TWI495675B - 熱塑性樹脂複合組合物、熱塑性樹脂複合材料及其製備方法 - Google Patents

熱塑性樹脂複合組合物、熱塑性樹脂複合材料及其製備方法 Download PDF

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TWI495675B
TWI495675B TW102125710A TW102125710A TWI495675B TW I495675 B TWI495675 B TW I495675B TW 102125710 A TW102125710 A TW 102125710A TW 102125710 A TW102125710 A TW 102125710A TW I495675 B TWI495675 B TW I495675B
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thermoplastic resin
resin composite
columnar
weight
parts
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TW201408719A (zh
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Sung-Min Kim
Ae-Ri Oh
Jae-Youl Joung
Hee-June Kim
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Lg Hausys Ltd
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Description

熱塑性樹脂複合組合物、熱塑性樹脂複合材料及其製備方法
本發明關於一種熱塑性樹脂複合組合物、熱塑性樹脂複合材料及其製備方法。
複合材料是通過結合兩種以上的材料而形成的材料,它具有被稱為增強相(reinforcing phase)的纖維、板、粒子形態的材料被埋於被稱為基質相(matrix phase)的樹脂形態的材料的結構。基質相應提供增強材料的側面支撐力,傳遞載荷,承受外部的衝擊,而增強材料則應具有高強度及高剛性的特性。
由於大部分熱塑性塑膠樹脂缺乏耐熱性並具有結晶性(cristallinity),因而存在衝擊強度差、成型時的收縮率高的缺點。為了改善上述缺點,目前已經開發了引入聚合物合金(alloy)或將無機物的玻璃纖維作為增強材料來投入的技術。
目前已有以利用木材的粉末對包含玻璃纖維的聚丙烯樹脂的物理性質進行改良為目的的樹脂組合物,但木粉僅僅起到填充材料的作用,而不是增強材料的作用,因此,無法期待能夠增強複合材料的剛性, 而且如果木粉含量變高,就會降低加工性,因而存在不適合注射及擠壓成型的缺點。
故,有必要提供一種熱塑性樹脂複合組合物,以解決習用技術所存在的問題。
根據本發明的一實例,提供一種物理剛性(modulus)和衝擊吸收性優秀,並且能夠將彎曲等的變形最小化的熱塑性樹脂複合組合物。
根據本發明的再一實例,提供一種對上述熱塑性樹脂複合組合物進行成型而製備的熱塑性樹脂複合材料。
根據本發明的另一實例,提供一種上述熱塑性樹脂複合材料的製備方法。
根據本發明的一實例,提供一種包含玻璃纖維、柱狀的木片以及熱塑性樹脂的熱塑性樹脂複合組合物。
在本發明之一實施例中,該柱狀可具有至少一個平坦面。
在本發明之一實施例中,該柱狀可包含針狀。
在本發明之一實施例中,該木片的該柱狀的高度與寬度的比可以是約1:10至約1:40。
在本發明之一實施例中,該柱狀的平均寬度可以是約6毫米至約40毫米。
在本發明之一實施例中,該玻璃纖維的平均直徑可以是約15微米至約17微米。
在本發明之一實施例中,該熱塑性樹脂可包含選自包括聚丙 烯、聚乙烯、聚醯胺及它們的組合的群組中的其中一種。
在本發明之一實施例中,該熱塑性樹脂複合組合物可包含 100重量份的該熱塑性樹脂、約25重量份至約80重量份的該玻璃纖維及約大於0重量份至約80重量份的該木片。
根據本發明的再一實例,提供一種在熱塑性樹脂基質分散有 玻璃纖維及柱狀的木片的熱塑性樹脂複合材料。
