200936681 六、發明說明： 【發明所屬之技術領域3 發明領域 5 ❹ 10 15 20 本發明係關於一種暗色素熱塑性彈性體組成物，特別 是，其使用於鞋類組件中。這類組件在磨損摩擦上較佳地 具有低斑紋特性，且更佳地是沒有斑紋特性。 【先前技術3 發明背景 熱塑性彈性體（T PE )組成物係以在室溫下表現如彈性 體橡膠’但當加熱時可類似塑膠般被加工之材料為主。這 些材料具有可比擬硫化過之橡膠的外觀和觸感，即便其等 技術、可使用性及回收利用性皆是典型之熱塑性產品。 最常在鞋底製造上使用中的TPE係苯乙烯嵌段共聚 物，諸如聚苯乙烯-丁二烯—苯乙烯（SBS)共聚物。 以SBS及/或熱塑性聚氨基甲酸酯（TPU )為主之TPE組成 物已被使用於鞋類工業中有幾年了；包含SBS、乙烯乙酸乙 烯酯（EVA)、油類、聚烯烴、TPU、填充物、抗氧化物、色 素及其他成份之配方在該工業中係廣為周知。這類配方之 改良已在習知技藝中被描述，例如經添加金屬茂聚烯烴所 獲得之「消光外觀」。（W0 01/25331) 在W0 2006/090221中揭示以聚氨基甲酸酯組份為主熱 塑性材料，該材料係供以形成輕泡沫化產品，特別是，以 形成用於鞋類之鞋底。 暗色之TPE已知具有接觸表面之不為所欲的斑紋效 3 200936681 應。特別是當該化合物被使用於製造鞋底時，這類表現係 不為所欲。對於獲得適合用於製造在接觸表面不具斑紋效 應的鞋底之TPE化合物的需求仍未被滿足。 【明内3 5 發明概要 本發明係關於一種適合用於製造物件，特別是，鞋類 組件之暗色素熱塑性彈性體組成物。這類組成物包含： (a) —或多苯乙烯—丁二烯—苯乙烯嵌段共聚物（SBS)，&/ 或至少（b)與（c)之一者，其中：（b)係一或多聚烯烴 10 彈性體’其係乙烯（ethene)(該用語ethylene較常被 使用）與一 烯烴共單體之烯烴共聚物，或丙烯與乙 稀或一 α-烯烴共單體之共聚物，及（c)係一或多熱塑 性聚氨基甲酸酯（TPU);及 (d) —黑色素組成物，其不具炭黑； 15 (e)選擇性地，聚二曱基矽氧烷（PDMS); (〇選擇性地’一或多選自增效劑油、填充物、硬度調節 劑、流動改良劑、抗撓曲龜裂性改良劑、安定劑、 UV安定劑、色素、發泡劑及抗嵌段試劑之成份。 以上所描述之TPE組成物可被特別地使用於製造暗色 20鞋類組件，諸如鞋底和鞋跟。 除此之外’根據本發明該TPE組成物可在其他TPE組成 #被使用且在摩擦之下具有低或無斑紋效應係為所欲之領 域中發現其他工業應用。 【貧施方式】 200936681 較佳實施例之詳細說明 根據本發明該TPE組成物使得生產經製造之物件可 行，特別疋自磨損摩擦中不具接觸表面斑紋之鞋底，其典 型地與本暗色素熱塑性彈性體化合物有關。 5 在本描述及巾請專利範圍巾，「料#鮮餘成粉」 暗色素熱塑性彈性體（TPE)組成物表示氏表一含有 一或多著色色素之崩磨炫彈尨邀鈕成#，其中於該轉塑餒 彈#邀鈕成物中總著色色素至少4〇重量百分比係一黑色色 素。 10 本發明中该ΤΡΕ組成物之各組份（a)、（b)及（C)可交替 地、單獨或如以下所指示與其它兩者之至少一者依重量比 率組合出現於該組成物中。該組份（d )構成本發明之特定且 有區別的特徵且總是出現在本發明之TPE組成物中。該組 份（e)及（〇係選擇性地出現於該τρΕ組成物中。根據本發 15明之-較佳實施例’列於⑴中之—或多成分係通常被這些 TPE組成物所包含。 该TPE組成物之該單一組份係更詳細地描述如下： 組份（a) 本組份係藉由一或多苯乙烯-丁二烯_苯乙烯（SBS)嵌 2〇段共聚物所組成，該共聚物具有二或多有區別的聚合物嵌 段，其中至少一者在工作溫度下係玻璃狀（如在玻璃轉化點 之下，因而易碎且堅硬）但在較高溫度下是為流體，且其中 至^、者在工作溫度下係彈性體（如在玻璃轉化點之上，因 而可彎曲或有彈性）。 5 200936681 根據本發明所利用之苯乙烯-丁二烯—苯乙烯嵌段共聚 物中，該苯乙烯（S)及丁二烯（B)單體可分別被其他乙烯芳 香族及1,3-共輕二稀單體所取代。因此，在本描述及申請 專利範圍中，若無另外明確說明，該用語「T二濰—茗乙輝 5 二#兹段弃求物」或「兹段為聚物」也包括那些笨 乙烯及丁二烯單體被其他乙烯芳香族及1，3-共軛二烯所取 代之嵌段共聚物，其之後將更詳細定義。 該SBS嵌段共聚物可以線性雙嵌段、三嵌段及多嵌段 SBS共聚物之形式存在或以放射SBS嵌段共聚物之形式存 10 在。 根據本發明，一線性SBS嵌段共聚物及放射SBS嵌段共 聚物之混合物也可被使用。 根據本發明，用於製造這些SBS嵌段共聚物以供使用之 方法在該技藝中係廣為周知。查照US 3, 251，905、此 15 3, 231，635、US 3, 598, 887及US 4, 219, 627以為例。 該SBS嵌段共聚物之玻璃狀嵌段係藉由一乙烯芳香埃 單體’諸如苯乙烯所製得。雖然笨乙烯係較佳單體，其他 乙烯芳香族單體也可被使用，諸如α-甲基苯乙烯、當笨環 由一至三個（Ci-co烷基所取代，該烷基較佳地係甲 20 基或乙基之其他苯乙烯衍生物、或選擇性地由一或二個甲 基或乙基所取代之乙烯萘。各笨乙烯玻璃狀聚合物嵌段含 有至少80莫耳百分比之總苯乙烯單體數量，其餘部分，如 果有的話，由其他乙稀芳香族單體’例如α-甲基笨乙歸所 組成。 6 200936681 5 10 15 20 根據本發明’被使用為該TPE組成物組份（&)的沾3欲段 共聚物之彈性體嵌段係藉由經聚合之共軛13_二稀諸如 丁二烯所製得。雖然1，3-丁二烯係較佳單體，其他具5__6個 碳原子之共軛二烯也可被使用，諸如異戊二稀、丨3戍二 稀、2, 3-二甲基-1，3-丁二浠及2, 4-己二烯。 這些共輛一稀可依1，2或1，4之方式聚合至一乙烯基含 量在5至80%(莫耳％)範圍之間。 該SBS嵌段共聚物之各彈性體嵌段含有一多於，較 佳至少70%(莫耳％)之總共輛二稀單體，諸如丁二稀或異戊 二稀’其餘部分，如果有的話，藉由其他可共聚合之單體 如乙稀芳香族單體所組成。 根據本發明，被使用為組份（a)之該SBS嵌段共聚物也 可被部分或完全氫化。 用以使用為組份（a)之較佳氫化SBS嵌段共聚物係其中 只有該彈性體嵌段係選擇性地氫化（於總不飽和度上通常 超過80% ’較佳超過99%(莫耳％))之SBS嵌段共聚物。 在一實施例中，該SBS嵌段共聚物中1，3-共扼二烯，較 佳係丁二烯；與乙烯芳香族單體，較佳係苯乙烯，之間的 比例係自90至10，較佳地係自80至20，更佳地係自70至 30(莫耳％)。 該SBS嵌段共聚物之總重量平均分子量較佳地係介於 100. 000至500.000之間，更佳地係介於150.000至 400.000(克/莫耳）。 該SBS嵌段共聚物可用碳氫增效劑油，諸如石蠟及/或 7 200936681 環烷油，在介於總經增效SBS嵌段共聚物〇至4〇重量百分比 間之數量，而被增效，該石蠟及/或環烷油其後將更詳細描 述。該增效劑油可以是已經包括於商業上可得之SBS嵌段共 聚物中。 5 基於該組成物之總重罝，該TPE組成物中組份（a)之數 量一般介於0至80重量百分比之間，較佳地〇至7〇之間，更 佳地介於0至60重量百分比之間。 適合用於本發明之TPE組成物之SBS嵌段共聚物包括 EUROPRENE SO 1 T172 SBS嵌段共聚物（義大利米蘭聖多拿多 ίο 米蘭市之波里梅理歐帕）、KRAT0N(美國德克薩斯州佛特沃 司市德克薩斯太平洋）、STERE0N(美國俄亥俄州阿肯市凡斯 頓）、FINAPRENE (比利時布魯塞爾道達爾石化彈性體）、 TUFPRENE (曰本東京旭化成株式會社）及其他。 基於該組成物之總重量，組份（a)之SBS嵌段共聚物材 15 料可被聚丁二烯聚合物（見表1中，「.纽汾/」為例）、聚烯 烴彈性體，諸如乙烯/丙烯共聚物，例如EPDM共聚物或苯 乙烯-丁二烯（SBR)共聚物，部分取代至40%重量。 組份（b) 本組份藉由一或多聚烯烴彈性體所組成。用以使用於 20 本發明TPE組成物中的組份（b)之烯烴共聚物係一具有 0· 86至0. 92 g/cm3之密度且係經由乙稀與α —稀煙共聚合 作用，或經由丙烯與乙烯或具有4至12個碳原子之α-烯 烴共聚合作用所獲得之烯烴共聚物。於一較佳實施例中’ 該烯烴共聚物係經由乙烯與α-烯烴共聚合作用，該α一烯 200936681 a - 烴包括，但不侷限於，丙烯及具有4至12個碳原子之 烯烴，且更佳係經由乙烯與卜丁烯、1-己烯或1—辛烯共聚 合作用所獲得。 5 ⑩ 10 15 ❹ 使用於形成組份（b)之乙烯或丙烯與烯烴共聚物之 α-烯烴，該稀烴具有4至12個碳原子的例子包括卜丁 烯、2-甲基-1-丁烯、3_甲基―卜丁稀、卜戊烯、4—甲基-卜 戊烯、卜己烯、1-辛烯、1—癸烯及卜十二烯。這些烯烴 可被單獨地或以二或多之組合使用以提供該烯烴共聚物 之結構單元。 組份（b)之烯烴共聚物可以是任何已知的材料。例如： 那些具有0.86至0.92 g/cm3之密度，選自包括可得自陶氏 化學公司之ENGAGE(產品名）、由艾克索美孚化學公司製造 之EXACT系列（產品名）、由三井石化工業公司製造之TAFMER 系列（產品名）及住友化學工業公司製造之ESPREN sp〇 N系 列（產品名）之產品。 用於使用於本發明中之以金屬茂為主的聚烯烴彈性體 (包括在例如次-金屬茂觸媒之金屬茂觸媒存在下製備且含 有幾何觸媒之彈性體）的例子係被描述在，例如，美國專利 4, 871，705，5322728及5272236中。特別地，於一乙稀及 共單體之良好分佈下，藉由共聚合乙烯與8%至4〇%(莫耳％) 之一具3至20個竣原子，較佳地具4至12個碳原子，更 佳地具6至10個碳原子之_烯烴所產生之金屬茂聚烯烴 係適合使用為組份（b)。除此之外’這類聚烯烴具有一低結 晶度係較佳的。 20 200936681 較佳地’這些金屬茂聚烯烴具有一介於〇. 5至40 g/min 之間（「MFI」在190°C/5kg ’與ISO 1133 —致而決定），較 佳地介於1. 0至30 g/min之融炫流動指數，且其等之密度 係介於0· 86至0. 89 kg/Ι之間’且較佳地係介於〇. 86至 5 0.885 kg/1。 可被利用為本發明之TPE組成物的組份（b)之商業上可 得的金屬茂聚烯烴係’例如，於商標AFFINITY及ENGAGE(由 陶氏化學公司）、EXACT(由艾克索美孚化學公司）及 TAMFER(來自三井石化工業公司）下銷售之乙烯（或乙烯）_ 〇 10 辛烯共聚物。 基於該組成物之總重量，本發明之TPE組成物中的組 伤（b)之數量可介於0至99重量百分比之間，較佳地介於〇 和80，更佳地介於〇和60。 組份（c) 15 本組份係藉由熱塑性聚錄甲酸醋（TPU)所組成，即藉 ·.. 由-二異氰_域物與至少—可與—異級基反應之纟 官能化合物及選擇性地-鏈延長劑所反應而獲得之物質， 該雙官能化合物較佳地係至少—雙官能多經基化合物。該 用語雙官能意指該異氛酸組成物或該多經基化合物之平均 20官能度係約2。該二異氰酸醋反應物可能是芳香族的或脂肪 族的。芳香族的二異氰酸酯包括，例如，“，及2 2，一二 苯基-甲烧二異氰酸醋⑽）及其相對應之同份異構混合 物。"亥-異氰酸醋組份也可能為一 MDI變體。謝變體係該 技藝中所習知，⑽別地包括藉㈣人碳二醯胺基至該二 10 200936681 異氰酸酯組成物中所獲得之液態產物。脂肪族及環脂肪族 的異氰酸化合物之例子包括1，6-六亞曱基〜二異氰酸酿 (HDI)、異佛爾酮二異氰酸酯（IPDI)、4, 4’ -、2, 2,-及 2, 4,- 5 10 15 20 甲烯雙環二異氰酸酯（H12MDI)，其等之同份異構混合物、 1，3-四亞甲基二甲苯二異氰酸醋、諾本（norbane)二異氰酸 酯及1,3-和1,4-二異氰酸曱基環己烷也可被使用於本發 明。