TW201823284A - 熱塑性樹脂組成物、彼之製法、及含彼之注射模塑物件 - Google Patents

熱塑性樹脂組成物、彼之製法、及含彼之注射模塑物件 Download PDF

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TW201823284A
TW201823284A TW106143941A TW106143941A TW201823284A TW 201823284 A TW201823284 A TW 201823284A TW 106143941 A TW106143941 A TW 106143941A TW 106143941 A TW106143941 A TW 106143941A TW 201823284 A TW201823284 A TW 201823284A
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weight
resin composition
thermoplastic resin
vibration
copolymer
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TW106143941A
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TWI746732B (zh
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鄭大山
韓承勳
金成龍
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南韓商Ｌｇ化學股份有限公司
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Abstract

本發明係關於熱塑性樹脂組成物、彼之製法、及包括彼之注射模塑物件。更特別地，本發明係關於具有優良的震動熔接性質及以ABS為底的樹脂特有的耐衝擊性、耐熱性等之熱塑性樹脂組成物，因為該熱塑性樹脂組成物含括以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；經橡膠改質的接枝共聚物，其包括平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和基質樹脂，及包括該熱塑性樹脂組成物之注射模塑物件。

Description

熱塑性樹脂組成物、彼之製法、及含彼之注射模塑物件
[0001] 本發明係關於熱塑性樹脂組成物、彼之製法、及包括彼之注射模塑物件。更特別地，本發明係關於具有優良的震動熔接性質及以ABS為底的樹脂特有的耐衝擊性、耐熱性等之熱塑性樹脂組成物，因為該熱塑性樹脂組成物含括特定比之兩種以ABS為底的接枝共聚物(其中之以共軛二烯為底的橡膠聚合物具有不同粒徑)；及包括該熱塑性樹脂組成物之注射模塑物件。
[0002] 以丙烯腈-丁二烯-苯乙烯為底的樹脂(以ABS為底的樹脂)具有優良的加工性、耐衝擊性和耐化學品腐蝕性，藉此被廣泛地作為建築材料、載具(如汽車和摩托車)的內部和外部材料、用於電力和電子產品的材料等。其中，作為汽車等的內部和外部材料之以ABS為底的樹脂逐漸被要求須具有高耐熱性和各種後處理特性。 　　[0003] 例如，由於汽車的後燈係利用例如熱熔接、震動熔接、或雷射熔接的方法將燈外殼與由聚(甲基丙烯酸甲酯)(PMMA)製得的透鏡偶合在一起而製得，當用於後燈外殼時，以ABS為底的樹脂必須具有對於PMMA透鏡的高熔接力及高耐熱性。 　　[0004] 同時，為了使耐熱性之以ABS為底的燈外殼與透鏡偶合，過去主要使用設備成本低的熱熔接法。但是，在此方法的情況中，最終製得的產品的外觀欠佳且產能低。 　　[0005] 據此，考慮外觀和產能，傾向使用震動熔接法。但是，在藉震動熔接製造以ABS為底的注射模塑物件的情況中，沿著以ABS為底的注射模塑物件之接合表面的形狀發生未熔接的情況。當針對未熔接現象而提高震動時間時會產生碎屑，此導致最終組裝的後車燈中的缺陷。為移除此碎屑，含括額外的程序，此造成產能降低。 　　[0006] 施用雷射熔接法可解決碎屑造成的問題。但是，雷射熔接法中使用的雷射熔接裝置昂貴，就經濟效益而言，其非較偏好者。因此，對於開發能夠針對因為外來物質造成的缺陷問題之材料有迫切的需求。 相關申請案之交互參照 　　[0007] 　　[專利文件] (專利文件1) KR 10-0528768 B1
