510832 A7 _____B7____ 五、發明說明（I ) 技術領域 本發明是有關於一種生產改良耐蝕性與吸附性之鋁散 熱片材料的方法，及以該方法生產之親水性鋁散熱片材料 Ο 本發明之背景 鋁和鋁合金材料具有重量輕、良好之加工性及熱傳導 性’使得其廣泛應用於熱交換器之元件，如汽車與室內空 調。特別是在部分機器上之熱交換器，鋁散熱片材料已應 用在許多實施例上。 當含有散熱片材料之空調於冷卻模式操作時，大氣中 空氣的水氣會凝聚在散熱片材料的表面，造成散熱片間阻 塞’並且減弱冷卻能力。爲移除凝結的水，一般的作法爲 於散熱片表面實施親水性處理。雖然已有於散熱片表面實 施排除水的處理方法，以此方法，大量的水因水排除劑而 掉落’導致散熱片間之阻塞，且冷卻能力亦大大地減弱， 因此，此方法於今日已很少使用。 散熱片材料表面的親水性處理如上所述是基本的處理 ，此親水性處理使得散熱片表面於水凝結的所有時間均保 持濕潤。因此，水穿透親水性被覆層而於散熱片材料及銲 接劑間形成高氧濃度的氣室，導致金屬腐蝕反應的產生， 或滲入的水中包含大氣的污染物，而導致水合作用，使得 產生金屬腐蝕反應。藉由如此反應而產生的腐蝕產物堆積 在散熱片表面，而降低其熱交換能力。還有一個問題是， 當於加熱模式下操作時，腐蝕的產物變成白色的粉末，並 4 I紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " (請先閱讀背面之注意事項再填寫本頁) · ---— II I « 1 I I I--I I . 510832 A7 -------B7 五、發明說明（丫） 隨著吹風機風扇所排出的熱風進入室內。 爲克服上述缺點，Japanese Kokai Publication Hei-5-125555揭示一種預被覆散熱片材料，其係藉由形成一親水 性被覆層而製造，該被覆層包括鹼矽酸鹽、親水聚合體， 其以一種特定的比例附著於鋁基材之染色鉻酸鹽被覆層之 上，且以加熱烘乾該親水被覆層。 發明槪要 當染色鉻酸鹽使用於上述之japanese K〇kai Publication Hei-5_125555，基本上由環境觀點觀之，使用 非鉻酸鹽化學轉換處理劑爲較佳。當使用含鉻磷酸鹽時， 化學轉換處理後必須以水溶液淸洗，以防止六價鉻殘留於 被覆層上’但以水溶液淸洗時所產生之含鉻廢水的處理將 產生其它問題。然而，尙未有一種可使用於非鉻酸鹽處理 劑之處理方法，以形成具有足夠之耐腐蝕性及耐濕性之散 熱片材料。因此，本發明的目的是提供一種使用對環境較 佳之非鉻酸鹽化學轉換處理劑，以生產鋁散熱片材料的方 法’同時滿足需求性能之特性，如耐腐蝕性及耐濕性，並 以此方法生產鋁散熱片材料。 依據本發明之鋁散熱片材料的生產方法，包括在鋁基 材之化學轉換處理步驟中，形成一種化學轉換被覆層，並 形成一種耐腐飩被覆層及/或由一種可浮於水上的（water-borne)樹脂所組成之親水性被覆層。 該化學轉換被覆層的獲得可藉由維持一種化學轉換處 理溶劑於下列組成範圍之內，並使得溶劑溫度處於30至 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)510832 A7 _____B7____ 5. Description of the Invention (I) Technical Field The present invention relates to a method for producing an aluminum heat sink material with improved corrosion resistance and adsorption properties, and a hydrophilic aluminum heat sink material produced by the method. O BACKGROUND OF THE INVENTION Aluminum and aluminum alloy materials have light weight, good processability and thermal conductivity, making them widely used in heat exchanger components, such as automobiles and room air conditioners. Especially for heat exchangers on some machines, aluminum heat sink materials have been used in many embodiments. When an air conditioner containing a fin material is operated in a cooling mode, the water vapor of the air in the atmosphere will condense on the surface of the fin material, causing blockage between the fins' and weakening the cooling capacity. To remove the condensed water, it is common practice to apply a