A7 B7 4425 3 0 五、發明說明（1 ) 發明背景 本發明係有關於聚合物摻合物，特別是難燃性摻合物 〇 長久以來，聚合物摻混人士之目標便在於改良聚合物 之抗性。火培抗性典型係由Underwriters Laboratories之 UL-94測試（A S T Μ步驟D 3 8 0 1 )評估。此測試中， V - 〇等級要求聚合物試樣在施予測試火焰後，不會隨火 焰燃燒超過1 0秒，而且5個試樣各經1 〇次火焰後，不 會隨火焰燃燒超過5 0秒；即，該試樣之「火焰熄滅時間 」不超過5 0秒。 有許多種化合物可作爲難燃添加劑，包括鹵化化合物 ，特別是溴化者，其通常必須與銻化合物（如三氧化銻） 與磷酸系化合物。此種添加劑通常與抗滴（anti-drip )劑 ，如，氟碳聚合物，併用。 在某些例子中會想排除磷酸系化合物之使用。但是總 要用大量此類化合物以得到所需難燃程度。所以，市售之 聚苯醚與烯烴聚合物之摻合物可能需要2 Op hr (每 1 0 0份樹脂中之重量份）的磷酸系化合物。若是聚碳酸 酯與烷烯芳族共聚物（如，苯乙烯，丙烯腈與丁二烯之共 聚物）摻合物的例子，典型則需要高於5 p h r之磷酸系 化合物。 於難燃添加劑中倂用有機粘土已被掲示。所用添加劑 大部份爲鹵系。 U S 4 5 8 2 8 6 6揭示一種共聚酯彈性體，其含有 t-----^---—訂--------錄： (請先閱讀背面之注意事項再填寫本頁〉 經濟部智慧pU.M工消費合作杜印製 本紙張尺度適用令國國家標準（CNS)A4規格（210x297公釐） -4- 經濟部智慧 Μ工消費合作社印製 4 42 53 0 A/ B7 五、發明說明G ) 作爲難燃劑之溴化合物與三氧化銻組合：作爲抗滴劑之經 四級銨級改質的粘土。英國專利1 1 1 4 1 7 4揭示，如 聚醯胺，聚苯乙烯與烯烴聚合物之聚合物與難燃添加劑（ 其可爲鹵素或磷酸系）及作爲抗滴劑之有機性陽離子改質 粘土之摻合物。依EP 132228，聚酯可藉鹵化化 合物及銻或磷化合物與有機改質層狀矽酸鹽之助而具有難 燃性。亦使用改質粘土作爲抗滴劑之摻合物可見於E P 2 3 9 9 8 6 ° 亦爲本案申請人申請中之序號0 8/9 5 0 0 9 2申 請案揭示一由下列成份所成之組合物：聚酯，鹵化難燃劑 ，有機粘土，氧化銻與氟碳聚合物。這些添加劑之組合可 減少所有幽化難燃劑與氧化銻。 但前述先前技藝並未建議聚合物摻合物可用之改良難 燃劑。再者亦無關排除磷系難燃劑之使用*且未指出任何 可用之協乘劑（synergists)。 發明簡述 本發明發現有機粘土於聚合物摻合物中可與磷酸系難 燃添加劑倂用而作爲協乘劑，使前述添加劑的用量降低。 有機粘土的作用不只是作爲抗滴劑；實際上其與磷酸系難 燃劑形成協乘組合，使後者用量降低。亦發現本發明特定 摻合物中，不需有氟碳聚合物。甚至其存在是不利的，因 其會降低摻合物之難燃性。 本發明涵括不含銻化合物且含下述及其任何反應產物 (請先閱讀背面之注意事項再填寫本頁) ----l· I I 訂--------1^. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -5- 44253 0 A7 B7 五、發明說明6 ) 之組成物： (A)主要量之第一熱塑性樹脂； (請先閲讀背面之注意事項再填寫本頁) (B )次要量之至少一種第二熱塑性樹脂，該次要量 爲成份A與B之約3 — 45wt% : (C )至少一種磷酸系有機化合物作爲唯一難燃劑； (D )至少一種有機粘土； 成份《：與0的量有效於得出乂 — 〇等級（111^ — 9 4測試 )或降低至少1 0 %之平均熄火時間。 詳細說明：較佳具體例 本發明組成成份間是否行化學交互作用而形成其他物 質並未得知且非本發明實質內容。所以，本發明係關於該 組成物，不論是否發生任何化學交互作用。易言之，本發 明包括含所述成份之組成物以及含所述成份反應產物之組 成物。 經濟部智慧_F..··貝工消費合作社印製 成份A與B爲第一與第二熱塑性樹脂，即，二者結構 單元互異。故成份A可爲均聚物而成份B爲含有成份A結 構單元與其他結構單元之共聚物。但通常成份六與3包含 完全不同之結構單元。 依上述，組成成份A與B之樹脂的化學結構並不同。 加成與縮合聚合物均可包括。熱塑性樹脂的例子有烯烴聚 合物，如，聚乙烯與聚丙烯；乙烯性不飽和羧酸及其官能 衍生物之聚合物’包括丙系酸系聚合物，如，聚（丙烯酸 烷酯），聚（甲基丙烯酸烷酯），聚丙烯醯胺，聚丙烯腈 -6 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 4 4253 0 A7 ___ B7 五、發明說明各) 與聚丙烯酸；烯基芳族聚合物，如，聚苯乙烯；二烯聚合 物，如，聚丁二烯與聚異戊二烯；聚醯胺，如，耐侖—6 與耐侖一6 6 ;聚酯，如，聚（對苯二甲酸乙二醇酯）與 聚（對苯二甲酸丁二醇酯）；聚碳酸酯，如，雙酚a聚碳 酸酯：以及聚芳醚，如，聚（2 ，6 —二甲基~1 ，4 一 苯醚）與共聚（2 ，6 —二甲基一1 ，4 —苯醚）—2 , 3 ，6~三甲基一1 ，4 一苯醚）。均聚物與共聚物均包 括’且後者可爲無規，嵌段或接枝類型。所以，例如，適 宜聚苯乙烯包括均聚物與共聚物，後者包括高衝擊聚苯乙 烯（Η I P S )，橡膠改良聚苯乙烯，其含摻合物與接枝 ，其中之橡膠爲聚丁二烯或約7 0 - 9 8%苯乙烯與2 _ 3 0%二烯單體所成橡膠狀共聚物。 成份Α與Β可爲相容，不相容或是以已知方法來化學 地或物理地相容。通常較好令成份B對成份A而言爲市售 習知佐劑，如，衝擊改良劑，或是市售聚合物摻合物之第 二成份。 基於眾多目的，較佳聚合物摻合物爲聚苯醚摻合物* 特別是與均聚與共聚苯乙烯（包括均聚苯乙烯與苯乙烯及 二烯橡膠之共聚物（如，高衝擊聚苯乙烯）之摻合物’以 及聚碳酸酯摻合物。聚碳酸酯摻合物包括下列：成份B包 括至少一種共聚苯乙輝者，特別是包括一或多種苯乙&共 聚物與脂族二烯與睛（如’丙烯腈-丁二烯一苯乙烯或 A B S共聚物）者。共聚苯乙烯與聚碳酸酯通常爲AB S 共聚物與苯乙烯-丙烯腈共聚物之混合物 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) i I I-- I l· β· ί ! !·^ i _ 經濟部智慧ιί._ ,員工消費合作社印製 442530A7 B7 4425 3 0 V. Description of the invention (1) Background of the invention The present invention relates to polymer blends, especially flame retardant blends. For a long time, the goal of polymer blenders has been to improve the polymer. Resistance. Fire resistance is typically assessed by Underwriters Laboratories' UL-94 test (ASTM Step D 3 801). In this test, the V-〇 rating requires that the polymer sample does not burn with the flame for more than 10 seconds after the test flame is applied, and that the five samples do not burn with the flame for more than 5 times after 10 flames each 0 seconds; that is, the "flame extinguishing time" of the sample does not exceed 50 seconds. There are many types of compounds that can be used as flame retardant additives, including halogenated compounds, especially brominated compounds, which must usually be combined with antimony compounds (such as antimony trioxide) and phosphoric acid-based compounds. Such additives are often used in combination with anti-drip agents, such as fluorocarbon polymers. In some instances it may be desirable to exclude the use