根據本發明的另一實例,提供一種熱塑性樹脂複合材料的製 備方法,其包括以下步驟:混合熱塑性樹脂及柱狀的木片的步驟;將玻璃纖維混合於上述熱塑性樹脂及上述木片的混合物的步驟;對上述熱塑性樹脂、上述木片及玻璃纖維的混合物進行壓縮成型的步驟;以及對由上述中間層、上述至少一個表面層及上述至少一個熱塑性樹脂層層壓的層壓體進行壓縮成型來製備層壓體的步驟。
在本發明之一實施例中,使用第一擠壓機混合熱塑性樹脂及 柱狀的木片,使用第二擠壓機將玻璃纖維混合於該熱塑性樹脂及該木片的混合物。
在本發明之一實施例中,在該第一擠壓機及上述第二擠壓機 中,可在約190℃至約230℃的溫度下進行混合。
在本發明之一實施例中,該熱塑性樹脂複合材料可通過長纖 維增強熱塑性塑膠的直接加工(LFT-D,Long Fiber Thermoplastic-Direct)法製備。
在本發明之一實施例中,對該熱塑性樹脂複合組合物進行成 型而製備的複合材料,其物理剛性(modulus)和衝擊吸收性優秀,且能夠 將彎曲等的變形最小化。
圖1是表示根據本發明的一實例的熱塑性樹脂複合材料的製備步驟的製備方法的示意圖。
圖2是通過壓縮成型而製備的實施例1及比較例1的熱塑性樹脂複合材料的照片。
以下,將對本發明的實例進行詳細說明。下述實例只是作為示例而提出的,本發明並不受限於此,本發明僅由所附的申請專利範圍來定義。
根據本發明的一實例,提供一種包含玻璃纖維、柱狀的木片以及熱塑性樹脂的熱塑性樹脂複合組合物。
上述熱塑性樹脂複合組合物通過在熱塑性樹脂中混合加強材料,提高物理剛性(modulus)與衝擊吸收性,能夠將在產品成型時成問題的彎曲等的變形最小化,並且,在價格方面,通過使用低廉的木片,能夠節省其製備成本。
上述熱塑性樹脂複合組合物通過包含柱狀的木片,在由上述熱塑性樹脂複合組合物成型而製備的複合材料中,通過上述木片的排列,提高排列方向剛性,並且提高上述複合材料的整體衝擊吸收性,與僅用玻璃纖維對熱塑性樹脂進行加強時相比,能夠改善熱塑性樹脂的收縮異方性,從而能夠將上述複合材料的彎曲最小化。
上述木片的柱狀可包含具有規定高度的所有杆狀。例如,上述柱狀可具有至少一個平坦面。上述平坦面的形狀可包含三角形、四角形等多角形,且平坦面的形狀不受限制。
並且,上述柱狀可包含針狀。上述針狀意味著以一面為基準,另一面的寬度逐漸變窄的針模樣的形狀,可包含所有具有規定高度的針狀。
上述木片的柱狀的高度與寬度的比具體地可以是約1:10至約1:40,具體地可以是約1:12至約1:16。通過使用具有上述形狀比的木片,能夠容易地實現通過包含如上所述的木片所能夠得到的優點。
上述“柱狀的高度”是指,一面的垂直長度;上述“柱狀的寬度”是指,橫跨柱狀的橫向的寬度。
例如,上述柱狀的平均寬度可以是約6毫米(mm)至約40毫米(mm)。例如,上述柱狀的平均高度可以是約1毫米(mm)至約2毫米(mm)。
上述木片可以無限制地使用任意一種工業用木材,例如,能夠使用松樹等木材,不僅能夠使用木材的芯材,還能夠使用對接近於除芯材之外的剩餘表面的部分進行破碎而獲得的木片。
具有上述柱狀的木片不僅起到填充材料作用,而且與玻璃纖維一同在材料內起到增強材料的作用,來增大熱塑性樹脂複合組合物的剛性。例如,上述木片的密度可以是1.1克/立方公分(g/cm3 )。
相對於100重量份的上述熱塑性樹脂,可包含約大於0重量份至約80重量份的上述木片,具體地可包含約20重量份至約50重量份。上述熱塑性樹脂複合組合物通過包含上述含量比的木片,能夠容易地實現通過 包含如上所述的木片所能夠得到的優點。
上述玻璃纖維不受特別限制,能夠無限制地使用公知的物質。例如,為了防止與組合物內的其他成分的分離現象,能夠使用塗層有用於提升表面粘合力的矽烷偶聯劑的玻璃纖維。再例如,上述玻璃纖維能夠使用無堿玻璃(E-glass)纖維連續纖維類型。
具體地,上述玻璃纖維主要採用平均直徑(filament diameter)為約15微米(μm)至約17微米(μm)的流動(roving)類型。上述玻璃纖維在製備過程中,在擠壓機內通過螺旋槳時其長度被切短,因此,不限制于特定長度的玻璃纖維。
相對於100重量份的上述熱塑性樹脂,可包含約25重量份至約80重量份的上述玻璃纖維,具體地可包含約20重量份至約40重量份。上述熱塑性樹脂複合組合物通過包含上述含量比的玻璃纖維,能夠使強度及收縮異方性的改善效果都變得優秀,同時在價格方面也能夠進行適當調整。