hydrophilic treatment to the surface of the heat sink. Although a method of removing water has been implemented on the surface of the heat sink, in this method, a large amount of water is dropped by the water removing agent, causing blockage between the heat sinks, and the cooling capacity is greatly weakened. Therefore, this method is used today Has been rarely used. The hydrophilic treatment of the surface of the heat sink material is a basic treatment as described above. This hydrophilic treatment keeps the surface of the heat sink wet at all times of water condensation. Therefore, water penetrates the hydrophilic coating layer to form a high oxygen concentration gas chamber between the heat sink material and the solder, which results in the generation of a metal corrosion reaction, or the infiltrated water contains atmospheric pollutants, resulting in hydration, making A metal corrosion reaction occurs. Corrosion products generated by such reactions accumulate on the surface of the heat sink, reducing its heat exchange capacity. Another problem is that when operating in the heating mode, the corrosion products become white powder, and the 4 I paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " (Please read the back first Please pay attention to this page and fill in this page again.) · ---— II I «1 II I--II. 510832 A7 ------- B7 V. Description of the invention (Y) With the hot air exhausted from the blower fan, enter the room . To overcome the above disadvantages, Japanese Kokai Publication Hei-5-125555 discloses a pre-coated heat sink material, which is manufactured by forming a hydrophilic coating layer, which includes an alkali silicate, a hydrophilic polymer, and a A specific proportion is attached to the dyed chromate coating layer of the aluminum substrate, and the hydrophilic coating layer is dried by heating. Summary of the Invention When dyeing chromate is used in the aforementioned Japanese Kokai Publication Hei-5_125555, basically from the environmental point of view, it is better to use a non-chromate chemical conversion treatment agent. When chromium-containing phosphate is used, it must be washed with an aqueous solution after chemical conversion treatment to prevent hexavalent chromium from remaining on the coating layer. But the treatment of