of phosphate compounds. However, large amounts of these compounds are always used to obtain the required flame resistance. Therefore, a blend of a commercially available polyphenylene ether and an olefin polymer may require 2 Op hr (parts by weight per 100 parts by weight of the resin) of a phosphoric acid-based compound. In the case of blends of polycarbonate and alkene aromatic copolymers (e.g., styrene, copolymers of acrylonitrile and butadiene), typically phosphate compounds higher than 5 p h r are required. The use of organoclay in flame retardant additives has been shown. Most of the additives used are halogen. US 4 5 8 2 8 6 6 discloses a copolyester elastomer, which contains t ----- ^ ----- order -------- Record: (Please read the precautions on the back before filling This page> Wisdom pU.M industrial and consumer cooperation of the Ministry of Economic Affairs printed on this paper The size of the paper is applicable to the national standard (CNS) A4 specification (210x297 mm) -4- Printed by the Ministry of Economic Affairs Wisdom Consumer Cooperative 4 42 53 0 A / B7 V. Description of the invention G) Combination of bromine compound as antiflammable agent and antimony trioxide: quaternary ammonium modified clay as anti-dripping agent. British patent 1 1 1 4 1 7 4 reveals that polymers such as polyamide, polystyrene and olefin polymers and flame retardant additives (which can be halogen or phosphoric acid) and organic cationic modification as anti-drip agents Blends of clay. According to EP 132228, polyesters can be made non-flammable with the aid of halogenated compounds and antimony or phosphorus compounds and organic modified layered silicates. Admixtures that also use modified clay as an anti-dripping agent can be found in EP 2 3 9 9 8 6 ° It is also the serial number 0 8/9 5 0 0 9 2 in the applicant's application for this application. Composition: polyester, halogenated flame retardant, organoclay, antimony oxide and fluorocarbon polymer. The combination of these additives reduces all of the deodorizing flame retardants and antimony oxide. However, the foregoing prior art does not suggest improved flame retardants useful in polymer blends. Furthermore, it does not preclude the use of phosphorus-based flame retardants * and does not indicate any available synergists. BRIEF SUMMARY OF THE INVENTION The present invention has found that organoclays can be used as a synergist with phosphoric acid-based flame retardant additives in polymer blends to reduce the amount of the aforementioned additives. Organoclay acts not only as an anti-dripping agent; in fact, it forms a synergistic combination with phosphoric acid-based flame retardants, which reduces the amount of the latter. It has also been found that the particular blends of the present invention do not require a fluorocarbon polymer. Even its presence is disadvantageous because it reduces the flame retardancy of the blend. This invention includes antimony-free compounds and contains the following and any reaction products (please read the precautions on the back before filling this page) ---- l · II Order -------- 1 ^. This Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -5- 44253 0 A7 B7 V. Invention Description 6) Composition: (A) The first thermoplastic resin in the main amount; (Please read first Note on the back page, please fill in this page again.) (B) at least one second thermoplastic resin in a minor amount, which is about 3-45 wt% of the components A and B: (C) at least one phosphoric acid-based organic compound as the sole Flame retardants; (D) at least one organoclay; the amount of the components ": and 0 is effective to obtain a 乂 -0 level (111 ^ -9 4 test) or reduce the average flameout time by at least 10%. Detailed description: preferred specific examples It is not known