1288159 (1) 玖、發明說明 【發明所屬之技術領域】 本發明是有關熱塑性樹脂組成物，其可製成具有良好 可加工性、可用性、耐刮性、耐磨性、尺寸安定性、表面 硬度、防污性、耐熱性和視覺品質（無光亮面），且低滑 動摩擦係數之表面特性的模製物體；及其製法及用途。更 特別的是，本發明是有關以離子聚合物爲主成分的熱塑性 樹脂組成物，其適合用於建材如地板、扶手和壁紙，汽車 內外零件、玩具、文具和雜物；及其製法及用途。 【先前技術】 離子聚合物中具有2至3〇重量％不飽和羧酸的乙烯/(甲 基）丙烯酸共聚物之羧基，被金屬離子中和後，和其他乙 烯共聚物相比，由於離子交聯其具有非常好的耐磨性和透明 度。例如，由日本公開專利申請案SHO 60 ( 1985) - 127 149 得知，利用離子聚合物此特性可增進建材和汽車內外零件表 面耐刮性。發表中述及汽車用內外材料具有良好的表面光澤 及耐刮性。另外。日本先行公開專利申請案HEI 8( 1 996)-25 4〇〇4也提到在建材中將離子聚合物樹脂用於非聚氯乙烯 型的地板表層，可防止桌椅移動或行走的磨損和刮傷。 上述塑合物的表層是離子聚合物，但由於離子聚合物 的特性有好的透明度和光滑度，需要一個處理其過度光亮 表面的方法。例如··使用壓花滾輪的無光亮面製法，但此 法有個缺點，很難用於立體塑造，如：押出成型的扶手或 -6 - (2) 1288159 管件。 甚者，即使用壓花滾輪製作無光亮面薄板仍有問題， 就像製作發泡薄板時，在發泡烤箱進行二次加熱過程中無 光亮面會消失。爲了解決這個問題可用下列二法：其一在 發泡烤箱過程後在發泡薄板上層合一層無光亮面薄膜以保 持無光亮面，另外就是藉壓花滾輪再次在發泡薄板上壓出 無光亮圖樣。然而實際使用上卻有個問題，由於離子聚合 物易附著在金屬上的特性，發泡薄板常常會融化黏在熱滾 輪上。 不同於前法，某些樹脂本身形成無光亮面的方法已被 了解。舉例，日本公開的專利申請案SHO 61(1986)-37836 或HEI 4(1 992)-86260等，提出一些方法如：混合對彼此 相容性低的聚合物或加入不同黏度的類橡膠聚合物。類似 這些方法，日本公開專利申請案HEI 11(1999)-140251中 提出，使用經苯乙烯/不飽和羧酸共聚物修飾的離子聚合 物組成物，已證實其無光亮面和增進抗熱性的效果。不 過，由於這些方法是利用低相容性，離子聚合物組成物仍 然會有破壞離子聚合物特性的問題，像是薄板彎曲時的強 烈白化、耐磨性降低等等。 基於上述理由，當最有效利用離子聚合物的絕佳耐磨 及耐刮性同時’本發明硏究一些加入耐熱性和彎曲不會引 起白化的無光亮面特性的方法。結果，我們終於發現當離 子聚合物和下述特定比例乙烯共聚物及丙烯/〇1_烯烴共聚 物混合時’可得到所需效果之離子聚合物組成物；同時， (3) 1288159 我們也發現此組成物可用作高勁度、高表面硬度和良好滑 動性的模製品。 因此’本發明的目標是提供具有良好可加工性、可用 性、耐磨性、耐刮性、勁度、表面硬度、防污性、視覺品 質（無光亮面）、耐熱性等的熱塑性樹脂組成物。另一個目 標是提供由此組成物製得具有良好表面特性的模製物體， 更特別的是提供給多層材料一具有良好表面特性的表層材 料0 【發明內容】 本發明是關於熱塑性樹脂組成物，其包含60至96.7 重量份之（A)離子聚合物，其中乙烯/(甲基）丙烯酸共聚物 的20至90重量份％羧基被金屬離子中和；0.3至10重量 份之（B)乙烯或α_烯烴共聚物，其含有（甲基）丙烯酸縮水 甘油酯或不飽和縮水甘油醚，可任意再含有乙烯酯或不飽 和羧酸酯；及3至30重量份之（C)丙烯/α-烯烴共聚物。 本發明也相關於一種製作上述具有不同優良特性之熱 塑性樹脂組成物和其應用。 本發明較佳實例 本發明所使用的離子聚合物（Α)中乙烯/(甲基）丙烯酸 共聚物的20至90莫耳％，最好是30至85莫耳％羧基被 金屬離子中和。接著，以乙烯/(甲基）丙烯酸共聚物當作基 礎聚合物，共聚物中（甲基）丙烯酸的含量介於2至30重 (4) 1288159 量％，最好是3至2 5重量。/〇，不僅乙烯和丙烯酸或甲基丙 烯酸的共聚物，而且用其他單體隨意共聚合之多單體形式 的共聚物也可作基礎聚合物。使用離子聚合物其酸含量低 於上述含量範圍的情形下，很難得到具有良好耐磨性及無 光亮面的組成物。 其他可隨意共聚合的單體例舉如下：乙烯基酯類例如 醋酸乙烯酯、丙酸乙烯酯；不飽和羧酸酯類例如丙烯酸甲 酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸異丁酯、丙烯酸 正丁酯、丙烯酸異辛酯、丙烯酸_2_乙基己酯、甲基丙烯 酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丁酯、順式丁烯 一^酸—*甲S曰、順式丁嫌一^酸一乙醋；一*氧化碳和二氧化 硫。雖然可以被共聚合的其他單體含量介於0至40重量 %，最好是〇至3 0重量％，但增加其含量通常會較難得到 具有良好耐磨、耐刮和耐熱的組成物，因此，寧可使用不 含其他單體的共聚物，或即便含其他單體，其含量最好少 於2 0重量％。 使用其在190 °C及2160克負載條件下熔融流速介於1 至1 000克/10分鐘，最好是2至800克/10分鐘的乙烯 /(甲基）丙烯酸共聚物是令人滿意的。上述共聚物能在高溫 高壓下以自由基共聚合反應製成。 被使用的離子聚合物（A)中上述共聚物的20至90莫 耳％，最好是30至85莫耳％羧基被金屬離子中和。以金 屬離子而言，二價金屬以鋅或鹼土族的鎂和鈣爲佳。二價 金屬和其他金屬如鹼金屬的鋰、鈉、鉀的組合可用。也就 -9- (5) 1288159 是說，與其他單單使用鹼金屬或不含任何二價金屬的鹼金 屬組合之離子聚合物相比，使用至少有一部分爲二價金屬 的金屬離子，較易得到具有極佳之無光亮面（柔亮面）、耐 熱性和無光亮面保持等等特性的組成物。 另外，考量模製性、機械性、及與其他成分混合性等 因素，最好使用其在190 °C及2160克負載條件下，熔融 流速爲0.01至100克/10分鐘，最好是0.1至50克/10分 鐘的離子聚合物。 本發明中共聚物（B)是乙烯或（X-烯烴的共聚物’其含 有（甲基）丙烯酸縮水甘油酯或不飽和縮水甘油醚，可任意 量再含有乙烯基酯或不飽和羧酸酯，其中的α-烯烴約有3 至8個碳原子如丙烯或卜丁烯。以成分（Β)而言，乙烯的 共聚物尤其特別好。 以（甲基）丙烯酸縮水甘油酯或是不飽和縮水甘油醚而 論，丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、乙烯縮 水甘油醚、烯丙基縮水甘油醚、2-甲基烯丙基縮水甘油醚 等皆可被引用。 乙烯或α-烯烴和上列縮水甘油基單體之共聚物不一 定需要是二元共聚物，也可以是多單體型式之共聚物’其 中其他單體如乙烯基酯或不飽和羧酸酯被共聚合。其他單 體的例子可以是上面已提到的離子聚合物（Α)之基礎聚合 物乙烯/(甲基）丙烯酸共聚物的其他單體。此外，在本發明 中，由乙烯、α-烯烴和上述縮水甘油基單體所組成之多單 體型式共聚物可被使用。 -10- (6) 1288159 在乙烯或α -烯烴和縮水甘油單體的共聚物（B )中， 乙烯或α-烯烴含量最好介於5〇至99重量％，52至98重 量％尤佳；而縮水甘油單體介於〇 . 5至20重量％，1至1 8 重量％尤佳；上述其他單體則介於〇至49.5重量％，0至 4〇重量％尤佳。當縮水甘油單體含量過低時，耐熱之增進 及無光亮面保持其成效不彰。反之，當含量過高時，對於 離子聚合物的反應性過高且有時因樹脂黏度增加難以模製 和（或）造成組成物中凝膠形成。 上述共聚物可能是不規則共聚物或接枝共聚物，通常 著眼於對離子聚合物反應的均一性最好使用不規則共聚 物。不規則共聚物可在高溫壓下以自由基共聚化反應製 成。 使用乙烯共聚物作上述之共聚物時，最好是使用在 190°C及2 160克負載條件下，其熔融流速介於0.01至 1000克/10分鐘，最好是〇.1至200克/10分鐘的共聚物。 本發明（C)丙烯/α-烯烴共聚物與（A)離子聚合物 和（Β)乙烯或α -烯烴及縮水甘油基單體共聚物一起使 用。藉由使用可輕易分散在其他成分中的丙烯/α -烯烴共 聚物，此樹脂組成物可輕易達到極佳之視覺品質、耐熱性、 耐磨性、耐刮性、防污性機械強度等等。 本發明所用之丙烯/α-烯烴共聚物（C)是以丙烯爲主成 分和其他α-烯烴的共聚物，此共聚物（C)其密度最好是介 於870至93 0公斤/立方米，880至920公斤/立方米更 好；而熔融流速在2160克負載及23 0°C條件下，介於〇· 1 -11 - (7) 1288159 至100克/10分鐘爲佳，0.2至80克/10分鐘則更好。 共聚物（c)中，與丙烯共聚合的α_烯烴最好有2至12 個碳原子’ 2至10個碳原子更好，具體地就α-烯烴而 言，乙烯、^丁烯、1-己烯、1-辛烯、1·癸烯、1-十二碳 烯、4-甲基-1-戊烯皆可作爲例子。α-烯烴可爲單、雙或多 種類別的組合。 共聚物（C)可能是不規則或嵌段共聚物，特別合適的 不規則共聚物是丙烯和乙烯的不規則共聚物，或是丙烯、 乙烯和其他α_烯烴的不規則共聚物，其中丙烯的含量介 於85至99.9重量。/。，90至99.5重量％尤佳。這些是在有 立體選擇性催化劑存在下的共聚合反應中產生的結晶聚合 物。 被用作共聚物（C)之上述嵌段共聚物，以連續的方法 由丙烯和其他α-烯烴的聚合或共聚合反應製成。通常嵌 段共聚合反應以結合單一或多次聚合階段製得，包含在（1) 丙烯的聚合之後，（2)丙烯和不少的α-烯烴共聚合和/或 (3)α-烯烴的聚合。在上述（1)丙烯的聚合中，有一個實例 是和少量α-烯烴共聚合，另一個實例是在（3) α-烯烴聚合 中和少量丙烯共聚合。不論是何種實例，上述嵌段共聚物 可由有立體選擇性催化劑存在下，經上述的多階段聚合反 應製成。適合選用的丙烯/α-烯烴嵌段共聚物是丙烯及乙 烯之嵌段共聚物，其中包含60至95重量％之（1)丙烯聚合 嵌段物。 本發明之熱塑性樹脂組成中的（A)，（Β)，（C)混合比 -12- (8) 1288159 例如下：60至96.7重量份之離子聚合物（A)，〇.3至重 量份之共聚物（B)和3至30重量份之丙烯/α-烯烴共聚物 (C);較佳是73至95.5重量份的（Α)，0.5至7重量份的 (Β)和4至20重量份的（C);最好的是8 1至94重量份的 (Α)，1至4重量份的（Β)和5至15重量份的（C)。 本發明之熱塑性樹脂可藉熔融混合離子聚合物（Α)、 乙烯或（X-烯烴/縮水甘油單體之共聚物（Β)、和丙烯/α-烯 烴共聚物（C)製成。採用熔融混合的方法時，一般常用的 混合裝置有螺桿擠壓機、滾筒混煉機和班伯里混煉機。另 外，雖然熔融混合可同時結合上述三種成分作處理，但大 部分傾向於先熔融混合（Β)和（C)，再熔融混合（Α)。此法 的好處是可以穩定製作具有許多優良品質之極佳特性的組 合物，因爲（Β)被（C)稀釋後較爲均勻而不會與（Α)局部反 應。應該避免在（Α)和（Β)熔融混合之後再混合（C)，因爲 當使用此法會局部反應產生凝膠。 本發明之樹脂組成物，在不損及本發明產品限度內， 可與其他聚合物和不同的添加物作化合。就其他聚合物的 例子而言，其他聚烯烴像是用金屬雙環戊二烯催化劑製成 之密度870至93 0公斤/立方米的乙烯/α-烯烴共聚物；另 外，由其他類之催化劑製成的線性低密度聚乙烯都可引 用。例如，該其他聚烯烴比例以不高於上述（A)，（Β)和（C) 總重量的十分之一作結合。 另外，就上述添加物而言，如：抗氧化劑、熱安定 劑、光穩定劑、紫外線吸收劑、色素、染料、助滑劑、抗 -13- (9) 1288159 結塊劑、抗靜電劑、抗模塑劑、抗菌劑、防火劑、防火輔 助劑、交聯劑、交聯輔劑、發泡劑、發泡輔劑、無機塡料 和纖維增強劑都是例子。 本發明之樹脂組成物可藉不同的成形方法模製成不同 形狀的物體，如：擠壓成形、射出成形、壓縮成形和中空 成形。例如，使用吹膜機或澆鑄薄膜/薄板機所製的塑合 物如薄板或薄膜呈現出無光亮面（柔亮面），且具有極佳之 尺寸安定性、表面硬度、防污性和視覺品質（無光亮面）， 同時保有離子聚合物之特性，如··拉伸或彎曲時不白化、 極佳之耐磨性和耐刮性。模製物如薄板或薄膜可能是單層 或使用黏性樹脂的層合板，此層合板是用共擠壓成形機製 成，目的是爲了增進和不同基材間的黏著性。 層合在本發明樹脂組成物上之黏性樹脂的代表性例子 可以是單一樹脂，或是兩種或更多樹脂的混合物，其樹脂 選自乙烯/不飽和羧酸共聚物、乙烯/不飽和羧酸/不飽和羧 酸烷基酯三聚物、乙烯/不飽和羧酸烷基酯共聚物、乙烯/ 乙烯基酯共聚物、乙烯/不飽和羧酸烷基酯/一氧化碳三聚 物和這些共聚物/三聚物與不飽和羧酸之接枝產物。 