201200350 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種金屬與塑膠的複合體及其製作方法，尤 其涉及一種結合力較強的金屬與塑膠的複合體及該複合 體的製作方法。 【先前技術】 [0002] 金屬材料通常用來作為3C產品的外殼或零元件。該金屬 材料與其他材料連接的方法有焊接、機械連接及黏接。 其中焊接係金屬最主要的連接方法。但當金屬與塑件連 Ο 接時，就需要用到黏接的方法。所述黏接方法，係指利 用膠黏劑作為中間的介面材料，將金屬與塑件結合於一 體的方法。 [0003] 所述黏接方法雖然可以實現金屬與塑件間的連接，但其 存在以下缺點：黏結強度不夠高，其結合力一般僅達 0. 5MPa ;難以自動化，受操作者熟練程度影響；工作溫 度受膠黏劑性能影響，一般只能在-50-1 00°C的溫度範圍 Q 内正常工作；在環境光、熱、濕氣等因素下，膠黏劑會 產生老化斷裂等現象；大部分膠黏劑有毒，操作過程中 會散發有刺激性的氣體，危害人體健康。 [0004] 目前，人們也試圖藉由模内注塑的方法將塑件直接注塑 結合於金屬的表面，然而該方法亦難以解決金屬與塑件 的結合力低的問題。 【發明内容】 [0005] 鑒於此，有必要提供一種結合力強的金屬與塑膠的複合 體。 099121123 表單編號 A0101 第 3 頁/共 12 頁 0992037247-0 201200350 [0006] 另外，還有必要提供一種上述金屬與塑膠的複合體的製 作方法。 , [0007] 一種金屬與塑膠的複合體，其包括一金屬基體及一注塑 結合於金屬基體表面的塑件，該金屬基體的表面形成有 複數奈米孔，該複數奈米孔的平均孔徑為30-55nm，該塑 件的材質為結晶型熱塑性塑膠。 [0008] 一種金屬與塑膠的複合體的製作方法，其包括如下步驟 [0009] 提供一金屬基體； [0010] 對該金屬基體進行化學清洗，使該金屬基體表面形成具 有平均孔徑為30-55nm的複數奈米孔； [0011] 將所述經化學清洗後的金屬基體置於一注塑成型模具中 ，並將該金屬基體加熱到1 00-350°C ; [0012] 向所述金屬基體的表面注塑溶融的結晶型熱塑性塑膠， 並瞬間冷卻，成型塑件，製得所述複合體。 [0013] 相較於習知技術，所述的金屬與塑膠的複合體的製作方 法藉由化學清洗處理，使金屬基體的表面形成奈米多孔 表面，從而以增強塑件與金屬基體之間的結合力；更重 要的係，在注塑塑件時，藉由先將金屬基體加熱使該金 屬基體熱脹，然後在注塑塑件後瞬間冷卻，藉由熱脹冷 縮原理使得所述的金屬與塑膠的複合體的結合力被大大 提升。 【實施方式】 099121123 表單編號A0101 第4頁/共12頁 0992037247-0 201200350 [0014] [0015] [0016]201200350 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a composite of metal and plastic, and a method for fabricating the same, and more particularly to a composite of metal and plastic with strong bonding force and the composite body Production Method. [Prior Art] [0002] Metal materials are commonly used as outer casings or zero components of 3C products. The method of joining the metal material to other materials is welding, mechanical connection and bonding. Among them, the most important connection method for welding metal. However, when the metal is connected to the plastic part, it is necessary to use the bonding method. The bonding method refers to a method of bonding a metal and a plastic member to one body by using an adhesive as an intermediate interface material. [0003] The bonding method can achieve the connection between the metal and the plastic part, but it has the following disadvantages: the bonding strength is not high enough, the bonding force is generally only 0. 5MPa; difficult to automate, affected by the operator's proficiency; The working temperature is affected by the performance of the adhesive. Generally, it can only work normally within the temperature range of -50-1 00 °C. Under the environmental light, heat, moisture and other factors, the adhesive will cause aging and breakage; Most of the adhesives are toxic, and irritating gases are emitted during the operation, which is harmful to human health. [0004] At present, attempts have been made to directly bond plastic parts to the surface of a metal by in-mold injection molding. However, this method is also difficult to solve the problem of low bonding force between metal and plastic parts. SUMMARY OF THE INVENTION [0005] In view of this, it is necessary to provide a composite of a metal and a plastic having a strong bonding force. 