chromium-containing wastewater generated when washed with an aqueous solution will cause other problems. However, there is no treatment method that can be used for a non-chromate treatment agent to form a heat sink material having sufficient corrosion resistance and moisture resistance. Therefore, the object of the present invention is to provide a method for producing an aluminum heat sink material using a non-chromate chemical conversion treatment agent that is better for the environment, and at the same time meet the required performance characteristics such as corrosion resistance and humidity resistance, and This method produces an aluminum heat sink material. The method for producing an aluminum heat sink material according to the present invention includes forming a chemical conversion coating layer in the chemical conversion treatment step of the aluminum substrate, and forming a corrosion-resistant coating layer and / or a floatable ( Water-borne) resin is a hydrophilic coating. The chemical conversion coating can be obtained by maintaining a chemical conversion treatment solvent within the following composition range and keeping the solvent temperature at 30 to 5. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). (Please read the notes on the back before filling this page)
^· ϋ I I t— n I n 一OJ· n n ϋ n m n n I 510832 锆離子 磷酸鹽離子 鋁離子 有效氟化物離子 A7 B7 五、發明說明（》） 70°C狀態下，處理時間1至10秒 10 至 10,000 ppm 10 至 10,000 ppm 100 至 10,000 ppm 1 至 500 ppm 具有至少一個酚的羥基存於分子中之有機酸10至1〇,〇〇〇 ppm pH 1.0 至 4.0 該具有至少一個酚的羥基存於分子中之有機酸包含至 少一部分從酚、酚酸性硫酸基酸、單寧酸及其衍生物中選 擇。 於形成該化學轉換被覆層之後，在無實施水之淸洗下 ，以滾動之方式將水以擠壓方式排出。且在之後形成耐腐 蝕性被覆層及/或由一種可浮於水上的（water-borne)樹脂 所組成之親水性被覆層。 本發明更進一步指出，鋁散熱片材料可藉由上述任何 方法獲得。較佳地鋁散熱片材料產品之化學轉換被覆層， 應冋時包含每一含量爲1至100 mg/m2之锆及磷酸鹽。 發明之細節說明 接下來，將詳細說明本發明。 於本發明之背景鋁散熱片材料是一種製造散熱片熱交 換器的材料。此散熱片材料是一個環形之板狀鋁板或滾軋 捲成線圈狀之鋁合金，且可選擇性地加以脫脂來獲得，接 著實施化學轉換處理，並形成耐腐蝕性被覆層及/或由一種 可浮於水上的（water-borne)樹脂所組成之親水性被覆層 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 公iT" (請先閱讀背面之注意事項再填寫本頁) 一裝------.II 訂--------- 510832 A7 ___— ____B7 五、發明說明) 使其具有親水性。以此方式所形成之具有化學轉換被覆層 、耐腐蝕性被覆層及/或親水性被覆層之散熱片材料，經過 裁切、加工及組裝成一熱交換器。 依據本發明之生產銘散熱片材料之方法，銘或銘合金 板需要時首先須脫脂。脫脂處理方法包括使用汽油或正己 院之丨谷劑脫脂，及使用含有氫氧化鈉、矽酸鈉或磷酸鈉之 鹼溶液之鹼脫脂。這些處理方法可依照鋁材料之條件來加 以適當的選擇使用。 在後繪的化學轉換處理步驟中，將化學轉換處溶液噴 灑於散熱片材料上。噴灑處理的時間，即化學轉換處溶液 接觸散熱片材料的時間爲1至10秒，且處理的溫度（溶液 的溫度）爲30至70 C，較佳爲40至60°C。