芳香族、脂肪族及環脂肪族的異氰酸酯之混合物也可 被使用。 包含芳香族二異氰酸酯之異氰酸酯組成物係較佳且更 佳地係MDI。 於一實施例中，該雙官能化合物，較佳地係一雙官能 多羥基化合物’具有500至20000之間之分子量，且可選 自下列化合物之衍生物：聚酯醯胺、聚硫醚、聚碳酸醋、 聚縮醛、聚烯烴、聚矽氧烷及尤其是聚酯、聚醚、聚己内 酯或其等之混合物。聚酯包括羥基聚酯、二羥基醇，諸如 乙二醇、丙二醇、二乙二醇、1,4-丁二醇、新戊二醇、2_ 甲基丙一醇、3-甲基戊炫-1,5-二醇、1，己二醇、或環己 烧一甲醇之反應產物或其等之混合物，及二叛酸或其醋 類，諸如己一酸醋、戊二酸自旨、琥轴酸醋、癸二酸g旨及對 苯二甲酸、鄰苯二甲酐、四氣鄰笨二甲酐或其等之混合物。 聚醚包括在必要之雙官能起始劑存在時，經由聚合一 環氧化物如乙烯、丙烯、丁烯氧化物或四氫呋喃所獲得之 產物。適當的起始劑化合物包括水、乙二醇、丙二醇、二 乙二醇、三乙二醇、二丙二醇、1，3_丙二醇、丨，4_丁二醇、 11 200936681 新戊二醇、1，5_戊二醇、1，6-己二醇及類似物。起始劑及/ 或環氧化物之混合物可被使用。 聚烯烴二醇包括端羥基丁二蛾之同元聚合物及共聚 物。 5 適當的鏈延長劑包括脂肪族二醇，諸如乙二醇、1，3- 丙二醇、1,4-丁二醇、1,5-戊二醇、1，6-己二醇、1,2-丙 二醇、2-甲基丙二醇、1,3-丁二醇、2, 3-丁二醇、1，3-戊 二醇、1，2-己二醇、3-甲基戊烷-1，5-二醇、新戊二醇、二 乙二醇、二丙二醇及三丙二醇及胺基醇，諸如乙醇胺、N-1〇 曱基二乙醇胺及類似物；1，4-丁二醇係較佳。 使用為本發明之TPE組成物的組份（c)之TPU可選擇性 地含有添加劑、安定劑、界面活性劑及泡沫安定劑、增塑 劑及類似物。 可與TPU混合之添加劑係，例如，聚氣乙烯或乙烯乙 15 酸乙烯酯、石蠟或環烷油、礦物性來源之填充物及類似物。 可被添加至TPU之安定劑包括抗靜電劑及抗氧化物及 抗UV劑。 可被添加至TPU之界面活性劑及泡沫安定劑包括，例 如，聚醚改性聚矽氧烷共聚物。 20 TPU組份之增塑劑包括，例如，烧基-鄰苯二甲酸酯及 烷基-苯曱酸鹽。 適當的TPU係商業上可得的，且尤其包括該等以 EPAM0ULD(義大利米蘭Epaflex聚氨基甲酸酯s.r. 1.)、 LARIPUR(義大利米蘭西提莫米蘭科姆&口八.）、APIL0N(義 200936681 大利維琴察慕索隆艾皮塑膠S.p. A. )、AVALON(美國猶他州 鹽湖城杭曼聚氨基甲酸酯）及ELAST0LLAN(德國蘭佛地 Elastogran GmbH)、PELLETHANE(美國密西根州米德蘭陶氏 化學公司）之名販售之TPU。 5 ❹ 10 15 20 基於該組成物之總重量，TPE組成物中組份（c)之數量 一般可介於0至80重量百分比之間，較佳地介於〇至， 更佳地介於0至40。 組份（d) 本組份構成本發明之TPE組成物的一必要特徵因其賦 予利用該TPE組成物所製造之鞋類暗性色調且不涉及任何 斑紋效應。如同此處所使用，一黑色素係一色素，當該色 素基於最終組成物之總重量，以0· 1至3重量百分比的程 度混合入一熱塑性聚合物或聚合物組成物時，會導致對於 波長介於400至700 nm之一小於15%之（該摻合物之）反射 率’如以一配備有積分球之光譜儀及使用一該光反射率之 鏡面組份係已包括之設定所測得。較佳該反射率係小於 12%。更佳該反射率係小於於一實施例中，該經著色聚 合物之反射率對於該波長模式係小於7%。 來自西塞爾儀器公司，用〆Ref lectanScan反射率分 光光度計，藉由分光光度計利用雙向（45°:0。or 0°:45°) 幾何學以测量反射率因子及顏色之ASTM E 1349標準測試 方法’可被使用以測量反射率。 該用語「黑色素」組成物，如同此處所使用，代表一 包含一黑色素之組成物，如以上所討論。 13 200936681 除了此處以上所界定組份（d)之黑色素，本發明之TPE 组成物可含有其他色素，該色素係非黑色素。 用於使用於本發明中，該黑色素組份（d)一般包含總色 素之至少40 wt%，該總色素係使用於暗色素熱塑性組成物 5中。若為所欲，該黑色素可包含總色素之大於60 Wt%、或 甚至大於70 wt/6，該總色素係使用於暗色.素熱塑性組成物 中。若為所欲，該黑色素可包含1〇〇 wt%添加至暗色素熱塑 性組成物之色素。 本組份之特徵在於其係不具炭黑。 © 10 用於使用於本發明之黑色素或色素的組合之例子包200936681 VI. Description of the Invention: [Technical Field 3 of the Invention] Field of the Invention 5 ❹ 10 15 20 The present invention relates to a dark pigment thermoplastic elastomer composition, particularly, which is used in a footwear assembly. Such components preferably have low speckle characteristics on wear and friction, and more preferably have no streaking characteristics. [Prior Art 3] The thermoplastic elastomer (T PE ) composition is mainly a material which exhibits, for example, an elastomer rubber at room temperature, but which can be processed like a plastic when heated. These materials have the appearance and feel of a comparable vulcanized rubber, even though their technology, workability and recyclability are typical thermoplastic products. TPE-based styrenic block copolymers, such as polystyrene-butadiene-styrene (SBS) copolymers, most commonly used in the manufacture of soles. TPE compositions based on SBS and/or thermoplastic polyurethane (TPU) have been used in the footwear industry for several years; including SBS, ethylene vinyl acetate (EVA), oils, polyolefins, Formulations of TPUs, fillers, antioxidants, pigments, and other ingredients are well known in the industry. Improvements in such formulations have been described in the art, such as the "dull appearance" obtained by the addition of a metallocene polyolefin. (W0 01/25331) It is disclosed in WO 2006/090221 that a polyurethane component is the predominant thermoplastic material which is provided to form a light foamed product, in particular to form a sole for footwear. Dark TPE is known to have undesired smudge effects on the contact surface 3 200936681 should. This type of performance is not desirable especially when the compound is used in the manufacture of soles. The need to obtain a TPE compound suitable for use in the manufacture of a sole that does not have a streak effect on the contact surface has not been met. BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a dark pigment thermoplastic elastomer composition suitable for use in the manufacture of articles, particularly footwear components. Such compositions comprise: (a) - or a polystyrene-butadiene-styrene block copolymer (SBS), & / or at least one of (b) and (c), wherein: (b) One or more polyolefin 10 elastomers which are ethene (the term ethylene is more commonly used) and an olefin copolymer of an olefin comonomer, or propylene and ethylene or an alpha olefin comonomer a copolymer, and (c) one or more thermoplastic polyurethane (TPU); and (d) a melanin composition which does not have carbon black; 15 (e) selectively, a polydimethyl fluorene oxide (PDMS); (〇 selectively 'one or more selected from synergist oils, fillers, hardness modifiers, flow improvers, flex crack modifiers, stabilizers, UV stabilizers, pigments, hair Ingredients for foaming agents and anti-blocking agents. The TPE compositions described above can be used in particular to make dark 20 footwear components, such as soles and heels. In addition, the TPE composition can be used in accordance with the present invention. Other TPE compositions # are used and have low or no speckle effect under friction for other industrial applications found in the desired field. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 200936681 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The TPE composition according to the present invention makes it possible to produce manufactured articles, particularly those that do not have contact surface streaks in abrasion friction, typically with the dark pigment thermoplastic elastomer compound Relevant. 5 In this description and the scope of the towel, please refer to the patent scope towel, "Material #鲜余粉" Dark pigment thermoplastic elastomer (TPE) composition means that the table contains one or more coloring pigments. #, wherein at least 4 重量% by weight of the total coloring pigment in the 馁 馁 邀 邀 邀 邀 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Optionally occurring, alone or as indicated below, in combination with at least one of the other two in weight ratios. The component (d) constitutes a particular and distinguishing feature of the invention and is always present In the TPE composition of the present invention, the components (e) and (the lanthanide are selectively present in the τρΕ composition. The preferred embodiment according to the present invention is listed in (1) - or a multi-component Department is usually used by these TPEs The composition of the TPE composition is described in more detail as follows: Component (a) This component is embedded by mono- or polystyrene-butadiene-styrene (SBS). a segmented copolymer having two or more distinct polymer blocks, at least one of which is glassy at the operating temperature (eg, below the glass transition point, and thus brittle and hard) but It is a fluid at high temperatures, and in which it is an elastomer at the working temperature (such as above the glass transition point, and thus can be bent or elastic). 5 200936681 Styrene-butadiene utilized in accordance with the present invention. In the olefin-styrene block copolymer, the styrene (S) and butadiene (B) monomers may be substituted with other ethylene aromatic and 1,3-co-diethylene monomers, respectively. Therefore, in the scope of this description and the patent application, the term "T 潍 潍 茗 辉 辉 5 二 二 二 二 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 也 也 也 也 也Block copolymers in which the butadiene monomer is replaced by other ethylene aromatic and 1,3-conjugated dienes will be defined in more detail later. The SBS block copolymer may be present in the form of linear diblock, triblock and multiblock SBS copolymers or in the form of a radioactive SBS block copolymer. According to the present invention, a mixture of a linear SBS block copolymer and a radioactive SBS block copolymer can also be used. Methods for making these SBS block copolymers for use in accordance with the present invention are well known in the art. U.S. Patent Nos. 3,251,905, 5,323, 635, 3, 598, 887 and 4,219, 627 are incorporated by reference. The glassy block of the SBS block copolymer is prepared by a vinyl aromatic monomer such as styrene. Although stupid vinyl is preferred as the monomer, other vinyl aromatic monomers may also be used, such as α-methylstyrene, and when the acyclic ring is substituted by one to three (Ci-co alkyl groups, the alkyl group is preferably a further styrene derivative of a methyl group or an ethyl group, or a vinyl naphthalene optionally substituted by one or two methyl or ethyl groups. Each of the stupid vinyl glass polymer blocks contains at least 80 mole percent The total amount of styrene monomer, the remainder, if any, consists of other ethylenic aromatic monomers, such as alpha-methyl stupid. 6 200936681 5 10 15 20 According to the invention 'is used as the TPE The elastomeric block of the composition component of the composition component (&) is prepared by polymerizing a conjugated 13-diester such as butadiene. Good monomers, other conjugated dienes having 5__6 carbon atoms can also be used, such as isoprene, 丨3戍 dilute, 2,3-dimethyl-1,3-butane, and 2, 4-hexadiene. These common vehicles can be polymerized in a range of 1, 2 or 1, 4 to a vinyl content ranging from 5 to 80% (mol%). Each elastomer block of the article contains a total of at least 70% (mole %) of a total of dilute monomers, such as butadiene or isoprene, the remainder, if any, Other copolymerizable monomers such as ethylene aromatic monomers. According to the present invention, the SBS block copolymer used as component (a) may also be partially or completely hydrogenated. Preferred hydrogenated SBS block copolymers of (a) are those in which only the elastomeric block is selectively hydrogenated (typically more than 80% 'preferably more than 99% (mole %) in total unsaturation) a block copolymer. In one embodiment, the SBS block copolymer has a 1,3-hexadiene, preferably a butadiene; and a vinyl aromatic monomer, preferably a styrene. The ratio is from 90 to 10, preferably from 80 to 20, more preferably from 70 to 30 (mol%). The total weight average molecular weight of the SBS block copolymer is preferably between 100,000. Between 500.000 and, more preferably, between 150.000 and 400.000 (g/mole). The SBS block copolymer can be used with hydrocarbon synergist oils such as paraffin and/or 7 20093 6681 Naphthenic oil, which is synergistic in amounts between the total synergistic SBS block copolymer and 4% by weight, which will be described in more detail later. The extender oil may be already included in a commercially available SBS block copolymer. 