201134925 六、發明說明： t 明所屬身軒々貝】 本發明係有關於無遷移、無_素之阻燃性熱塑性聚胺 曱酸酯組成物。 【先前技術3 發明背景 熱塑性聚胺曱酸酯（T P U)彈性體具有範圍廣泛的可撓 性，及可藉由從射出成型至擠壓與吹塑成型的多種方法製 造。其等亦提供透明度、耐磨損性、耐化學品與碳氫化合 物性質、承重能力及高抗張強度之性能優勢。因此，發現 其等在需要阻燃性的眾多應用中之用途。用於TPU組成物 中的傳統阻燃劑含有鹵素(所謂鹵化阻燃劑）。然而，由於對 於環境與安全性日益關切，對於非鹵化阻燃劑(HFFR)物質 之需求增加’而構成TPU式組成物之一項重大挑戰。 液態有機磷酸酯（如間苯二酚雙(磷酸二笨酯）(RDP)或 雙齡-A雙（磷酸二苯酯）(BDP))常用於聚合物中，以製得 HFFR調配物。然而，以含有液態磷酸g旨的HFFR tpu組成 物所製成之產品隨著時間而經歷磷酸酯阻燃劑之遷移，及 因此無法符合一些應用諸如電線與電纜外皮及絕緣層之非 遷移需求。 【發明内容】 發明概要 本發明之一方面係提供無鹵素卩且燃性組成物，其包含 基於該組成物總重之至少2〇重量百分比之包含一種熱塑性 201134925 聚胺曱酸酯的一樹脂連續相；基於該組成物總重之至少5重 量百分比之一種熔點至少5 0 °C的芳族有機磷酸酯阻燃劑； 及基於該組成物總重之至少20重量百分比之一種無機水合 物阻燃劑。該等組成物所包含之熔點為25°C以下的有機阻 燃劑係不超過基於該組成物總重之1 〇重量百分比。 在一些實施例中，該組成物包含基於該組成物總重之 至少30重量百分比之包含一種熱塑性聚胺曱酸酯的一樹脂 連續相；基於該組成物總重之至少5重量百分比之一種熔點 至少50°C的芳族有機磷酸酯阻燃劑，其中該芳族有機阻燃 性係一種芳族聚磷酸酯；及基於該組成物總重之至少30重 量百分比之一種無機水合物阻燃劑。在一些該等實施例 中，該組成物包含一種熔點為25°C以下的有機阻燃劑，其 中熔點為25°C以下的有機阻燃劑之重量百分比，係等於或 低於熔點至少50°C的芳族有機磷酸酯阻燃劑之重量百分 比。在一些該等實施例中，該組成物不含熔點為25°C以下 的有機阻燃劑。 該組成物的一些實施例之特徵在於由如本發明的一組 成物所組成之一電纜在50°C與80%相對濕度48小時後並不 展現遷移。 在一些實施例中，該組成物如藉由UL 1581-2001所測 量的熱變形率係不超過20%。 在一些實施例中，該組成物進一步包含一種環氧化酉分 酿清漆樹脂。 在一些實施例中，該組成物進一步包含分散於樹脂連 201134925 續相中或與樹脂連續相共連續之一種極性聚烯烴。 在一些實施例中，熔點至少50°C的芳族有機磷酸酯陴 燃劑係高分子量間苯二酚雙(磷酸二苯酯）、間苯二酚雙(磷 酸二曱苯酯）或其組合物。 本發明的另一方面係提供用於一電線或電纜的外皮成 絕緣層，其包含如本發明的一組成物。 圖式簡單說明 第1圖係用於本發明組成物的非遷移試驗之設置示意圖。 C實施方式】 較佳實施例之詳細說明 本發明的一方面係提供具有良好的機械與阻燃性性質 之一種無ii素、熱塑性聚胺曱酸酯式組成物。該組成物包 括在模製產品諸如電纜與電線外皮中並不展現遷移之阻燃 性有機磷化合物。該組成物包括包含一種熱塑性聚胺甲酸 龜彈性體之—樹脂連續相，至少一種熔點至少5〇°c的芳族 有機磷酸酷阻燃劑及一種無機水合物阻燃劑。在室溫，該 芳族有機磷酸酯阻燃劑在由本發明的組成物所製成的模製 物件中係一固體，及因此相對於使用液態有機磷酸酯阻燃 劑之可相比的阻燃劑組成物而言，該等組成物提供增進的 非遷移性質。 “無齒素”與類似詞彙係指該組成物沒有或實質上沒有 鹵素含量’亦即所含有的鹵素如藉由離子層析法(IC)或一種 類似的分析方法測得係低於2〇〇〇毫克/公斤。對於該摻合物 作為例如一種電線或電纜套之功效而言，低於該量的函素 201134925 含量被認為無關緊要。 該組成物係適用於多種模製熱塑性物件，包括電線與 電纜用外皮及絕緣層、汽車零件、屋與建築材料、玩具、 人造皮及電器與電子裝置。 熱塑性聚胺曱酸酯： 如用於此之“熱塑性聚胺曱酸酯”（或“TPU”），係指一種 二異氰酸酯、一或多種聚合型二醇及選擇性地一或多種雙 官能基鏈延長劑之反應產品。TPU可藉由預聚合物、半預 聚合物或一次性方法製備。二異氰酸酯在TPU中形成一硬 鏈段，及可為一芳族、脂族或環脂族二異氰酸酯及該等化 合物中的二或多者之組合物。衍生自二異氰酸酯（OCN-R-NCO)的結構單元之一個非限制性實例，係由下列化學式(I) 所代表： I? ? —C—HN-R-NH—C— ⑴ 其中R係一個伸烷基、伸環烷基或伸芳基。該等二異氰酸酯 的代表性實例可見於第4,385,133號、第4,522,975號及第 5,167,899號美國專利。適宜的二異氰酸酯之非限制性實例 包括4,4’-二-異氰酸基二苯基-甲烷、對伸苯基二異氰酸酯、 1，3-雙（異氰酸基甲基)-環已烷、M-二-異氰酸基-環已烷、 六亞曱基二異氰酸酯、1,5-萘二異氰酸酯、3,3’-二甲基-4,4’-聯苯基二異氰酸酯、4,4’-二-異氰酸基-二環己基曱烷及2,4-甲苯二異氰酸酯。 聚合型二醇在所產生的TPU中形成軟鏈段。聚合型二 201134925 醇的分子量（數目平均）例如可位於自200至10,000克/莫耳 之範圍。可使用一種以上的聚合型二醇。適宜的聚合型二 醇之非限制性實例包括聚醚二醇類（產生一種“聚醚 TPTJ”）；聚酯二醇類（產生一種“聚酯TPU”）；端羥基聚碳酸 酯類（產生一種“聚碳酸酯TPU”）；端羥基聚丁二烯類；端羥 基聚丁二烯-丙烯腈共聚物；二烷基矽氧烷與環氧烷諸如環 氧乙烷、環氧丙烷之端羥基共聚物；天然油脂二醇類，及 其任一組合物。前述聚合型二醇中之一或多者可與一種端 胺基聚醚及/或一種端胺基聚丁二烯-丙烯腈共聚物混合。 雙官能基鏈延長劑可為在鏈中具有2至10碳原子之脂 族直鏈與支鏈二醇。該等二醇的說明例為乙二醇、1,3-丙二 醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇之類； 1,4-環已烷二甲醇；氫醌雙-(羥基乙基）醚；伸環己基二醇 (1,4-、1,3-及1，2-異構物）、異亞丙基雙(環已醇）；二乙二醇、 二丙二醇、乙醇胺、N-曱基-二乙醇胺之類；及上述任一者 之混合物。如先前所述，在一些情況下，可以三官能基延 長劑置換較小比例（低於約2 0當量百分比）的雙官能基延長 劑，而不減損所產生的TPU之熱塑性；該等延長劑的說明 例為甘油、三經甲基丙烧之類。 在聚胺甲酸醋中所納入之鏈延長劑的量，係由特定反 應物組分之選擇、硬與軟鏈段的所欲量及足以提供良好的 機械性質之指標諸如模量與撕裂強度決定。 選擇性地，可使用少量之通常稱為“鏈停止劑”的單羥 基官能基或單胺基官能基化合物，以控制分子量。該等鏈 7 201134925 停止劑的說明例為丙醇類、丁醇類、戊醇類及己醇類。 適宜的TPU之非限制性實例，包括皆可自路博潤 (Lubrizol Corporation)公司取得之 PELLETHANEIM、 ESTANE™' TECOFLEX™' TECOPHILIC™ > TECOTHANE™ 及TECOPLASTTM熱塑性聚胺甲酸酯；可自巴斯夫（BASF) 公司取得之ELASTOLLAN™熱塑性聚胺甲酸酯及其他熱 塑性聚胺曱酸酯；及可自拜耳（Bayer)公司、亨斯邁 (Huntsman)公司、麥金莎（Merquinsa)公司及其他供應商取 得之附加的熱塑性聚胺甲酸酯材料。 在本發明的實施中所用之樹脂連續相的聚胺曱酸酯組 分，可含有如上述二或多者TPU之組合物。 TPU典型係以基於該組成物總重之至少20重量百分比 (重量％)之一量存在。其包括含有基於該組成物總重之至少 30重量％的TPU之組成物。例如，在一些實施例中，該組成 物包括約20至70重量％的TPU’約30至50重量％的TPU，或 約30至40重量％的TPU。 極性烯烴聚合物： 該無_素、TPU式組成物可選擇性地包括一或多種附 加的聚合物，諸如極性聚烯烴。其等可分散於該組成物之 樹脂連續相中或與樹脂連續相共連續。 “稀烴聚合物”稀烴型聚合物烯烴型互聚物” 聚烯烴”、”烯烴式聚合物”與類似詞彙，係指含有基於該聚 合物總重之大部份的重量百分比之一種聚合形式的烯烴例 如乙烯或丙烯之一種聚合物。熱塑性聚烯烴同時包括烯烴 201134925 同元聚合物與互聚物。“互聚物，，係指藉由聚合至少二種不 同的單體所製備之聚合物。互聚物可為隨機、嵌段、均相、 非均相等。該通稱係包括共聚物即通常用於指自二種不同 的單體所製備之聚合物，及包括二種以上的不同單體所製 備之聚合物如三元聚合物、四元聚合物等。 一種“極性烯烴聚合物”係含有一或多個極性基(有時稱 作極性官能度）之一種烯烴聚合物。如用於此之“極性基”， 係將一鍵偶極矩賦予在其他情況為實質上非極性烯烴分子 之任一基團。例示性極性基包括羰基、羧酸基、羧酸酐基、 叛酸酯基、環氧基、續醢基、腈基、醯胺基、石夕烧基之類。 該等基可經由接枝或共聚合作用而引入烯烴式聚合物中。 極性烯烴式聚合物的非限制性實例包括乙烯/丙烯酸 (EAA)、乙烯/甲基丙稀酸(EMA)、乙稀/丙烯酸酯或甲基丙 烯酸酯、乙烯/乙酸乙烯酯(EVA)、聚（乙浠-共-乙烯基三甲 氧基矽烷)共聚物、順丁烯二酸酐接枝型或矽烷接枝型烯烴 聚合物、聚（四氟乙烯-alt-乙烯)(ETFE)、聚（四氟乙烯-共-六氟-丙烯）(FEP)、聚（乙烯-共-四氟乙烯-共-六氟丙烯 (EFEP)、聚（二氟亞乙烯)(PVDF)，聚（氟乙烯）(PVF)之類。 較佳的極性稀烴聚合物包括DuPont ELVAXTM乙烯乙酸乙 烯酯（EVA)樹脂、來自陶氏(Dow)化學公司之AMPLIFY™。 烯乙基丙烯酸酯（EEA)共聚物、來自陶氏化學公司之 PRIMACOR™乙烯/丙烯酸共聚物及來自陶氏化學公司之 SI-LINK™聚（乙烯-共-乙烯基三曱氧基矽烷)共聚物。 EVA係一種較佳的極性烯烴聚合物。其包括EVA與選 201134925 自（^至(：6烷基丙烯酸酯、（^至(：6烷基甲基丙烯酸酯、丙烯 酸與曱基丙烯酸的一或多種共單體之共聚物。 當極性烯烴聚合物存在時，其典型用量範圍係基於該 組成物總重之自1至40重量％。 非遷移性芳族磷酸酯阻燃劑： 該無鹵素、阻燃性組成物包括至少一種芳族有機攝酸 酉旨式阻燃劑化合物諸如填酸S旨，其炫點係低至足以使其在 熔融加工處理與擠壓溫度（如2150°c)熔化，但高至使其在室 溫(23°C)的最終模製產品中以固體形式存在及通過下列實 例中所述的非遷移試驗。非遷移性芳族有機磷酸酯式阻燃 劑在擠壓期間以液體形式存在及藉此作用為潤滑劑係有利 的。因此，在一些實施例中，非遷移性芳族有機磷酸酯式 阻燃劑化合物的熔點為至少50°C、至少7〇°C、至少80°C或 至少100°C。 適宜的非遷移性芳族有機磷酸酯阻燃劑之實例包括芳 族聚磷酸酯，諸如高分子量間苯二酚雙（磷酸二苯酯）(P-RDP)與間苯二酚雙(磷酸二曱苯酯）(XDP)，其等之結構係如 下所示。 RDP的化學結構：201134925 VI. INSTRUCTIONS: t Ming Ming Xuan Mubei] The present invention relates to a non-migrating, non-volatile flame-retardant thermoplastic polyurethane phthalate composition. [Prior Art 3] The thermoplastic polyamine phthalate (T P U) elastomer has a wide range of flexibility and can be produced by various methods from injection molding to extrusion and blow molding. They also offer the performance advantages of transparency, abrasion resistance, chemical and hydrocarbon properties, load bearing capacity and high tensile strength. Therefore, it has been found to be useful in numerous applications requiring flame retardancy. Conventional flame retardants used in TPU compositions contain halogens (so-called halogenated flame retardants). However, due to increasing concerns about the environment and safety, the increased demand for non-halogenated flame retardant (HFFR) materials has become a major challenge for TPU-type compositions. Liquid organophosphates such as resorcinol bis(diphenyl phosphate) (RDP) or double age-A bis(diphenyl phosphate) (BDP) are commonly used in polymers to make HFFR formulations. However, products made with HFFR tpu compositions containing liquid phosphoric acid g undergo a migration of phosphate flame retardants over time and thus fail to meet the non-migration requirements of some applications such as wire and cable sheathing and insulation. SUMMARY OF THE INVENTION One aspect of the present invention provides a halogen-free cerium and flammable composition comprising a continuous resin comprising a thermoplastic 201134925 polyamine phthalate based on at least 2% by weight based on the total weight of the composition An aromatic organophosphate flame retardant having a melting point of at least 50 ° C based on at least 5 weight percent of the total weight of the composition; and an inorganic hydrate flame retardant based on at least 20 weight percent based on the total weight of the composition Agent. The organic flame retardant having a melting point of 25 ° C or less contained in the compositions does not exceed 1% by weight based