爲了增進由本發明樹脂組成物所製之薄板和薄膜的抗 靜電性和高頻率焊接特性，此組成物可藉不同成形方法， 最好是用共擠壓成形機和特定鉀離子聚合物、鉀離子聚合 物和多元醇之組成物、或再任意含有乙烯聚合物的組成物 共擠壓。即使抗靜電劑未被加入本發明之樹脂組成物中， 層合之鉀離子聚合物層扮演顯著降低樹脂組成物層之電荷 -14- (10) 1288159 衰退時間的角色。因此使用在23 °C且相對濕度50%條件 下表面阻値不大於1〇"Ω，最好不大於101()Ω的鉀離子聚 合物、鉀離子聚合物和多元醇之組成物、或再加入任意量 之乙烯聚合物的組成物是非常適合的。 當鉀離子聚合物之基礎聚合物乙烯/(甲基）丙烯酸共聚 物的酸含量過低，或者鉀離子聚合物中被鉀離子中和的程 度過低時，會變得不易製得其表面阻値如上述範圍的鉀離 子聚合物或其組成物。因此使用乙烯/(甲基）丙烯酸共聚物 之鉀離子聚合物，最好其中（甲基）丙烯酸含量介於10至 25重量％，12至20重量％尤佳，且被鉀離子中和的程度 不得少於6〇%，最好不少於70%。 多元醇是一種包含二或多個醇式羥基的化合物，就這 樣的醇而論，如聚氧化伸烷基二醇，其分子量以2000或 更低爲佳，最好是1〇〇〇或更低，例如聚乙二醇、聚丙烯 二醇、聚丁撐二醇、聚氧化乙/聚氧化丙二醇；甘油、三 羥甲基丙烷、季戊四醇、山梨糖醇、二甘油、三甘油、和 環氧乙烷加合物或是其部分酯類可被引用。 舉例’在乙烯/(甲基）丙烯酸共聚物的鉀離子聚合物 中’多兀醇較佳的結合量是介於〇至1 5重量。/。，〇至i 〇 重量％則更好。 就表面阻値滿足於上述分布區間而言，乙烯聚合物可 和鉀離子聚合物，或是鉀離子聚合物與多元醇之組成物結 合。例如乙燃聚合物的含量可介於0至85重量％，〇至 8 0重量％尤佳。就乙烯共聚物而論，可例舉如下：高壓低 -15- (11) 1288159 密度聚乙烯，線性低密度聚乙烯，金屬雙環戊二烯聚乙 烯’乙烯和乙烯酯如醋酸乙烯酯及丙酸乙烯酯之共聚物， 乙烯和不飽和羧酸酯如丙烯酸甲酯、丙烯酸乙酯、丙烯酸 異丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸己酯、丙烯 酸異辛酯、甲基丙烯酸甲酯、馬來酸甲酯及馬來酸乙酯的 共聚物，和乙烯/ 一氧化碳/乙烯酯或不飽和羧酸酯之三元 共聚物。 (1)單層薄板，（2)外層爲本發明組成物且內層爲前述 黏性樹脂之多層薄板，或者（3)除了中間層爲鉀離子聚合 物或鉀離子聚合物和多元醇的組成物或是再任意含有乙烯 聚合物的組成物外其餘和多層薄板（2)—樣，藉由熱層合 法、加熱滾輪法、加熱壓縮成形法、乾式層合法（黏性塗 裝法）等可將（1)(2)(3)層合在基材表面。 至於上述基材可以是紙張或印刷紙，各種的金屬箔， 各種的金屬板如鋼板，木質材料如木板或三夾板，聚乙 烯、聚丙烯、TPO等的聚烯烴類薄膜、薄板或模製物體， 或是含有各種塡料的類似薄膜、薄板或模製物體，PVC地 磚或薄板及編織布或不織布。 就本發明樹脂組成物之其他擠壓成形的例子而言，如 用擠壓塗佈機使樹脂組成物熱鍵結在其他基材的表面上形 成層合板；至於基材可以是紙張，各種的金屬箔，各種的 金屬板如鋼板，聚烯烴類的薄膜或薄板，編織布，不織布 等等可被引用。在擠壓塗佈製程中，藉由控制本發明樹脂 組成物之成分的熔融流速和比例，可在擠壓可模製性和表 -16- (12) 1288159 面特性如耐磨、耐刮及無光亮面之間取得一個良好的平衡 點如後述的實施例所示。 當本發明之樹脂組成物以擠壓塗佈機層合在其他基材 表面上時，樹脂組成物可被直接層合，或者是透過黏性樹 脂層以共擠壓塗佈機層合。黏性樹脂的代表例子，可以是 單一樹脂或混合二或多種選自前述各種的乙烯共聚物和此 共聚物與不飽和羧酸之接枝產物的樹脂。 【實施方式】 [實施例] 以下，經由幾個實施例來解釋此發明，但此發明並不 限制於這些實施例。 實施例和比較例所使用的原料之組成及特性，及由這 些原料所製得的薄板和薄膜，其特性的評估方法，描述如 下·· 1.原料 (1)離子聚合物（A) 離子聚合物 1 基礎聚合物：乙烯/甲基丙烯酸共聚物（曱基丙烯酸 含量：1 1重量 〇/0)， 金屬陽離子來源：鋅 中和度：6 3莫耳。/。 熔融流速（MFR): 5克/10分鐘 -17- (13) 1288159 離子聚合物 2 基礎聚合物：乙烯/甲基丙烯酸共聚物（甲基丙烯酸 含量：10重量 ％)， 金屬陽離子來源：鋅 中和度：6 8莫耳 ％ 熔融流速（MFR) : 1 .3克/10分鐘 離子聚合物 3 基礎聚合物：乙烯/甲基丙烯酸共聚物（甲基丙烯酸 含量：10重量 ％)， 金屬陽離子來源：鋅 中和度：8 0莫耳 ％ 熔融流速（MFR): 0.9克/10分鐘 (2) α-烯烴/縮水甘油單體共聚物（Β) GMA共聚物： 乙烯/甲基丙烯酸縮水甘油酯共聚物（甲基丙烯酸縮 水甘油酯含量：12重量 ％) 熔融流速（MFR): 3.0克/10分鐘 (3) 丙烯/α-烯烴共聚物（C) 不規則 ΡΡ (丙烯/乙烯不規則共聚物（出自 Grandpolymer 公司的 Grand P〇lypro F229BA，密度：900 公斤/立方公尺，熔融流速（MFR): 9.0克/1〇分鐘 （230 °C )) -18- (14) 1288159 嵌段PP (丙烯/乙烯嵌段共聚物（出自Grandpolymer 公司的 Grand Polypro F707V，密度：900公斤/立方公 尺，熔融流速（MFR): 6.5克/10分鐘 （23 0°C)) 2.特性評估方法 使用一 50微米厚度的中空薄膜，其製法於下文中提 到，來評估薄膜的特性。使用一 200微米厚度的T-模薄 板，其製法於下文中提到，來評估其對熱水壺的耐受性。 利用一 3毫米厚度的壓縮成形薄板來量測表面硬度及尺寸 安定性，此薄板的製法爲在1 8 0 °C時加熱5分鐘，1 8 0 °C 時壓縮5分鐘，接著在20 °C時冷卻5分鐘。 (1) 薄膜觀察（凝膠形成） 用肉眼檢查上述中空薄膜中凝膠的形成 凝膠形成：沒有 凝膠形成：很多 (2) 光學特性 光澤度：以JIS Z874 1爲基礎 (3) 無光亮圖樣的維持（視覺品質） 將測試薄膜放在傳動烘箱中加熱至1 8 0 °C維持1分 鐘，拿出並冷卻至室溫。比較加熱前後薄膜光澤度的變 光澤度大於加熱前：X 加熱前後光澤度無變化：〇 (4) 滑動特性 (15) 1288159 根據ASTM D1980A，當固定在一 63.5毫米平方支架 上的測試薄膜以1 5 0毫米/分鐘的速度在一固定在基座上 的相同薄膜上面滑行所得的負載（A)除以支架的負載（B)的 比例爲其滑動摩擦係數。 (5) 抗張特性 根據JIS K678 1，依照下列的情況來評估薄膜伸長至 破裂時及變白的形成： 測試速度：500毫米/分鐘 用來固定測試薄膜的夾子之間距離：90毫米 爲了量測而標記在薄膜上的線條長度：40毫米 (6) 熱密封性 根據JTIS Z 1 707，觀察15毫米寬的測試薄膜被剝下時 其密封界面的情況。爲了這觀察，用一根1 0毫米寬且加 熱至140 °C的密封棒壓在測試薄膜上約1秒鐘，然後24 小時後將其剝下。 (7) 熱水壺的耐受性 將一裝有2.2升沸騰熱水的不銹鋼水壺直接放在200 微米厚的測試薄板上並停留1分鐘，此薄板的製法後面會 提到。根據下面的觀察來評估其對熱水壺的耐受性。1288159 (1) Description of the Invention [Technical Field] The present invention relates to a thermoplastic resin composition which can be made to have good processability, usability, scratch resistance, abrasion resistance, dimensional stability, and surface hardness. a molded object having antifouling properties, heat resistance and visual quality (no glossy surface), and surface characteristics of a low sliding friction coefficient; and a method and a method thereof. More particularly, the present invention relates to a thermoplastic resin composition containing an ionic polymer as a main component, which is suitable for use in building materials such as flooring, handrails and wallpapers, automotive interior and exterior parts, toys, stationery, and sundries; and its preparation and use. . [Prior Art] The carboxyl group of an ethylene/(meth)acrylic acid copolymer having 2 to 3% by weight of an unsaturated carboxylic acid in an ionic polymer, after being neutralized by a metal ion, compared with other ethylene copolymers, due to ion exchange It has very good wear resistance and transparency. For example, it is known from the Japanese laid-open patent application SHO 60 (1985) - 127 149 that the use of this property of ionic polymers can improve the surface scratch resistance of building materials and automotive interior and exterior parts. The materials mentioned in the publication and the automotive interior and exterior materials have good surface gloss and scratch resistance. Also. Japan's first published patent application HEI 8 (1 996)-25 4〇〇4 also mentions the use of ionic polymer resins in non-PVC-type floor coverings in building materials to prevent table and chair movement or walking wear and Scratch. The surface layer of the above-mentioned plastic compound is an ionic polymer, but since the characteristics of the ionic polymer have good transparency and smoothness, a method of treating the excessively bright surface is required. For example, the method of using the embossing roller without the bright surface, but this method has a disadvantage, it is difficult to use for three-dimensional modeling, such as: extruded handrails or -6 - (2) 1288159 pipe fittings. In other words, the use of embossing rollers to make a