若上述之處理 時間少於1秒，將無法形成足量之化學轉換被覆層。從另 一方面言之，當處理的時間超過10秒，亦無法期望可進一 步升功Sb特丨生’且以成本觀之是不利的。若處理的溫度 低於30°C ’化學轉換處理劑之反應性太低，以至於無法形 成足量之化學轉換被覆層。從另一方面言之，若處理溫度 超過70°C，亦無法期望可進一步提升功能特性，且以成本 觀之是不利的。於本發明的實施例中，將以浸入或其它技 術來取代該噴灑處理。 使用於上述化學轉換處理之化學轉換處理溶液之組成 爲··鉻離子10至10，_ ppm，較佳爲100至1，〇〇〇 ppm ;磷 酸鹽離子10至1〇,〇〇〇 PPm，較佳爲1〇〇至！，〇〇〇 ppm ;鋁離 子100至1〇,〇〇〇 PPm，較佳爲500至5,000 ppm ;有效氟化 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁)^ · Ϋ II t— n I n—OJ · nn ϋ nmnn I 510832 Zirconium ion Phosphate ion Aluminum ion Effective fluoride ion A7 B7 V. Description of the invention (》) Processing time 1 to 10 seconds at 70 ° C 10 To 10,000 ppm 10 to 10,000 ppm 100 to 10,000 ppm 1 to 500 ppm organic acid with at least one phenolic hydroxyl group in the molecule 10 to 10,000 ppm pH 1.0 to 4.0 the hydroxyl group with at least one phenol exists The organic acid in the molecule contains at least a part selected from phenol, phenolic sulfuric acid, tannic acid and derivatives thereof. After the chemical conversion coating is formed, the water is squeezed out in a rolling manner without being washed with water. Then, a corrosion-resistant coating layer and / or a hydrophilic coating layer composed of a water-borne resin is formed. The invention further indicates that the aluminum heat sink material can be obtained by any of the methods described above. Preferably, the chemical conversion coating of the aluminum heat sink material product should contain zirconium and phosphate at a content of 1 to 100 mg / m2. DETAILED DESCRIPTION OF THE INVENTION Next, the present invention will be described in detail. In the background of the present invention, an aluminum heat sink material is a material for manufacturing a heat sink heat exchanger. The heat sink material is a ring-shaped plate-shaped aluminum plate or a rolled aluminum alloy that is rolled into a coil, and can be selectively degreased to obtain a chemical conversion treatment to form a corrosion-resistant coating and / or A hydrophilic coating composed of a water-borne resin. The paper size is applicable to China National Standard (CNS) A4 specifications (210 X male iT " (Please read the precautions on the back before filling this page). Equipment ------. II Order --------- 510832 A7 ___— ____B7 V. Description of the invention) Make it hydrophilic. The