whether chemical interactions between the constituents of the present invention form other substances and are not the essence of the present invention. Therefore, the present invention relates to the composition regardless of whether any chemical interaction occurs. In other words, the present invention includes a composition containing the ingredients and a composition containing a reaction product of the ingredients. Wisdom of the Ministry of Economic Affairs _F .. ·· Printed by Beigong Consumer Cooperative Ingredients A and B are the first and second thermoplastic resins, that is, the structural units of the two are different from each other. Therefore, component A may be a homopolymer and component B may be a copolymer containing the structural unit of component A and other structural units. But usually the components six and three contain completely different structural units. As described above, the chemical structures of the resins A and B are different. Both addition and condensation polymers can be included. Examples of thermoplastic resins are olefin polymers such as polyethylene and polypropylene; polymers of ethylenically unsaturated carboxylic acids and their functional derivatives include acrylic acid-based polymers such as poly (alkyl acrylate), poly (Alkyl methacrylate), Polyacrylamide, Polyacrylonitrile-6-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 4 4253 0 A7 ___ B7 (Each description of the invention) With polyacrylic acid; alkenyl aromatic polymers, such as polystyrene; diene polymers, such as polybutadiene and polyisoprene; polyamines, such as Nail-6 and Nail-6 6; polyesters such as poly (ethylene terephthalate) and poly (butylene terephthalate); polycarbonates such as bisphenol a polycarbonate: and polyarylene ethers such as , Poly (2,6-dimethyl ~ 1,4-monophenyl ether) and copolymer (2,6-dimethyl-1,4-phenylene ether) -2, 3, 6 ~ trimethyl-1, 4 Monophenyl ether). Both homopolymers and copolymers include ' and the latter can be of random, block or graft type. So, for example, suitable polystyrenes include homopolymers and copolymers, the latter including high-impact polystyrene (Η IPS), rubber modified polystyrene, which contains blends and grafts, of which the rubber is polybutadiene Olefin or about 70-9 8% styrene and 2 _ 30% diene monomer formed from a rubbery copolymer. Ingredients A and B may be compatible, incompatible or chemically or physically compatible by known methods. It is generally preferred to make component B a commercially available adjuvant for component A, such as an impact modifier, or a second component of a commercially available polymer blend. For many purposes, preferred polymer blends are polyphenylene ether blends * especially with homopolymers and copolymers of styrene (including copolymers of homostyrene and styrene and diene rubbers (eg, high impact Polystyrene) blends and polycarbonate blends. Polycarbonate blends include the following: Component B includes at least one copolymerized stilbene, especially one or more stilbene & copolymers With aliphatic diene and eyes (such as' acrylonitrile-butadiene-styrene or ABS copolymer). Copolystyrene and polycarbonate is usually a mixture of ABS copolymer and styrene-acrylonitrile copolymer This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) i I I-- I l · β · ί!! · ^ I _ Economy Ministry of Wisdom._, Printed by Employee Consumer Cooperatives 442530
五、發明說明Φ ) 經濟部智慧員工消費合作社印製 (A 0)：P(0)0[A20P(0)(0Ai)0]nAlV. Description of the Invention Φ) Printed by the Consumer Cooperatives of the Ministry of Economic Affairs (A 0): P (0) 0 [A20P (0) (0Ai) 0] nAl