matte sheet is still a problem, just like when making a foamed sheet, the non-glazed surface disappears during the secondary heating of the foaming oven. In order to solve this problem, the following two methods can be used: one is to laminate a matte glossy film on the foamed sheet after the foaming oven process to maintain a matte surface, and the other is to press the embossing roller to press the light-free sheet again. pattern. However, there is a problem in practical use. Due to the tendency of the ionic polymer to adhere to the metal, the foamed sheet often melts and adheres to the hot roller. Unlike the previous method, some methods in which the resin itself forms a matte surface have been known. For example, Japanese Published Patent Application No. SHO 61(1986)-37836 or HEI 4(1 992)-86260, etc., proposes methods such as mixing polymers having low compatibility with each other or adding rubber-like polymers of different viscosities. . Similar to these methods, Japanese Laid-Open Patent Application No. HEI 11 (1999)-140251 proposes the use of an ionic polymer composition modified with a styrene/unsaturated carboxylic acid copolymer, which has been confirmed to have no bright side and improved heat resistance. . However, since these methods utilize low compatibility, the ionic polymer composition still has the problem of deteriorating the characteristics of the ionic polymer, such as strong whitening when the sheet is bent, and reduced wear resistance. For the above reasons, when the ionic polymer is most effectively utilized, the excellent abrasion resistance and scratch resistance are simultaneously made. The present invention is directed to a method of adding heat-resistant properties and bending-free surface characteristics which do not cause whitening. As a result, we have finally found that when the ionic polymer is mixed with the specific ratio of the ethylene copolymer and the propylene/〇1_olefin copolymer described below, the ionic polymer composition which can obtain the desired effect; and, (3) 1288159, we also find This composition can be used as a molded article of high stiffness, high surface hardness, and good slidability. Therefore, the object of the present invention is to provide a thermoplastic resin composition having good processability, usability, abrasion resistance, scratch resistance, stiffness, surface hardness, antifouling property, visual quality (no gloss surface), heat resistance and the like. . Another object is to provide a molded object having good surface characteristics by the composition, and more particularly to provide a multilayer material having a surface property of good surface characteristics. [Invention] The present invention relates to a thermoplastic resin composition, It comprises 60 to 96.7 parts by weight of the (A) ionic polymer, wherein 20 to 90 parts by weight of the carboxyl group of the ethylene/(meth)acrylic copolymer is neutralized by the metal ion; 0.3 to 10 parts by weight of the (B) ethylene or An α-olefin copolymer containing glycidyl (meth)acrylate or an unsaturated glycidyl ether, optionally containing a vinyl ester or an unsaturated carboxylic acid ester; and 3 to 30 parts by weight of (C) propylene/α- Olefin copolymer. The present invention is also related to a thermoplastic resin composition having the above-described various excellent properties and its application. BEST MODE FOR CARRYING OUT THE INVENTION From 20 to 90 mol%, preferably from 30 to 85 mol%, of the ethylene/(meth)acrylic copolymer in the ionic polymer (yttrium) used in the present invention is neutralized by metal ions. Next, an ethylene/(meth)acrylic copolymer is used as the base polymer, and the content of the (meth)acrylic acid in the copolymer is from 2 to 30 parts by weight (4) 1,288,159% by weight, preferably from 3 to 25 parts by weight. /〇, not only a copolymer of ethylene and acrylic acid or methacrylic acid, but also a copolymer of a plurality of monomers which are optionally copolymerized with other monomers can also be used as the base polymer. In the case where the ionic polymer has an acid content lower than the above content range, it is difficult to obtain a composition having good abrasion resistance and a non-shining surface. Other monomers which can be copolymerized as desired are exemplified by vinyl esters such as vinyl acetate and vinyl propionate; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate and isobutyl acrylate. , n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, cis-butene-acid - * A曰, 顺丁丁一一酸-乙乙醋; a * carbon oxide and sulfur dioxide. Although the content of other monomers which can be copolymerized is from 0 to 40% by weight, preferably from 30% to 30% by weight, it is generally difficult to obtain a composition having good abrasion resistance, scratch resistance and heat resistance by increasing the content thereof. Therefore, it is preferred to use a copolymer which does not contain other monomers, or even if it contains other monomers, its content is preferably less than 20% by weight. It is satisfactory to use an ethylene/(meth)acrylic copolymer having a melt flow rate of from 1 to 1 000 g/10 min, preferably from 2 to 800 g/10 min, at 190 ° C and a load of 2160 g. . The above copolymer can be produced by radical copolymerization under high temperature and high pressure. 