heat sink material having the chemical conversion coating layer, the corrosion-resistant coating layer and / or the hydrophilic coating layer formed in this way is cut, processed, and assembled into a heat exchanger. According to the method for producing a material for a heat sink of the present invention, the Ming or Ming alloy plate must first be degreased when necessary. Degreasing methods include degreasing with gasoline or cereals, and alkaline degreasing with alkaline solutions containing sodium hydroxide, sodium silicate, or sodium phosphate. These treatment methods can be appropriately selected and used according to the conditions of the aluminum material. In the chemical conversion treatment step shown below, the chemical conversion solution is sprayed on the heat sink material. The spray treatment time, that is, the time at which the solution at the chemical conversion contacts the heat sink material, is 1 to 10 seconds, and the treatment temperature (the temperature of the solution) is 30 to 70 C, preferably 40 to 60 ° C. If the above treatment time is less than 1 second, a sufficient chemical conversion coating layer cannot be formed. On the other hand, when the processing time is longer than 10 seconds, it is impossible to expect further improvement in power Sb characteristics and it is disadvantageous in terms of cost. If the processing temperature is lower than 30 ° C, the reactivity of the chemical conversion treatment agent is too low to form a sufficient chemical conversion coating layer. On the other hand, if the processing temperature exceeds 70 ° C, further improvement of the functional characteristics cannot be expected, and it is disadvantageous in terms of cost. In the embodiment of the present invention, the spraying treatment will be replaced by immersion or other techniques. The composition of the chemical conversion treatment solution used in the above chemical conversion treatment is: chromium ion 10 to 10,-ppm, preferably 100 to 1,000 ppm; phosphate ion 10 to 10,000 ppm, It is preferably 100 to! ， 00ppm; aluminum ion 100 to 10,000PPm, preferably 500 to 5,000 ppm; effective fluorination 7 This paper size applies Chinese National Standard (CNS) A4 specification (210 x 297 mm) ( (Please read the notes on the back before filling out this page)