5 Based on the total weight of the composition, the amount of component (a) in the TPE composition is generally from 0 to 80% by weight. Preferably, it is between 7 and 60, more preferably between 0 and 60. The SBS block copolymer suitable for use in the TPE composition of the present invention comprises EUROPRENE SO 1 T172 SBS block copolymer. (Italian Milano San Donato ίο Milano's Polimerie Opa), KRAT0N (Texas, Texas, Texas Pacific), STERE0N (Ark, Ohio, USA) D), FINAPRENE (Total Petrochemical Elastomer in Brussels, Belgium), TUFPRENE (Sakamoto Asahi Kasei Co., Ltd.) and others. The SBS block copolymer material 15 of the component (a) may be a polybutadiene polymer based on the total weight of the composition (see Table 1, ". New Zealand" as an example), a polyolefin elastomer. For example, an ethylene/propylene copolymer such as an EPDM copolymer or a styrene-butadiene (SBR) copolymer is partially substituted to 40% by weight. Component (b) The component consists of one or more polyolefin elastomers. The olefin copolymer of the component (b) used in the TPE composition of the present invention has a density of from 0.86 to 0.92 g/cm3 and is copolymerized by ethylene and α-smoke. Or an olefin copolymer obtained by copolymerization of propylene with ethylene or an α-olefin having 4 to 12 carbon atoms. In a preferred embodiment, the olefin copolymer is copolymerized via ethylene with an alpha-olefin, including, but not limited to, propylene and an olefin having from 4 to 12 carbon atoms, More preferably, it is obtained by copolymerization of ethylene with butene, 1-hexene or 1-octene. 5 10 10 15 α an α-olefin used for forming the copolymer of component (b) or a copolymer of propylene and olefin, and examples of the hydrocarbon having 4 to 12 carbon atoms include butene and 2-methyl-1- Butene, 3-methyl-butadiene, pentene, 4-methyl-p-pentene, hexene, 1-octene, 1-decene and dodecene. These olefins may be used singly or in combination of two or more to provide a structural unit of the olefin copolymer. The olefin copolymer of component (b) may be any known material. For example: those with a density of 0.86 to 0.92 g/cm3, selected from ENGAGE (product name) available from The Dow Chemical Company, EXACT series (product name) manufactured by ExxonMobil Chemical Co., Ltd., by Mitsui Petrochemical Industries The TAFMER series (product name) manufactured by the company and the ESPREN sp〇N series (product name) manufactured by Sumitomo Chemical Industries. An example of a metallocene-based polyolefin elastomer (including an elastomer prepared in the presence of a metallocene catalyst such as a secondary-metallocene catalyst and containing a geometric catalyst) for use in the present invention is described. In, for example, U.S. Patent Nos. 4,871,705, 5,322,728 and 5,272,236. In particular, with a good distribution of ethylene and comonomer, by copolymerizing ethylene with one of 8% to 4% by mole (mol%) having 3 to 20 germanium atoms, preferably 4 to 12 A metallocene polyolefin produced by a carbon atom, more preferably an olefin having 6 to 10 carbon atoms, is suitably used as component (b). In addition to this, polyolefins of this type have a low crystallinity. 20 200936681 Preferably, 'the metallocene polyolefins have a Between 0.5 and 40 g/min ("MFI" is determined at 190 ° C / 5 kg ' and ISO 1133), preferably between 1 0 to 30 g/min of the condensed flow index, and its density is between 0.86 and 0.88 kg / ' 'and preferably between 〇. 86 to 5 0.885 kg / 1 . Commercially available metallocene polyolefins which can be utilized as component (b) of the TPE composition of the invention 'for example, under the trademarks AFFINITY and ENGAGE (by The Dow Chemical Company), EXACT (by Axel Mobil) Ethylene (or ethylene) _ 〇 10 octene copolymer sold under the chemical company) and TAMFER (from Mitsui Petrochemical Industries, Ltd.). The amount of the group injury (b) in the TPE composition of the present invention may be between 0 and 99% by weight, preferably between 〇 and 80, more preferably 〇 and based on the total weight of the composition. 