on the total weight of the composition. In some embodiments, the composition comprises at least 30 weight percent of a continuous phase of the resin comprising a thermoplastic polyamine phthalate based on the total weight of the composition; a melting point of at least 5 weight percent based on the total weight of the composition An aromatic organophosphate flame retardant of at least 50 ° C, wherein the aromatic organic flame retardant is an aromatic polyphosphate; and an inorganic hydrate flame retardant based on at least 30% by weight based on the total weight of the composition . In some such embodiments, the composition comprises an organic flame retardant having a melting point of 25 ° C or less, wherein the weight percentage of the organic flame retardant having a melting point of 25 ° C or less is at least 50 ° or less than the melting point. The weight percentage of the aromatic organophosphate flame retardant of C. In some of these embodiments, the composition is free of organic flame retardants having a melting point below 25 °C. Some embodiments of the composition are characterized in that the cable consisting of one of the compositions of the present invention does not exhibit migration after 50 hours at 50 ° C and 80% relative humidity. In some embodiments, the composition has a coefficient of thermal deformation of no more than 20% as measured by UL 1581-2001. In some embodiments, the composition further comprises an epoxidized enamel varnish resin. In some embodiments, the composition further comprises a polar polyolefin dispersed in a continuous phase of the resin 201134925 or co-continuous with the continuous phase of the resin. In some embodiments, the aromatic organophosphate igniting agent having a melting point of at least 50 ° C is high molecular weight resorcinol bis(diphenyl phosphate), resorcinol bis (diphenyl phenyl phosphate) or a combination thereof Things. Another aspect of the present invention provides an outer insulating layer for a wire or cable comprising a composition as in the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the arrangement of a non-migration test for the composition of the present invention. C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One aspect of the present invention provides an ii-free, thermoplastic polyamine phthalate composition having good mechanical and flame retardant properties. The composition includes flame retardant organophosphorus compounds that do not exhibit migration in molded products such as cable and wire sheaths. The composition comprises a resin continuous phase comprising a thermoplastic polyurethane elastomer, at least one aromatic organic phosphate flame retardant having a melting point of at least 5 ° C and an inorganic hydrate flame retardant. At room temperature, the aromatic organophosphate flame retardant is a solid in the molded article made from the composition of the present invention, and thus comparable to the flame retardant using a liquid organophosphate flame retardant For compositions, the compositions provide enhanced non-migrating properties. "Adentate" and like words mean that the composition has no or substantially no halogen content', ie the halogen contained is as low as 2 by means of ion chromatography (IC) or a similar analytical method. 〇〇mg/kg. For the efficacy of the blend as, for example, a wire or cable jacket, a content below the amount of the element 201134925 is considered irrelevant. The composition is suitable for a variety of molded thermoplastic articles, including sheaths and insulation for wires and cables, automotive parts, house and building materials, toys, artificial leather, and electrical and electronic devices. Thermoplastic polyamine phthalate: as used herein, "thermoplastic polyamine phthalate" (or "TPU"), means a diisocyanate, one or more polymeric diols, and optionally one or more difunctional groups A reaction product of a chain extender. The TPU can be prepared by a prepolymer, a semi-prepolymer or a one-shot process. The diisocyanate forms a hard segment in the TPU and can be an aromatic, aliphatic or cycloaliphatic diisocyanate and a combination of two or more of these compounds. A non-limiting example of a structural unit derived from a diisocyanate (OCN-R-NCO) is represented by the following chemical formula (I): I??-C-HN-R-NH-C- (1) wherein R is a An alkyl group, a cycloalkyl group or an aryl group. Representative examples of such diisocyanates are found in U.S. Patent Nos. 4,385,133, 4,522,975, and 5,167,899. Non-limiting examples of suitable diisocyanates include 4,4'-di-isocyanatodiphenyl-methane, p-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)-cyclo Alkane, M-di-isocyanato-cyclohexane, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-di-isocyanato-dicyclohexyldecane and 2,4-toluene diisocyanate. The polymeric diol forms a soft segment in the TPU produced. Polymeric Type II 201134925 The molecular weight (number average) of the alcohol can be, for example, in the range of from 200 to 10,000 g/mole. More than one polymeric diol can be used. Non-limiting examples of suitable polymeric diols include polyether diols (which produce a "polyether TPTJ"); polyester diols (which produce a "polyester TPU"); hydroxyl terminated polycarbonates (produced) A "polycarbonate TPU"); a hydroxyl terminated polybutadiene; a hydroxyl terminated polybutadiene-acrylonitrile copolymer; a dialkyl siloxane and an alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl copolymer; natural oil diols, and any combination thereof. One or more of the aforementioned polymeric diols may be mixed with a terminal amino polyether and/or a terminal amine polybutadiene-acrylonitrile copolymer. The difunctional chain extender may be an aliphatic straight chain and a branched diol having 2 to 10 carbon atoms in the chain. Examples of such diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like; , 4-cyclohexanediethanol; hydroquinone bis-(hydroxyethyl)ether; cyclohexyl glycol (1,4-, 1,3- and 1,2-isomer), isopropylidene double (cyclohexanol); diethylene glycol, dipropylene glycol, ethanolamine, N-mercapto-diethanolamine, and the like; and a mixture of any of the above. As previously stated, in some cases, a trifunctional extender can be substituted for a smaller proportion (less than about 20 equivalent percent) of the difunctional extender without detracting from the thermoplasticity of the TPU produced; such extenders Illustrative examples are glycerin, trimethoprim and the like. The amount of chain extender incorporated in the polyurethane is determined by the choice of the particular reactant component, the desired amount of hard and soft segments, and an indicator sufficient to provide good mechanical properties