所欲解決技術問題 　　[0008] 因此，鑑於以上問題進行本發明，且本發明的一個目的是提出一種熱塑性樹脂組成物，其具有改良的震動熔接性和優良之以ABS為底的樹脂特有的機械強度、耐熱性等，及製造彼之方法。 　　[0009] 本發明的另一目的是提出一種自該熱塑性樹脂組成物製得的注射模塑物件，該注射模塑物件展現改良的震動熔接性。據此，在製造用於汽車的後燈方面，本發明有助於降低製造成本、降低缺陷率、提高產能等。 　　[0010] 藉以下描述之本揭示可完成以上和其他目的。 解決問題之技術手段 　　[0011] 根據本發明的一方面，提出一種熱塑性樹脂組成物，其包括：(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂，其中，當自該熱塑性樹脂組成物製得的模塑物件震動熔接至由聚(甲基丙烯酸甲酯)(PMMA)製得且其一表面上包含震動熔接酸之模塑物件時(在230 Hz的頻率，480 kgf的壓力、和1.2 mm的振幅之條件下)，藉以下的數學式1計算得到的震動熔接性是6或更低： [數學式 1] 　　震動熔接性(秒) = T2 - T1 　　其中T2是在與熔接酸的方向呈80°的方向震動熔接所需的時間，和T1是在與熔接酸的方向平行的方向震動熔接所需的時間。 　　[0012] 根據本發明的另一方面，提出一種製造熱塑性樹脂組成物之方法，該方法包含捏和及壓出下列之步驟：(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂。 　　[0013] 根據本發明的另一方面，提出一種注射模塑物件，其係藉注射模塑該熱塑性樹脂組成物而製得。 　　[0014] 根據本發明的又另一方面，提出一種用於汽車的後燈模組，其中該後燈模組係藉由將該射出模製物件震動熔接至由PMMA製得的透鏡而製得。 　　發明對照先前技術之功效 　　[0015] 由前述者顯見，本發明有利地提出一種熱塑性樹脂組成物，其提供改良的震動熔接性，同時維持耐熱性之以ABS為底的樹脂特有的機械強度和耐熱性，及自彼製造的注射模塑物件。 　　[0016] 此外，根據本發明之注射模塑物件具有改良的震動熔接性，藉此在製造用於汽車的後燈模組方面，有助於產製成本降低、產品品質提高、和產能提高。
[0017] 下文中，將詳細描述本發明之熱塑性樹脂組成物。 　　[0018] 本發明之熱塑性樹脂組成物包括(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂，其中，當自該熱塑性樹脂組成物製得的片(寬130mm，長130mm)震動熔接至由聚(甲基丙烯酸甲酯)(PMMA)製得且其一表面上包含震動熔接酸之片(寬130mm，長130mm)時(在230 Hz的頻率，480 kgf的壓力、和1.2 mm的振幅之條件下)，藉以下的數學式1計算得到的震動熔接性是6或更低： [數學式 1] 　　震動熔接性(秒) = T2 - T1 　　其中T2是在與熔接酸的方向呈80°的方向震動熔接所需的時間，和T1是在與熔接酸的方向平行的方向震動熔接所需的時間。 　　[0019] 另一具體實施例中，本揭示之熱塑性樹脂組成物包括(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂，其中該平均粒徑為0.6至10µm之以共軛二烯為底的橡膠聚合物對該平均粒徑為0.25至0.35µm的橡膠聚合物之重量比為1:15至1:2或1:13至1:5。 　　[0020] 下文中，將詳係描述本揭示之熱塑性樹脂組成物中所含括的各成分。 (A) 以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物 　　[0021] 該以ABS為底的接枝共聚物(A)係平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物(下文中稱為“小直徑橡膠聚合物”)與芳族乙烯基化合物和乙烯基氰化物接枝而製得之共聚物。 　　[0022] 本揭示中，該以共軛二烯為底的橡膠聚合物是指具有雙鍵和單鍵交替排列的結構之共軛化合物的聚合物。 　　