60. Component (c) 15 This component consists of a thermoplastic poly-capric acid vinegar (TPU), which is a functional compound that reacts with a diisocyanate-domain and at least a hetero-group. And a substance obtained by reacting selectively a chain extender, preferably a bifunctional compound. The term difunctional means that the quaternary acid composition or the polybasic compound has an average 20 functionality of about 2. The diisocyanate reactant may be aromatic or aliphatic. The aromatic diisocyanate includes, for example, ", and 2,2-diphenyl-methane diisocyanate (10)) and their corresponding isomeric mixtures. "Hai-isocyanate component It is also possible to have a MDI variant. The Shearing System is known in the art, and (10) additionally includes a liquid product obtained by the (iv) human carbodiamine group to the bis 10 200936681 isocyanate composition. Aliphatic and cyclic fats Examples of the family of isocyanate compounds include 1,6-hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), 4, 4'-, 2, 2,- and 2 , 4,- 5 10 15 20 methylene bicyclic diisocyanate (H12MDI), its isomeric mixture, 1,3-tetramethylene xylene diisocyanate, norbane diisocyanate 1,3- and 1,4-diisocyanatononylcyclohexane can also be used in the present invention. Mixtures of aromatic, aliphatic and cycloaliphatic isocyanates can also be used. Containing aromatic diisocyanates The isocyanate composition is preferably and more preferably MDI. In one embodiment, the bifunctional compound is preferably a bifunctional The hydroxy compound 'has a molecular weight of between 500 and 20,000 and may be selected from derivatives of the following compounds: polyester decylamine, polythioether, polycarbonate, polyacetal, polyolefin, polyoxyalkylene and especially poly a mixture of an ester, a polyether, a polycaprolactone or the like. The polyester includes a hydroxy polyester, a dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol. a reaction product of 2-methylpropanol, 3-methylpentan-1,5-diol, 1, hexanediol, or cyclohexane-methanol, or a mixture thereof, and ditoxaic acid or vinegar thereof Classes, such as hexanoic acid vinegar, glutaric acid, succinic acid, azelaic acid, and terephthalic acid, phthalic anhydride, tetrahydrogenated phthalic anhydride or the like. The ethers include products obtained by polymerizing an epoxide such as ethylene, propylene, butylene oxide or tetrahydrofuran in the presence of the necessary difunctional starter. Suitable starter compounds include water, ethylene glycol, propylene glycol, Ethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propanediol, hydrazine, 4-butanediol, 11 200936681 neopentyl glycol 1,5-pentanediol, 1,6-hexanediol, and the like. A mixture of a starter and/or an epoxide may be used. The polyolefin diol includes a homopolymer of a terminal hydroxyl group Copolymer. 5 Suitable chain extenders include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 2-methylpropanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, 3-methylpentane -1,5-diol, neopentyl glycol, diethylene glycol, dipropylene glycol and tripropylene glycol and amino alcohols such as ethanolamine, N-1 mercapto diethanolamine and the like; 1,4-butanediol It is preferred. The TPU used as component (c) of the TPE composition of the present invention may optionally contain additives, stabilizers, surfactants, and foam stabilizers, plasticizers, and the like. Additives which may be admixed with TPU are, for example, polystyrene or vinyl ethylene vinyl acetate, paraffin or naphthenic oils, fillers of mineral origin and the like. Stabilizers that can be added to the TPU include antistatic agents and antioxidants and anti-UV agents. Surfactants and foam stabilizers that can be added to the TPU include, for example, polyether modified polyoxyalkylene copolymers. The plasticizers of the 20 TPU component include, for example, alkyl-phthalate and alkyl-benzoate. Suitable TPUs are commercially available, and include, inter alia, EPAM0ULD (Epaflex Polyurethane sr 1.), LARIPUR (Italian Milan Sitimo Milan Coom & mouth VIII.), APIL0N (Yi 200936681 Da Li Vicenza Mussolone Aipi Plastic SpA), AVALON (Hangman City, Utah Salt Lake City) and ELAST0LLAN (Elastogran GmbH, Lancaster, Germany), PELLETHANE (Midland, Michigan, USA) TPU sold under the name Dow Chemical Company. 5 ❹ 10 15 20 The amount of component (c) in the TPE composition may generally range from 0 to 80% by weight, based on the total weight of the composition, preferably between 〇, and more preferably 0. To 40. Component (d) This component constitutes an essential feature of the TPE composition of the present invention because it imparts a dark shade to the footwear made using the TPE composition and does not involve any streaking effect. As used herein, a melanin-based pigment, when the pigment is mixed into a thermoplastic polymer or polymer composition in an amount of from 0.1 to 3 weight percent based on the total weight of the final composition, results in a wavelength-dependent The reflectance of less than 15% (of the blend) at 400 to 700 nm is measured as determined by a spectrometer equipped with an integrating sphere and a mirror component that uses the reflectance of the light. Preferably, the reflectance is less than 12%. More preferably, the reflectance is less than in one embodiment, the reflectance of the colored polymer being less than 7% for the wavelength mode. From Sissel et al., using the 〆Ref lectanScan reflectance spectrophotometer, using a bidirectional (45°: 0. or 0°: 45°) geometry to measure reflectivity factors and colors by ASTM E 1349 The standard test method 'can be used to measure reflectivity. The term "melanin" composition, as used herein, refers to a composition comprising a melanin, as discussed above. 