20 to 90 mol%, preferably 30 to 85 mol% of the carboxyl group of the above copolymer in the ionic polymer (A) to be used is neutralized by metal ions. In the case of metal ions, the divalent metal is preferably zinc or alkaline earth magnesium and calcium. A combination of a divalent metal and other metals such as lithium, sodium and potassium of an alkali metal is available. In other words, -9-(5) 1288159 means that it is easier to use at least a part of the metal ion of a divalent metal compared with other ionic polymers which are combined with an alkali metal or an alkali metal which does not contain any divalent metal. A composition having excellent properties such as a matte side (soft side), heat resistance, and no matte side retention is obtained. In addition, considering the moldability, mechanical properties, and compatibility with other components, it is preferred to use a melt flow rate of 0.001 ° C to 100 g / 10 min, preferably 0.1 to 190 ° C and a load of 2160 g. 50 g/10 min ionic polymer. The copolymer (B) in the present invention is ethylene or (copolymer of X-olefin) which contains glycidyl (meth)acrylate or unsaturated glycidyl ether, and may further contain a vinyl ester or an unsaturated carboxylic acid ester in an arbitrary amount. The α-olefin has about 3 to 8 carbon atoms such as propylene or butene. The copolymer of ethylene is particularly preferred in terms of the component (Β). The glycidyl (meth)acrylate or the unsaturated In the case of glycidyl ether, glycidyl acrylate, glycidyl methacrylate, ethylene glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, etc. can be cited. Ethylene or α- The copolymer of the olefin and the above-mentioned glycidyl monomer does not necessarily need to be a binary copolymer, but may also be a copolymer of a multi-monomer type in which other monomers such as a vinyl ester or an unsaturated carboxylic acid ester are copolymerized. Examples of the other monomer may be other monomers of the base polymer ethylene/(meth)acrylic copolymer of the above-mentioned ionic polymer (Α). Further, in the present invention, ethylene, α-olefin and The above glycidyl single The monomeric copolymer of the composition may be used. -10- (6) 1288159 In the copolymer (B) of ethylene or an α-olefin and a glycidyl monomer, the ethylene or α-olefin content is preferably 5 〇 to 99% by weight, particularly preferably 52 to 98% by weight; and glycidol monomer is preferably between 0.5 and 20% by weight, preferably from 1 to 18% by weight; the other monomers mentioned above are from 〇 to 49.5% by weight. 0 to 4% by weight is particularly preferred. When the content of glycidol monomer is too low, the heat resistance is enhanced and the non-glossy surface is kept ineffective. Conversely, when the content is too high, the reactivity to the ionic polymer is too high. And sometimes it is difficult to mold and/or cause gel formation in the composition due to the increase in resin viscosity. The above copolymer may be an irregular copolymer or a graft copolymer, and usually focuses on the uniformity of the reaction to the ionic polymer. An irregular copolymer is used. The irregular copolymer can be produced by a free radical copolymerization reaction under high temperature pressure. When an ethylene copolymer is used as the above copolymer, it is preferably used at 190 ° C and a load of 2 160 g. , its melting flow rate is between 0.01 and 1000 g/10 minutes Preferably, it is a copolymer of from 1 to 200 g/10 minutes. The invention (C) a propylene/α-olefin copolymer and (A) an ionic polymer and (Β) ethylene or an α-olefin and a glycidyl monomer The copolymer is used together. By using a propylene/α-olefin copolymer which can be easily dispersed in other components, the resin composition can easily achieve excellent visual quality, heat resistance, abrasion resistance, scratch resistance, and antifouling. Mechanical strength, etc. The propylene/α-olefin copolymer (C) used in the present invention is a copolymer of propylene as a main component and other α-olefins, and the copolymer (C) preferably has a density of 870 to 870. 93 kg/m3, 880 to 920 kg/m3 is better; and the melt flow rate is 2160 g load and 23 0 ° C, between 〇·1 -11 - (7) 1288159 to 100 g/10 min Preferably, 0.2 to 80 g/10 minutes is even better. In the copolymer (c), the α-olefin copolymerized with propylene preferably has 2 to 12 carbon atoms '2 to 10 carbon atoms, particularly for the α-olefin, ethylene, ?butene, 1 Hexene, 1-octene, 1-decene, 1-dodecene, and 4-methyl-1-pentene are all examples. The α-olefins may be a combination of one, two or more categories. The copolymer (C) may be an irregular or block copolymer, and a particularly suitable irregular copolymer is an irregular copolymer of propylene and ethylene, or an irregular copolymer of propylene, ethylene and other α-olefins, of which propylene The content is between 85 and 99.9 weight. /. 