[0023] 例如，該以共軛二烯為底的橡膠聚合物可包括丁二烯聚合物、丁二烯-苯乙烯共聚物、丁二烯-丙烯腈共聚物、乙烯-丙烯共聚物、和自彼衍生的聚合物中之一或多者。較佳地，該以共軛二烯為底的橡膠聚合物是丁二烯聚合物或丁二烯-苯乙烯共聚物。 　　[0024] 本揭示中，“自彼衍生的聚合物”是指藉由聚合單體化合物或原始聚合物中未含括的聚合物而製得的聚合物，或藉由聚合共軛化合物之衍生物而製得的聚合物。 　　[0025] 本揭示中，“衍生物”是指原始化合物的氫原子或原子團經，例如，鹵素或烷基取代的化合物。 　　[0026] 該小直徑橡膠聚合物可具有0.25至0.35µm、0.27至0.35µm、或0.28至0.32µm的平均粒徑。在此範圍內，最終的模塑物件具有優良的機械性質(如，耐衝擊強度)和外觀特性。 　　[0027] 本揭示中，平均粒徑可以根據動態光散射法藉 Nicomp 380 裝置測定。 　　[0028] 該以ABS為底的接枝共聚物(A)可包括，例如，40至70重量%的該小直徑橡膠聚合物、12至35重量%的該芳族乙烯基化合物、和6至25重量%的該乙烯基氰化物。在此範圍內，例如機械強度、加工性、和耐熱性之性質優良。 　　[0029] 另一具體實施例中，該以ABS為底的接枝共聚物(A)可包括45至68重量%的該小直徑橡膠聚合物、14至35重量%的該芳族乙烯基化合物、和6至20重量%的該乙烯基氰化物。此情況中，例如耐熱性和機械強度的性質之間的平衡優良。 　　[0030] 另一具體實施例中，該以ABS為底的接枝共聚物(A)可包括48至65重量%的該小直徑橡膠聚合物、20至35重量%的該芳族乙烯基化合物、和7至17重量%的該乙烯基氰化物。此情況中，例如耐熱性和機械強度之性質優良。 　　[0031] 本揭示中，該芳族乙烯基化合物可為，例如，選自苯乙烯、α-甲基苯乙烯、對-甲基苯乙烯、和乙烯基甲苯中之一或多者。較佳地，該芳族乙烯基化合物包括苯乙烯。 　　[0032] 本揭示中，該乙烯基氰化物可為，例如，選自丙烯腈、甲基丙烯腈、和乙基丙烯腈中之一或多者。較佳地，該乙烯基氰化物包括丙烯腈。 　　[0033] 一個特別的具體實施例，該以ABS為底的接枝共聚物(A)可為小直徑丁二烯橡膠聚合物-苯乙烯-丙烯腈共聚物。此情況中，最終產物具有優良的性質。 　　[0034] 基於該以ABS為底的接枝共聚物(A)、該經橡膠改質的接枝共聚物(B)、和該基質樹脂(C)的總重，該以ABS為底的接枝共聚物(A)含量較佳為20至30重量%、22至30重量%、或23至27重量%。此情況中，提供優良的性質平衡等。 (B) 經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得 　　[0035] 經橡膠改質的接枝共聚物(B)係該平均粒徑為0.6至10µm之以共軛二烯為底的橡膠聚合物(下文中稱為“大直徑橡膠聚合物”)和芳族乙烯基化合物及乙烯基氰化物之共聚物。 　　[0036] 該大直徑橡膠聚合物可具有，例如，0.6至10µm、0.6至8µm、0.65至5µm，0.65至3µm、5至10µm、或6至9µm的平均粒徑。在此範圍內，該熱塑性樹脂組成物的機械強度優良且其震動熔接性獲得改良。 　　[0037] 經橡膠改質的接枝共聚物(B)可包括，例如，5至20重量%的該大直徑橡膠聚合物、50至70重量%的該芳族乙烯基化合物、和10至30重量的該乙烯基氰化物。在此範圍內，性質(如，機械強度和耐熱性)優良且在震動熔接時的熔接性獲得改良。 　　[0038] 另一具體實施例中，經橡膠改質的接枝共聚物(B)可包括8至15重量%的該大直徑橡膠聚合物、52至75重量%的該芳族乙烯基化合物、和12至35重量%的該乙烯基氰化物。在此範圍內，例如機械強度和耐熱性的性質優良，且因為改良的震動熔接性，使得缺陷率降低及後加工的產能提高。 　　[0039] 該芳族乙烯基化合物和該乙烯基氰化物可包括與在該以ABS為底的接枝共聚物(A)中含括者相同的化合物。 　　[0040] 特別的具體實施例中，經橡膠改質的接枝共聚物(B)可為大直徑丁二烯橡膠聚合物-苯乙烯-丙烯腈共聚物。此情況中，最終產物具有優良的性質且其震動熔接性獲得改良。 　　[0041] 基於該以ABS為底的接枝共聚物(A)、該經橡膠改質的接枝共聚物(B)、和該基質樹脂(C)的總重，該經橡膠改質的接枝共聚物(B)含量較佳為2至10重量%、3至10重量%、3至7重量%。在此範圍內，該熱塑性樹脂組成物具有優良的性質平衡且其熔接性獲得改良。 　　