such as modulus and tear strength. Decide. Alternatively, a small amount of a monohydroxy functional group or a monoamino functional compound, commonly referred to as a "chain stopper", can be used to control the molecular weight. Examples of such chains 7 201134925 Stoppers are propanols, butanols, pentanols and hexanols. Non-limiting examples of suitable TPUs include PELLETHANEIM, ESTANETM 'TECOFLEXTM' TECOPHILICTM > TECOTHANETM and TECOPLASTTM thermoplastic polyurethanes available from Lubrizol Corporation; available from BASF ( BASF) Company's ELASTOLLANTM thermoplastic polyurethane and other thermoplastic polyamine phthalates; and from Bayer, Huntsman, Merquinsa and other suppliers Additional thermoplastic polyurethane material obtained. The polyamine phthalate component of the continuous phase of the resin used in the practice of the present invention may contain a composition of two or more TPUs as described above. The TPU is typically present in an amount of at least 20 weight percent (wt%) based on the total weight of the composition. It comprises a composition comprising at least 30% by weight of TPU based on the total weight of the composition. For example, in some embodiments, the composition comprises from about 20 to 70 weight percent TPU' of from about 30 to 50 weight percent TPU, or from about 30 to 40 weight percent TPU. Polar olefin polymer: The non-element, TPU composition may optionally include one or more additional polymers, such as polar polyolefins. They may be dispersed in the continuous phase of the resin of the composition or may be co-continuous with the continuous phase of the resin. "Dilute hydrocarbon polymer" dilute hydrocarbon type polymer olefin type interpolymer "polyolefin", "olefin type polymer" and similar terms mean a polymerization containing a weight percentage based on a majority of the total weight of the polymer. A form of olefin such as a polymer of ethylene or propylene. Thermoplastic polyolefins include both olefins 201134925 homopolymers and interpolymers. "Interpolymer," refers to a polymer prepared by polymerizing at least two different monomers. The interpolymers may be random, block, homogeneous, and non-equal. The generic term includes copolymers that are commonly used. Refers to polymers prepared from two different monomers, and polymers prepared from two or more different monomers such as terpolymers, quaternary polymers, etc. A "polar olefin polymer" contains An olefin polymer of one or more polar groups (sometimes referred to as polar functionalities), such as the "polar group" used herein, imparts a one-bond dipole moment to other substantially non-polar olefin molecules. Any of the groups. Exemplary polar groups include a carbonyl group, a carboxylic acid group, a carboxylic anhydride group, a tickate group, an epoxy group, a fluorenyl group, a nitrile group, a decyl group, a sulfonyl group, and the like. It can be introduced into the olefin polymer via grafting or copolymerization. Non-limiting examples of polar olefin polymers include ethylene/acrylic acid (EAA), ethylene/methyl acrylate (EMA), ethylene/acrylate Or methacrylate, ethylene/vinyl acetate (EVA), poly (B) -co-vinyltrimethoxydecane copolymer, maleic anhydride grafted or decane grafted olefin polymer, poly(tetrafluoroethylene-alt-ethylene) (ETFE), poly(tetrafluoroethylene- Co-hexafluoro-propylene) (FEP), poly(ethylene-co-tetrafluoroethylene-co-hexafluoropropylene (EFEP), poly(difluoroethylene) (PVDF), poly(fluoroethylene) (PVF) Preferred polar dilute hydrocarbon polymers include DuPont ELVAXTM ethylene vinyl acetate (EVA) resin, AMPLIFYTM from Dow Chemical Company. Ethyl Ethyl Acrylate (EEA) Copolymer, from The Dow Chemical Company PRIMACORTM ethylene/acrylic acid copolymer and SI-LINKTM poly(ethylene-co-vinyltrimethoxy decane) copolymer from The Dow Chemical Company. EVA is a preferred polar olefin polymer including EVA. And selected 201134925 from (^ to (6 alkyl acrylate, (^ to (: 6 alkyl methacrylate, acrylic acid and methacrylic acid copolymer of one or more comonomers. When polar olefin polymer exists The typical amount range is from 1 to 40% by weight based on the total weight of the composition. Non-migratory aromatic Phosphate flame retardant: The halogen-free, flame-retardant composition comprises at least one aromatic organic acid-reducing flame retardant compound such as acid-filling S, which has a sleek point that is low enough to be processed in a melt processing process. The extrusion temperature (e.g., 2150 ° C) melts, but is high enough to be present in solid form in the final molded product at room temperature (23 ° C) and passed the non-migration test described in the following examples. The organophosphorus ester type flame retardant is present in a liquid form during extrusion and thereby acting as a lubricant. Accordingly, in some embodiments, the melting point of the non-migratory aromatic organophosphate flame retardant compound It is at least 50 ° C, at least 7 ° C, at least 80 ° C or at least 100 ° C. Examples of suitable non-migratory aromatic organophosphate flame retardants include aromatic polyphosphates such as high molecular weight resorcinol bis(diphenyl phosphate) (P-RDP) and resorcinol bis (phosphoric acid) Phenylphenyl ester) (XDP), and the structures thereof are as follows. The chemical structure of RDP:
XDP的化學結構： 10 201134925Chemical structure of XDP: 10 201134925
就高分子量Ρ-RDP而言，η可為例如1.7至1.8，及分子 量]Mw可為650至700。 非遷移性、芳族有機磷酸酯阻燃劑典型的存在量，係 基於該組成物總重之至少5重量％。其包括含有基於該組成 物總重之至少10重量°/〇的非遷移性、芳族有機磷酸酯阻燃 劑之組成物。例如，在一些實施例中，該組成物包括約5至 20重量％的非遷移性、芳族有機磷酸酯阻燃劑，或約10至15 重量％的非遷移性、芳族有機磷酸酯阻燃劑。 其他有機阻燃劑： 除了非遷移性、芳族有機磷酸酯阻燃劑之外，本發明 的組成物可選擇性地包括一或多種液態（在室溫）有機磷酸 酿限燃劑。在室溫，該等液態有機磷酸酯阻燃劑在由該組 成物所製成的模製物件中係以液態形式存在，及/或具有相 對較低的熔點藉此其等有助於阻燃劑在該模製物件中之遷 多例如，6亥專液態有機礙酸酯阻燃劑之特徵可在於熔點 為5 C以下。该組成物中之該等液態有機碟酸醋阻燃劑的 濃度應低，較佳地低於非遷移性芳族磷酸酯阻燃劑的濃 在本發明的組成物中選擇性地可包括之液態有機填酸 =阻燃劑的實例，係芳族聚磷酸酯諸如液態rdp與雙酚A二 磷酸酯（BPADP)及單磷酸酯諸如磷酸三丁氧乙醋（TBEp)、 碟酸三甲基酯（TMP)及磷酸三乙基酯（TEp)。 201134925 在本發明的組成物中可包含之其他有機阻燃劑，係包 括磷式與氮式阻燃劑。其等包括但不限於磷酸鹽類、膦酸 鹽類及含氮阻燃劑。 在一些實施例中，該組成物不含有液態（在室溫;)有機阻 燃劑。在其他實施例中’該組成物所包含之液態（在室溫） 有機阻燃劑係不超過10重量％、不超過8重量％或不超過5 重量％，以該組成物的總重為基礎。例如，該組成物可包 括基於該組成物總重之0.1至10重量％的液態（在室溫）有機 阻燃劑。其包括其中該組成物包含基於該組成物總重之2至8 重置％的液態（在室溫)有機阻燃劑之實施例。 在一些實施例中，除了非遷移性芳族有機磷酸酯阻燃 劑以外，該組成物完全不含有機阻燃劑。在其他實施例中， 除了非遷移性芳族有機磷酸酯阻燃劑以外，該組成物包含 不超過10重量❶/。、不超過8重量％或不超過5重量％的有機阻 燃劑，以該組成物的總重為基礎。例如，除了非遷移性芳 族有機磷酸酯阻燃劑以外，該組成物可包括〇丨至川重量％ 的有機阻燃劑，以該組成物的總重為基礎。其包括其中除 了非遷移性芳族有機磷酸酯阻燃劑以外，該組成物包括基於 該組成物總重之2至8重量％的有機阻燃狀實施例。 無機水合物： 本發明的組成物中之無機水合物賦予該組成物阻燃性 質。適宜的實例包括但秘於金錢氧化物，諸如氫氧化 #(亦稱為ATH或三水合旬與氫氧化鎂（㈣為二氮氧化 鎂）。其他實例包括氫氧_、鹼式碳酸㉝、驗式破酸錯、 12 201134925 水滑石、碳I弓鎂礦及水菱鎂礦。 無機水合物的典型用量係至少20重量％，以該組成物 的總重為基礎。其包括其中該無機水合物的用量係基於該 組成物總重之至少30重量％之實施例。例如，在一些實施 例中，該無機水合物的用量係20至50重量％，以該組成物 的總重為基礎。其包括其中該無機水合物的用量係基於該 組成物總重之30至40重量％之實施例。 環氧化酚醛清漆樹脂： 本發明的組成物可選擇性地包括一或多種成炭劑，以 避免或盡量減少燃燒期間的熔滴現象。