TWI542471B - 複合體及其製備方法 - Google Patents

複合體及其製備方法 Download PDF

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TWI542471B
TWI542471B TW102102765A TW102102765A TWI542471B TW I542471 B TWI542471 B TW I542471B TW 102102765 A TW102102765 A TW 102102765A TW 102102765 A TW102102765 A TW 102102765A TW I542471 B TWI542471 B TW I542471B
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fiber
coupling agent
decane coupling
composite
prepreg
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秦姚姚
周書祥
徐秋江
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富智康（香港）有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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Description

複合體及其製備方法
本發明涉及一種複合體及其製備方法，尤其涉及一種纖維複合材料與塑膠的複合體及其製備方法。
纖維預浸布是由纖維束含浸未熟化的樹脂所構成，是目前最常用來製作高性能複合材料的原材料。使用纖維預浸布成型的產品具有質輕、強度高、耐化學腐蝕等優點。纖維預浸布成型產品的方法常使用heat-press技術，該技術通常包括如下步驟：根據需要對纖維預浸布進行裁剪；將纖維預浸布放入成型模具中；模具壓合併在模具內加熱加壓；最後開模，冷卻即制得所述纖維複合材料產品。
然而，纖維預浸布通常用來成型平板狀結構的產品，且通常無法直接成型出其他的功能性的零部件。現有的方法是將成型後的纖維複合材料產品的表面黏附固體或液體的黏結層，然後將零部件黏附於黏結層表面使二者結合於一體。然而，該種方法，纖維複合材料產品與零部件的結合強度不高，使用過程中二者容易脫離。
有鑒於此，有必要提供一種複合體，其含有纖維複合材料件及塑膠件，且二者結合牢固。
另外，還有必要提供一種上述複合體的製備方法。
一種複合體，其包括纖維複合材料件及結合於該纖維複合材料件表面的塑膠件，該塑膠件注塑形成於該纖維複合材料件上，該纖維複合材料件由含浸環氧樹脂的纖維束熱壓成型；在該纖維複合材料件和該塑膠件之間設置有一水解的矽烷偶聯劑層和一膠黏劑層，其中水解的矽烷偶聯劑層與該纖維複合材料件直接結合，膠黏劑層與塑膠件直接結合，該膠黏劑層含有單組份聚氨酯。
一種複合體的製備方法，其包括如下步驟：提供纖維預浸布，該纖維預浸布中含有纖維束及浸潤纖維束的未熟化的環氧樹脂；在纖維預浸布表面塗布一層水解的矽烷偶聯劑溶液並乾燥形成一矽烷偶聯劑層；在該矽烷偶聯劑的表面繼續塗布膠黏劑形成膠黏劑層，該膠黏劑主要含有單組份聚氨酯；將經上述處理的纖維預浸布放置於注塑模具內，注塑模具壓合且注塑模具內加熱加壓，注射熔融的塑膠材料於纖維預浸布形成有膠黏劑層的表面，冷卻後成型為塑膠件，同時纖維預浸布中的環氧樹脂也固化成型使纖維預浸布成型為纖維複合材料件。
本發明的複合體，先在纖維預浸布的表面塗覆水解的矽烷偶聯劑，再在矽烷偶聯劑的表面進一步塗覆含單組份聚氨酯的膠黏劑，再將經上述處理的纖維預浸布放入注塑模具中注塑塑膠件於纖維預浸布的表面，同時纖維預浸布本身也固化成型為纖維複合材料件，使纖維複合材料件與塑膠件結合牢固。
10‧‧‧複合體
11‧‧‧纖維複合材料件
13‧‧‧塑膠件
15‧‧‧矽烷偶聯劑層
17‧‧‧膠黏劑層
圖1為本發明一較佳實施例複合體的剖面示意圖。