[0042] 該以ABS為底的接枝共聚物(A)對該經橡膠改質的接枝共聚物(B)的重量比較佳為1:3至1:10，更佳為1:5至1:9。在此範圍內，最終的模塑物件具有優良的性質平衡和改良的震動熔接性。 　　[0043] 基於本揭示之熱塑性樹脂組成物總重，該以ABS為底的接枝共聚物(A)和該經橡膠改質的接枝共聚物(B)的總含量較佳地為20至40重量%或25至35重量%。在此範圍內，性質平衡和加工性優良且震動熔接性獲得改良。 　　[0044] 此外，本揭示之熱塑性樹脂組成物中之該大直徑橡膠聚合物對該小直徑橡膠聚合物的重量比較佳地為1:15至1:3或1:13至1:6。在此範圍內，震動熔接性獲得改良，且以ABS為底的樹脂特有的機械強度、加工性、耐熱性等未降低，藉此製造具有優良品質的模塑物件。 (C) 基質樹脂 　　[0045] 該基質樹脂可為此技術中已知之耐熱之以苯乙烯為底的樹脂。例如，該基質樹脂可包括α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物、α-烷基苯乙烯-乙烯基氰化物共聚物、順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物、或其全部。當該耐熱之以苯乙烯為底的樹脂含括於該基質樹脂中時，該熱塑性樹脂組成物具有優良的機械強度及優良的加工性和耐熱性。 　　[0046] 本揭示中，該α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物中的芳族乙烯基化合物不是α-烷基苯乙烯。 　　[0047] 該耐熱之以苯乙烯為底的樹脂的玻璃化轉變溫度為，例如，115℃或更高，或115至140℃。在此範圍內，最終樹脂組成物具有優良的加工性和耐熱性。 　　[0048] 本揭示中，玻璃化轉變溫度係藉差示掃描卡計(DSC)測得。 　　[0049] 該α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物可包括，例如，50至80重量%或60至75重量%的α-烷基苯乙烯、0至15重量%或0至10重量%的芳族乙烯基化合物、和20至50重量%或25至40重量%的乙烯基氰化物。此情況中，所得樹脂組成物具有優良的機械強度、耐熱性等。 　　[0050] 本揭示中，該α-烷基苯乙烯可為選自α-甲基苯乙烯和α-乙基苯乙烯中之一或多者。較佳地，該α-烷基苯乙烯包括α-甲基苯乙烯。 　　[0051] 特別的具體實施例中，該α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物可為α-甲基苯乙烯-苯乙烯-丙烯腈共聚物，而該α-烷基苯乙烯-乙烯基氰化物共聚物可為α-甲基苯乙烯-丙烯腈共聚物，但應注意到本揭示不限於此。 　　[0052] 該順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物包括，例如，30至70重量%的順丁烯二醯亞胺化合物、30至60重量%的芳族乙烯基化合物、和0至10重量%的順丁烯二酸酐。此情況中，所得樹脂組成物具有優良的機械性強度等、和高耐熱性。 　　[0053] 另一具體實施例中，該順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物可包括40至60重量%的順丁烯二醯亞胺化合物、40至55重量%的芳族乙烯基化合物、和大於0且8重量%或更低的順丁烯二酸酐。在此範圍內，耐熱性優良。 　　[0054] 該順丁烯二醯亞胺化合物可為，例如，選自由N-苯基順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-丁基順丁烯二醯亞胺、和N-環己基順丁烯二醯亞胺所組成群組中之一或多者。較佳地，該順丁烯二醯亞胺化合物包括N-苯基順丁烯二醯亞胺。 　　[0055] 特別的具體實施例中，該順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物可為N-苯基順丁烯二醯亞胺-苯乙烯-順丁烯二酸酐共聚物，但應注意到本揭示不限於此。 　　[0056] 此外，該基質樹脂可藉由混合芳族乙烯基化合物-乙烯基氰化物共聚物和耐熱性之以苯乙烯為底的樹脂而製得，以改良加工性。 　　