例如，該組成物的 一些實施例係包括作為成炭劑之一種環氧化盼醒清漆樹 脂。“環氧化酚醛清漆樹脂”係表氯醇與酚式酚醛清漆聚合 物在一種有機溶劑中之反應產物。適宜的有機溶劑之非限 制性實例包括丙酮、曱基乙基酮、曱基戊基酮及二曱苯。 環氧化酚醛清漆樹脂可為一種液體、半固體、固體及其組 合物。 環氧化酚醛清漆樹脂典型的用量範圍係自0.1至5重量 %，以該組成物的總重為基礎。其包括其中該環氧化酚醛 清漆樹脂的用量範圍係基於該組成物總重之自1至3重量％ 之實施例；及進一步包括其中該環氧化酚醛清漆樹脂的用 量範圍係基於該組成物總重之自1.5至2.5重量％之實施例。 選擇性添加劑與填料： 本發明的組成物選擇性地亦可含有添加劑及/或填 料。代表性添加劑包括但不限於抗氧化劑、加工助劑，著 13 201134925 ^劑、紫外線安定劑（包括紫外線吸叫抗靜電劑、成核 劑，滑劑、塑化劑、潤滑劑、黏度控制劑、增黏 塊劑、表面活性劑、調合、，山触 ''員、除酸劑及金屬減活劑。該 4添加劑典型地係以—習用 白用方式與習用量使用，如基於該 組成物總重之自0.01重量。/ η 里里以下至1〇重量％以上。 代表性填料包括但不限於各種金屬氧化物如二氧化 Τ金屬碳酸鹽諸如碳酸鎂與碳金屬硫化物與硫酸 鹽諸如二硫⑽與硫金屬爾鹽諸如魏鎖、偏蝴 U、彌鋅及偏硼酸鋅；金屬_如贿；黏土諸如石夕 藻土、咼嶺土與蒙脫土；碳鈣鎂礦；矽鈣石；石綿；研磨 礦物質；及鋅齡。料_典魏仙—制方式與習 用量使用，如基於該組成物重量之自5重量％以下至50重量 %以上。 適宜的紫外光安定劑包括受阻胺光安定劑(HALS)及紫 外光吸收劑(UVA)添加劑。 抗氧化劑之實例包括但不限於受阻酚類諸如肆[亞甲 基(3,5-二-三級丁基-4-羥氫-桂皮酸酯曱烷；雙[({3_(3,5_二 三級丁基-4-羥基苄基)_甲基羧乙基)]硫化物、4,4’-硫代雙 (2-曱基-6-三級丁基苯酚）、4,4’-硫代雙(2-三級丁基-5-甲基 苯酚）、2,2，-硫代雙(4-甲基-6-三級丁基苯酚)及硫代二乙烯 雙(3,5-二-三級丁基-4-羥基）氫桂皮酸酯；亞磷酸酯與亞膦 酸酯諸如參(2,4-二-三級丁基苯基）亞磷酸酯與二-三級丁基 苯基-亞膦酸酯；硫代化合物諸如二月桂基硫代二丙酸酯、 硫二丙酸二肉豆蔻基酯及硫二丙酸二硬脂基酯；各種矽氧 14 201134925 名δ型2,2,4-二甲基-1，2-二氫啥琳、二甲基 戊基-对伸苯基二胺）、烷基化二笨基胺、4,4，-雙(α，α_二曱基 苄基)一笨基胺、二苯基-對伸苯基二胺、混合型二_芳基對 伸苯基二胺，及其他受阻胺抗降解劑或安定劑。 加工助劑的實例包括但不限於羧酸的金屬鹽類諸如硬 脂酸鋅或硬脂酸鈣；脂肪酸類諸如硬脂酸、油酸或芥子酸； 脂肪酿胺類諸如硬脂醯胺、油醯胺、芥子醯胺或Ν，Ν，-乙稀 雙-硬脂醯胺；聚乙烯蠟；氧化聚乙烯蠟；環氧乙烷的聚合 物；環氧乙烷與環氧丙烷的共聚物；植物蠟；石油蠟；非 離子性表面活性劑；矽油類與聚矽氧烷類。 組成物性質： 該組成物之特徵可在於其等的抗遷移性以及其等良好 的機械與阻燃性質。 非遷移性： 由本發明的組成物所製成的電纜之遷移試驗，係使用 下列實例（“非遷移性試驗”）中所述之設置，在5〇°C與80%相 對濕度進行48小時。 熱變形： 依據UL 1581-2001，經本發明組成物的一些實施例塗 覆之電線在15(TC及350克的負載(3·5士0.2N)所展現之熱變 形率一般低於30%。在一些實施例中，依據UL 1581-2001 在150。(：及350克的負載(3.5 土 0.2Ν)測量，經塗覆的電線所展 現的熱變形係不超過25百分比或甚至不超過20百分比。 阻燃性： 15 201134925 經該組成物的一些實施例塗覆之電線，係通過1^ VW-1火焰評級。“VW-1”係一項針對電線與套管之保險業實 驗室（Underwriters’ LaboratoryXUL)火焰評級。其表示“垂直 電線第1級”’其係電線或套管在^^^ 1441規格下所能得到的 最咼火焰評級。該試驗係藉由將電線或套管置於一垂直位 置而進行。火焰係置於其下方一段時間，然後移開。然後指 出套管的特性。vw-i火焰試驗係依的方法1080 測定。 抗張強度與斷裂伸長度： 本發明的組成物之特徵可在於其等斷裂時之抗張強度 (以MPa為單位）及斷裂時之伸長度（％)。可在依據aSTM D4703製備的壓縮模製試樣上，依據astmd_638試驗程序 測量抗張強度與伸長度。斷裂伸長度或致斷伸長度係當斷 裂時之一試樣上的應變。其通常以百分比表示。 本發明組成物之一些實施例在斷裂時的抗張強度係至 少10 MPa ^其包括在斷裂時的抗張強度係至少12 Mpa之組 成物，及進一步包括在斷裂時的抗張強度係至少15 Mpa2 組成物。 本發明組成物的一些實施例之斷裂伸長度係至少 200°/^其包括斷裂伸長度係至少3〇〇%之組成物，及進一步 包括斷裂伸長度係至少320%之組成物。 炼體流動速率： 依據ASTMD1238-04程序C，在條件19〇它/2 16公斤測 量熔體流動速率(MFR)。該組成物的一些實施例之MFR係至 201134925 少10克/10分鐘。其包括MFR係至少12克/10分鐘之組成物。 複合作用： 可藉由混合TPU、任何附加的聚合物、無機水合物、 非遷移性磷酸酯阻燃劑及任何附加的有機阻燃劑、環氧化 酚醛清漆樹脂、添加劑及填料，而形成該組成物。該混合 作用可以逐步方式或以單—步驟進行，及可在習用的滾筒 裝置中進行。可在高於該非遷移性磷酸酯阻燃劑的熔點之 一溫度’複合該組成物。In the case of the high molecular weight ruthenium-RDP, η may be, for example, 1.7 to 1.8, and the molecular weight] Mw may be 650 to 700. Non-migratory, aromatic organophosphate flame retardants are typically present in an amount of at least 5% by weight based on the total weight of the composition. It comprises a composition comprising a non-migratory, aromatic organophosphate flame retardant based on at least 10 weight percent per gram of the total weight of the composition. For example, in some embodiments, the composition comprises from about 5 to 20 weight percent non-migrating, aromatic organophosphate flame retardant, or from about 10 to 15 weight percent non-migratory, aromatic organophosphate resistance Burning agent. Other Organic Flame Retardants: In addition to the non-migratory, aromatic organophosphate flame retardant, the compositions of the present invention may optionally include one or more liquid (at room temperature) organophosphate flame retardant. At room temperature, the liquid organophosphate flame retardant is present in a liquid form in a molded article made of the composition, and/or has a relatively low melting point thereby contributing to flame retardancy The migration of the agent in the molded article, for example, may be characterized by a melting point of 5 C or less. The concentration of the liquid organic dish vinegar flame retardant in the composition should be low, preferably lower than the concentration of the non-migratory aromatic phosphate flame retardant, optionally included in the composition of the present invention. Examples of liquid organic acid-filling = flame retardant are aromatic polyphosphates such as liquid rdp and bisphenol A diphosphate (BPADP) and monophosphates such as tributyloxyacetate (TBEp), trimethyl silicate Ester (TMP) and triethyl phosphate (TEp). 201134925 Other organic flame retardants which may be included in the compositions of the present invention include phosphorus and nitrogen flame retardants. These include, but are not limited to, phosphates, phosphonates, and nitrogen-containing flame retardants. In some embodiments, the composition does not contain a liquid (at room temperature;) organic flame retardant. In other embodiments, the liquid (at room temperature) organic flame retardant comprised by the composition is no more than 10% by weight, no more than 8% by weight, or no more than 5% by weight, based on the total weight of the composition. . For example, the composition may include a liquid (at room temperature) organic flame retardant based on 0.1 to 10% by weight based on the total weight of the composition. It includes embodiments in which the composition comprises a liquid (at room temperature) organic flame retardant based on a 2 to 8 percent by weight of the total weight of the composition. In some embodiments, the composition is completely free of organic flame retardants except for the non-migratory aromatic organophosphate flame retardant. In other embodiments, the composition comprises no more than 10 weights ❶/, in addition to the non-migratory aromatic organophosphate flame retardant. The organic flame retardant is not more than 8% by weight or not more than 5% by weight based on the total weight of the composition. For example, in addition to the non-migratory aromatic organophosphate flame retardant, the composition may include a weight percent organic flame retardant based on the total weight of the composition. It includes embodiments in which, in addition to the non-migratory aromatic organophosphate flame retardant, the composition comprises from 2 to 8 wt% of an organic flame retardant based on the total weight of the composition. Inorganic hydrate: The inorganic hydrate in the composition of the present invention imparts flame retardancy to the composition. Suitable examples include but are secretive to monetary oxides such as hydroxide # (also known as ATH or trihydrate and magnesium hydroxide ((iv) is magnesium oxynitride). Other examples include hydrogen oxygen, basic carbonic acid 33, test Acid-destroy, 12 201134925 hydrotalcite, carbon I-magnesium ore and hydromagnesite. The inorganic hydrate is typically used in an amount of at least 20% by weight based on the total weight of the composition, including the inorganic hydrate therein. The amount is based on at least 30% by weight of the total weight of the composition. For