上述熱塑性樹脂不受特別限制,能夠無限制地使用公知的可成型為膜或片的熱塑性樹脂。上述熱塑性樹脂的具體例子可包含選自包括聚丙烯、聚乙烯、聚醯胺及它們的組合的組中的一種。根據一實例,上述熱塑性樹脂能夠使用均聚聚丙烯(homo-PP)、共聚聚丙烯(co-PP)樹脂或它們的組合,例如,上述熱塑性樹脂可以是流動指數(g/10分鐘)為約40至約800的樹脂。
根據所要實現的物理性質,上述熱塑性複合樹脂組合物可還包含選自包括熱穩定劑、偶聯劑等以及它們的組合的組中的添加劑。相對於100重量份的上述熱塑性樹脂,可包含約1重量份至約5重量份的上述添加 劑。
根據本發明的再一實例,提供一種在熱塑性樹脂基質上分散有玻璃纖維及柱狀的木片的熱塑性樹脂複合材料。
上述熱塑性樹脂複合材料能夠通過對上述熱塑性樹脂複合組合物進行成型而製備。對上述熱塑性樹脂複合組合物進行成型的具體方法將記載於後述內容中。根據後述的方法製備的上述熱塑性樹脂複合材料,在上述熱塑性樹脂基質上均勻地分散有上述玻璃纖維和上述木片。
上述熱塑性樹脂、上述玻璃纖維、上述柱狀的木片相關內容如上所述。
上述熱塑性樹脂複合材料的拉伸性及彎曲剛性、耐衝擊性優秀,收縮異方性問題得到改善,將有效改善產品成型時彎曲等的變形問題。並且,上述熱塑性樹脂複合材料使用價格相對低廉的木片,從而能夠降低製備成本,具體地,能夠作為汽車輕量化材料,能夠有效地應用于車底護板(underbody cover)或座椅靠背(seat back)等。
根據本發明的另一實施例,提供一種熱塑性樹脂複合材料的製備方法,包括以下步驟:混合熱塑性樹脂及柱狀的木片的步驟;將玻璃纖維混合於上述熱塑性樹脂及上述木片的混合物的步驟;對上述熱塑性樹脂、上述木片及玻璃纖維的混合物進行壓縮成型的步驟;以及對由上述中間層、上述至少一個表面層及上述至少一個熱塑性樹脂層層壓的層壓體進行壓縮成型來製備層壓體的步驟。
根據上述製備方法,能夠製備上述熱塑性樹脂複合材料。
圖1是表示根據本發明的一實例的熱塑性樹脂複合材料的製 備步驟的製備方法的示意圖。
根據圖1,準備兩台擠壓機,即第一擠壓機及第二擠壓機,利用上述兩台擠壓機,例如,首先,混合以粒料(pellet)形態製備的熱塑性樹脂和上述柱狀的木片,投入於第一擠壓機,接著,將玻璃纖維投入於第二擠壓機後,對通過上述步驟獲得的熱塑性樹脂、玻璃纖維及木片的混合物進行壓縮成型,來製備上述熱塑性樹脂複合材料。
在上述第一擠壓機及上述第二擠壓機中,氣缸筒的溫度能夠根據熱塑性樹脂的類型進行適當調整,具體地,可以在約190℃至約230℃的溫度下完成擠壓捏合。
如上所述,首先,通過將熱塑性樹脂和木片一同混合投入於第一擠壓機,提高木片對於熱塑性樹脂的浸漬性,從而能夠提高加工性。
在混合上述柱狀的木片的情況下,存在由於加工性下降因而不適合注射及擠壓成型的憂慮,但通過採用上述製備方法,消除了這種憂慮,並且,由於木片具有如上所述的柱狀,因而在與玻璃纖維一同排列時,能夠得到向著所排列的方向能夠增大物理性質的效果。
在一實例中,上述熱塑性樹脂複合材料的製備方法可通過長纖維增強熱塑性塑膠的直接加工(LFT-D,Long Fiber Thermoplastic-Direct)法執行。
以下將記載本發明的實施例及比較例。但下述實施例僅僅是本發明的一實施例,本發明並不限定於下述實施例。
實施例1
按照長纖維增強熱塑性塑膠的直接加工(LFT-D)法,首先將通過對聚丙烯 樹脂進行成型而製備的100重量份的粒料及33.3重量份的木片(wood chip,柱狀的平均寬度為15mm,柱狀的高度與寬度的比為14)混合投入第一擠壓機,接著,在第二擠壓機中投入用矽烷類偶聯劑塗敷的玻璃纖維(SE4121_聚丙烯上漿(Polypropylene Sizing);歐文斯科寧(OCV)製造)33.3重量份,獲取LFT束(Strand)。如上所述,上述LTF束通過投入材料並在220℃的第一擠壓機氣缸筒及220℃的第二擠壓機的氣缸筒分別擠壓捏合而獲得,接著,在63℃成型架中對上述LTF束進行50秒鐘左右的擠壓成型,製備出熱塑性樹脂複合材料。
實施例2
除上述木片的投入量為23.08重量份、玻璃纖維的投入量為30.77重量份之外,採用與上述實施例1相同的方法,製備出熱塑性樹脂複合材料。
實施例3
除上述木片的投入量為14.28重量份、玻璃纖維的投入量為28.57重量份之外,採用與上述實施例1相同的方法,製備出熱塑性樹脂複合材料。