[0057] 特別的具體實施例中，該基質樹脂可包括15至35重量%的順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物和65至85重量%的芳族乙烯基化合物-乙烯基氰化物共聚物。此情況中，耐熱性和加工性皆優良。 　　[0058] 另一具體實施例中，該基質樹脂可包括25至33重量%的順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物和67至75重量%的芳族乙烯基化合物-乙烯基氰化物共聚物。此情況中，耐熱性和加工性優良。在此範圍內，耐熱性、加工性等優良。 　　[0059] 該芳族乙烯基化合物-乙烯基氰化物共聚物可包括，例如，60至80重量%的芳族乙烯基化合物和20至40重量%的乙烯基氰化物。在此範圍內，所得樹脂組成物具有優良的加工性。 　　[0060] 特別的具體實施例中，該芳族乙烯基化合物-乙烯基氰化物可為苯乙烯-丙烯腈共聚物，但應注意到本揭示不限於此。 　　[0061] 此外，該芳族乙烯基化合物-乙烯基氰化物較佳地具有，例如，60,000至200,000 g/mol，或80,000至180,000 g/mol的重量平均分子量。在此範圍內，所得樹脂組成物具有改良的流動性且耐熱性未降低，藉此具有優良的加工性。 　　[0062] 本揭示中，重量平均分子量可藉凝膠穿透層析法，在將樣品溶於溶劑(如，THF)的前處理之後測得。 　　[0063] 根據本發明之熱塑性樹脂組成物係藉兩種以ABS為底的接枝共聚物(此二種接枝共聚物分別包括具有不同平均粒徑之以二軛二烯為底的橡膠聚合物)和耐熱性基質樹脂製得，藉此具有改良的震動熔接性，同時維持以ABS為底的樹脂特有的耐衝擊性、耐熱性等。 　　[0064] 特別地，當自該熱塑性樹脂組成物製得的模塑物件震動熔接至由聚(甲基丙烯酸甲酯)(PMMA)製得且其一表面上包含震動熔接酸之物件時(在230 Hz的頻率，480 kgf的壓力、和1.2 mm的振幅之條件下)，藉以下的數學式1計算得到的震動熔接性是6或更低，5.5或更低，5.0或更低，或4.5或更低。 　　[0065] 此外，必要時，本發明之熱塑性樹脂組成物可以選擇性地另包括至少一種此技術中已知的添加劑。 　　[0066] 該添加劑可為選自，例如，潤滑劑、抗氧化劑、熱安定劑、光安定劑、著色劑、抗靜電劑等中之一或多者。 　　[0067] 在本發明涵蓋的技術領域中一般實施的範圍內，對於在本發明之熱塑性樹脂組成物的描述中未明確描述的其他添加劑沒有特別的限制，且必要時可經適當地選擇和使用。 　　[0068] 下文中，描述製備本揭示之熱塑性樹脂組成物之方法。 　　[0069] 製備本發明之熱塑性樹脂組成物之方法包含捏和及壓出下列之步驟：(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂。 　　[0070] 捏和時，必要時，可以另含括添加劑，如，潤滑劑、抗氧化劑、光安定劑、或著色劑。 　　[0071] 基於100重量份該以ABS為底的接枝共聚物(A)、該經橡膠改質的接枝共聚物(B)、和該基質樹脂(C)的重量總和，該添加劑含量可為0.1至5重量份或0.5至3重量份。在此範圍內，可展現因為添加添加劑所得的效果，但未減損最終產物的性質，如，機械強度和耐熱性。 　　[0072] 該捏和及壓出可於100至800 rpm或150至750 rpm和200至300℃或220至280℃進行。在此範圍內，可提供優良的加工性和模塑性。 　　[0073] 本揭示之熱塑性樹脂組成物可藉由注射模塑程序製成注射模塑物件。該注射模塑物件具有，例如，95℃或更高，或95至112℃，的熱變形溫度，藉此具有優良的耐熱性。 　　[0074] 本揭示中，根據ASTM D648，熱變形溫度可以在18.5 kgf/cm2 的載重條件下以具1/4”的厚度之試樣測定。 　　[0075] 根據本揭示之注射模塑物物件具有優良的性質(如，耐熱性和耐衝擊性)，因而可被施用在用於各種目的的產品。特別地，具有改良的震動熔接性之該注射模塑物件可被用作為汽車的後燈模組，其係經由震動熔接以接合後燈外殼等而製得。 　　[0076] 例如，根據本揭示之注射模塑物物件可為汽車的後燈外殼。該後燈外殼可以藉震動熔接法與由PMMA製造的透鏡接合，藉此製成汽車的後燈模組。 　　