510832 ___B7 ___ 五、發明說明（^ ) 物離子1至500 ppm，較佳爲1至10 ppm ;具有至少一個 酚的羥基存於分子中之有機酸10至10,000 ppm，較佳爲 100 至 1,000 ppm ; pHl.O 至 4.0，較佳爲 1.5 至 2.5。 上述所提之锆離子乃由氟锆酸、鋰、鈉、鉀、銨及其 它氟锆酸、锆硫酸鹽、锆硝酸鹽、锆醯硝酸鹽、氟化锆諸 如此類之鹽類所獲得。若銷離子的含量少於10 ppm，因所 得之化學轉換被覆層中之锆含量太低而降低耐腐蝕性及親 水性被覆層之附著性。若超過1〇,〇〇〇 ppm，亦無法期望可 進一步提升其功能特性，且以成本觀之是不利的。 磷酸鹽離子可藉由加入選自於磷酸、磷酸銨、與鹼金 屬磷酸鹽諸如磷酸鈉、磷酸鉀等，鹼土金屬磷酸鹽諸如磷 酸鈣、磷酸鎂等的鹼土金屬磷酸鹽以及濃磷酸中之磷酸化 合物而得到。若磷酸鹽離子的量低於10 ppm，因所得之化 學轉換被覆層中之磷酸鹽離子含量太低而降低耐腐蝕性。 若超過10,000 ppm，亦無法期望可進一步提升其功能特性 ，且易形成沈澱物。 上述所提之鋁離子可由氟化鋁、氧化鋁、硫酸鋁明攀 、矽酸鋁、鋁酸鹽如鋁酸鈉等、及氟鋁酸如氟鋁酸鈉等等 來提供。鋁離子亦可由鋁散熱片材料來獲得。若鋁離子的 量低於1〇〇 ppm，將無法促進化學轉換被覆層的反應，而 導致耐腐蝕性的減弱；若其量超過10,000 ppm，相反地將 妨礙化學轉換被覆層的形成，並導致在化學轉換處理溶液 中形成沈澱物。 上述所提之有效氟化物離子可由氫氟酸、氟化銨、氫 8 1紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -----I--^ ------I-- 510832 ___ B7___ 五、發明說明（h ) 氟化銨、氟化鈉、氫氟化鈉等等來提供，當使用如前述之 锆離子提供者之含氟化物的化合物時，如氟锆酸或氟锆酸 銨，锆離子提供者亦同時提供一部分的氟化物離子。有效 氟化物離子其意爲，於處理溶液中之自由氟化物濃度。有 效氟化物離子濃度可藉含有氟化物離子電極之設備量測處 理溶液來獲得。若有效氟化物離子低於1 ppm，散熱片材 料表面將無法予以足夠的蝕刻，而致使無法形成足量之化 學轉換被覆層。若超過500 ppm，化學轉換處理溶液中之 鋁離子濃度將因爲過度蝕刻而超過本發明之範圍，並造成 反應受阻，同時形成大量的沈澱物。 爲進一步改良耐蝕性及耐濕性，本發明之處理溶液包 含具有至少一個酚的羥基存於分子中之有機酸，其濃度爲 10至10,000 ppm。若其濃度低於10 ppm，因爲添加的量不 足，對功能特性的提升亦有限。若其超過10,⑻0 ppm，亦 無法更進一步提升其功能特性。較佳之有機酸包括酚、單 寧酸及酚酸性硫酸基酸。 若該化學轉換處理溶液之pH低於1.0，將會造成過度 腐蝕，而使得化學轉換被覆層難以形成，並且降低耐蝕性 。若超4.0，化學轉換被覆層亦難以形成而降低耐蝕性。分 析化學轉換處理溶液的成分，依據本發明的範圍使用濃縮 溶液調整溶液的成分。 處理溶液可包含其它添加物，例如已知之抑制劑，如 鉬酸及鎢酸，金屬離子如鈦、鎳、釩、給、鐵及鋅，化學 轉換加速劑如亞硝酸鹽及過氧化氫，及鉗合劑以保持鋁離 9 B氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) 一 (請先閱讀背面之注意事項再填寫本頁) --------訂---------線^^- 510832 A7 ___B7______ 五、發明說明（"]) 子。 鋁散熱片材料經過前述之化學轉換處理後，可選擇以 水淸洗2至10秒，或使用橡膠滾輪擠出，或類似的方式將 水排除。在本發明中所使用之化學轉換處理溶液，足以橡 膠滾輪擠出或類似的方式將水排除，而不需以水溶液清洗 ，殘留的化學轉換處理溶液對於後續的步驟不但無不利的 效應，相對可提升耐蝕性。其意謂著可輕易維持並減少廢 水處理負荷。於此步驟所形成之較佳的化學轉換被覆層同 時包含锆及磷，每一種的含量範圍爲1至100 mg/m2。若量 少於1 mg/m2，耐蝕性將會意料之外的降低。若超過1〇〇 mg/m2，則會意料之外的降低附著性。 在下一步驟中，於前述之化學轉換被覆層上，形成使 用樹脂及/或使用主要成分爲可浮於水上的（water-borne) 樹脂之親水性處理水溶液之親水性被覆層所組成之耐腐蝕 被覆層。於前述之化學轉換被覆層上，該耐腐蝕被覆層可 在不形成該親水性被覆層的狀況下形成，或該親水性被覆 層可於不形成該耐腐蝕被覆層的狀況下形成。更甚者，耐 腐蝕被覆層及親水性被覆層兩者可同時形成。 爲提供潤滑性，由可浮於水上的樹脂所得之潤滑性被 覆層，可藉由上述之方法進一步於親水性被覆層上形成。 所以，於化學轉換被覆層上可形成任何之（1 )由可浮 於水上的樹脂所形成之親水性被覆層（2層處理），（2) 由可浮於水上的樹脂所形成之親水性被覆層，及在其上由 可浮於水上的樹脂形成潤滑性被覆層（3層處理），（3) 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---I--------------I I ^ ------I-- (請先閱讀背面之注意事項再填寫本頁) 510832 A7 _B7_^_ 五、發明說明（g ) 由樹脂形成耐蝕性被覆層（2層處理），（4)由樹脂形成 耐蝕性被覆層，及在其上由可浮於水上的樹脂所形成之親 水性被覆層（3層處理），（5)由水玻璃及可浮於水上的 樹脂所形成之親水性被覆層（2層處理），（6)由水玻璃及 可浮於水上的樹脂所形成之親水性被覆層，及在其上由可 浮於水上的樹脂形成潤滑性被覆層（3層處理），（7)由 膠狀二氧化矽及可浮於水上的樹脂所形成之親水性被覆層 (2層處理），或（8)由膠狀二氧化矽及可浮於水上的樹 脂所形成之親水性被覆層，及在其上由可浮於水上的樹脂 形成潤滑性被覆層（3層處理）。 