其中A1各爲單價C6-2 0芳基’ A2各爲二價C _只6 2 0方基 ，η爲〇至5，且較好爲丨。該芳基可爲烴基或取代烴基 ，以烴基爲佳。「芳基」一詞包括單環或多環稠合與鍵結 環基，包括烷芳基，如，甲苯基，二甲苯基與2 , 2 一 — (4 —伸苯基）丙烷’即’衍生自雙酣a之基團。 適宜二磷酸芳酯包括氫醌二（磷酸二苯酯），間苯二 酚二（磷酸二苯酯），雙酚A二（磷酸二苯酯）與間苯二 酉分——2 ’ 6 - 一甲本基隣酸醋）。較佳二磷酸酯通 常爲間苯二酚二（磷酸二苯酯）與雙酚A二（磷酸二苯醒 )0 成份C爲本發明組成物中惟一難燃劑，所以並未存在 有鹵化難燃劑。 成份D爲至少一種有機粘土。文中「有機粘土」一詞 指層狀粘土 ’通常爲矽酸鹽粘土，其由層狀礦物所衍生且 化學倂入有機部份，通常藉由與有機離子及/或鎰化合物 離子交換，特別是陽離子交換。有機離子的例子有單銨與 多銨陽離子’如，三甲基十二烷基銨與N，Ν^_二（十 二烷基）咪唑鐵。 層狀礦物的例子有高嶺土與蒙脫土"亦可使用伊利石 (lllite )類礦物，包括水雲母，多矽白雲母，brammallite ，海綠石，綠土等。一般而言，較佳層狀礦物包括那些稱 ------------^·--I h--~ I 訂------I--结' (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 2町公* ) - 8 - 經濟部智慧:·,員工消費合作社印製 44253 0 A7 ---B7 五、發明說明（6 ) 爲2 : 1層狀矽酸鹽礦物者，包括白雲母，蛭石，皂石， 水輝石’蒙脫土 ’以後者最佳。層狀礦物可由合成製得， 但通常其爲天然物且爲市售可得。適宜層狀礦物之詳細說 明可參考US 5530052，其揭示倂入本文參考。 適宜之市售可得或易製成的有機粘土的特定例有： CLAYTONE HY〔經甲基二（氫化牛油）銨離子 陽離t父換之蒙脫土（得自Southern Clay Products )〕以 及經十二烷基銨’三甲基十二烷基銨，N，N — -二（十 二烷基）咪唑鎰，N，N - -二（十四烷基）苯甲基咪哗 鏺或甲基二（羥乙基）（氫化牛油）銨等離子經陽離子交 換之蒙脫土。 本發明組成物可含有此類聚合物摻合物之習知添加劑 ，惟不使用銻化合物作爲添加劑。適宜添加劑包括抗滴劑 ’安定劑’塡料’顏料，染料，抗靜電劑，結晶助劑與脫 模劑。因爲其爲此技藝公知，此處不再詳述。 組成物中當成份A爲聚苯醚，特別是當成份B爲一或 多種乙烯性不飽和單體之聚合物，成份C含量很低時，較 好不以氟碳聚合物作爲抗滴劑。所以本發明較佳具體例爲 聚苯醚摻合物，其中成份C含量低於2 0重量份/1 〇 〇 份成份A與B ( p h r )，該摻合物不含有氟碳聚合物。 若存在有該聚合物將降低難燃性，如U L _ 9 4等級，境 火時間或二者。 本發明組成物中各成份比例可在大範圍中變動。成份 A佔成份A與B總和之大部份，成份B爲該總和之約3 \ (請先閱讀背面之注意事項再填寫本頁) 裝----l·丨|r訂----------续 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- 442 5 3 0 經濟部智慧財？，.灰員工消費合作社印製 A7 B7 五、發明說明) 4 5 w t %，較好約 5 — 4 0 w t %。 成份C與D之量有效於UL — 9 4測試中產生V— 〇 等級，或是降低平均熄火時間至少1 0 %，此數量與成份 A與B種類有關。 當成份A爲聚苯醚，且特別當成份B爲一或多種乙嫌 性不飽和單體之加成聚合物時，成份C之比例通常爲1 ◦ 一 25phr ，較好爲15 — 20phr。若含量高於 2 ◦ P h r ，通常不需使用成份D便能得到可接受之難燃 性；若低於1 5 P h r ，即使同時使用成份C與D，則不 可能提供所需難燃性與其他性質之平衡。 在聚碳酸酯摻合物中，特別當加有乙烯性不飽和單體 之聚合物時，成份C的比例爲5-15phr ，較好爲7 - 1 1 p h r。低比例可能僅有低或是沒有難燃性，即使 成份D亦存在，至於高比例亦不需要且可能降低成份D之 功效。 通常，成份D的用量在0·08—0.6phr是有 利的，較高用量並不會增加優點，有時甚至會降低難燃性 及/或使摻合物中的聚碳酸酯降解。即使在上述範圍內， 應注意功效上的變化，特別是在成份C之臨界含量時。熟 習此技藝人士應可依簡單實驗輕易決定有效用量= 在以氟碳聚合物，最常是聚四氟乙烯（PTFE)， 作爲抗滴劑之摻合物中，其用量約爲0 . 1 — 0 . 5 p h r 。 本發明組成物可用習知熱塑性樹脂之摻合技術製成， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- ------------t----------訂--------錄. (請先閲讀背面之注意事項再填寫本頁) 442 5 3 0 A7 B7 經濟部智慧財人員工消費合作杜印製 五、發明說明（8 ) 可包括溶液摻合與熔融摻合。較佳爲熔融摻合，特別是適 合連續操作之方法，如，擠製。 本發明以下列實例舉例說明。所有「份」與百分比係 以重量計。分子量爲重量平均且以凝膠滲透層析測得。固 有黏度係於氯仿中’ 2 5 °C時測量。U L _ 9 4測試以1 /16〃 （ 1 . 6 m m )試樣進行。 實例1 以下述摻合物進行一系列之實驗：此摻合物含 64 . 32份固有黏度爲〇 . 46d Ι/g之聚（2，6 —二甲基—1 ，4 —苯醚）；35 · 68 份 HI PS (分 子量爲2 1 0000 — 250000、橡膠含量爲 1〇 - 3%及熔融流動指數爲2 . 2 — 3 · lg/ΙΟ分 鐘）；5 . 4 9份習知添加劑，包括安定劑，衝擊改良劑 與脫模劑；0 15份50%聚（四氟乙烯）與50%苯 乙烯-丙烯腈共聚物摻合物，其含7 2%苯乙烯單元（「 P T F E摻合物」；以及各種比例，包括5 . 3 2， 工〇，63，15.95 與 21 .26phr ，之間苯二 酚二（瞵酸二苯酯）。將這些成份於Henschel混合器中混 合’於1 20 — 232 °C之溫度，20 — mm雙螺桿擠製 機之對轉螺桿上擠製。發現需要使用2 1 . 2 6 p h r該 二磷酸酯方能得出U L - 9 4測試之V — 〇等級。 製備類似之含2 1 · 2 6 p h r該二磷酸酯的摻合物 ’且含有或不含有PTFE與CLAYTONE HY有 本紙張尺度適用中國國家標準〈CNS)A4規格（210 X 297公釐） -11 - ------------ 裝----l·—訂----------鋏. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 442530 A7 五、發明說明$ ) 機粘土。ϋ L - 9 4測試結果與各5個試樣之5組測試之 平均熄火時間（F Ο Τ )結果列於表1。 表1 摻合物 1 2 3 4 有機粘土， 0 0 0.50 0.50 phr PTFE 0.15 0 0.15 0 摻合物1 phr UL-94等級 V-0 V-0 V-0 V-0 FOT，秒 22.0 28.9 23.3 21.2 FOT%降低 -- 一 -- 26.6 摻合物2 . 4與摻合物1 · 3.的比較可明顯看出在該 二鱗酸醋濃度時，PTF Ε可改善F ΟΤ。在PTF Ε存 在時，有機粘土沒有不利影響（摻合物2與4 )。當 P T F Ε不存在時，則有有利效果（摻合物1與3 )。 實例2 製備並測試類似實例1之摻合物（但其含1 5 . 9 5 P h r二磷酸酯）。結果如表I I 。 — — — II - / — — — I— · I I I Γ <請先閱讀背面之注意事項再填寫本頁) --- 訂 --------韓 i 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -12 - 4425 3 π Α7 Β7 經濟部智慧財彦局員工消費合作社印製 五、發明說明㈧ ）Wherein A1 is each a monovalent C6-2 0 aryl group 'A2 is each a divalent C_only 6 2 0 square group, η is 0 to 5, and preferably 丨. The aryl group may be a hydrocarbon group or a substituted hydrocarbon group, and a hydrocarbon group is preferred. The term "aryl" includes monocyclic or polycyclic fused and bonded ring groups, including alkaryl groups such as tolyl, xylyl and 2, 2-a- (4-phenylene) propane 'that is' Derived from a group of bis-a. Suitable aryl diphosphates include hydroquinone di (diphenyl phosphate), resorcinol di (diphenyl phosphate), bisphenol A di (diphenyl phosphate) and resorcinol-2 '6- 1 methylbenzyl vinegar). The preferred diphosphates are usually resorcinol di (diphenyl phosphate) and bisphenol A di (diphenyl phosphate). Component C is the only flame retardant in the composition of the present invention, so there is no difficulty in halogenation.