099121123 Form No. A0101 Page 3 of 12 0992037247-0 201200350 [0006] In addition, it is also necessary to provide a method of manufacturing the above composite of metal and plastic. [0007] A composite of metal and plastic, comprising a metal substrate and a plastic part injection-molded to the surface of the metal substrate, the surface of the metal substrate is formed with a plurality of nanopores, and the average pore diameter of the plurality of nanopores is 30-55nm, the plastic part is made of crystalline thermoplastic. [0008] A method for fabricating a composite of metal and plastic, comprising the following steps [0009] providing a metal substrate; [0010] chemically cleaning the metal substrate to form an average pore diameter of 30-55 nm on the surface of the metal substrate a plurality of nanopores; [0011] placing the chemically cleaned metal substrate in an injection molding mold and heating the metal substrate to 100-350 ° C; [0012] toward the metal substrate The composite body is prepared by injection molding a molten crystalline thermoplastic plastic and instantaneously cooling and molding a plastic part. [0013] Compared with the prior art, the metal-plastic composite is fabricated by chemical cleaning treatment to form a nanoporous surface on the surface of the metal substrate to enhance the relationship between the plastic part and the metal substrate. Bonding force; more importantly, in the injection molding of plastic parts, the metal matrix is thermally expanded by first heating the metal substrate, and then cooled instantaneously after injection molding, and the metal is caused by the principle of thermal expansion and contraction. The bonding strength of the plastic composite is greatly enhanced. [Embodiment] 099121123 Form No. A0101 Page 4 / Total 12 Pages 0992037247-0 201200350 [0014] [0016]
[0017] ❹ [0018] 請參閱圖1，本發明一較佳實施方式的金屬與塑膠的複合 體100包括一金屬基體11、一形成於金屬基體11表面的防 氧化膜12、及一形成於金屬基體11及防氧化膜12表面的 複數塑件13。 金屬基體11的材質可為鋁合金、鎂合金、不銹鋼、銅或 銅合金。 請參閱圖2，所述金屬基體11的表面形成有複數奈米孔 111，該複數奈米孔111的平均孔徑為30-55nm。從圖2可 以看到，所述複數奈米孔111在金屬基體11表面的分佈較 均勻。該複數奈米孔111的存在可使得注塑所述塑件13的 塑膠嵌入到該複數奈米孔111中，從而增強了複數塑件13 與金屬基體11的結合力。所述複數奈米孔111可藉由對所 述金屬基體11進行化學清洗處理而形成。 防氧化膜12為一有機膜。所述防氧化膜12用以保護所述 金屬基體11不被氧化，以防止氧化膜的生成而影響金屬 基體11與塑件13的結合力。 塑件13以模内注塑的方式結合於金屬基體11及防氧化膜 12的表面。注塑塑件13的塑膠可為具有高流動性的結晶 型熱塑性塑膠，如聚苯硫醚（PPS)與玻璃纖維的混合物 、聚醯胺（PA)、聚對苯二甲酸乙二醇酯（PET)或聚對 苯二曱酸丁二醇酯（PBT)塑膠。其中玻璃纖維在聚苯硫 醚與玻璃纖維的混合物中的品質百分含量可為20-50%。 本發明一較佳實施方式的製作上述金屬與塑膠的複合體 的方法包括如下步驟： 099121123 表單編號A0101 第5頁/共12頁 0992037247-0 [0019] 201200350 [0020] 提供一金屬基體11。該金屬基體11的材質可為鋁合金、 鎂合金、不銹鋼、銅或銅合金。 [0021] 對該金屬基體11進行化學清洗處理，以使該基體11的表 面清潔。該化學清洗處理包括如下步驟： [0022] 脫臘處理，即將所述金屬基體11浸潰於含除臘水的水溶 液中。所述除臘水可為市面上出售的金屬常用的除臘水 。該除臘水的濃度可為30-80ml/L。浸潰時，保持所述 除臘水的水溶液溫度在5 5 - 6 5 °C之間。該浸潰的時間在5 分鐘以上。脫臘處理後對所述金屬基體11進行水洗。 [0023] 脫脂處理，即將所述金屬基體11浸潰於含脫脂劑的水溶 液中。所述脫脂劑可為市面上出售的金屬常用的脫脂劑 。該脫脂劑的濃度可為90-1 50g/L。浸潰時，保持所述 脫脂劑的水溶液的溫度在20-30°C之間。該浸潰的時間為 1-6分鐘。脫脂處理後對所述金屬基體11進行水洗。 [0024] 除氧化膜，即將所述金屬基體11浸潰於含酸性退氧化膜 劑的水溶液中去除金屬基體11表面的氧化膜。