請參閱圖1，本發明一較佳實施方式的複合體10，其包括纖維複合材料件11及結合於該纖維複合材料件11表面的塑膠件13。該纖維複合材料件11由含浸環氧樹脂的纖維束熱壓成型，該纖維束可為碳纖維束、玻璃纖維束或聚醯胺纖維束。該塑膠件13由常見的熱塑性樹脂注塑形成，該纖維複合材料件11與該塑膠件13為一體化同時成型，該纖維複合材料件11與該塑膠件13於同一模具(圖未示)中固化成型。
在該纖維複合材料件11和該塑膠件13之間設置有一水解的矽烷偶聯劑層15和一膠黏劑層17，其中水解的矽烷偶聯劑層15與該纖維複合材料件11直接結合，膠黏劑層17與塑膠件13直接結合。該膠黏劑層17含有單組份聚氨酯。
該膠黏劑層17中還含有適量的常用於膠黏劑的常規乳化劑、pH調整劑。
經實驗測試，本發明的複合體10，纖維複合材料件11與塑膠件13間的拉拔力達到3.28Mpa，而未設置有水解的矽烷偶聯劑層的複合體的纖維複合材料與塑膠間的拉拔力僅為2.64Mpa。可見，本實施例中複合體10的纖維複合材料件11與塑膠件13結合牢固。
本明的複合體10的製備方法，其包括如下步驟：
(1)提供纖維預浸布(圖未示)，該纖維預浸布中含有纖維束及浸潤該纖維束的未熟化的環氧樹脂。該纖維束可為碳纖維束、 玻璃纖維束或聚醯胺纖維束。
(2)使用高頻交流電壓對該纖維預浸布進行表面電暈放電處理，使纖維預浸布周圍的氣體產生低溫等離子體。該低溫等離子體使纖維預浸布表面的環氧樹脂分子結構重新排列，產生更多的極性部位，增加纖維預浸布表面的附著能力。該高頻交流電壓的電壓值達到5000~15000V/m2，工作頻率為15~24kHZ。
(3)在纖維預浸布表面塗布一層水解的矽烷偶聯劑溶液並乾燥形成一矽烷偶聯劑層15。
配置矽烷偶聯劑溶液的方法是：將矽烷偶聯劑與有機溶劑按照3~5：95~97的質量比例混合均勻，並緩慢添加相對矽烷偶聯劑質量的3%~5%的去離子水使矽烷偶聯劑水解。該有機溶劑優選為乙醇，但不限於乙醇。所述乾燥處理為在80~120℃的溫度條件烘烤15~60分鐘。
乾燥過程中，該矽烷偶聯劑水解產生的活性矽羥基【-Si(OH)3】與環氧樹脂中的羥基(-OH)脫水縮聚，從而形成Si-O鍵分佈於纖維預浸布表面，矽烷偶聯劑的另外一端的有機鏈(含活性基團矽羥基)裸露，從而增加了纖維預浸布表面的活性。
(4)在所述矽烷偶聯劑層15的表面繼續塗布膠黏劑形成膠黏劑層17。
該膠黏劑主要含有單組份聚氨酯，並含有適量的常用於膠黏劑的常規乳化劑、pH調整劑及稀釋劑。該膠黏劑的固含量為40%~60%。
該膠黏劑中含有的活性基團(氨基)可與該矽烷偶聯劑有機鏈上的 活性基團(矽羥基)反應結合，藉由分子間的作用提高了膠黏劑與纖維預浸布的附著力。所述矽烷偶聯劑在纖維預浸布與膠黏劑之間起到一個橋接的作用，可使纖維預浸布與塑膠件達到更牢固的結合。
此外，單組份聚氨酯含有異氰酸端基(-NCO)，其可逐漸滲透穿過較薄的矽烷偶聯劑層，直接跟纖維預浸布中的環氧樹脂發生聚合反應。反應式為：膠黏劑-NCO+HO-環氧樹脂→膠黏劑-NHCOO-環氧樹脂。
如此，藉由膠黏劑與矽烷偶聯劑層及纖維預浸布中的環氧樹脂的反應，可有效提高黏合強度。
(5)將纖維預浸布植入注塑模具注塑成型塑膠件。
將經上述處理的纖維預浸布放置於注塑模具內(未圖示)，注塑模具壓合且注塑模具內加熱加壓，注射熔融的熱塑性的塑膠材料於纖維預浸布形成有膠黏劑層17的表面，冷卻後成型為塑膠件13，同時纖維預浸布中的環氧樹脂也在模具中固化成型使纖維預浸布成型為纖維複合材料件11。該塑膠件13可為卡扣或螺柱等零部件。由於膠黏劑的黏合作用，所述塑膠件13能牢固地結合於纖維複合材料件11的表面。
本發明較佳實施例複合體10，先在纖維預浸布的表面塗覆水解的矽烷偶聯劑，再在矽烷偶聯劑的表面進一步塗覆含單組份聚氨酯的膠黏劑，再將經上述處理的纖維預浸布放入注塑模具中注塑塑膠件13於纖維預浸布的表面，同時纖維預浸布本身也固化成型為纖維複合材料件11，使纖維複合材料件11與塑膠件13一體化同時 成型，因而該纖維複合材料件11與塑膠件13結合牢固。
10‧‧‧複合體
11‧‧‧纖維複合材料件
13‧‧‧塑膠件
15‧‧‧矽烷偶聯劑層
17‧‧‧膠黏劑層