13 200936681 In addition to the melanin of component (d) as defined herein above, the TPE composition of the present invention may contain other pigments which are non-melanin. For use in the present invention, the melanin component (d) generally comprises at least 40% by weight of the total pigment used in the dark pigment thermoplastic composition 5. If desired, the melanin may comprise greater than 60 Wt% of the total pigment, or even greater than 70 wt/6, which is used in the dark pigment thermoplastic composition. If desired, the melanin may comprise 1% by weight of a pigment added to the dark pigment thermoplastic composition. This component is characterized in that it does not have carbon black. © 10 Example package for the combination of melanin or pigment used in the present invention
括，例如’那些經由義大利米蘭科萊恩色母粒S. p. A.以商 標名 RENOL PV90050120 - BN/GUM 及 RENOL PC GUM NERO CBF 所販售之物。 基於該組成物之總重量，該TPE組成物中組份（d)之數 15 量可介於〇. 1至3重量百分比之間。 粗份（e) Ο 本組份係一聚二有機矽氧烷，該聚二有機矽氧烷在 w 25°C時具有至少一百萬厘斯之黏度。如此之添加劑可被添 加以進一步增加已發展配方之耐磨性，以及作為内部潤滑 20 劑及脫模劑。 基於該組成物之總重量，TPE組成物中組份（e)之數量 可介於0至4%重量之間。 狃份（f) TPE組成物之本選擇性組份可包含增效劑油’其除了原 14 200936681 本可被包括入SBS嵌段共聚物（組份（a))中之數量外，可被 添加至全組成物摻合物，如以上所描述。 該等增效劑油係衍生自石油精煉之產物，其具有小於 30重量百分比之芳香族碳氫化合物。 5 基於該組成物之總重量，當增效劑油出現於該組成物 摻合物中時，排除可被包括入組份（a)之數量，可被添加至 全組成物摻合物之增效劑油之數量介於〇至4〇重量百分比 之間。 商業上可得之增效劑油包括，例如，來自義大利利佛 10 諾史塔格諾 ENI S. p. A.之 CELTIS 902。 可選擇性地出現於本發明之TPE組成物中的其他成份 包括，例如，礦物性來源之填充物，諸如黏土、矽土、滑 石石反酸辦、礬土及類似物；硬度調節劑諸如聚苯乙稀 ^曰曰，其他（非黑）色素及化學性或物理性發泡劑。當降低 5該TPE之密度至0.5 kg/ι係為所欲時，發泡劑係通常被添 加至該TPE組成物之其他組份中。 使用於泡泳熱塑性產品製備之任何已知發泡劑可被使 用於本發明中。該發泡劑通常係根據已知方法而添加，諸 如描述於WO 00/4彻中之方法，其中該發泡劑係經囊封 扣及包含於特殊微球體中而添加至顆粒化τρΕ摻合混合物， 或根據WO 2006/090221中揭露之方法。 任何熱性上可延展之微球體均可被使用於本發明中。 然而’含有礙氫化合物，特別是脂肪族或環脂肪族之碳氫 化合物的微球體係較佳。 15 200936681 含有發泡劑之微胞或微球體係藉由經囊封發泡劑之具 有丙烯酸/甲基丙烯腈或丙烯腈/丙烯酸或酯類/烯烴官能 基之共聚物所組成，該發泡劑係根據以上提及之方法併入 該TPE摻合混合物中。 適合之物理性發泡劑之例子包括揮發性脂質，諸如氟 氣碳化物、部分鹵化之碳氫化合物或非齒化之碳氫化人 物，如丙烷、η-丁烷、異丁烷、n—戊烷、異戊烷及/或新戊 烷。 含有脂肪族或環脂肪族碳氫化合物之微球體係商業上 春 10可得的，例如，以商標名EXPANCELL(荷蘭阿姆斯特丹AKZ〇 諾貝爾工業）或MICROPEARL(日本大阪府松本油脂製藥株式 會社）販售。 . 及熱性及放熱性化學性發泡劑兩者皆可被使用。適當 的化學性發泡劑之例子包括氣相化合物，諸如氮氣或二i 15化碳；成氣（例如C〇2)化合物，諸如偶氮二甲醯胺、碳酸鹽、 碳酸氫鹽、擰檬酸鹽、硝酸鹽、硼氫化物；碳化物，諸如 鹼土及鹼土金屬碳酸鹽及碳酸氫鹽，例如碳酸氫鈉及碳酸 〇 鈉 '碳酸銨、氨苯颯、醯穽、丙二酸、檸檬酸、單檸檬酸 納、尿素、偶氮二破酸甲醋、二氮二環辛烧及酸/碳酸鹽混 20 合物。 較佳吸熱性發泡劑包含碳酸氫鹽或摔檬酸鹽。 偶氮二甲醯胺型發泡劑係較佳，如同放熱性發泡劑。 此處之上總括式地標明為組份（f)之選擇性成份的數 量，排除增效劑油，整體而言，可介於〇至4重量百分比 16 200936681 之間。 特別是，發泡劑之數量，當被使用時，可介於1至3 重量百分比之間。 5 ❹ 10 15 Ο 20 根據本發明之一實施例，適合用於無斑紋效應的鞋底 之製造的ΤΡΕ組成物具有無或低聚苯乙烯及礦物性填充物 含量，且具有無或低程度之增塑劑。 可了解的是本發明之ΤΡΕ的各組份（a)至（f)之總百分 比數量，各分別坐落於上述所界定之區間内，必須加總至 百分之百，且基於該組成物之總重量，TPE組成物中組份（a) 及/或（b)及（c)之至少一者之總數量必須至少是55重量百 分比’較佳地至少百分之70 ’更佳地至少百分之8〇。 丄匕合及射出成_彬 用於本發明之TPE組成物的配方係根據熟習此藝者所 習知之化合程序而製備。實務中，所有組份係藉使用一滾 筒混合機在可變速度下混合，而後於140-220°C下馈給至 一同向雙螺桿押出機。 該押出串係經水冷且顆粒化。該顆粒係使用一具有射 出單元組之射出成形機器在120°C至16(TC之下模製以獲 得片狀體及鞋底原型。 觀 片狀體及鞋底原型係被測試磨損抗性、拉力強度、延 長及撕裂強度。 該測試係根據表2中所指示之DIN方法在片狀體上實 施。在手動分離一表面上之經模製片狀體樣品，例如磚瓦、 17 200936681 硬木、乙烯基地板後’斑紋效應係藉視覺審視評估。 實施例 以下組份係使用於表1中所報導之實施例中。 祕 A: EUROPRENE Sol τ 172 SBS 嵌段共聚物，70%(莫耳 5 %) 丁二烯，30%苯乙烯，用石蠟油（每1〇〇聚合物用50 pbw) 增效；來自義大利米蘭聖多拿多米蘭市之波里梅理歐帕。 組份B: ENGAGE 8200，乙烯/辛烯共聚物，來自密西根州 米德蘭陶氏化學公司美國）。 組份EPAMOULD 80A，以聚酯為主之熱塑性聚氨基曱酸 10 酯；來自Epaflex聚氨基甲酸酯Sri-(義大利）米蘭。 組份D: RENOL PV 90050120-BN/GUM，來自不具炭黑之色 素組成物的黑色母混入PE-EVA ;來自科萊恩色母粒 SpA -(義大利）米蘭。 、组份E:在25°C時具有兩千萬厘斯黏度之聚二甲基石夕氧烧 15 (MP50來自陶氏康寧公司）。 組份F: CELTIS 902，石蠟油；來自ENI SpA -史塔格諾（利 佛諾-義大利）。 組份G: SARMAPRENE Nero tech ;來自科萊恩色母粒SpA - 米蘭（義大利）。 2〇 礦物性填充物碳酸鈣，來自歐米亞SpA-米蘭（義 大利）。 、组# Ι:·聚苯乙稀結晶，在19〇°C、5kg時之融溶流動指數 係25 ;來自伊可塑膠Sri -米蘭（義大利）。 組份J: JSR RB 840/830 ’對位性聚丁二稀聚合物；來自 18 200936681 JSR公司-東京（日本）。 所有化合物係混合且化合，如以上所描述。 由此獲得之小丸或顆粒係射出成形入片狀體中，其係 進行如以上所描述之測試。 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 ΪΓ施 例7 資施 例8 % wt % wt % wt % Wt % wt % wt % wt % wt 组份A 47. 2 48.9 72.5 66.3 24.8 24.5 0.0 0. 0 組份B 0· 0 0.0 0.0 0.0 0. 0 0. 0 99.0 99. 〇 组份C 0. 0 0. 0 0. 0 0. 0 74. 3 73.5 0. 0 0. 0 组份D 0. 0 Γ 0. 0 1. 0 1. 0 0. 0 1.0 0. 0 1.0 組份E 0. 0 0.0 1.0 1.0 0. 0 1.0 0.0 ^〇7〇~ 組份F 13. 3 17.1 14.2 6.9 0. 0 0. 0 0.0 ~〇7〇~ 组份G 1. 0 10. Π). 0 0. 0 1. 0 0.0 1.0 0. 0~ 组份Η 0. 0 2.4 0. 0 卜0·0 0· 0 0.0 0.0 0.0— 组份I 9. 3 7. 3 0. 0 0. 0 0. 0 0. 0 0· 0 0. 0 组份J 29. 2 23.2 11.4 24. 9 0. 0 0. 0 0. 0 0. 0 實施例1、2、5及7係比較性實施例，其係根據該技 藝之狀態之教示而實行。 φ 實施例3、4、6及8係本發明不設立任何該發明的限 制之代表。 10 於片狀體上實行之測試結果係報導於以下之表2中。 表2 實施 例1 ΪΤ施 例2 實施 例3 實施 例4 方法 單位 磨損抗性 DIN 53516 mm3 120 165 220 140 硬度 DIN 53505 ShA 65 65 65 65 拉力強度 DIN 53504 N/mm 2 5 6.5 5 7 19 200936681 延長 DIN 53504 % 700 700 750 750 撕裂強度 DIN 53515 N/mm 24 24 23 23 斑纹 (於磚瓦上） 斑紋 斑紋 無 斑 紋 無 斑 紋 實施 例 5 實施 例 6 實施 例 7 實施 例 8 方法 單位 磨損抗性 DIN 53516 mm3 75 70 146 125 "^5 DIN 53505 ShA 70 70 67 67 拉力強度 DIN 53504 N/mm2 18 18 8 8. 