用於形成該親水性被覆層之可浮於水上的樹脂可以是 一般使用之樹脂。例如，（a)含有羰基及/或羰基群之不 飽和聚合可浮於水上的聚合物化合物、（b)含有羰基及/ 或羥基或其衍生物之天然聚合物化合物，（c)可浮於水上 的醇酸樹脂，（d)可浮於水上的雄性酸油（maleiated oil )，（e)可浮於水上的聚酯樹脂，（f)可浮於水上的聚 丁二烯樹脂，（g)可浮於水上的聚氨基化合物樹脂，（h )可浮於水上的環氧樹脂，（i)可浮於水上的多氨基鉀酸 酯樹脂，（j)可浮於水上的酚樹脂，（k)可浮於水上的 氨基樹脂，及上述之混合物。若需要，交聯劑可使用於這 些樹脂之組合中。 如 Japanese Kokai Publication Hei-7-102189 所揭示， 使用至少一種上述之可浮於水上的樹脂(a)至(k)，組合成可 浮於水上的聚合物化合物，亦爲較佳之方法，其含量不得 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之达意事項再填寫本頁) ^--------^--------- 510832 A7 __B7_______ 五、發明說明（y ) 低於固體基礎下聚氧環烯鏈之1〇重量％。 (請先閲讀背面之注意事項再填寫本頁) 以具有羰基及/或羥基之該不飽和聚合可浮於水上的聚 合物化合物（a)爲例，其包括聚（甲基）丙烯酸，（甲基 )丙烯酸一（甲基）丙烯酯共聚合物，苯乙烯一（甲基） 丙烯酸酯共聚合物，由部分聚乙烯醋酸鹽樹脂皂化所得之 聚乙烯醇、聚乙烯四氫吡咯酮，（甲基）丙烯醯胺衍生聚 合物如 N-甲基羥（甲基）丙烯醯胺（N-methylol(meth)acrylamide)諸如此類。 含有羰基及/或羥基或其衍生物之天然聚合物化合物（ b)，在此可舉例者爲纖維素衍生物如羰基甲基纖維素（ CMC)、羥基乙基纖維素（HEC)、羥基丙基纖維素（ HPC)、甲基纖維素（CM)、乙基纖維素（EC)、乙基 羥基乙基纖維素（EHEC)等；甲基纖維素衍生物，及其鈉 、鉀及銨鹽等等。 可浮於水上的醇酸樹脂（〇在此提及之化合物爲從脫 水濃縮之聚羥得之，如甘油、五赤藻醇、乙烯甘油、三甲 基羥乙烷等，伴隨著一油-衍生的較高脂肪酸，例如二元酸 ，如棕櫚酸、酞酐、順丁烯二酸酐等。 可浮於水上的聚酯樹脂（e)在此提及之化合物爲藉由 一聚酯樹脂之羥基與苯三甲酸酐之半酯化反應得之，以胺 類中和殘留之羧基群，並爲親水性緩和生成物，並藉由聚 乙烯甘油與多元酸的反應來獲得化合物，並爲親水性調和 聚酯生成物。 可浮於水上的聚丁二烯樹脂（f)在此提及者爲含丁二 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 510832 A7 ____B7_ 五、發明說明（ίϋ) 烯之親水性含群共聚合物單體。可浮於水上的聚氨基化合 物樹脂（g)在此提及者爲由ε -己內醯胺或聚合濃縮含己 二酸之六亞甲基二氛之開環聚合作用（ring-opening polymerization)所得之聚醯胺溶化後得之。 可浮於水上的環氧樹脂（h)，在此所提之可浮於水上 的環氧樹脂如脂肪族的聚羥、二或多丙烯酸之其一，二羰 酸、二丙烯酸之其一，含氮異含環環氧化合物等，水分散 環氧樹脂可藉由添加某種乳化劑至水中或水與某種有機溶 劑之混合溶液，再加入分散的/乳化的某種環氧樹脂於其中 ，或調和某種環氧樹脂以便於溶於或分散/乳化樹脂於水中 〇 可浮於水上的多氨基鉀酸酯樹脂（i)，在此提及之化 合物爲藉由引入陰離子或陽離子群於分子中來溶解而獲得 。在此提及之樹脂亦可由添加重亞硫酸鹽至氨基鉀酸酯預 聚合物之最終的異氰酸基群（isocyanato group)中，來阻 止異氰酸基群（isocyanato group)並藉由磺鹽（sulfonate )之親水性來溶解樹脂。在此提及之樹脂亦可由以阻塞劑 來阻止氨基鉀酸酯預聚合物，然後以力來使其乳化/分散。 可浮於水上的酚樹脂（j)，在此提及之含酚羥基之化 合物的多濃縮產物，如酚，二甲酚，對烷基酚（P-alkylphenol )，對苯基酸（p-phenylphenc^ ) ’ 氯苯酣 (chlorophenol)，2,2-雙對酚甲烷，苯酚磺酸，間苯二酚等 偕同乙醛，如甲醛，糠醛或類似化合物。眾所週知者爲酚-甲醛樹脂，甲酚-甲醛樹脂，酚-糠醛樹脂，間苯二酚樹脂 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ·.. ------------.—------^--------- (請先閱讀背面之注意事項再填寫本頁) 510832 A7 ___ B7___ _ 五、發明說明（Μ) 等等。 可浮於水上的氨基樹脂（ι〇，在此提及者爲密胺樹脂 ，例如丁酸（n-butylated )密胺樹脂，異丁酸（ isobutylated)密胺樹脂及其類似化合物，和尿素樹脂，以 上所有均已成爲水溶性。 