90 to 99.5% by weight is particularly preferred. These are crystalline polymers produced in the copolymerization reaction in the presence of a stereoselective catalyst. The above block copolymer used as the copolymer (C) is produced by a polymerization or copolymerization reaction of propylene and other α-olefins in a continuous manner. Usually block copolymerization is carried out in combination with single or multiple polymerization stages, including (1) copolymerization of propylene and a plurality of alpha-olefins and/or (3) alpha-olefins after polymerization of (1) propylene. polymerization. Among the above (1) polymerization of propylene, there is an example of copolymerization with a small amount of α-olefin, and another example is copolymerization of a small amount of propylene in (3) α-olefin polymerization. In either case, the above block copolymer can be produced by the above-described multistage polymerization reaction in the presence of a stereoselective catalyst. A suitable propylene/α-olefin block copolymer is a block copolymer of propylene and ethylene comprising 60 to 95% by weight of (1) a propylene polymer block. In the thermoplastic resin composition of the present invention, (A), (Β), (C) mixing ratio -12-(8) 1288159 For example: 60 to 96.7 parts by weight of ionic polymer (A), 〇.3 to parts by weight Copolymer (B) and 3 to 30 parts by weight of the propylene/α-olefin copolymer (C); preferably 73 to 95.5 parts by weight of (Α), 0.5 to 7 parts by weight of (Β) and 4 to 20 parts by weight Parts by weight of (C); most preferably from 8 1 to 94 parts by weight of (Α), from 1 to 4 parts by weight of (Β) and from 5 to 15 parts by weight of (C). The thermoplastic resin of the present invention can be produced by melt-mixing an ionic polymer (Α), ethylene or (a copolymer of X-olefin/glycidyl monomer (Β), and a propylene/α-olefin copolymer (C). In the mixing method, the commonly used mixing devices are a screw extruder, a drum mixer, and a Banbury mixer. In addition, although melt mixing can be combined with the above three components for treatment, most of them tend to melt and mix first. (Β) and (C), remelted and mixed (Α). The advantage of this method is that it can stably produce a composition with excellent properties of many excellent qualities, because (Β) is more uniform after being diluted by (C) It will react partially with (Α). It should be avoided to mix (C) after the melt mixing of (Α) and (Β), because when this method is used, the gel will be partially reacted. The resin composition of the present invention is not damaged. Within the limits of the product of the invention, it can be combined with other polymers and different additives. For other examples of polymers, other polyolefins are made with a metal dicyclopentadiene catalyst having a density of 870 to 93 0 kg / Cubic meter of ethylene/α- An olefin copolymer; in addition, a linear low-density polyethylene made of other types of catalysts can be cited. For example, the ratio of the other polyolefins is not higher than the total weight of the above (A), (Β) and (C) In addition, for the above additives, such as: antioxidants, thermal stabilizers, light stabilizers, UV absorbers, pigments, dyes, slip agents, anti--13- (9) 1288159 agglomeration Agents, antistatic agents, anti-molding agents, antibacterial agents, fire retardants, fire protection adjuvants, crosslinking agents, crosslinking adjuvants, foaming agents, foaming adjuvants, inorganic coatings and fiber reinforcing agents are all examples. The resin composition of the present invention can be molded into objects of different shapes by different forming methods, such as extrusion molding, injection molding, compression molding, and hollow molding, for example, using a film blowing machine or a cast film/thin plate machine. Plastics such as sheets or films exhibit a matte finish (soft surface) with excellent dimensional stability, surface hardness, stain resistance and visual quality (no glossy side) while retaining the properties of ionic polymers. When stretching or bending Non-whitening, excellent abrasion resistance and scratch resistance. Molding materials such as sheets or films may be a single layer or a laminate using a viscous resin. The laminate is made by a co-extrusion molding machine for the purpose of The adhesion between the different substrates is improved. A representative example of the viscous resin laminated on the resin composition of the present invention may be a single resin or a mixture of two or more resins selected from ethylene/not. Saturated carboxylic acid copolymer, ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid alkyl ester terpolymer, ethylene/unsaturated carboxylic acid alkyl ester copolymer, ethylene/vinyl ester copolymer, ethylene/unsaturated carboxylic acid Alkyl ester/carbon monoxide trimer and graft product of these copolymer/trimer with unsaturated carboxylic acid. In order to improve the antistatic property and high frequency welding characteristics of the thin plate and film made of the resin composition of the present invention, The composition may be co-extruded by a different forming method, preferably by a co-extrusion molding machine and a composition of a specific potassium ion polymer, a potassium ion polymer and a polyol, or a composition optionally containing an ethylene polymer. Even if the antistatic agent is not added to the resin composition of the present invention, the laminated potassium ion polymer layer plays a role of significantly lowering the charge of the resin composition layer -14-(10) 1288159. Therefore, a composition of a potassium ion polymer, a potassium ion polymer and a polyol having a surface resistance of not more than 1 〇 " Ω, preferably not more than 101 () Ω at 23 ° C and a relative humidity of 50%, or It is also very