通常來說 ，金屬原材料或經成型加工後的金屬基材通常會在其表 面形成一氧化物膜，該氧化物膜的存在會改變金屬的表 面性能，因此需要去除。該除氧化膜處理中所用的酸性 退氧化膜劑可為市面上出售的金屬常用的酸性退氧化膜 劑。該酸性退氧化膜劑的濃度可為30-80ml/L。浸潰時 ，保持所述酸性退氧化膜劑的水溶液溫度在2 0 - 3 0 °C之間 。該浸潰的時間為卜1 0分鐘。除氧化膜處理後對所述金 屬基體Π進行水洗。 099121123 表單編號A0101 第6頁/共頁 0992037247-0 201200350 [0025] [0026] G [0027] [0028] [0029] 所述金屬基體11經上述化學清洗後，在其表面形成了具 有年·均孔徑為30-55 nm的複數奈米孔1丨1 (參圖2)。 對所述經化學清洗後的金屬基體11進行防氧化處理。該 防氧化處理包括將所述金屬基體11浸漬於水溶性的抗氧 化劑中的步驟。所述抗氧化劑可為市面上出售的金屬常 用的有機抗氧化劑。浸潰時，保持所述抗氧化劑的溫度 在2 0 - 3 0 °C之間。該浸潰的時間為1_ 5分鐘。該防氧化處 理可於金屬基體11的表面形成一有機的防氧化膜12。防 氧化處理後對所述金屬基體11進行水洗及乾燥。 提供一注塑成型模具，並將經乾燥的金屬基體11置於該 模具中，且加熱該金屬基體11致100_350°C。該加熱的 方式可為電磁感應加熱。 向所述加熱後的金屬基體11的表面注塑熔融的結昴型熱 塑性塑膠，並瞬間冷卻，成型塑件13，製得所述複合體 '' π ΡΕ ί； Μ 1〇〇 ο 對所述金屬與塑膠的複合體100進行了抗拉強度及剪切強 度蜊試。測試結果表明’該複合體100的抗拉強度可達 WliPa，剪切強度町達25MPa。且對經上述測試後的複合 趙！〇0在進行冷熱衡擊試驗（48小時’ _40_85t：，4小時 /cycle，12cycles)後發現，該複合體1〇〇的抗拉強度 及剪切強度均無明顯滅小。 相較於習知技術，所述的金屬與塑膠的複合體100的製作 方法藉由化學清洗處理，使金屬基體11的表面形成奈米 多孔表面，並在化學清洗後對金屬基體11進行防氧化處 099121123 表幕碥號A0101 0992037247-0 [0030] 201200350 理，使得金屬基體11表面無氧化物雜質形成，而增強了 塑件13與金屬基體11的結合力。更重要的係，在注塑塑 件13時，藉由先將金屬基體11加熱使該金屬基體11熱脹 ，然後在注塑塑件13後瞬間冷卻，藉由熱脹冷縮原理使 得所述的金屬與塑膠的複合體100的結合力被大大提升。 【圖式簡單說明】 [0031] [0032] [0033] [0034] [0035] [0036] [0037] 圖1係本發明一較佳實施方式的金屬與塑膠的複合體的剖 視示意圖。 圖2係本發明一較佳實施方式的金屬基體經化學清洗後的 掃描電鏡圖。 【主要元件符號說明】 複合體：100 余屬基體：11 防氧化膜：12 塑件：13 奈米孔：111 099121123 表單編號A0101 第8頁/共12頁 0992037247-0[0018] Referring to FIG. 1 , a metal-plastic composite 100 according to a preferred embodiment of the present invention includes a metal substrate 11 , an oxidation preventing film 12 formed on the surface of the metal substrate 11 , and a film formed on the surface of the metal substrate 11 . A plurality of plastic members 13 on the surface of the metal substrate 11 and the oxidation preventing film 12. The material of the metal base 11 may be an aluminum alloy, a magnesium alloy, stainless steel, copper or a copper alloy. Referring to FIG. 2, the surface of the metal substrate 11 is formed with a plurality of nanoholes 111 having an average pore diameter of 30 to 55 nm. As can be seen from Fig. 2, the distribution of the plurality of nanopores 111 on the surface of the metal substrate 11 is relatively uniform. The presence of the plurality of nanoholes 111 allows the plastic injection molding of the plastic member 13 to be embedded in the plurality of nanoholes 111, thereby enhancing the bonding force of the plurality of plastic members 13 to the metal substrate 11. The plurality of nanoholes 111 can be formed by subjecting the metal substrate 11 to a chemical cleaning treatment. The oxidation preventing film 12 is an organic film. The oxidation preventing film 12 serves to protect the metal substrate 11 from oxidation, thereby preventing the formation of an oxide film and affecting the bonding force between the metal substrate 11 and the plastic member 13. The plastic member 13 is bonded to the surfaces of the metal substrate 11 and the oxidation preventing film 12 by in-mold molding. The plastic of the injection molded part 13 can be a crystalline thermoplastic having high fluidity, such