Claims (9)

  1. 一種複合體，其包括纖維複合材料件及結合於該纖維複合材料件表面的塑膠件，該塑膠件注塑形成於該纖維複合材料件上，其改良在於：該纖維複合材料件由含浸環氧樹脂的纖維束熱壓成型；在該纖維複合材料件和該塑膠件之間設置有一水解的矽烷偶聯劑層和一膠黏劑層，其中水解的矽烷偶聯劑層與該纖維複合材料件直接結合，膠黏劑層與塑膠件直接結合，該膠黏劑層含有單組份聚氨酯。
  2. 如申請專利範圍第1項所述之複合體，其中該纖維複合材料件與該塑膠件為一體化成型，且該纖維複合材料件與該塑膠件於同一模具中固化成型。
  3. 如申請專利範圍第1項所述之複合體，其中該纖維束為碳纖維束、玻璃纖維束或聚醯胺纖維束。
  4. 如申請專利範圍第1項所述之複合體，其中該塑膠件由熱塑性樹脂注塑形成。
  5. 一種複合體的製備方法，其包括如下步驟：提供纖維預浸布，該纖維預浸布中含有纖維束及浸潤纖維束的未熟化的環氧樹脂；在纖維預浸布表面塗布一層水解的矽烷偶聯劑溶液並乾燥形成一矽烷偶聯劑層；在該矽烷偶聯劑的表面繼續塗布膠黏劑形成膠黏劑層，該膠黏劑主要含有單組份聚氨酯；將經上述處理的纖維預浸布放置於注塑模具內，注塑模具壓合且注塑模具內加熱加壓，注射熔融的塑膠材料於纖維預浸布形成有膠黏劑層的表 面，冷卻後成型為塑膠件，同時纖維預浸布中的環氧樹脂也固化成型使纖維預浸布成型為纖維複合材料件。
  6. 如申請專利範圍第5項所述之複合體的製備方法，其中該方法還包括在形成矽烷偶聯劑層前使用高頻交流電壓對該纖維預浸布進行表面電暈放電處理。
  7. 如申請專利範圍第6項所述之複合體的製備方法，其中該高頻交流電壓的電壓值達到5000~15000V/m2，工作頻率為15~24kHZ。
  8. 如申請專利範圍第5項所述之複合體的製備方法，其中該矽烷偶聯劑溶液中含有矽烷偶聯劑、有機溶劑及去離子水，其中矽烷偶聯劑與有機溶劑的質量比為3~5：95~97，去離子水的質量為矽烷偶聯劑質量的3%~5%。
  9. 如申請專利範圍第5項所述之複合體的製備方法，其中所述矽烷偶聯劑溶液的乾燥處理為在80~120℃的溫度條件烘烤15~60分鐘。
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