2 延長 DIN 53504 % 850 850 1200 1201 撕裂強廋 DIN 53515 N/mm 30 30 33 33 i蚊— (於磚瓦上） 一 斑紋 無斑 紋 斑紋 無斑 紋 以上測試結果顯示本發明之Τρε組成物使得暗色素物 件之製造可行，特別是，鞋類，諸如維持用於其等之使用 所需要之功能性特徵（例如磨損抗性、撕裂及拉力強度，等 5等）的鞋底及鞋跟，且不會顯示任何不為所欲之斑紋效應。 除此之外，藉由比較實施例1及2與實施例3及4，斑紋 效應不僅關係該材料之磨損抗性或其他機械性質係證據充 分的。 【明式簡单說明】 10 (無） 【主要元件符號說明】 (無） 20These include, for example, those sold under the trade names RENOL PV90050120 - BN/GUM and RENOL PC GUM NERO CBF by Italian Clariant Masterbatch S. p. A. The amount of the component (d) in the TPE composition may be between 0.1 and 3 weight percent based on the total weight of the composition. Crude (e) Ο The component is a polydiorganooxynonane having a viscosity of at least one million cSt at w 25 °C. Such additives can be added to further increase the abrasion resistance of the developed formulations, as well as internal lubricants 20 and release agents. The amount of component (e) in the TPE composition may be between 0 and 4% by weight based on the total weight of the composition. The optional component of the (f) TPE composition may comprise a synergist oil which may be included in the SBS block copolymer (component (a)) in addition to the original 14 200936681. Add to the full composition blend as described above. The synergist oils are derived from petroleum refined products having less than 30 weight percent aromatic hydrocarbons. 5 based on the total weight of the composition, when the builder oil is present in the composition blend, the amount that can be included in the component (a) is excluded and can be added to the total composition blend. The amount of the effect oil ranges from 〇 to 4% by weight. Commercially available synergist oils include, for example, CELTIS 902 from E. S. p. A. Other ingredients which may optionally be present in the TPE compositions of the present invention include, for example, mineral-derived fillers such as clay, alumina, talc, alumina, and the like; hardness modifiers such as poly Phenylethylene, other (non-black) pigments and chemical or physical foaming agents. When it is desired to reduce the density of the TPE to 0.5 kg/m, a blowing agent is usually added to the other components of the TPE composition. Any known blowing agent used in the preparation of a blister thermoplastic product can be used in the present invention. The blowing agent is usually added according to known methods, such as the method described in WO 00/4, wherein the blowing agent is added to the granulated τρΕ blend by being encapsulated and contained in a special microsphere. Mixture, or according to the method disclosed in WO 2006/090221. Any thermally extensible microspheres can be used in the present invention. However, a microsphere system containing a hydrogen-blocking compound, particularly an aliphatic or cycloaliphatic hydrocarbon, is preferred. 15 200936681 A microcapsule or microsphere system containing a blowing agent consisting of a copolymer having an acrylic acid/methacrylonitrile or acrylonitrile/acrylic acid ester/olefin/olefin functional group encapsulated by a blowing agent, the foaming The agent is incorporated into the TPE blending mixture according to the methods mentioned above. Examples of suitable physical blowing agents include volatile lipids such as fluorine gas carbides, partially halogenated hydrocarbons or non-toothed hydrocarbon characters such as propane, η-butane, isobutane, n-pentane Alkanes, isopentane and/or neopentane. Microsphere systems containing aliphatic or cycloaliphatic hydrocarbons are commercially available in the spring, for example, under the trade name EXPANCELL (AKZ Nobel Industries, Amsterdam, The Netherlands) or MICROPEARL (Japan Matsumoto Oil & Fat Pharmaceutical Co., Ltd.) Sold. Both thermal and exothermic chemical blowing agents can be used. Examples of suitable chemical blowing agents include gas phase compounds such as nitrogen or di-carbonized carbon; gas-forming (e.g., C〇2) compounds such as azomethicin, carbonates, bicarbonates, and lemons. Acid salts, nitrates, borohydrides; carbides, such as alkaline earth and alkaline earth metal carbonates and hydrogencarbonates, such as sodium hydrogencarbonate and sodium bismuth carbonate 'ammonium carbonate, ammonia hydrazine, hydrazine, malonic acid, citric acid , sodium monocitrate, urea, azodicarboxylic acid methyl vinegar, diazodicyclooctane and acid/carbonate mixed compound. Preferably, the endothermic blowing agent comprises bicarbonate or sulphate. The azomethicone type foaming agent is preferred as an exothermic blowing agent. The amount of the optional component of component (f) is generally indicated above, excluding the synergist oil, and overall, it can range from 〇 to 4 weight percent 16 200936681. In particular, the amount of blowing agent, when used, may range from 1 to 3 weight percent. 