example, in some embodiments, the inorganic hydrate is used in an amount of 20 to 50% by weight based on the total weight of the composition. An example in which the inorganic hydrate is used in an amount of from 30 to 40% by weight based on the total weight of the composition. Epoxidized novolac resin: The composition of the present invention may optionally include one or more char formers to avoid Or to minimize the phenomenon of droplets during combustion. For example, some examples of the composition include an epoxidized varnish resin as a carbon-forming agent. "Epoxidized novolac resin" is epichlorohydrin and phenol novolac a reaction product of a lacquer polymer in an organic solvent. Non-limiting examples of suitable organic solvents include acetone, mercaptoethyl ketone, decyl amyl ketone and diphenyl benzene. The epoxidized novolac resin can be a liquid, Semi-solid, solid, and combinations thereof. The epoxidized novolac resin is typically used in an amount ranging from 0.1 to 5% by weight based on the total weight of the composition, which includes wherein the amount of the epoxidized novolac resin is based on The composition has a total weight of from 1 to 3% by weight of the embodiment; and further includes an embodiment wherein the epoxidized novolac resin is used in an amount ranging from 1.5 to 2.5% by weight based on the total weight of the composition. And filler: The composition of the present invention may optionally further contain additives and/or fillers. Representative additives include, but are not limited to, antioxidants, processing aids, 13 201134925 ^ agent, ultraviolet stabilizer (including ultraviolet absorption antistatic) Agent, nucleating agent, slip agent, plasticizer, lubricant, viscosity control agent, viscosity increasing agent, surfactant, blending, mountain contact, 'acid scavenger And a metal deactivator. The 4 additive is typically used in a conventional manner and in a conventional amount, such as from 0.01 weight based on the total weight of the composition. / η 里里以下至1〇重量% or more. Including but not limited to various metal oxides such as cerium oxide metal carbonates such as magnesium carbonate and carbon metal sulfides and sulphates such as disulfide (10) and sulphur metal salts such as Weisuo, smectite U, zinc and zinc metaborate; Metals such as bribes; clays such as Shixiazao, Qiling and montmorillonite; carbon-calcium-magnesium ore; calcareous; asbestos; grinding minerals; and zinc age. It is used, for example, from 5% by weight or less to 50% by weight or more based on the weight of the composition. Suitable ultraviolet light stabilizers include hindered amine light stabilizers (HALS) and ultraviolet light absorber (UVA) additives. Examples of antioxidants include, but are not limited to, hindered phenols such as hydrazine [methylene (3,5-di-tertiary butyl-4-hydroxyhydro-cinnamate decane; double [({3_(3,5_) Di-tertiary butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulfide, 4,4'-thiobis(2-mercapto-6-tertiary butylphenol), 4,4' - thiobis(2-tert-butyl-5-methylphenol), 2,2,-thiobis(4-methyl-6-tertiary butylphenol) and thiodiethylene bis (3, 5-di-tertiary butyl-4-hydroxy)hydrocinnamate; phosphites and phosphonites such as ginseng (2,4-di-tertiary butylphenyl) phosphite and di- to tertiary Butyl phenyl-phosphonite; thio compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate; various cesium oxides 14 201134925 δ type 2,2,4-dimethyl-1,2-dihydroanthracene, dimethylpentyl-p-phenylenediamine), alkylated dimethanolamine, 4,4,-bis ( α,α-Dimercaptobenzyl)-stupylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamine, and other hindered amine antidegradants or stabilizers. Examples of processing aids include, but are not limited to, metal salts of carboxylic acids such as zinc stearate or calcium stearate; fatty acids such as stearic acid, oleic acid or sinapic acid; fatty amines such as stearamide, oil Guanidine, mustard amide or hydrazine, hydrazine, -ethylene bis-stearylamine; polyethylene wax; oxidized polyethylene wax; polymer of ethylene oxide; copolymer of ethylene oxide and propylene oxide; Vegetable wax; petroleum wax; nonionic surfactant; eucalyptus oil and polyoxyalkylene. Composition Properties: The composition may be characterized by its resistance to migration and its good mechanical and flame retardant properties. Non-migration: The migration test of the cable made of the composition of the present invention was carried out at 5 ° C and 80% relative humidity for 48 hours using the settings described in the following examples ("non-migration test"). Thermal Deformation: According to UL 1581-2001, the wire coated by some embodiments of the composition of the present invention exhibits a thermal deformation rate generally less than 30% at 15 (TC and 350 gram load (3.5 ft. 0.2N). In some embodiments, the coated wire exhibits a thermal deformation of no more than 25 percent or even no more than 20 percent, measured according to UL 1581-2001 at 150. (and a load of 350 grams (3.5 soil 0.2 Torr)). Flame Retardancy: 15 201134925 Wires coated by some embodiments of this composition are rated by 1^VW-1 flame. "VW-1" is an insurance laboratory for wires and casings (Underwriters) 'LaboratoryXUL' flame rating. It means "vertical wire level 1" 'the best flame rating that can be obtained by wire or casing under ^^^ 1441. The test is by placing a wire or sleeve The flame is placed underneath for a period of time and then removed. The characteristics of the casing are then indicated. The vw-i flame test is determined by the method 1080. Tensile strength and elongation at break: Composition of the invention The object may be characterized by its tensile strength when it is broken. Degree (in MPa) and elongation at break (%). Tensile strength and elongation can be measured on a compression molded specimen prepared according to aSTM D4703 according to the astmd_638 test procedure. Elongation at break or elongation at break Degree is the strain on one of the samples when fractured. It is usually expressed as a percentage. Some examples of the composition of the present invention have a tensile strength at break of at least 10 MPa ^ which includes at least tensile strength at break. The composition of 12 Mpa, and further comprising a tensile strength at break is at least 15 Mpa2 composition. Some embodiments of the composition of the invention have an elongation at break of at least 200°/^ which includes an elongation at break of at least 3〇. The composition of 〇%, and further comprising a composition having an elongation at break of at least 320%. Refining fluid flow rate: The melt flow rate (MFR) is measured according to ASTM D1238-04 Procedure C, under conditions 19 /2 2 / 16 kg. Some embodiments of the composition have an MFR of 10 g/10 min less than 201134925. It comprises a composition of at least 12 g/10 min of MFR. Composite effect: by mixing TPU, any additional polymer, inorganic a composition, a non-migratory phosphate flame retardant, and any additional organic flame retardants, epoxidized novolak resins, additives, and fillers to form the composition. The mixing can be carried out in a stepwise manner or in a single step, and This can be carried out in a conventional roller unit. The composition can be compounded at a temperature above the melting point of the non-migratory phosphate flame retardant.