suitable to add a composition of any amount of ethylene polymer. When the acid content of the base polymer ethylene/(meth)acrylic copolymer of the potassium ion polymer is too low, or the degree of neutralization by potassium ions in the potassium ion polymer is too low, it becomes difficult to obtain the surface resistance thereof. A potassium ionomer or a composition thereof as in the above range. Therefore, a potassium ionomer of an ethylene/(meth)acrylic copolymer is preferably used, wherein the (meth)acrylic acid content is preferably from 10 to 25% by weight, particularly preferably from 12 to 20% by weight, and is neutralized by potassium ions. Not less than 6〇%, preferably not less than 70%. The polyol is a compound containing two or more alcoholic hydroxyl groups. For such an alcohol, such as a polyoxyalkylene glycol, the molecular weight is preferably 2,000 or less, preferably 1 Torr or more. Low, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyoxyethylene/polyoxypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, sorbitol, diglycerin, triglycerin, and epoxy Ethane adducts or some of their esters can be cited. For example, in the potassium ionomer of the ethylene/(meth)acrylic acid copolymer, the preferred amount of the polyhydric alcohol is from 〇 to 15重量. /. , 〇 to i 〇 Weight % is better. The ethylene polymer may be combined with a potassium ion polymer or a potassium ion polymer and a polyol composition insofar as the surface resistance is satisfied in the above distribution interval. For example, the content of the ethylene flammable polymer may be from 0 to 85% by weight, particularly preferably from 80% by weight. As far as the ethylene copolymer is concerned, it can be exemplified as follows: high pressure low -15-(11) 1288159 density polyethylene, linear low density polyethylene, metal dicyclopentadiene polyethylene 'ethylene and vinyl esters such as vinyl acetate and propionic acid a copolymer of vinyl ester, ethylene and an unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, methyl methacrylate a copolymer of methyl maleate and ethyl maleate, and a terpolymer of ethylene/carbon monoxide/vinyl ester or unsaturated carboxylic acid ester. (1) a single-layer sheet, (2) an outer layer of the composition of the present invention and an inner layer of the above-mentioned multi-layered viscous resin, or (3) except that the intermediate layer is composed of a potassium ion polymer or a potassium ion polymer and a polyol The material or the composition containing any ethylene polymer is the same as the multi-layer sheet (2), by thermal lamination, heating roller method, heating compression molding method, dry lamination method (viscous coating method), etc. (1) (2) (3) is laminated on the surface of the substrate. The above substrate may be paper or printing paper, various metal foils, various metal plates such as steel plates, wood materials such as wood boards or triple plates, polyolefin films such as polyethylene, polypropylene, TPO, thin plates or molded objects. , or similar films, sheets or molded objects containing various kinds of tanning materials, PVC floor tiles or sheets and woven or non-woven fabrics. For the other examples of extrusion molding of the resin composition of the present invention, the resin composition is thermally bonded to the surface of other substrates by an extrusion coater to form a laminate; as for the substrate, it may be paper, various Metal foils, various metal sheets such as steel sheets, polyolefin-based films or sheets, woven fabrics, non-woven fabrics and the like can be cited. In the extrusion coating process, by controlling the melt flow rate and ratio of the components of the resin composition of the present invention, the moldability in extrusion and the surface characteristics such as abrasion resistance and scratch resistance of Table 16-(12) 1288159 can be obtained. A good balance between the matte surfaces is shown in the examples described below. When the resin composition of the present invention is laminated on the surface of other substrates by an extrusion coater, the resin composition may be directly laminated or laminated by a co-extruding coater through a layer of a viscous resin. A representative example of the viscous resin may be a single resin or a mixture of two or more kinds of resins selected from the foregoing various ethylene copolymers and graft products of the copolymer and the unsaturated carboxylic acid. [Embodiment] [Examples] Hereinafter, the invention will be explained by way of several examples, but the invention is not limited to the examples. The composition and characteristics of the raw materials used in the examples and comparative examples, and the evaluation methods of the properties of the thin plates and films obtained from these raw materials are as follows: 1. Raw materials (1) Ionic polymer (A) Ion polymerization 1 Base polymer: ethylene/methacrylic acid copolymer (mercaptoacrylic acid content: 11 weight 〇/0), metal cation source: zinc neutralization degree: 6 3 moles. /. Melting flow rate (MFR): 5 g/10 min -17- (13) 1288159 Ionic polymer 2 base polymer: ethylene/methacrylic acid copolymer (methacrylic acid content: 10% by weight), metal cation source: zinc Degree: 6 8 mol% Melt flow rate (MFR): 1.3 g/10 min ionic polymer 3 base polymer: ethylene/methacrylic acid