as a mixture of polyphenylene sulfide (PPS) and glass fiber, polyamine (PA), polyethylene terephthalate (PET). ) or polybutylene terephthalate (PBT) plastic. The glass fiber may have a mass percentage of 20-50% in the mixture of polyphenylene sulfide and glass fiber. A method for fabricating the above composite of metal and plastic according to a preferred embodiment of the present invention comprises the following steps: 099121123 Form No. A0101 Page 5 of 12 0992037247-0 [0019] 201200350 [0020] A metal substrate 11 is provided. The material of the metal base 11 may be an aluminum alloy, a magnesium alloy, stainless steel, copper or a copper alloy. [0021] The metal substrate 11 is subjected to a chemical cleaning treatment to clean the surface of the substrate 11. The chemical cleaning treatment comprises the following steps: [0022] A dewaxing treatment, that is, the metal substrate 11 is immersed in an aqueous solution containing dewaxed water. The dewaxed water may be a dewaxed water commonly used in commercially available metals. The concentration of the dewaxed water may be 30-80 ml/L. During the impregnation, the temperature of the aqueous solution in which the dewaxing water is maintained is between 5 5 and 65 ° C. The dipping time is more than 5 minutes. The metal substrate 11 is washed with water after the dewaxing treatment. [0023] Degreasing treatment, that is, the metal substrate 11 is immersed in an aqueous solution containing a degreasing agent. The degreaser can be a degreaser commonly used in commercially available metals. The concentration of the degreaser can range from 90 to 50 g/L. At the time of impregnation, the temperature of the aqueous solution holding the degreaser is between 20 and 30 °C. The time of the impregnation is 1-6 minutes. The metal substrate 11 is washed with water after the degreasing treatment. [0024] In addition to the oxide film, the metal substrate 11 is immersed in an aqueous solution containing an acidic deoxidizing film to remove an oxide film on the surface of the metal substrate 11. Generally, a metal raw material or a metal substrate which has been subjected to a molding process usually forms an oxide film on the surface thereof, and the presence of the oxide film changes the surface properties of the metal and thus needs to be removed. The acidic deoxidizing film used in the deoxidation film treatment may be an acid deoxidizing film commonly used for commercially available metals. The acid deoxidizing agent may have a concentration of 30 to 80 ml/L. At the time of impregnation, the temperature of the aqueous solution of the acidic deoxidizing film agent is maintained between 20 and 30 °C. The time of the impregnation is 10 minutes. The metal matrix crucible was washed with water after the oxide film treatment. 