201200347 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種鋁或鋁合金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鋁或鋁合金與塑膠的複 合體及該複合體的製作方法。 [先前技術] [0002] 鋁或鋁合金作為3C產品的外殼或零元件，其與其他材料 連接的方法有焊接、機械連接及黏接。其中焊接係鋁或 鋁合金最主要的連接方法。但當鋁或鋁合金與塑件連接 0 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，將鋁或銘合金與塑件結合 於一體的方法。 [0003] 所述黏接方法雖然可以實現鋁或鋁合金與塑件間的連接 ，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，人們藉由研究發現，將鋁或鋁合金經過某些特殊 的表面蝕孔處理後可直接與注塑塑膠相結合，且二者之 間的結合力較強。該特殊的表面蝕孔處理包括：水溶液 浸潰，如將鋁或鋁合金浸潰於水溶性的胺類化合物的稀 溶液中，利用水溶液的弱鹼性使鋁或鋁合金表面微細地 浸蝕，在浸潰的同時發生胺類化合物分子向鋁或鋁合金 099120968 表單編號A0101 第3頁/共12頁 0992036979-0 201200347 表面的吸附；以及陽極氧化處理，即使鋁或鋁合金表面 形成多孔的氧化鋁膜。然而，上述水溶液浸潰的方法需 用到有毒有害的胺類化合物，而陽極氧化處理製程較長 ，導致生產效率較低。 【發明内容】 [0005] [0006] [0007] [0008] [0009] [0010] [0011] 099120968 鑒於此，有必要提供一種結合力強、且可克服上述缺陷 的鋁或鋁合金與塑膠的複合體。 另外，還有必要提供一種上述鋁或鋁合金與塑膠的複合 體的製作方法，該製作方法無需使用胺類化合物，且製 程短，效率高。 一種鋁或鋁合金與塑膠的複合體，其包括一鋁或鋁合金 基體及一注塑結合於鋁或鋁合金基體表面的塑件，該鋁 或鋁合金基體的表面形成有複數納米孔，該複數納米孔 的平均孔徑為20-60nm，該鋁或鋁合金基體的表面粗糙度 Ra值為0. W"m，所述塑件的材質為聚醯胺塑膠或聚苯 硫醚塑膠與玻璃纖維的混合物。 一種鋁或鋁合金與塑膠的複合體的製作方法，其包括如 下步驟： 提供一鋁或鋁合金基體； 對該銘或銘合金基體進行化學蚀刻，使該銘或銘合金基 體表面粗化； 對上述鋁或鋁合金基體進行電化學蝕刻，使該鋁或鋁合 金基體表面形成具有平均孔徑為20-60nra的複數納米孔， 且使該鋁或鋁合金基體的表面粗糙度Ra值為0. 1-1 /zm ; 表單編號A0101 第4頁/共12頁 0992036979-0 201200347 [0012]將所述經電化學蝕刻後的紹或鋁合金基體置於—注塑成 [0013] 型模具中，注塑塑件結合於铭或紹合金基體的表面製得 所述複合體’所述塑件的材質為聚酿胺塑勝或聚苯硫域 塑膠與玻璃纖維的混合物° 相較於習知技術，所述的鋁或鋁合金與塑膠的複合體藉 由化學蝕刻及電化學蝕刻處理’在鋁或鋁合金基體的表 面形成具有平均孔徑為20-60nm的複數納米孔’且使該鋁 或鋁合金基體的表面粗糙度Ra值為〇· 1-1 "m，使得該鋁 〇 或鋁合金基體與聚苯硫醚塑膠或聚醯胺塑膠具有較強的 結合力。本發明避.先了使用有毒有害的胺類化合物，且 相較於陽極氧化縮短了製程’提高了效率。 [0014] 【實施方式】 請參閱圖1，本發明一較佳實施方式的叙或鋁合金與塑膠 的複合體100包括一鋁或鋁合金基體11、及一形成於鋁或 紹合金基體11表面的複數塑件13 » [0015] 〇 請參閱圖2，所述鋁或鋁合金基體11的表面形成有複數納 米孔111，該複數納米孔111的平均孔徑為2〇-6〇nm。從 圖2可以看到，所述複數納米孔ill在鋁或鋁合金基體u 表面的分佈較均勻。該複數納米孔111的存在可使得注塑 所述塑〜件13的塑膠嵌入到該複數納米孔111中，從而增強 了複數塑件13與鋁或鋁合金基體11的結合力。所述鋁或 銘合金基體11的表面粗糙度Ra值為〇. 1-丨以m。所述複數 納米孔111可藉由對所述鋁或鋁合金基體丨丨進行電化學蝕 刻處理而形成。 [0016] 099120968 塑件13以模内注塑的方式結合於鋁或鋁合金基體u的表 表單編號A0101 第5頁/共12頁 0992036979-0 201200347 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，如聚醯胺（PA)塑膠、聚笨硫醚（PPS)塑膠與 玻璃纖維的混合物等。所述玻璃纖維的質量百分含量可 為10-50%。 [0017] [0018] [0019] [0020] [0021] 本發明一較佳實施方式的製作上述鋁或鋁合金與塑膠的 複合體的方法包括如下步驟： 提供一鋁或鋁合金基體11 〇 對該鋁或鋁合金基體11進行脫脂除油處理，以使該基體 11的表面清潔。該脫脂狳油處理包括將所述鋁或鋁合金 基體11浸潰於含鈉鹽的溶液中的步驟。所述含鈉鹽的溶 液中可包含有30-50g/L的碳酸鈉，30-50g/L的磷酸鈉 ，以及3-5g/L的矽酸鈉。浸潰時，保持所述含鈉鹽的溫 度在50_6〇 C之間。該浸潰的時間可為5-1 5分鐘。脫脂 除油處理後對所述鋁或鋁合金基體11進行水洗。 對經脫脂除油處理後的鋁或鋁合金基體11進行化學蝕刻 處理，以使該基體Η的表面粗化。該化學蝕刻處理包括 將所述铭或紹合金基體1 1浸潰於驗性溶液中的步驟。所 述驗性溶液中包含有1G_5Qg/L的氫氧化納。對該紹或銘 α金基體11進行化學餘刻處理在室溫下進行約3-5分鐘。 化學钮刻處理後對所祕或銘合金基體11進行水洗。 對經化學蝕刻處理後的鋁或鋁合金基體11進行電化學蝕 刻處理以在該基體11的表面形成平均孔徑為2〇_6〇nm 的複數納米孔洞⑴°該電化學姓刻處理可在硫酸及填酸 的必e,合液中通電進行，並以該鋁或鋁合金基體η作為 099120968 表單編號A0101 第6頁/共12頁 0992036979-0 201200347 [0022] ❹ [0023] Ο [0024] 099120968 陽極’以不銹鋼板或鉛板作為陰極。該硫酸的體積濃度 可為30-50ml/L，該磷酸的體積濃度可為20-60ml/L。 電化學蝕刻時，使藉由所述混合溶液的電流密度為 2-^/61112。該電化學蝕刻的時間可為8-15分鐘，遠低於 陽極氧化所需要的時間（約15-60分鐘）。電化學蝕刻後 對所述鋁或鋁合金基體11進行水洗並乾燥。 提供一注塑成型模具，並將經電化學蝕刻後的鋁或鋁合 金基體11置於該模具中，注塑塑件13結合於基體u的表 面，製得所述複合體100。注翠塑件13的塑膠可為具有高 流動性的結晶型熱塑性塑膠，和PPS，PA等1注塑時控制 模具的溫度在12〇-i4〇°C之間。 對所述鋁或鋁合金與塑膠的複合體1〇〇進杆了抗拉強度及 剪切強度測試。