比較例1
除不使用上述木片而使用熱塑性樹脂100重量份及玻璃纖維25重量份之外,採用與上述實施例1相同的方法,製備出熱塑性樹脂複合材料。
比較例2
除以平均直徑為2mm的木粉替代上述木片之外,採用與上述實施例1相同的方法,製備出熱塑性樹脂複合材料。
對於在實施例1~實施例3及比較例1~比較例2中製備的熱塑性樹脂複合材料,採用下列方法測定了物理性質。
彎曲剛性
為了測定由於含有木片而提升的剛性,依據ASTM D790,沿著增強材料的排列方向,製備出長度為5英寸、寬度為1/2英寸的試片,測定彎曲剛性並將結果顯示於下述表1。
拉伸剛性
為了測定由於含有木片而提升的剛性,依據ASTM D638,沿著增強材料的排列方向,製備了狗骨頭(dog bone)形狀的試片,測定拉伸剛性並將結果顯示於下表1。
衝擊強度
為了測定由於含有木片而提升的衝擊強度性,依據ISO180/1A,在常溫下測定缺口衝擊強度(izod notch),並將結果顯示於下述表1。
改善收縮異方性
在上述實施例及比較例中,製備熱塑性樹脂複合材料時,從約220℃的第二擠壓機氣缸筒獲得的上述LTF束,放入約63℃的擠壓機的成型架時,隨著冷卻將產生收縮。圖2是通過壓縮成型而製備的實施例1及比較例1的熱塑性樹脂複合材料的照片,從照片中可以確認,實施例1的熱塑性樹脂複合材料與比較例1的熱塑性樹脂複合材料相比,收縮異方性得到了改善。
表1
雖然本發明已以較佳實施例揭露,然其並非用以限制本發明,任何熟習此項技藝之人士,在不脫離本發明之精神和範圍內,當可作各種更動與修飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (12)

  1. 一種熱塑性樹脂複合組合物,其包括:玻璃纖維、柱狀的木片以及熱塑性樹脂,其中該木片具有至少一個平坦面,該木片的該柱狀的高度與寬度的比為1:10至1:40,且該柱狀的平均寬度為6毫米至40毫米。
  2. 根據申請專利範圍第1項所述之熱塑性樹脂複合組合物,其中該玻璃纖維的平均直徑為15微米至17微米。
  3. 根據申請專利範圍第1項所述之熱塑性樹脂複合組合物,其中該熱塑性樹脂包含選自包括聚丙烯、聚乙烯、聚醯胺及它們的組合的群組中的其中一種。
  4. 根據申請專利範圍第1項所述之熱塑性樹脂複合組合物,其中包括100重量份的該熱塑性樹脂、25重量份至80重量份的該玻璃纖維及大於0重量份至80重量份的該木片。
  5. 一種熱塑性樹脂複合材料,其中在熱塑性樹脂基質分散有玻璃纖維及柱狀的木片,其中該柱狀包括針狀,該木片的該柱狀的平均寬度為6毫米至40毫米,該玻璃纖維的平均直徑為15微米至17微米。
  6. 根據申請專利範圍第5項所述之熱塑性樹脂複合材料,其中該柱狀具有至少一個平坦面。
  7. 根據申請專利範圍第5項所述之熱塑性樹脂複合組合物,其中該熱塑性樹脂包含選自包括聚丙烯、聚乙烯、聚醯胺及它們的組合的群組中的其中一種。
  8. 根據申請專利範圍第5項所述之熱塑性樹脂複合材料,其中包括100重量份的該熱塑性樹脂基質、25重量份至80重量份的該玻璃纖維及大於0重量 份至80重量份的該木片。
  9. 一種熱塑性樹脂複合材料的製備方法,包括以下步驟:混合熱塑性樹脂及柱狀的木片的步驟,其中該木片具有至少一個平坦面,該木片的該柱狀的高度與寬度的比為1:10至1:40,且該柱狀的平均寬度為6毫米至40毫米;將玻璃纖維混合於該熱塑性樹脂及該木片的混合物的步驟;對該熱塑性樹脂、該木片及該玻璃纖維的混合物進行壓縮成型的步驟;以及對由上述中間層、上述至少一個表面層及上述至少一個熱塑性樹脂層層壓的層壓體進行壓縮成型來製備層壓體的步驟。
  10. 根據申請專利範圍第9項所述之熱塑性樹脂複合材料的製備方法,其中,使用第一擠壓機混合熱塑性樹脂及柱狀的木片,使用第二擠壓機將玻璃纖維混合於該熱塑性樹脂及該木片的混合物。
  11. 根據申請專利範圍第9項所述之熱塑性樹脂複合材料的製備方法,其中,在該第一擠壓機及上述第二擠壓機中,在190℃至230℃的溫度下進行混合。
  12. 根據申請專利範圍第9項所述之熱塑性樹脂複合材料的製備方法,其係通過長纖維增強熱塑性塑膠的直接加工法執行。
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