099121123 Form No. A0101 Page 6 / Total Page 0992037247-0 201200350 [0025] [0029] [0029] [0029] After the above-mentioned chemical cleaning of the metal substrate 11, the surface of the metal substrate 11 is formed on the surface thereof. A plurality of nanopores 1丨1 with a pore size of 30-55 nm (see Figure 2). The chemically cleaned metal substrate 11 is subjected to an oxidation prevention treatment. The oxidation preventing treatment includes the step of immersing the metal substrate 11 in a water-soluble antioxidant. The antioxidant may be a commonly used organic antioxidant for commercially available metals. When impregnating, the temperature of the antioxidant is maintained between 20 and 30 °C. The time of the impregnation is 1 to 5 minutes. This oxidation preventing treatment forms an organic oxidation preventing film 12 on the surface of the metal substrate 11. The metal substrate 11 is washed with water and dried after the oxidation prevention treatment. An injection molding die is provided, and the dried metal substrate 11 is placed in the mold, and the metal substrate 11 is heated to 100 to 350 °C. This heating can be by electromagnetic induction heating. A molten crucible thermoplastic is injection molded onto the surface of the heated metal substrate 11 and instantly cooled to form a plastic part 13 to obtain the composite '' π ΡΕ ί; Μ 1〇〇ο The tensile strength and shear strength of the composite 100 with the plastic were tested. The test results show that the composite 100 has a tensile strength of up to WliPa and a shear strength of 25 MPa. And after the above test, the composite Zhao! 〇0 After performing the cold and heat balance test (48 hours ' _40_85t:, 4 hours / cycle, 12 cycles), it was found that the tensile strength and shear strength of the composite 1无 were not significantly reduced. Compared with the prior art, the metal-plastic composite 100 is formed by chemical cleaning treatment to form a nanoporous surface on the surface of the metal substrate 11, and to prevent oxidation of the metal substrate 11 after chemical cleaning. At 099121123, the nickname A0101 0992037247-0 [0030] 201200350, the surface of the metal substrate 11 is formed without oxide impurities, and the bonding force of the plastic member 13 and the metal substrate 11 is enhanced. More importantly, when the plastic part 13 is injection molded, the metal base 11 is thermally expanded by first heating the metal base 11, and then instantaneously cooled after the injection molding of the plastic part 13, and the metal is made by the principle of thermal expansion and contraction. The bonding force with the plastic composite 100 is greatly enhanced. BRIEF DESCRIPTION OF THE DRAWINGS [0037] FIG. 1 is a schematic cross-sectional view showing a composite of metal and plastic according to a preferred embodiment of the present invention. 2 is a scanning electron micrograph of a metal substrate after chemical cleaning according to a preferred embodiment of the present invention. [Main component symbol description] Composite: 100 Dependent substrate: 11 Anti-oxidation film: 12 Plastic parts: 13 Nano hole: 111 099121123 Form number A0101 Page 8 of 12 0992037247-0