燃 剂。 Fuel agent. Ingredient D is at least one organoclay. The term "organoclay" in the text refers to a layered clay, usually a silicate clay, which is derived from a layered mineral and chemically penetrates into the organic part, usually by ion exchange with organic ions and / or rhenium compounds, especially Cation exchange. Examples of organic ions are monoammonium and polyammonium cations' such as trimethyldodecylammonium and N, N ^ _di (dodecyl) imidazole. Examples of layered minerals are kaolin and montmorillonite. "Illite (lllite) minerals can also be used, including hydromica, polysilica, brammallite, chlorite, smectite, and the like. Generally speaking, the preferred layered minerals include those called ------------ ^ · --I h-- ~ I order ------ I-- knot '(Please read first Note on the back, please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇x 2 Machiko *)-8-Wisdom of the Ministry of Economic Affairs: ·, printed by employee consumer cooperative 44253 0 A7 --- B7 V. Description of the invention (6) Those with 2: 1 layered silicate minerals, including muscovite, vermiculite, soapstone, and hectorite 'montmorillonite' are the best. Layered minerals can be made synthetically, but are usually natural and commercially available. A detailed description of suitable layered minerals can be found in US 5530052, the disclosure of which is incorporated herein by reference. Specific examples of suitable commercially available or easily made organoclays are: CLAYTONE HY [via methyldi (hydrogenated tallow) ammonium ion, montmorillonite (from Southern Clay Products)], and Via dodecylammonium'trimethyldodecylammonium, N, N — -di (dodecyl) imidazolium, N, N — -di (tetradecyl) benzyl imidazole or Cation exchanged montmorillonite for methylbis (hydroxyethyl) (hydrogenated tallow) ammonium plasma. The compositions of the present invention may contain conventional additives of such polymer blends, but do not use antimony compounds as additives. Suitable additives include anti-dripping agents " stabilizers " pigments, dyes, antistatic agents, crystallization aids and release agents. Because it is well known for this technique, it will not be described in detail here. When the component A is a polyphenylene ether in the composition, especially when the component B is a polymer of one or more ethylenically unsaturated monomers and the content of the component C is very low, it is better not to use a fluorocarbon polymer as an anti-dripping agent. Therefore, the preferred embodiment of the present invention is a polyphenylene ether blend, wherein the content of component C is less than 20 parts by weight / 100 parts of components A and B (phr), and the blend does not contain a fluorocarbon polymer. The presence of the polymer will reduce flame resistance, such as U L _ 9 4 grade, environmental fire time or both. The proportion of each component in the composition of the present invention can be varied within a wide range. Ingredient A accounts for most of the sum of ingredients A and B, and ingredient B is about 3 of the sum (Please read the precautions on the back before filling this page) Equipment ---- l · 丨 | Order ------ continued This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -9- 442 5 3 0 Printed by the Grey Cooperative Consumer Cooperative A7 B7 V. Invention Description) 4 5 w t%, preferably about 5-40 w t%. The amount of components C and D is effective to produce a V—0 level in the UL-9 4 test, or to reduce the average flameout time by at least 10%. This amount is related