[0077] 特別地，藉震動熔接法之接合程序可包括在由PMMA製得的上部表面上形成震動熔接酸，將形成有震動熔接酸的表面面對由本發明之熱塑性樹脂組成物製造的注射模塑物件(下部)的一面，及藉震動熔接機熔化介於上部和下部之間的震動熔接酸以使得上部和下部彼此接合的程序。 　　[0078] 現在，將參照以下較佳實例，更詳細地描述本發明。但是，所提出的這些實例僅作為說明之用。嫻於此技術者將理解在未背離本發明之範圍和精神的情況下，各種修飾、增添和取代具可能性。因此，顯見修飾、增添和取代屬本發明之範圍內。 　　[0079] 實例和比較例用使用的材料如下： 　　A) 包括小直徑橡膠聚合物之以ABS為底的接枝共聚物 　　A1) 使用包括具有0.3µm的平均粒徑之丁二烯橡膠聚合物，LG chemistry製造的DP270，作為ABS接枝共聚物。 　　B) 包括大直徑橡膠聚合物之以ABS為底的接枝共聚物 　　B1) 使用包括具有0.7µm的平均粒徑之丁二烯橡膠聚合物，Nippon A&L製造的AT-08，作為ABS樹脂。 　　B2) 使用包括具有1.2µm的平均粒徑之丁二烯橡膠聚合物，LG chemistry製造的MA201，作為ABS樹脂。 　　B3) 使用包括具有8µm的平均粒徑之丁二烯橡膠聚合物，LG chemistry製造的MA210，作為ABS樹脂。 　　C) 基質樹脂 　　C1) 使用LG chemistry製造的98UHM作為(α-甲基苯乙烯)-苯乙烯-丙烯腈共聚物。 　　C2) 使用Denka製造的MS-NB作為N-苯基順丁烯二醯亞胺-苯乙烯-順丁烯二酸酐共聚物。 　　C3) 使用LG chemistry製造的92HR作為苯乙烯-丙烯腈共聚物。 [實施例] 實例1至8和比較例1至9 　　[0080] 藉雙螺桿壓出機，將以下的表1和2中彙整的成分以其中所揭示的含量在230℃和200rpm的條件下壓出，分別製得根據實例1至8和比較例1至9的粒型樹脂組成物。 　　[0081] 注射模塑(230℃，150bar)此粒型樹脂組成物，藉此製成用於測定性質的試樣。 [0082] [試驗例] 　　[0083] 藉下列方法測定根據實例和比較例各者製造的試樣的性質。其結果彙整於以下的表3和4。 　　[0084] 1) 熱變形溫度(HDT，g/10min)：在120℃/小時的升溫速率和18.5 kgf/cm2 的載重條件下，使用具有1/4”的厚度的試樣，根據ASTM D648測定。 　　[0085] 2) 震動熔接性評估：用於震動熔接性評估，具有表1中所揭示的成分和含量之樹脂組成物經注射模塑，藉此製造平坦的下部，其具有130mm的寬度和130mm的長度。由PMMA製造上部並在該上部上形成震動熔接酸。將其上具有震動熔接酸的上部注射模塑成與該平坦的下部具有相同的尺寸和形狀。 　　[0086] 將該上部和下部裝載於震動熔接機(730e，Daeyoung ultrasonic)中，使得上部之有震動熔接酸形成於其上的表面面對下部的一表面。接著，在230Hz的頻率，480kgf的壓力、和1.2mm的振幅，1mm的深度模式之條件下，測定在與熔接酸的方向平行的方向震動熔接所需的時間(T1，秒)，並測定在相同條件下，在與熔接酸的方向呈80°的方向震動熔接所需的時間(T2，秒)。T2和T1之間的差異小者，震動熔接性較佳。 　　[0087] 3) Izod耐衝擊強度(IMP，kgcm/cm)：使用具有1/4”厚度的試樣，根據ASTM D256測定。 　　[0088] 4) 外觀評估：以肉眼評估試樣的表面狀態(O：極佳，Δ：良好，X：欠佳) [0089] 如表3和4中所示者，可證實相較於比較例之試樣，自本揭示之熱塑性樹脂組成物製造的試樣展現優良的震動熔接性和外觀特性、及相同或較佳的耐衝擊強度和熱變形溫度。 　　[0090] 特別地，可證實，當含括N-苯基順丁烯二醯亞胺-苯乙烯-順丁烯二酸酐共聚物作為基質樹脂時，進一步改良耐熱性，但震動熔接性略為降低。

Claims (14)

  1. 一種熱塑性樹脂組成物，其包含： 　　(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂， 　　其中，當自該熱塑性樹脂組成物製得的片(寬130mm，長130mm)震動熔接至由聚(甲基丙烯酸甲酯) (PMMA)製得且其一表面上包含震動熔接酸之片(寬130mm，長130mm)時(在230Hz的頻率，480kgf的壓力、和1.2mm的振幅之條件下)，藉以下的數學式1計算得到的震動熔接性是6或更低： [數學式1] 　　震動熔接性(秒) = T2 - T1 　　其中T2是在與熔接酸的方向呈80°的方向震動熔接所需的時間，和T1是在與熔接酸的方向平行的方向震動熔接所需的時間。