該組成物的複合作用可藉由標準複合設備達成。複合 設備的實例為批式密閉混合器，諸如BanburyTM或B〇1UngTM 密閉混合器。任擇地，可使用連續式單螺桿或雙螺桿混合 器，諸如Farrel™連續式混合器、Werner & pfleidererTM雙螺 桿混合器或Buss™連續式捏合擠壓機。所用的混合器類型 及該混合器的操作條件’將影響組成物的性質諸如黏度、 體積電阻率及擠製表面平滑度。所產生的組成物最好可模 製與成形成為一物件’諸如供進一步加工處理之電線外 皮、型材、板或丸狀物。 物件： 本發月的另方面係提供包含本發明的一或多種組成 物之物件，諸如模製或擠製物件。 物件已括電線與電甓外皮與絕緣層。因此，在一些實 把例中’該物件包括—金屬導體與該金屬導體上的一塗 層以提（、可傳輸電力之一“絕緣，，電線。如用於此之“金屬 導體”係用於傳輸電力；_ , 、 电刀及/或電信號之至少一種金屬組分。電 17 201134925 線人電也的可撓性通常為所需的，因而該金屬導體可具有 -個固態橫截面或擇優地可由較細的電線股所組成，而增 加既定的整料體聽之可撓性。魏通常由數種也分諸 如形成-個内芯的多條絕緣電線所組成，_由提供保護 作用與美觀❸卜觀之電紐㈣關繞。魏被覆系統可 納入金屬層諸如㈣材或鐘裝，及典型地在表面上具有一聚 合物層。在保護性/美觀性電歷覆中所納人的—或多個聚 合物層，通常稱作電纜“外皮”。就-些電纜而言，該被覆 僅為圍繞—電妓之—聚合型外皮層。亦有-些電纜在導 體周圍僅有單層聚合物圍繞，而該單層聚合物同時扮演絕 緣層與外皮之角色。本發明的組成物可在全系列的電線與 電纜產品中使用作為該聚合型組分或用於該聚合型組分 中，包括電力電繞及金屬與光纖通訊應用。可使用各種類 型的擠壓機如單螺桿或雙螺桿型製備一電纜，而該電纜所 含有的一絕緣層係包含本發明的一組成物。 下列貫例係說明本發明的不同實施例。所有部分與百 分比係以重量為基礎’除非另有說明。 具體實施例 下列實例係說明用於製造如本發明的熱塑性組成物之 方法實施例。 材料· 本實例中所用的TPU係聚伸丁二醇醚TPU(路博潤先進 材料（Lubrizol Advanced Materials)公司之PELLETHANE™ 2103-90AE)及一種醚式TPU(路博潤先進材料公司之 201134925The composite action of the composition can be achieved by standard composite equipment. An example of a composite device is a batch closed mixer such as a BanburyTM or B〇1 UngTM closed mixer. Alternatively, a continuous single screw or twin screw mixer such as a FarrelTM continuous mixer, a Werner & pfleidererTM twin screw mixer or a BussTM continuous kneading extruder can be used. The type of mixer used and the operating conditions of the mixer will affect the properties of the composition such as viscosity, volume resistivity and extruded surface smoothness. Preferably, the resulting composition can be molded and formed into an article such as a wire sheath, profile, sheet or pellet for further processing. Object: Another aspect of the present month provides articles, such as molded or extruded articles, comprising one or more of the compositions of the present invention. The object has included wires and an electric sheath and insulation. Therefore, in some practical examples, the object includes a metal conductor and a coating on the metal conductor (", one of the transmittable power" is insulated, and the wire is used as a "metal conductor" for this purpose. For transmitting electrical power; at least one metal component of an electric knife and/or an electrical signal. Electricity 17 201134925 The flexibility of the line human power is also generally required, and thus the metal conductor may have a solid cross section or Preferably, it can be composed of thin wire strands and increase the flexibility of a given monolith. Wei is usually composed of several insulated wires, such as forming an inner core, to provide protection. It is closed with the beautiful electric power (4). The Wei coating system can be incorporated into a metal layer such as (four) material or clock, and typically has a polymer layer on the surface. In the protective / aesthetic electrical calendar Human- or multiple polymer layers, commonly referred to as cable "skins." For some cables, the coating is only around the --polymeric outer skin layer. There are also some cables around the conductor. a single layer of polymer surrounded by the single layer polymer The role of the insulating layer and the outer skin. The composition of the present invention can be used as a polymeric component or in the polymeric component in a full range of wire and cable products, including power electrical winding and metal to optical fiber communication. Application. A cable can be prepared using various types of extruders, such as a single screw or twin screw type, and the cable contains an insulating layer comprising a composition of the present invention. The following examples illustrate different embodiments of the present invention. All parts and percentages are based on weight 'unless otherwise stated. DETAILED DESCRIPTION OF THE INVENTION The following examples illustrate method examples for the manufacture of thermoplastic compositions as in the present invention. Materials · TPUs used in this example Glycol Ether TPU (PELLETHANETM 2103-90AE from Lubrizol Advanced Materials) and an etheric TPU (201134925 from Lubrizol Advanced Materials)
ESTANE® 58219)。在使用之前，TPU試樣係在真空與90°C 預乾燥至少6小時。 使用氫氧化鋁(ATH)作為無機水合物(H42M等級，來自 昭和（Showa)化學工業株式會社）。 在第1比較例中使用間苯二酚雙(磷酸二苯酯）(RDP)(來 自旭瑞達（Supresta)公司之Fyrolflex® RDP等級）；及在第2 比較例與第3至5發明例中，以所取得形式使用雙(磷酸二苯 酯）(BDP)(自艾迪科(Adeka)公司取得及等級名稱為FP600)。 用於發明實例中之非遷移性芳族有機磷酸酯阻燃劑係 間苯二酚雙（磷酸二甲苯酯）(來自大八(Daihachi)化學工業 株式會社之PX-200XPD)及在室溫為固體及具有55至60°C 的熔點與670至680的分子量之高分子量粉狀RDP(來自雅克 (Yoke)化學公司之p-RDP)。 該實例包括一種環氧酚醛清漆（來自陶氏化學公司之 DEN438)及下列添加劑/填料··（1)四氟乙烯-共_苯乙烯-共· 丙浠腈（來自大金(Daikin)公司之AD001等級）；（2)二氧化鈦 (來自杜邦(DuPont)公司之RMO);⑺一種抗氧化劑（來自汽 巴特殊化學品（C.iba Specialty Chemicals)公司之爾加諾斯 (Irganox) 1010 ;來自汽巴特殊化學品公司之爾加弗斯 (Irgafos) 126 ;及來自汽巴特殊化學品公司之爾加弗斯 (Irgafos) MD1024) ; (4)—種加工安定劑（來自汽巴特殊化學 品公司之爾加弗斯(Irgafos) 168); (5) —種紫外線安定劑（來自 汽巴特殊化學品公司之堤努梵(Tinuvin) 866);及一種配色 添加劑（來自科萊恩(Clariant)公司之科萊恩(Clariant；) MB)。 19 201134925 方法： 第A表中所示之組成物係在一種雙螺桿擠壓機上製 備’及針對其擠壓特性與關鍵性質進行評估。顯示比較實 例（CE)與發明實例（IE)。下列步驟係用於材料製備作用與評 估作用。在50公升的高速混合器中，添加所有的τρυ樹脂 及一部分的三水合氧化鋁填料及混合1〇秒。然後在混合物 中添加剩餘的三水合氧化鋁以及固態鱗酸酯 及如果存在的液態磷酸酯出1^與111：)1>)。將經預熱的環氧化 酚醛清漆逐步用勺加入混合器中。然後添加爾加諾斯 (Irganox) 1〇1〇與爾加弗斯(Irgaf〇s) 168添加劑。 旦在混合器中添加所有組分之後’其等在1800 RPM 作匕& 1刀知。經預混的摻合物然後藉由料筒溫度為、 螺才干直徑為3 5.5毫米及L / D為3 8 6之一種雙螺桿擠壓機擠 製’及產出約為20公斤/小時。最後，所產生的丸狀物在12〇 °C乾燥6小時。 第A表 调配物 (以重量％為 單位之比例） CEl CE2 IE1 IE2 IE3 IE4 IE5 2103-90AE(TPU) 33.03 33.03 33.03 58219(TPU) Λ χττ 33.03 33.03 33.03 33.03 A1 ri ri r\n 39.69 39.69 39.69 39.69 39.69 39.69 KUr .13.04 BDP 13.04 2.00 2.00 6.50 PX-200 13.04 11.04 6 50 P-RDP DEN438 13.04 11.04 1,74 1.74 1.74 1.74 1.74 1.74 0.86 AD-001 0.06 0.06 0.06 0.06 0.06 0.06 0.06 168 6.09 0.09 0.09 0.09 0.09 0.09 0.09 1010 0.52 0.52 0.52 0.52 0.52 0 52 〇 52 二氧化鈦 8.9 8.9 8.9 8.9 8.9 8.9 8.90 UV 886 i.oo 1.00 1.00 1.00 1.00 1.00 1.00 科萊恩(Clariant) 1.93 1.93 1.9T1 1.93 1.93 1.93 2.00 20 201134925 MB 總和 100.00 100.00 100.00 100.00 100.00 100.00 100.00 模擬VW-1 通過 通過 通過 通過 通過 通過 通過 抗張伸長度，％ 367 342 336 303 318 228 322 抗張強度，MPa 12.74 15.25 16.35 13.64 16.1 14.3 15.2 MFR(I90°C、2_16 公斤) 10.55 7.94 9.30 12.80 6.00 10.12 12.50 熱變形，％ 42 32 11 30 17 16 16 非遷移試驗 未通過 未通過 通過 通過 通過 通過 Γϋ過 特性分析： 依據ASTM D-638 ’在室溫及50毫米/分鐘的速度測量 在斷裂時的抗張強度與斷裂伸長度。