5 ❹ 10 15 Ο 20 According to one embodiment of the present invention, a ruthenium composition suitable for use in the manufacture of a sole without a streak effect has a content of no or low polystyrene and mineral filler, and has a low or a low increase Plasticizer. It can be understood that the total percentage of each component (a) to (f) of the present invention is located within the above-defined interval, and must be added up to 100%, and based on the total weight of the composition, The total amount of at least one of components (a) and/or (b) and (c) in the TPE composition must be at least 55 weight percent 'preferably at least 70 percent', more preferably at least 8 percent Hey. Coupling and Injection The formulation of the TPE composition for use in the present invention is prepared according to a compounding procedure known to those skilled in the art. In practice, all components are mixed at variable speeds using a roller mixer and then fed to a twin-screw extruder at 140-220 °C. The extruded string is water cooled and granulated. The pellets were molded using an injection molding machine with an ejection unit set at 120 ° C to 16 (TC to obtain a sheet-like body and a sole prototype. The sheet-like body and the sole prototype were tested for wear resistance and tensile strength. , elongation and tear strength. The test was carried out on a sheet according to the DIN method indicated in Table 2. Manually separating a molded sheet sample on a surface, such as brick, 17 200936681 Hardwood, vinyl The post-base layer 'streak effect' was evaluated by visual inspection. EXAMPLES The following components were used in the examples reported in Table 1. Secret A: EUROPRENE Sol τ 172 SBS block copolymer, 70% (mole 5% Butadiene, 30% styrene, synergistic with paraffin oil (50 pbw per 1 〇〇 polymer); from Borromeo Opal, Milan, San Antonio, Milan, Italy. Component B: ENGAGE 8200, ethylene/octene copolymer from Midland Dow Chemical Company, Michigan, USA). Component EPMOMODL 80A, polyester-based thermoplastic polyaminophthalic acid 10 ester; from Epaflex polyurethane Sri- (Italy) Milan. Component D: RENOL PV 90050120-BN/GUM, black mother from non-carbon black colorant composition mixed into PE-EVA; from Clariant masterbatch SpA - (Italy) Milan. , Component E: Polydimethyl oxalate 15 (MP50 from Dow Corning) having a viscosity of 20 million psi at 25 °C. Component F: CELTIS 902, paraffin oil; from ENI SpA - Stargano (Livorno-Italy). Component G: SARMAPRENE Nero tech; from Clariant Masterbatch SpA - Milan (Italy). 2〇 Mineral filler calcium carbonate from Omega SpA-Milan (Italy). , Group # Ι: · Polystyrene crystal, melt flow index at 25 ° C, 5 kg when the system is 25; from the Iraqi plastic Sri - Milan (Italy). Component J: JSR RB 840/830 'coordinated polybutadiene polymer; from 18 200936681 JSR Corporation - Tokyo (Japan). All compounds were mixed and combined as described above. The pellets or granules thus obtained are injection molded into a sheet-like body which is subjected to the test as described above. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8% wt % wt % wt % Wt % wt % wt % wt % wt Component A 47. 2 48.9 72.5 66.3 24.8 24.5 0.0 0. 0 Component B 0· 0 0.0 0.0 0.0 0. 0 0. 0 99.0 99. 〇Component C 0. 0 0. 0 0. 0 0. 0 74. 3 73.5 0. 0 0. 0 Component D 0. 0 Γ 0. 0 1. 0 1. 0 0. 0 1.0 0. 0 1.0 Component E 0. 0 0.0 1.0 1.0 0. 0 1.0 0.0 ^〇7〇~ Component F 13. 3 17.1 14.2 6.9 0. 0 0. 0 0.0 ~〇7〇~ Component G 1. 0 10. Π). 0 0. 0 1. 0 0.0 1.0 0. 0~ Component Η 0. 0 2.4 0. 0 卜0·0 0· 0 0.0 0.0 0.0—Component I 9. 3 7. 3 0. 0 0. 0 0. 0 0. 0 0· 0 0. 0 Component J 29. 2 23.2 11.4 24. 9 0. 0 0. 0 0. 0 0. 0 Embodiments 1, 2, 5 and 7 are comparative examples which are carried out in accordance with the teachings of the state of the art. φ Examples 3, 4, 6 and 8 are not representative of any of the limitations of the invention. 10 Test results performed on the sheet are reported in Table 2 below. Table 2 Example 1 Example 2 Example 3 Example 4 Method Unit Wear Resistance DIN 53516 mm3 120 165 220 140 Hardness DIN 53505 ShA 65 65 65 65 Tensile Strength DIN 53504 N/mm 2 5 6.5 5 7 19 200936681 Extended DIN 53504 % 700 700 750 750 Tear strength DIN 53515 N/mm 24 24 23 23 Streaks (on bricks) Streaked streaks without markings No embossing Example 5 Example 6 Example 7 Example 8 Method Unit Wear Resistance DIN 53516 mm3 75 70 146 125 "^5 DIN 53505 ShA 70 70 67 67 Tensile strength DIN 53504 N/mm2 18 18 8 8. 2 Extension DIN 53504 % 850 850 1200 1201 Tear strength DIN 53515 N/mm 30 30 33 33 i mosquitoes - (on bricks) a stripe-free speckle-free speckle-free test results show that the Τρε composition of the present invention makes the manufacture of dark pigmented articles feasible, in particular, footwear, such as maintenance for use thereof Sole and heel that require functional features (such as abrasion resistance, tear and tensile strength, etc.) and do not show any undesired streaking effects. In addition, by comparing Examples 1 and 2 with Examples 3 and 4, the streak effect is not only related to the wear resistance or other mechanical properties of the material. [Simple description of the Ming style] 10 (none) [Explanation of main component symbols] (None) 20