copolymer (methacrylic acid content: 10% by weight), source of metal cation :Zinc neutralization: 80 mole % Melt flow rate (MFR): 0.9 g/10 min (2) α-olefin/glycidyl monomer copolymer (Β) GMA copolymer: Ethylene/glycidyl methacrylate Copolymer (glycidyl methacrylate content: 12% by weight) Melt flow rate (MFR): 3.0 g/10 min (3) Propylene/α-olefin copolymer (C) Irregular ΡΡ (propylene/ethylene irregular copolymer) (Grand P〇lypro F229BA from Grandpolymer, density: 900 kg / m ^ 3 , melt flow rate (MFR): 9.0 g / 1 〇 min (230 ° C)) -18- (14) 1288159 Block PP (propylene /ethylene block copolymer (Grand Polypro F707V from Grandpolymer) , density: 900 kg / m ^ 3, melt flow rate (MFR): 6.5 g / 10 min (23 0 ° C)) 2. Characterization method using a 50 μm thick hollow film, the method of which is mentioned below, To evaluate the properties of the film. A 200 micron thick T-die sheet was used, which was prepared as described below to evaluate its resistance to the hot water bottle. The surface hardness was measured using a compression molded sheet of 3 mm thickness. And dimensional stability, the sheet is prepared by heating at 1880 ° C for 5 minutes, at 180 ° C for 5 minutes, and then at 20 ° C for 5 minutes. (1) Film observation (gel formation) Visually inspect the gel formation in the above hollow film: no gel formation: many (2) optical characteristics gloss: based on JIS Z874 1 (3) maintenance of no light pattern (visual quality) will be tested The film was placed in a transmission oven and heated to 180 ° C for 1 minute, taken out and cooled to room temperature. The gloss of the film before and after heating was greater than that before heating: X before and after heating without change: 〇 (4 ) Sliding characteristics (15) 1288159 according to ASTM D1980A, when the test film fixed on a 63.5 mm square bracket slides over the same film fixed on the susceptor at a speed of 150 mm/min (A) divided by the load of the bracket (B) The ratio is its sliding friction coefficient. (5) Tensile properties According to JIS K678 1, the film elongation was evaluated to the time of rupture and whitening according to the following conditions: Test speed: 500 mm/min The distance between the clips used to fix the test film: 90 mm for the amount The length of the line marked on the film was measured: 40 mm (6) Heat-sealing According to JTIS Z 1 707, the sealing interface of the 15 mm-wide test film was observed when it was peeled off. For this observation, a test bar of 10 mm width and heated to 140 ° C was pressed against the test film for about 1 second, and then peeled off after 24 hours. (7) Tolerance of the hot water A stainless steel kettle containing 2.2 liters of boiling hot water was placed directly on a 200 micron thick test sheet and left for 1 minute. This method of making the sheet will be mentioned later. The tolerance to the hot water bottle was evaluated according to the following observations.
測試薄板被熔化黏住水壺=X 測試薄板容易從水壺脫離，但有一些皺縮：〇 測試薄板容易從水壺脫離，且根本沒有皺縮：◎ (8 )表面硬度 根據JIS K7215，使用2毫米厚之薄板來量測表面硬 -20- (16) 1288159 度，此薄板的製法後面會提到。 (9)勁度 根據JIS K7 106，使用2毫米厚之薄板來量測勁度， 此薄板的製法後面會提到。 [實施例1-4] 根據表1所列的比例，將GMA共聚物和不規則PP 或嵌段PP熔融混合得到的組成，和離子聚合物1熔融揉 捏。使用吹膜機器在1 90°C的加工溫度下將此混合物塑造 成5 0微米厚的薄膜。評估此薄膜的特性。利用裝備有 400毫米寬的T-模且直徑爲40毫米的單螺桿擠壓機，在 T-模溫度200°C的狀況下將此混合物塑造成200微米厚的 薄板。評估此薄板對熱水壺的耐受性。 另外，使用一 3毫米厚之壓製薄板來測試硬度和勁 度，此薄板的製法後面會描述。 結果列於表1中。 [比較例1] 按照類似實施例1的方法由離子聚合物2來製造5 0 微米厚的薄膜，200微米厚和3毫米厚的薄板並且用和實 施例1相同的方法來評估薄膜特性，對熱水壺的耐受性， 硬度和勁度。結果連帶地列於表1中。 (18) 1288159 [實施例5，比較例2- 3] 將GMA共聚物和不規則PP熔融揉捏得到的組成物和 離子聚合物3，以離子聚合物3/GMA 共聚物/不規則 P P = 8 3 / 2 /1 5的比例（重量比例）注入單螺桿擠壓機中，在 樹脂溫度21 0°C下熔融揉捏得到樹脂組合物顆粒。 使用單層吹膜機器在樹脂溫度2 10°C下，將這些顆粒製 成150微米厚的薄膜。根據JIS A5705，A1454的方法，針對 表2所列的試劑來評估此薄膜的防污性。結果列於表2中。 另外作爲比較，用滾輪在16(TC下塑合一含有20重量％ 的塑化劑DOP，聚合度1050且厚度爲200微米的聚氯乙烯薄 膜，和由澆鑄薄膜機器所塑合的厚度1 50微米的共聚尼龍 6/66薄膜（來自 Ube Industies，Ltd的 UBE尼龍 5033B)，按 照類似的方法來評估其防污性。其結果列於表2中。 從上面的結果顯示，本發明的樹脂組合物具有較好的防 污性。 -23- (19) 1288159 表2 試劑 實施例5 比較例2 比較例3 聚氯乙烯 尼龍6/66 30%硫酸 B 3 5 %鹽酸 A (A) B 60%硝酸 B (A) B 1 0 0 %冰醋酸 _ 沒有評估 5%醋酸 B 1 0 %檸檬酸 辈 A 40%氫氧化鈉 _ A 20%碳酸鈉 . 響 沒有評估 1 〇 %氨水 擊 _ 沒有評估 2 8 %氨水 _ A 5 %酚水溶液 - A B 9 5 %曱醇 A A 9 5 %乙醇 一 A A 9 5 %丙酮 麵 A 9 5 %乙酸乙酯 _ B (B) 一 9 5 %四氯化碳 A B (B) 9 5 %苯 B 9 5 %油酸 - A 沒有評估 汽油 -(A) B (B) 煤油 A 獅 動物油（豬油） _ 牛奶 _ 醬油 • -24- (23) 1288159 本發明的樹脂組成物和由其所製得的模製物體顯示好 的視覺品質（無光亮面），在保持離子聚合物的特性上證明 有很好的耐刮性和耐磨性，且拉伸或彎曲時不會變白。再 者它們有較好的耐熱性，當二次加工時暴露在高溫中無光 亮面仍可維持等等。 例如，將含有上面所提樹脂組成物的表面層層合在一 基材上製得一多層薄板，其中基材含有混合著發泡劑，發 泡助劑，無機充塡劑等等的可發泡樹脂層，當此多層薄板 放進發泡烘箱發泡時，不只可避免其黏著在熱滾輪上的麻 煩，同時不會破壞其無光亮面。 再者，本發明的樹脂組合物和由其所製得的模製物體 具有一個優點就是和離子聚合物相比其具有較大的薄膜強 度例如破裂時所需的撕裂強度及拉張強度，而且它們不需 要滑動劑或抗結塊劑等添加劑就能產生適中的滑移特性。 另外，它們具有其他優點例如在建材的外層薄板所必須的 良好防污性。 再者，使用丙烯/α-烯烴共聚物 （C)，大大地提高此 組成物的耐熱性，而且和離子聚合物相比增進其薄板強度 例如勁度或表面硬度。從這些特性，本發明的樹脂組成物 適合於一般地板材料的表層薄板，裝飾薄板，防污薄板或 保護薄板，汽車的地板材料，建材的木頭戳板或夾板，鋼 板和壁紙，傢倶和佈告板；塑合物例如扶手；汽車內外零 件類似皮革的套子或外殼，袋子，口袋書和字典；窗簾用 的模製物體或表層，隔板，工業用薄板，桌墊，桌巾，滑 -28- (24) 1288159 鼠墊，標識膜，玩具和文具；地毯的表層或底部；使用在 真空形式製程的薄板。 -29-The test sheet is melted and adhered to the kettle = X The test sheet is easily detached from the kettle, but there is some shrinkage: the test sheet is easily detached from the kettle and there is no shrinkage at all: ◎ (8) Surface hardness is 2 mm thick according to JIS K7215 The thin plate is used to measure the surface hardness of -20- (16) 1288159 degrees, which will be mentioned later. (9) Stiffness According to JIS K7 106, a 2 mm thick sheet is used to measure the stiffness, which will be mentioned later. [Example 1-4] According to the ratios listed in Table 1, the composition obtained by melt-mixing the GMA copolymer and the irregular PP or the block PP, and the ionic polymer 1 were melt-kneaded. This mixture was molded into a 50 μm thick film using a blown film machine at a processing temperature of 1 90 °C. The characteristics of this film were evaluated. This mixture was molded into a 200 μm thick sheet at a T-die temperature of 200 ° C using a single screw extruder equipped with a 400 mm wide T-die and a diameter of 40 mm. The resistance of the sheet to the kettle was evaluated. In addition, a 3 mm thick pressed sheet was used to test the hardness and stiffness, and the method of making the sheet will be described later. The results are shown in Table 1. [Comparative Example 1] A 50 μm thick film, a 200 μm thick and a 3 mm thick thin plate was produced from the ionic polymer 2 in the same manner as in Example 1 and the film properties were evaluated in the same manner as in Example 1, The tolerance of the kettle, hardness and stiffness. The results are shown in Table 1. (18) 1288159 [Example 5, Comparative Example 2 - 3] The composition obtained by melt-kneading the GMA copolymer and the irregular PP and the ionic polymer 3 were ionic polymer 3/GMA copolymer/irregular PP = The ratio (weight ratio) of 8 3 / 2 / 1 5 was injected into a single screw extruder, and kneaded at a resin temperature of 21 ° C to obtain pellets of the resin composition. These pellets were formed into a 150 μm thick film using a single layer blown film machine at a resin temperature of 2 10 °C. The antifouling properties of this film were evaluated in accordance with the method of JIS A5705, A1454 for the reagents listed in Table 2. The results are shown in Table 2. In addition, for comparison, a polyvinyl chloride film containing 20% by weight of a plasticizer DOP, a degree of polymerization of 1050 and a thickness of 200 μm, and a thickness of 50 50 molded by a cast film machine were molded by a roller at 16 (TC). A micron-copolymerized nylon 6/66 film (UBE nylon 5033B from Ube Industries, Ltd.) was evaluated for its antifouling property in a similar manner. The results are shown in Table 2. From the above results, the resin combination of the present invention was shown. The material has good antifouling properties. -23- (19) 1288159 Table 2 Reagent Example 5 Comparative Example 2 Comparative Example 3 Polyvinyl chloride nylon 6/66 30% sulfuric acid B 3 5 % Hydrochloric acid A (A) B 60% Nitric acid B (A) B 1 0 0 % glacial acetic acid _ No evaluation of 5% acetic acid B 1 0 % citric acid generation A 40% sodium hydroxide _ A 20% sodium carbonate. No evaluation of 1 〇% ammonia water hammer _ No evaluation 2 8 % ammonia water _ A 5 % phenol aqueous solution - AB 9 5 % decyl alcohol AA 9 5 % ethanol - AA 9 5 % acetone surface A 9 5 % ethyl acetate _ B (B) 9.55% carbon tetrachloride AB ( B) 9 5 % benzene B 9 5 % oleic acid - A no evaluation of gasoline - (A) B (B) kerosene A lion animal oil (lard) _ Milk _ soy sauce • -24- (23) 1288159 The resin composition of the present invention and the molded object produced therefrom exhibit good visual quality (no glossy surface) and prove good in maintaining the characteristics of the ionic polymer. It has scratch resistance and abrasion resistance, and does not turn white when stretched or bent. Moreover, they have good heat resistance, and when exposed to high temperatures during secondary processing, no bright surface can be maintained, etc. For example, Laminating a surface layer containing the above-mentioned resin composition on a substrate to obtain a multi-layered sheet, wherein the substrate contains a foamable resin mixed with a foaming agent, a foaming aid, an inorganic filler, and the like. When the multi-layer sheet is placed in a foaming oven for foaming, it is not only prevented from sticking to the hot roller, but also does not damage its matte side. Further, the resin composition of the present invention and the resin composition thereof are prepared therefrom. The molded object has the advantage of having a greater film strength than the ionic polymer, such as the tear strength and tensile strength required for cracking, and they do not require additives such as slip agents or anti-caking agents. Produce moderate slip In addition, they have other advantages such as good antifouling properties required for the outer sheet of the building material. Further, the use of the propylene/α-olefin copolymer (C) greatly improves the heat resistance of the composition, and the ion The polymer improves its sheet strength, such as stiffness or surface hardness. From these characteristics, the resin composition of the present invention is suitable for surface sheets of general flooring materials, decorative sheets, antifouling sheets or protective sheets, automotive flooring materials, wood stamping boards or plywood for building materials, steel sheets and wallpapers, furniture and notices. Plastics such as handrails; covers and casings of leather inside and outside the car, bags, pocket books and dictionaries; molded objects or skins for curtains, partitions, industrial sheets, table mats, tablecloths, slides -28 - (24) 1288159 Rat pads, marking films, toys and stationery; the surface or bottom of carpets; sheets used in vacuum form processes. -29-