to the types of components A and B. When component A is polyphenylene ether, and especially when component B is an addition polymer of one or more ethylenically unsaturated monomers, the ratio of component C is usually 1 ◦ to 25 phr, preferably 15 to 20 phr. If the content is higher than 2 ◦ P hr, it is generally not necessary to use component D to obtain acceptable flame retardancy; if it is lower than 15 P hr, even if components C and D are used at the same time, it is impossible to provide the required flame retardancy. Balance with other properties. In the polycarbonate blend, especially when a polymer of an ethylenically unsaturated monomer is added, the proportion of component C is 5-15 phr, preferably 7-1 1 p h r. Low proportions may only be low or non-flammable. Even if component D is present, high proportions are not needed and may reduce the efficacy of component D. In general, the amount of component D in the range of 0.08 to 0.6 phr is beneficial. Higher amounts do not increase the advantages, and sometimes even reduce the flame resistance and / or degrade the polycarbonate in the blend. Even within the above range, attention should be paid to changes in efficacy, especially at the critical content of component C. Those skilled in the art should be able to easily determine the effective amount based on simple experiments. In a blend of fluorocarbon polymers, most commonly polytetrafluoroethylene (PTFE), as an anti-dripping agent, the amount is about 0.1 — 0.5 phr. The composition of the present invention can be made by the conventional thermoplastic resin blending technology. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -10- ------------ t ---------- Order -------- Record. (Please read the precautions on the back before filling out this page) 442 5 3 0 A7 B7 Ministry of Economic Affairs, Smart Wealth, Staff, Consumer Cooperation Printing 5. Description of the invention (8) may include solution blending and melt blending. Melt blending is preferred, especially methods suitable for continuous operation, such as extrusion. The invention is illustrated by the following examples. All "parts" and percentages are by weight. The molecular weight is weight average and measured by gel permeation chromatography. The inherent viscosity is measured at ‘25 ° C in chloroform. The U L _ 9 4 test is performed with a 1 / 16〃 (1.6 mm) sample. Example 1 A series of experiments were performed with the following blend: This blend contained 64.32 parts of poly (2,6-dimethyl-1,4-phenylene ether) having an inherent viscosity of 0.46 d / g; 35 · 68 parts of HI PS (molecular weight of 21 000-250,000, rubber content of 10-3%, and melt flow index of 2.2-3 · lg / 10 minutes); 5. 4 9 parts of conventional additives, including Stabilizer, impact modifier and release agent; 0 15 parts of 50% poly (tetrafluoroethylene) and 50% styrene-acrylonitrile copolymer blend, which contains 72% styrene units ("PTFE blend And various ratios, including 5.3, 0.2, 63, 15.95, and 21.26 phr, catechol di (diphenyl gallate). Mix these ingredients in a Henschel mixer 'at 1 20 — 232 ° C, extrusion on the counter-rotating screw of a 20 — mm twin-screw extruder. It was found that 2 1. 2 6 phr of this diphosphate was required to obtain the UL-9 4 test V — 〇 rating. Prepare similar blends containing 2 1 · 2 6 phr of the diphosphate ester with or without PTFE and CLAYTONE HY Standard <CNS) A4 specification (210 X 297 mm) -11------------- equipment ---- l · —order ---------- 铗. ( Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 442530 A7 V. Invention Description $) Machine clay. ϋ L-9 4 test results and the average flameout time (F Ο Τ) results of 5 groups of tests of each 5 samples are shown in Table 1. Table 1 Blend 1 2 3 4 Organoclay, 0 0 0.50 0.50 phr PTFE 0.15 0 0.15 0 Blend 1 phr UL-94 