測試結果表明，該複合艟1〇〇的抗拉強度 可達lOMPa，剪切強度可達20MPa ^且對經上述測試後的 複合體100在進行溫濕度存儲試驗（72小時，85°C，85% 相對濕度）及冷熱衝擊試驗（48小時，-40-85¾，4小 時/cycle，12CyCle$)後發現，該複合體1〇〇的抗拉強 度及剪切強度均無明顯減小。 相較於S知技術，所述的銘或銘合金與塑膠的複合體 藉由化學ϋ刻及電化學制處理，在銘聽合金基㈣ 的表面化成具有平均孔徑為2G~6Gnm的複數納米孔111， 且使_或㉟合金基趙11的表面_她值為G.卜 Λ鋁或鋁合金基體1丨與聚笨硫醚塑膠及聚醯胺塑 膝具有較強的結合力。避免了使用有毒有害的胺類化合 物相對於陽極氧化縮短了對紹或紹合金基體進 MM _ S 7 論 0992036979-0 201200347 面處理的時間，提高了效率。 【圖式簡單說明】 [0025] 圖1係本發明一較佳實施方式的鋁或鋁合金與塑膠的複合 體的剖視示意圖。 [0026] 圖2係本發明一較佳實施方式的鋁或鋁合金基體經電化學 處理後的掃描電鏡圖。 【主要元件符號說明】 [0027] 複合體：100 [0028] 鋁或鋁合金基體：11 [0029] 塑件：13 [0030] 納米孔：111 0992036979-0 099120968 表單編號A0101 第8頁/共12頁201200347 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a composite of aluminum or aluminum alloy and plastic and a manufacturing method thereof, and more particularly to a composite of aluminum or aluminum alloy with a strong bonding force and plastic The body and the method of making the composite. [Prior Art] [0002] Aluminum or aluminum alloy is used as a casing or a zero component of a 3C product, and the method of joining it with other materials is welding, mechanical connection, and bonding. Among them, welding is the most important connection method for aluminum or aluminum alloy. However, when aluminum or aluminum alloy is connected to the plastic part, it is necessary to use the bonding method. The bonding method refers to a method in which an aluminum or an alloy and a plastic part are integrated by using an adhesive as an intermediate interface material. [0006] Although the bonding method can realize the connection between the aluminum or the aluminum alloy and the plastic part, it has the following disadvantages: the bonding strength is not high enough, the bonding force is generally only 0. 5MPa; it is difficult to automate, and is skilled by the operator. Degree of influence; working temperature is affected by the performance of the adhesive, generally only works within the temperature range of -50-1 00 °C; under the conditions of ambient light, heat, moisture, etc., the adhesive will cause aging fracture, etc. Phenomenon; most adhesives are toxic, and irritating gases are emitted during operation, which is harmful to human health. [0004] At present, people have discovered through research that aluminum or aluminum alloy can be directly combined with injection molded plastic after some special surface etching treatment, and the bonding force between the two is strong. The special surface etching treatment includes: aqueous solution impregnation, such as impregnation of aluminum or aluminum alloy in a dilute solution of a water-soluble amine compound, and the aluminum or aluminum alloy surface is slightly etched by the weak alkalinity of the aqueous solution. Simultaneous impregnation of amine compound molecules to aluminum or aluminum alloy 099120968 Form No. A0101 Page 3 / Total 12 Page 0992036979-0 201200347 Surface adsorption; and anodizing treatment, even if the aluminum or aluminum alloy surface forms a porous aluminum oxide film . However, the above aqueous solution impregnation method requires the