  2. 如請求項1之熱塑性樹脂組成物，其中該平均粒徑為0.6至10µm之以共軛二烯為底的橡膠聚合物對該平均粒徑為0.25至0.35µm的橡膠聚合物之重量比為1:15至1:2。
  3. 如請求項1之熱塑性樹脂組成物，其中該以ABS為底的接枝共聚物(A)包含40至70重量%之平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物、12至35重量%的芳族乙烯基化合物、和6至25重量%的乙烯基氰化物。
  4. 如請求項1之熱塑性樹脂組成物，其中該經橡膠改質的接枝共聚物(B)包含5至20重量%之平均粒徑為0.6至10µm的橡膠聚合物、50至70重量%的芳族乙烯基化合物、和10至30重量%的乙烯基氰化物。
  5. 如請求項1之熱塑性樹脂組成物，其中該基質樹脂(C)包含一或多種α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物或α-烷基苯乙烯-乙烯基氰化物共聚物；和順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物，其中該α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物中的芳族乙烯基化合物不是α-烷基苯乙烯。
  6. 如請求項5之熱塑性樹脂組成物，其中該基質樹脂(C)包含15至30重量%的順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物和70至85重量%的芳族乙烯基化合物-乙烯基氰化物共聚物。
  7. 如請求項5之熱塑性樹脂組成物，其中該α-烷基苯乙烯-芳族乙烯基化合物-乙烯基氰化物共聚物包含50至80重量%的α-烷基苯乙烯、0至15重量%的芳族乙烯基化合物、和20至50重量%的乙烯基氰化物。
  8. 如請求項5之熱塑性樹脂組成物，其中該順丁烯二醯亞胺化合物-芳族乙烯基化合物共聚物包含30至70重量%的順丁烯二醯亞胺化合物、30至60重量%的芳族乙烯基化合物、和0至10重量%的順丁烯二酸酐。
  9. 如請求項8之熱塑性樹脂組成物，其中該順丁烯二醯亞胺化合物係選自由N-苯基順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-丁基順丁烯二醯亞胺、和N-環己基順丁烯二醯亞胺所組成群組中之一或多者。
  10. 一種製造熱塑性樹脂組成物之方法，該方法包含捏和及壓出下列之步驟：(A) 20至30重量%之以ABS為底的接枝共聚物，其包含平均粒徑為0.25至0.35µm之以共軛二烯為底的橡膠聚合物；(B) 2至10重量%之經橡膠改質的接枝共聚物，其包含平均粒徑為0.6至10µm的橡膠聚合物且係藉連續整體聚合反應製得；和(C) 60至80重量%的基質樹脂， 　　其中，當自該熱塑性樹脂組成物製造的模製物件震動熔接至由聚(甲基丙烯酸甲酯)(PMMA)製得且其一表面上包含震動熔接酸之物件時(在230 Hz的頻率，480 kgf的壓力、和1.2 mm的振幅之條件下)，藉以下的數學式1計算得到的震動熔接性是6或更低： [數學式1] 　　震動熔接性(秒) = T2 - T1 　　其中T2是在與熔接酸的方向呈80°的方向震動熔接所需的時間，和T1是在與熔接酸的方向平行的方向震動熔接所需的時間。
  11. 一種注射模塑物件，其藉注射模塑請求項1至9中任一項之熱塑性樹脂組成物製得。
  12. 如請求項11之注射模塑物件，其中該注射模塑物件具有95℃或更高的熱變形溫度(在120℃/小時的升溫速率和18.5 kgf/cm2 的載重條件下)。
  13. 如請求項11之注射模塑物件，其中該注射模塑物件係用於汽車的後燈外殼。
  14. 一種用於汽車的後燈模組，其中該後燈模組係藉由將請求項13之注射模塑物件震動熔接至由PMMA製得的透鏡而製得。
TW106143941A 2016-12-28 2017-12-14 熱塑性樹脂組成物、彼之製法、及含彼之注射模塑物件 TWI746732B (zh)

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