚乙烯，（d)非 常低密度聚乙烯和（e)高密度聚乙烯；及其混合物； (3 )選自下列之各物之乙烯乙酸乙烯酯或聚烯烴：（a) 包含25-90重量％乙稀和10-75重量％乙酸乙稀S旨之乙稀乙酸 乙烯酯，（b )線性低密度聚乙烯，（c)低密度聚乙烯，（d) 非常低密度聚乙烯和（e)高密度聚乙烯；及其混合物；其 中每一種皆以0 . 0 5 - 3重量％的其羧酸或酸酐接枝；和 (4 )無機填料， ' 其中組份（1)佔摻合物之：! - 6 0_重量％，組份（2 )佔摻合 物之1 - 5 0重量％，組份（3 )佔摻合物之1 - 4 0重量％，而組份 (4 )佔摻合物之2 0 - 8 5重量％。 2 .根據申請專利範圍第1項之摻合物，其中組份（1 )佔摻 合物之5 - 2 5重量％，組份（2 )佔摻合物之5 - 2 5重量％，組份 (3)佔摻合物之卜15重量％，而組份（4)佔摻合物之5 0 - 7 5重 量％ 〇 3 .根據申請專利範圍第1項之摻合物，其中組份（1)佔摻 合物之5-1 5重量％，組份（2)佔摻合物之1 0-20重量％，組份 (3 )佔摻合物之3 - 1 0重量％，而組份（4 )佔摻合物之6 0 - 7 0重 量％。 聚合物組合物，其包含由下列
    O:\54\54236.ptc 第1頁 2000.11.06.013 470770
    O:\54\54236.ptc 第2頁 2000. 11.06.014
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