use of toxic and harmful amine compounds, and the anodizing treatment process is long, resulting in low production efficiency. In view of the above, it is necessary to provide an aluminum or aluminum alloy and a plastic which have strong bonding strength and can overcome the above defects. Complex. Further, it is also necessary to provide a method for producing a composite of the above aluminum or aluminum alloy and plastic, which does not require the use of an amine compound, and has a short process and high efficiency. A composite of aluminum or aluminum alloy and plastic, comprising an aluminum or aluminum alloy substrate and a plastic part injection-molded on the surface of the aluminum or aluminum alloy substrate, the surface of the aluminum or aluminum alloy substrate being formed with a plurality of nanopores, the plural The average pore diameter of the nanopore is 20-60 nm, and the surface roughness Ra of the aluminum or aluminum alloy substrate is 0. W"m, the plastic material is made of polyamide or polyphenylene sulfide plastic and glass fiber. mixture. A method for manufacturing a composite of aluminum or aluminum alloy and plastic, comprising the steps of: providing an aluminum or aluminum alloy substrate; chemically etching the alloy body of the Ming or Ming alloy to roughen the surface of the alloy body of the Ming or Ming alloy; The surface roughness Ra of the aluminum or aluminum alloy substrate is 0.1. The surface roughness Ra of the aluminum or aluminum alloy substrate is 0.1. The aluminum or aluminum alloy substrate is formed by a plurality of nanopores having an average pore diameter of 20-60 nra. -1 /zm ; Form No. A0101 Page 4 / Total 12 Page 0992036979-0 201200347 [0012] The electrochemically etched or aluminum alloy substrate is placed into a mold of [0013], injection molding The composite is formed by bonding the surface of the composite body to the surface of the alloy or the alloy. The material of the plastic part is a mixture of polyacrylamide or polyphenylene sulfide plastic and glass fiber. Compared with the prior art, A composite of aluminum or aluminum alloy and plastic is formed by chemical etching and electrochemical etching to form a plurality of nanopores having an average pore diameter of 20-60 nm on the surface of an aluminum or aluminum alloy substrate and to make the aluminum or aluminum alloy matrix Thick surface Ra value of the square · 1-1 " m, such that the aluminum or aluminum alloy square matrix plastic and a polyphenylene sulfide or polyamide plastic with a strong binding force. The present invention avoids the use of toxic and harmful amine compounds and shortens the process' to improve efficiency compared to anodization. [0014] Referring to FIG. 1 , a composite body 100 of an aluminum alloy and a plastic according to a preferred embodiment of the present invention includes an aluminum or aluminum alloy substrate 11 and a surface formed on the aluminum or alloy substrate 11 . The plurality of plastic parts 13 » [0015] Referring to FIG. 2, the surface of the aluminum or aluminum alloy substrate 11 is formed with a plurality of nanopores 111 having an average pore diameter of 2〇-6〇nm. As can be seen from Fig. 2, the distribution of the plurality of nanoholes ill on the surface of the aluminum or aluminum alloy substrate u is relatively uniform. The presence of the plurality of nano-holes 111 allows the plastic injection of the plastic-like member 13 to be embedded in the plurality of nano-holes 111, thereby enhancing the bonding force of the plurality of plastic members 13 to the aluminum or aluminum alloy substrate 11. The aluminum or the alloy base 11 has a surface roughness Ra of 〇. 1-丨 in m. The plurality of nanoholes 111 can be formed by electrochemically etching the aluminum or aluminum alloy substrate ruthenium. [0016] 099120968 The plastic part 13 is bonded to the aluminum or aluminum alloy substrate u by in-mold molding. Form No. A0101 Page 5 of 12 0992036979-0 201200347 No. The plastic of the injection molded part 13 can be a crystalline thermoplastic plastic having high fluidity, such as polyamide (PA) plastic, polystyrene sulfide (PPS) plastic and glass fiber mixture. The glass fiber may have a mass percentage of 10 to 50%. [0018] [0021] A method for fabricating the above-described aluminum or aluminum alloy and plastic composite comprises a step of: providing an aluminum or aluminum alloy substrate 11 The aluminum or aluminum alloy substrate 11 is subjected to a degreasing and degreasing treatment to clean the surface of the substrate 11. The defatted eucalyptus oil treatment comprises the step of immersing the aluminum or aluminum alloy substrate 11 in a solution containing a sodium salt. The sodium salt-containing solution may contain 30-50 g/L of sodium carbonate, 30-50 g/L of sodium phosphate, and 3-5 g/L of sodium citrate. The temperature of the sodium-containing salt is maintained between 50_6 〇 C during the impregnation. The time of the impregnation can be from 5 to 15 minutes. The aluminum or aluminum alloy substrate 11 is washed with water after degreasing and degreasing treatment. The aluminum or aluminum alloy substrate 11 subjected to the degreasing and degreasing treatment is subjected to a chemical etching treatment to roughen the surface of the substrate crucible. The chemical etching treatment includes the step of immersing the inscription or the alloy substrate 11 in an inert solution. The test solution contained 1 G_5 Qg/L of sodium hydroxide. The chemical residue treatment of the Shao or Ming α gold matrix 11 is carried out at room temperature for about 3-5 minutes. After the chemical button treatment, the secret or alloy substrate 11 is washed with water. The chemically etched aluminum or aluminum alloy substrate 11 is subjected to electrochemical etching treatment to form a plurality of nano-holes (1) having an average pore diameter of 2 〇 6 〇 nm on the surface of the substrate 11 . And the acid filling must be carried out in