grade V-0 V-0 V-0 V-0 FOT, seconds 22.0 28.9 23.3 21.2 FOT% reduction-1-26.6 Blend 2.4 compared with Blend 1.3. It can be clearly seen that PTF E can improve F0T at this diphosphonate concentration. In the presence of PTF E, the organoclay has no adverse effects (blends 2 and 4). When P T F Ε is absent, it has an advantageous effect (blends 1 and 3). Example 2 A blend similar to Example 1 was prepared and tested (but it contained 15.95 Phr diphosphate). The results are shown in Table I I. — — — II-/ — — — I — · III Γ < Please read the notes on the back before filling out this page) --- Order -------- Han i This paper size applies to Chinese national standards ( CNS) A4 specifications (210 χ 297 mm) -12-4425 3 π Α7 Β7 Printed by the Consumers ’Cooperative of the Wisdom Finance and Economics Bureau of the Ministry of Economic Affairs 5. Description of the invention）)
表I I 摻合物 5 6 7 8 有機粘土， 0 0 0.50 0.50 p hr PTFE 0.15 0 0.15 0 摻合物， phr UL-94等級 V-1 V-0/V-1 V-1 V-0 F〇T，秒 40.9 35.3 35.8 29.6 FOT%降低 „ _ _ 12.5 16.1 在此二磷酸酯濃度（低於20phr) ，PTFE降 低摻合物難燃性，其可由摻合物5，7與摻合物6，8之 比較看出。有機粘土則顯著降低F Ο T，無論P T F E存 在與否（摻合物7，8與摻合物5，6 )。 實例3 製備並測試類似實例1之摻合物（但其含2 5 . 8 0 p h r雙酚A二（磷酸二苯酯））。結果如表I I I 。 ------------ I _ I--l· ---訂--------|_'^ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- ^4253 0 A7 B7 五、發明說明（11 ) 表I I I 摻合物 9 10 11 12 有機粘土， phr 〇 0 0.50 0.50 PTFE 摻合物， phr 0 0.14 0 0.14 UL-94等級 V-0 V-0 V-0 V-0 FOT，秒 38.25 40.5 29.5 31.25 FOT%降低 __ _ _ 22.9 22.8 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 再次可看到，有機粘土提供之優異。P T F E對難燃 性則無顯著效應。 實例4 製備實例3之摻合物但含1 9 . 3 5 p h r雙酚A二 (磷酸二苯酯）進行測試。結果如表I V。 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） "2530 五、發明說明卩2 ) 表I V 摻合物 13 14 15 16 有機粘土， phr 0 0 0.50 0.50 PTFE 摻合物， phr 0 0.14 0 0.14 UL-94等級 V-0 V-1 V-0 V-1 FOT，秒 40.8 57.9 32.6 54.0 FOT%降低 _ _ __ 20.1 6.7 {請先閱讀背面之注意事項再填寫本頁} 再次可看到，有機粘土改善難燃性，在此濃度之二磷 酸酯，P T F E則降低這些性質。 實例5 經濟部智慧財產局員工消費合作社印製 使用實例1摻合步驟製備包含下列之摻合物：約 81·7%固有黏度爲〇·50dΙ/g之線型雙酣A聚 碳酸酯樹脂；約1 8 · 3 %下述加成共聚物之混合物：( 1) 45.5%市售乳液聚合ABS接枝共聚物’其含非 連續彈性體相（平均粒徑約3 0 0 n m之聚丁二稀）與剛 性熱塑性相（7 5 p bw苯乙烯與2 5 p bw丙烯睛共聚 物）與（2) 54 . 5%分子量約90 ，0〇〇之苯乙烯 -丙烯腈共聚物（SAN，7 5份苯乙烯/2 5份丙烯腈 );9.5phr間苯二酚二（磷酸二苯酯）；及0.4 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ο 3 5 2 4 4 A7B7 五、發明說明（<3 ) ph r PTFE摻合物。這些摻合物中聚碳酸酯與加成 聚合物的比例有非實質之差異，咸信這些差異不會對所硏 究的性質造成影響。結果如表V。 表V 摻合物 17 18 19 20 有機粘土， 0 0.1 0.25 0.50 phr UL-94等級 V-0 V-0 V-0 V-0 FOT，秒 27.5 22.25 3 1 36.75 F0T%，降低 _ 19.0 .. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表V結果顯示在此二磷酸酯濃度下，僅有〇 . 1 p h r有機粘土能改善難燃性。 實例6 製備並測試類似實例5之摻合物（但其含約8 2 %聚 碳酸酯，18%加成聚合物及7.5phr二磷酸酯）。 結果如表V I 。 本紙張尺度適用中囤國家標準（CNS)A4規格（210 X 297公釐） -16- 442530 A7 B7 五、發明說明W )Table II Blend 5 6 7 8 Organoclay, 0 0 0.50 0.50 p hr PTFE 0.15 0 0.15 0 Blend, phr UL-94 grade V-1 V-0 / V-1 V-1 V-0 F. T, seconds 40.9 35.3 35.8 29.6 FOT% reduction _ _ _ 12.5 16.1 Here the diphosphate concentration (less than 20phr), PTFE reduces the flame retardance of the blend, which can be blended 5, 6 and blend 6, The comparison of 8 shows that organoclay significantly reduces F 0 T, whether PTFE is present or not (blends 7, 8 and 5, 6). Example 3 A blend similar to Example 1 was prepared and tested (but It contains 2 5.80 phr of bisphenol A bis (diphenyl phosphate). The results are shown in Table III. ------------ I _ I--l-- ----- ------ | _ '^ (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -13- ^ 4253 0 A7 B7 V. Description of the invention (11) Table III Blend 9 10 11 12 Organoclay, phr 〇0 0.50 0.50 PTFE blend, phr 0 0.14 0 0.14 UL-94 grade V-0 V-0 V-0 V-0 FOT, seconds 38.25 40.5 29.5 31.25 FOT% reduction __ _ _ 22.9 22.8 (please first (Please read the note on the back and fill in this page again.) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, we can see again that the organic clay provides excellent. PTFE has no significant effect on flame retardancy. But it contains 19.3 5 phr of bisphenol A bis (diphenyl phosphate) for testing. The results are shown in Table IV. -14- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " 2530 V. Description of the invention 卩 2) Table IV Blend 13 14 15 16 Organoclay, phr 0 0 0.50 0.50 PTFE blend, phr 0 0.14 0 0.14 UL-94 grade V-0 V-1 V-0 V- 1 FOT, seconds 40.8 57.9 32.6 54.0 FOT% reduction _ _ __ 20.1 6.7 {Please read the precautions on the back before filling in this page} Once again, you can see that the organoclay improves the flame retardancy. At this concentration, the diphosphate, PTFE These properties are reduced. Example 5 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Use Example 1 Blending steps to prepare a blend including the following: approximately 81 · 7% linear bifluorene A polycarbonate resin with an inherent viscosity of 0.550dI / g; 18.3% mixture of the following addition copolymers: (1) 45.5% of a commercially available emulsion polymerized ABS graft copolymer 'containing a discontinuous elastomer phase (polybutadiene with an average particle size of about 300 nm) ) And rigid thermoplastic phase (7 5 p bw styrene and 2 5 p bw acryl copolymer) and (2) 54. 5% styrene-acrylonitrile copolymer (SAN, 7 5 Parts styrene / 2 5 parts acrylonitrile); 9.5phr resorcinol di (diphenyl phosphate); and 0.4 -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ο 3 5 2 4 4 A7B7 V. Description of the invention (< 3) ph r PTFE blend. There are insubstantial differences in the ratio of polycarbonate to addition polymer in these blends, and it is believed that these differences will not affect the nature of the study. The results are shown in Table V. Table V Blend 17 18 19 20 Organoclay, 0 0.1 0.25 0.50 phr UL-94 grade V-0 V-0 V-0 V-0 FOT, seconds 27.5 22.25 3 1 36.75 F0T%, decrease _ 19.0 .. ( Please read the notes on the back before filling out this page) The printed form V produced by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs shows that at this diphosphate concentration, only 0.1 phr of organoclay can improve the flame resistance. Example 6 A blend similar to Example 5 was prepared and tested (but containing about 82% polycarbonate, 18% addition polymer, and 7.5 phr diphosphate). The results are shown in Table VI. This paper size applies to the national standard (CNS) A4 specification (210 X 297 mm) -16- 442530 A7 B7 V. Description of the invention W)
表V I 摻合物 17 18 19 20 有機粘土， 0 0.1 0.25 0.50 phr UL-94等級 V-1 V-1 V-1 V-1 FOT,秒 69.75 61 40.25 65.75 FOT%，降低 •響 12.5 42.3 5.7 (請先閱讀背面之注意事項再填寫本頁) 在此二磷酸酯濃度下，0 . 1 - 0 . 25phr之有 機粘土可對難燃性有預期之改善。 實例7 製備並測試類似實例5之摻合物（但其含約8 2 . 4 %聚碳酸酯，17 . 6%加成聚合物與6 . Ophr二磷 酸酯）。結果如表V I。Table VI Blends 17 18 19 20 Organoclay, 0 0.1 0.25 0.50 phr UL-94 grade V-1 V-1 V-1 V-1 FOT, 69.75 61 40.25 65.75 FOT% in seconds, reduced 12.5 42.3 5.7 ( Please read the notes on the back before filling this page.) At this diphosphate concentration, 0.1 to 0.25 phr of organoclay can have an expected improvement in flame resistance. Example 7 A blend similar to Example 5 was prepared and tested (but containing about 82.4% polycarbonate, 17.6% addition polymer and 6.0 Ophr diphosphonate). The results are shown in Table VI.
表V I 摻合物 21 22 23 24 有機粘土， 0 0.1 0.25 0.50 phr UL-94等級 V-1 V-1 V-1 V-1 FOT,秒 84.5 86.5 157.25 152.5 FOT%，降低 __ __ _ _ _ 經濟部智慧財"局員工消費合作社印製 在此二磷酸酯濃度下，沒有任何含量之有機粘土對難 燃性有改善。 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Table VI Blend 21 22 23 24 Organoclay, 0 0.1 0.25 0.50 phr UL-94 grade V-1 V-1 V-1 V-1 FOT, seconds 84.5 86.5 157.25 152.5 FOT%, decrease __ __ _ _ _ _ Printed by the Consumer Cooperative of the Ministry of Economic Affairs' Bureau of Employees, at this diphosphate concentration, the organoclay without any content has improved flame resistance. -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)