抗張試驗係在英斯特 朗（INSTRON) 5565抗張測試儀上進行。用於抗張試驗之試 樣係壓縮模製板，其在185。(：的成型溫度使用一低壓循環以 促進炼化作用及接著暴露於高壓以成形該丨4χ2〇〇χ2〇〇毫 米的板而製備。該模具係維持在高壓（15MPa)，及在8分鐘 期間冷卻至室溫以固化該板。 模擬VW-1試驗係在一個UL-94箱中進行。試驗樣品的 尺寸為200*2.7*1.9微米。該試樣係掛在一個失子上，藉由 在其下端施用50克的負載而使得其長軸垂直。在電線頂端 放置一紙製旗子（2*〇.5公分）。火焰底部（燃燒器預示的最高 點）與旗子底部之間的距離為18公分。連續施用火焰45秒。 在火焰時間之後(AFT)，記錄燃燒期間與之後之未燒焦的電 線長度（UCL)與未燒毁的旗子面積百分比（未燒毀的旗 子）。武驗各試樣之四或五個樣品。若有下列現象中之任一 者’將導致評級為“未通過，，：⑴試樣品下方的棉花被點燃； (2)旗子被燒盡；或(3)觀察到火焰的熔滴現象。 依據UL 1581-2001進行熱變形試驗。針對各調配物， 21 201134925 將二個平行試樣板置於一烘箱中及於15(TC預熱丨小時。經 預熱的試樣然後在15(rc以相同負載按壓〖小時。之後，在 不移除重量之情況下，將經按壓的試樣置於溫度設定為23 之ASTM至中再1小時。§己錄試樣板的厚度變化，及依據 HDyo^Dc-D^D^loo%計算熱變形率，其中％代表原始的 試樣厚度及表在變形過程後的試樣厚度。將該二平行 試樣計算所得的變形率加以平均。 以第1圖所示之裝配枕座進行非遷移試驗。由如本發明 之一組成物所組成之二條電纜丨〇 2係夾在二個塑膠板丨〇 4之 間，而塑膠板又夾在二個玻璃板1〇6之間，及在該總成頂部 置有500克的負載1〇8。所用的塑膠板為pc、ABS及pc/ ABS。電纜係在三種板中的各類型上進行試驗（亦即三次— 各以一種類型的板進行）。電纜直徑並非關鍵。可使用直徑 約0.5毫米至約10毫米的電纜。各板的尺寸為9公分χ6公 分。二條電纜係突出超過壓板（寬度為6〇毫米八該總成然後 在50°C、80%相對濕度中儲存48小時。然後以9〇〇/。乙醇清潔 塑朦板。就本揭露内容之目的而言，藉由目視檢查判定， 若在試驗後在PC、ABS及PC/ABS板上未觀察到殘餘或蝕 刻，則一組成物通過非遷移性試驗。 結果· 第1比較例係使用RDP作為磷酸酯式阻燃劑，及第2比 較例係使用BDP作為磷酸醋式阻燃劑。由液態碟酸能阻燃 劑所製成之該二比較實例並未通過非遷移性試驗，在所有 塑膠板上皆造成威重敍刻。 22 201134925 相較之下，其中液態RDP與BDP被一種非遷移性固態 磷酸酯阻燃劑(PX-200或P-RDP)置換之第1與2發明例，則通 過非遷移性試驗。相對於比較實例，獲致至少相當的燃燒 性能與機械性質。 第3與4發明例使用2% BDP與11.04%固態磷酸酯（PX-200或P-RDP)作為磷酸酯式阻燃劑。該二組成物亦通過非遷 移性試驗。相對於比較實例，獲致至少相當的燃燒性能與 機械性質。 第5發明例使用6.5% BDP與6.5%固態磷酸酯（卩乂-200) 作為ί粦酸酯式阻燃劑。該組成物亦通過非遷移性試驗。相 對於比較實例，獲致至少相當的燃燒性能與機械性質。該 等實例的結果顯示當BDP的添加量低至2%或6.5%時，最終 的電纟覽仍可通過非遷移性試驗。調配物中所存在的BDP， 可協助預混合該調配物中之一種高黏度液體DEN438。 所有提及的元素週期表係指CRC出版有限公司於2003 年出版及版權所有之元素週期表。同時，任何提及之一或 多族’應為該元素週期表使用供族編號所用的IUPAC系統 所反映之一或多族。除非有相反的說明，從上下文所隱含 或技藝中所習用，所有部分與百分比係以重量為基礎，及 所有試驗方法在本揭露内容的申請日係最新的。就美國專 利實務之目的而言，任何所引述的專利、專利申請案或公 開案之内各係在此完整地併入本案以為參考資料（或其等 效的美國版本係在此併入本案以為參考資料），特別是關於 &成技術、產品與加工設計、聚合物、催化劑、定義（在不 23 201134925 抵觸本揭露内容所明確提供的定義之程度）及技藝常識之 揭露内容。 本揭露内容中的數值範圍係約略，除非另有說明。數 值範圍係包括自較小數值至較讀值之_ —單位遞增之 所有數值，前提在於在任—較小數值與任-較大數值之間 至少間隔二個單位。舉例而言，若_組成、物理或其他性 質諸如例如抗張強度、斷裂伸長度等係自100至1，_，則 其意圖係明確地列舉所有個別數值諸如100、101、102等及 子範圍諸如100至丨44、155至】70、197至2〇〇等。就含有小 於1的數值或含有大於i的分數(如丨」、丨5等)之範圍而言， 一單位係在適當情況下視為〇 〇〇〇1、〇 〇〇1、〇 〇1或〇 1。就 含有小於_個位數數值(如⑴)之範圍而言，_單位典^ 地視為0_1。其等僅為所具體預期者之實例，及所列舉的最 小數值與最大數值之_數值之所有可驗合，係視為明 確地述於本揭露内容中。 如用於有關—化學化合物方面’除非明確地另有說 明，早數詞彙係包括所有異_彡式及反之純(例如” 係個別或集體地包括己烷的所有異構物）。“化合物，，與^ 物，，等詞係以可互換方式用於指有機化合物、無機化合^ 有機金屬化合物。 或5司係指個別及任-組合的所列成員，除非 說明。 M F另有 雖然經由前述說明、圖 本發明，該細節係為了說明 式及實例’已相當詳細地說明 之目的。嫻熟技藝者可進行眾 24 201134925 多變化與改質，而不偏離如所附申請專利範圍所述之本發 明的精神與範圍。 【圖式簡單說明3 第1圖係用於本發明組成物的非遷移試驗之設置示意圖 【主要元件符號說明】 102…電纜 104··.塑膠板 106...玻璃板 108... 500克的負載 25ESTANE® 58219). Prior to use, the TPU samples were pre-dried under vacuum at 90 ° C for at least 6 hours. Aluminum hydroxide (ATH) was used as the inorganic hydrate (H42M grade, from Showa Chemical Industry Co., Ltd.). In the first comparative example, resorcinol bis(diphenyl phosphate) (RDP) (Fyrolflex® RDP grade from Supresta Co., Ltd.) was used; and in the second comparative example and the third to fifth invention examples In the obtained form, bis(diphenyl phosphate) (BDP) (obtained from Adeka Corporation and grade name FP600) was used. The non-migratory aromatic organophosphate flame retardant used in the inventive example is resorcinol bis (xylylene phosphate) (from PX-200XPD of Daihachi Chemical Industry Co., Ltd.) and at room temperature A solid and a high molecular weight powdered RDP having a molecular weight of 55 to 60 ° C and a molecular weight of 670 to 680 (p-RDP from Yoke Chemical Co., Ltd.). This example includes an epoxy novolac (DEN 438 from The Dow Chemical Company) and the following additives/fillers (1) tetrafluoroethylene-co-styrene-co-acrylonitrile (from Daikin) AD001 grade); (2) Titanium dioxide (from RPont of DuPont); (7) An antioxidant (Irganox 1010 from C.iba Specialty Chemicals); from steam Irgafos 126 of Pakistan Specialty Chemicals; Irgafos MD1024 from Ciba Specialty Chemicals; (4) Kind of processing stabilizer (from Ciba Specialty Chemicals) Irgafos 168); (5) UV stabilizer (Tinuvin 866 from Ciba Specialty Chemicals); and a color matching additive (from Clariant) Clariant; MB). 19 201134925 Method: The composition shown in Table A is prepared on a twin-screw extruder and evaluated for its extrusion properties and critical properties. A comparative example (CE) and an inventive example (IE) are shown. The following steps are used for material preparation and evaluation. In a 50 liter high speed mixer, add all of the τρυ resin and a portion of the alumina trihydrate filler and mix for 1 second. The remaining alumina trihydrate and the solid sulphate are then added to the mixture and, if present, the liquid phosphate is 1 & 111:) >). The preheated epoxidized novolac is gradually added to the mixer with a spoon. Then add Irganox 1〇1〇 and Irgaf〇s 168 Additive. Once all the components have been added to the mixer, they are then treated at 1800 RPM. The premixed blend was then extruded by a twin screw extruder having a barrel temperature of 35.5 mm and a L/D of 386 and yielded about 20 kg/hr. Finally, the resulting pellets were dried at 12 ° C for 6 hours. Formula A Formulation (proportion by weight %) CEl CE2 IE1 IE2 IE3 IE4 IE5 2103-90AE (TPU) 33.03 33.03 33.03 58219(TPU) Λ χττ 33.03 33.03 33.03 33.03 A1 ri ri r\n 39.69 39.69 39.69 39.69 39.69 39.69 KUr .13.04 BDP 13.04 2.00 2.00 6.50 PX-200 13.04 11.04 6 50 P-RDP DEN438 13.04 11.04 1,74 1.74 1.74 1.74 1.74 1.74 0.86 AD-001 0.06 0.06 0.06 0.06 0.06 0.06 0.06 168 6.09 0.09 0.09 0.09 0.09 0.09 0.09 1010 0.52 0.52 0.52 0.52 0.52 0 52 〇52 Titanium dioxide 8.9 8.9 8.9 8.9 8.9 8.9 8.90 UV 886 i.oo 1.00 1.00 1.00 1.00 1.00 1.00 Clariant 1.93 1.93 1.9T1 1.93 1.93 1.93 2.00 20 201134925 MB Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Simulated VW-1 by pass-through by passing tensile elongation, % 367 342 336 303 318 228 322 Tensile strength, MPa 12.74 15.25 16.35 13.64 16.1 14.3 15.2 MFR (I90 ° C, 2_16 kg) 10.55 7.94 9.30 12.80 6.00 10.12 12.50 Thermal deformation, % 42 32 11 30 17 16 16 Non-migration Test fail fail pass through characteristics by analysis by Γϋ: tensile strength and elongation at break 'at room temperature and speed of 50 mm / min at break measured according to ASTM D-638. The tensile test was performed on an INSTRON 5565 tensile tester. The test piece used for the tensile test was a compression molded plate at 185. The molding temperature of (: was prepared using a low pressure cycle to promote refining and subsequent exposure to high pressure to form the plate of 丨4χ2〇〇χ2 mm. The mold was maintained at high pressure (15 MPa) and during 8 minutes. Cool to room temperature to cure the plate. The simulated VW-1 test was performed in a UL-94 chamber. The size of the test sample was 200*2.7*1.9 microns. The sample was hung on a missing piece by Apply a load of 50 grams to the lower end so that its long