the liquid mixture, and the aluminum or aluminum alloy substrate η is used as 099120968. Form No. A0101 Page 6 / Total 12 Page 0992036979-0 201200347 [0022] ❹ [0023] Ο [0024] 099120968 The anode 'is a stainless steel plate or a lead plate as a cathode. The sulfuric acid may have a volume concentration of 30 to 50 ml/L, and the phosphoric acid may have a volume concentration of 20 to 60 ml/L. In the electrochemical etching, the current density by the mixed solution is 2-^/61112. The electrochemical etching time can be from 8 to 15 minutes, which is much lower than the time required for anodization (about 15-60 minutes). The aluminum or aluminum alloy substrate 11 is washed with water and dried after electrochemical etching. An injection molding die is provided, and an electrochemically etched aluminum or aluminum alloy substrate 11 is placed in the mold, and an injection molded plastic member 13 is bonded to the surface of the substrate u to prepare the composite body 100. The plastic of the plastic parts 13 can be a crystalline thermoplastic with high fluidity, and the temperature of the mold is controlled between 12 〇-i4 〇 °C during injection molding of PPS, PA, etc. The aluminum or aluminum alloy and the plastic composite 1 were tested for tensile strength and shear strength. The test results show that the tensile strength of the composite 艟1〇〇 can reach 10 MPa, the shear strength can reach 20 MPa ^ and the temperature and humidity storage test is performed on the composite 100 after the above test (72 hours, 85 ° C, 85). After % relative humidity) and thermal shock test (48 hours, -40-853⁄4, 4 hours/cycle, 12CyCle$), it was found that the tensile strength and shear strength of the composite were not significantly reduced. Compared with the S-knowledge technology, the composite of the Ming or Ming alloy and the plastic is chemically etched and electrochemically processed, and the surface of the alloy base (4) is formed into a plurality of nanopores 111 having an average pore diameter of 2G to 6Gnm. And the surface of the _ or 35 alloy base Zhao 11 _ her value is G. Λ Λ aluminum or aluminum alloy matrix 1 丨 with polyphenylene sulfide plastic and polyamide plastic knee has a strong binding force. Avoiding the use of toxic and harmful amine compounds relative to anodization shortens the time to the surface treatment of the MM_S 7 theory 0992036979-0 201200347, improving the efficiency. BRIEF DESCRIPTION OF THE DRAWINGS [0025] FIG. 1 is a cross-sectional view showing a composite of aluminum or an aluminum alloy and a plastic according to a preferred embodiment of the present invention. 2 is a scanning electron micrograph of an aluminum or aluminum alloy substrate after electrochemical treatment according to a preferred embodiment of the present invention. [Main Component Symbol Description] [0027] Composite: 100 [0028] Aluminum or Aluminum Alloy Substrate: 11 [0029] Plastic Parts: 13 [0030] Nanopore: 111 0992036979-0 099120968 Form No. A0101 Page 8 of 12 page