axis is vertical. Place a paper flag (2*〇.5 cm) at the top of the wire. The distance between the bottom of the flame (the highest point predicted by the burner) and the bottom of the flag is 18 Centimeters. Continuous application of flame for 45 seconds. After the flame time (AFT), record the unburned wire length (UCL) during and after the burn with the percentage of unburned flag area (unburned flag). Four or five samples. If any of the following phenomena will result in a rating of "failed,: (1) the cotton under the test sample is ignited; (2) the flag is burned out; or (3) observed Dropping to the flame. According to UL 1581-2001 Thermal deformation test. For each formulation, 21 201134925 Two parallel sample plates were placed in an oven and preheated at 15 (TC). The preheated sample was then pressed at 15 (rc with the same load) After that, the pressed sample is placed in ASTM to a temperature of 23 for 1 hour without removing the weight. § The thickness of the sample plate is changed, and according to HDyo^Dc-D ^D^loo% calculates the thermal deformation rate, where % represents the original sample thickness and the thickness of the sample after the deformation process. The deformation rate calculated from the two parallel samples is averaged. The assembly pillow is subjected to a non-migration test. Two cable clamps 2 composed of one composition of the present invention are sandwiched between two plastic sheets 4, and the plastic sheets are sandwiched between two glass sheets 1〇6. Between the top and the top of the assembly is a load of 500 〇 8. The plastic plates used are pc, ABS and pc/ABS. The cable is tested on each of the three types (ie three times each) In one type of plate). Cable diameter is not critical. Use a diameter of about 0.5 mm to 10 mm cable. The dimensions of each plate are 9 cm χ 6 cm. The two cables protrude beyond the pressure plate (width is 6 mm mm. The assembly is then stored at 50 ° C, 80% relative humidity for 48 hours. Then 9 〇 〇/. Ethanol cleans the plastic board. For the purposes of this disclosure, by visual inspection, if no residue or etching is observed on the PC, ABS, and PC/ABS boards after the test, a composition is passed. Non-migration test. Results · The first comparative example used RDP as a phosphate ester type flame retardant, and the second comparative example used BDP as a phosphoric acid vinegar type flame retardant. It was made of a liquid dish acid flame retardant. The two comparative examples did not pass the non-migration test, which caused heavy weight characterization on all plastic panels. 22 201134925 In contrast, the first and second invention examples in which liquid RDP and BDP are replaced by a non-migratory solid phosphate flame retardant (PX-200 or P-RDP) pass the non-migration test. At least comparable combustion performance and mechanical properties were obtained with respect to the comparative examples. The inventive examples 3 and 4 used 2% BDP and 11.04% solid phosphate (PX-200 or P-RDP) as a phosphate flame retardant. The two compositions also passed the non-migration test. At least comparable combustion performance and mechanical properties were obtained with respect to the comparative examples. The fifth invention used 6.5% BDP and 6.5% solid phosphate (卩乂-200) as a phthalate type flame retardant. The composition also passed the non-migration test. At least comparable combustion performance and mechanical properties were obtained with respect to the comparative examples. The results of these examples show that when the amount of BDP added is as low as 2% or 6.5%, the final electrical view can still pass the non-migration test. The BDP present in the formulation assists in premixing a high viscosity liquid DEN 438 in the formulation. All references to the Periodic Table of the Elements refer to the Periodic Table of the Elements published and copyrighted by CRC Publishing Co., Ltd. in 2003. At the same time, any reference to one or more of the families should be one or more of the IUPAC systems used for the use of the family number for the periodic table. All parts and percentages are based on weight, and all test methods are current on the filing date of this disclosure, unless otherwise indicated by the context or in the art. For the purposes of U.S. Patent Practice, any reference to the patents, patent applications, or publications herein is hereby incorporated by reference in its entirety in its entirety in References, in particular, about & technology, product and process design, polymers, catalysts, definitions (in the absence of 23 201134925 against the definitions explicitly provided in this disclosure) and the disclosure of technical common sense. Numerical ranges in the present disclosure are approximate unless otherwise stated. The range of values includes all values from the smaller value to the _-unit increment of the lesser reading, provided that there is at least two units between the arbitrarily-smaller value and the arbitrarily-larger value. For example, if _ composition, physical or other properties such as, for example, tensile strength, elongation at break, etc., are from 100 to 1, _, then the intent is to explicitly recite all individual values such as 100, 101, 102, etc. and subranges. Such as 100 to 丨 44, 155 to 】 70, 197 to 2 〇〇, and the like. In the case of a range containing values less than 1 or containing fractions greater than i (eg 丨, 丨 5, etc.), a unit is considered to be 〇〇〇〇 1, 〇〇〇 1, 〇〇 1 or 〇1. For a range containing values less than _ single digits (e.g., (1)), the _ unit is considered to be 0_1. They are only examples of the specific intended embodiments, and all the combinations of the numerical values listed and the numerical values of the maximum values are considered to be explicitly stated in the disclosure. As used in relation to - chemical compounds, unless otherwise explicitly stated, the early vocabulary includes all isoforms and vice versa (eg, "all isoforms that include hexane individually or collectively." The words "," and "," are used interchangeably to refer to organic compounds, inorganic compounds, and organometallic compounds. Or 5 divisions means the listed members of the individual and any-combination unless stated otherwise. M F, although the invention has been described in considerable detail for the purposes of illustration and example. A person skilled in the art can make a variety of changes and modifications without departing from the spirit and scope of the invention as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the arrangement of a non-migration test for the composition of the present invention [Description of main components] 102... Cable 104··. Plastic plate 106... Glass plate 108... 500 g Load 25