當該可浮於水上的聚合物化合物含有於固體基礎下， 不低於10重量％之聚氧環烯鏈，在此提及者爲聚乙烯氧化 物（PE0)、乙烯氧化物-丙烯氧化物共聚合物、乙烯氧化 物-亞甲基氧化物共聚合物等等。 上述所提及之親水性處理水溶液通常以水來稀釋濃縮 水溶液後使用，較佳之稀釋後可浮於水上的樹脂濃度爲1 至50重量％，更佳爲2至20重量％。 前述所提之交聯劑可以是可浮於水上的交聯劑，其爲 金屬化合物，可與每一該可浮於水上的樹脂形成複雜之化 合物。例如，在此所提及之化合物包括氧化物、氧化物鹽 、鹵化物、硝酸鹽、硫酸鹽、主要或次要磷酸鹽、矽酸鹽 、碳酸鹽、有機酸鹽或鉻、鈦、鋁、鋅、锆之複鹽等。 用來形成該親水性被覆層之可浮於水上的樹脂，於不 同範圍內可用各種的添加劑而不致於對可浮於水上的樹脂 薄膜的形成有不利的影響。例如，在此提及者爲潤滑劑、 防腐劑、防菌劑、抗菌劑、介面活性劑、顏料及染色。爲 施予較高水準之親水性，添加膠狀二氧化矽或水玻璃爲較 佳。 上述可浮於水上的處理溶液之被覆方法包括滾輪塗佈 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 --------訂--------- (請先閱讀背面之注意事項再填寫本頁) 510832 A7 __B7 ___ 五、發明說明（i L) 法（roll coater method)、帶鍍法（bar coater method )、 浸鍍法、噴霧法及刷鍍法及其它類似的方法。於該被覆方 法中，當使用滾輪塗佈法時，例如，親水性被覆層可於於 150至270°C將被覆層乾燥10秒至1分鐘後來獲得。依使 用可浮於水上的樹脂的種類，當烘烤的溫度低於150°C時 ，薄膜的形成將無法符合要求，且當超過270°C時，將因 爲過度烘烤而失去親水性。 親水性被覆層的厚度較佳爲小於0.05 g/m2，更佳爲0.1 至2 g/m2。若被覆層薄膜的厚度小於〇·〇5 g/m2，親水性的 壽命及散熱片材料的可製程性將會不佳。 當樹脂使用於該耐腐蝕被覆層之形成時，可使用那些 一般用來增進耐腐蝕性的樹脂。 用來形成潤滑性被覆層之可浮於水上的樹脂並無特別 限制，但在該可浮於水上的樹脂中，可使用那些可溶於水 中之樹脂。 依本發明之上述方法所生產的鋁散熱片材料，是一種 於其上形成化學轉換被覆層之鋁散熱片材料，且於上述之 化學轉換被覆層頂部，同時形成耐腐蝕被覆層及/或親水性 被覆層。較佳者’化學轉換被覆層同時包含錯與磷，每_ 種的含量爲1至mg/m2。 依據本發明所生產之鋁散熱片材料，其主要由使用含 某特定範圍鋁離子之處理溶液之化學轉換處理所組成，Μ 於其上施以親水性處理。因爲上述鋁離子與有效氣化物_ 子可形成堅韌的化學轉換被覆層，當耐腐蝕被覆層及/或親 15 (請先閱讀背面之注意事項再填寫本頁) --------訂---------線應 本紙張尺度適用中國國家標準(CNS)A4規格（210 x 297公釐） ---- 510832 五、發明說明（I V) 水性被覆層於化學轉換被覆層上形成時，將可產生較傳統 鉻酸鹽處理之散熱抑料肺同等或顏之耐候性、耐濕 性及吸附性之散熱片材料。 0胃月中上述生產方法所生產之鋁散熱片材料 具有優良之耐候性、耐濕性及吸附性，故可廣泛應用於熱 ’如空調系統及類似設備。 實施例 接下來以貫施例及比較例來更進一步詳細說明本發明 〇 實施例1 藉由加入氟錯酸、磷酸及氫氟酸以相同的總量來製備 化學轉換處理溶液，每一離子的個別的濃度如表丨所示， 其後添加500 ppm之單寧酸及氨水將pH値調整至2。锆、 磷酸及鋁離子以Kyoto Koken’s ICP來測定；有效氟離子以 氟化物離子計來測定；及單寧酸以於建立校正曲線 Shimadzu公司之T0C來測定。 然後，鋁散熱片材料（JIS-A1100)切成200X250公 厘之試驗試片。這些試驗試片於70°C下，以1重量％濃度 之脫脂劑（Surf Cleaner 340，Nippon Paint Co.的產品）噴 灑5秒，然後以水淸洗。使用上述之化學轉換處理溶液， 於處理溶液溫度55°C條件下，試驗片連續地一個接一個被 施以化學轉換處理，噴灑時間5秒。於連續化學轉換處理 期間，處理溶液的組成濃度漸漸地被稀釋。因此，爲維持 化學轉換處理溶液之每一個組成的濃度，溶液以組成分析 16 (請先閱讀背面之注意事項再填寫本頁) ---— III— ·11111111- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 510832 A7 _____J7____ 五、發明說明（/f) 來監控，並以濃縮液來調整。結果，鋁離子從試驗片中洗 提出來，漸漸於化學轉換處理溶液中聚集，最後達到1，〇〇〇 ppm的濃度。爲更進一步提升鋁離子濃度，將硝酸鋁溶於 其中，其組成溶液的濃度爲2,000 ppm。 試驗片由上述最初組成及鋁離子濃度分別爲50、200 、1，〇〇〇及2,000 ppm之溶液處理後，以親水性之有機/無 機複合調質劑（Surf Alcoat 131，Nippon Paint Co.)來處 理獲得親水性，以製備鋁散熱片材料，用以下所描述之方 法來評估耐腐蝕性及耐濕性。結果，在鋁離子濃度不超過 200 ppm下，於耐腐蝕性及耐濕性均獲得令人滿意的結果 。此結果如表1所示。 <耐腐蝕性> 鹽霧試驗：試驗片於35°C下以5%氯化鈉水溶液噴灑 評估於500小時後生成白鏽之程度 ◎ 無鏽斑形成 〇 輕微鏽斑形成 Δ 中度鏽斑形成 X 可觀的鏽斑形成 XX:全面形成鏽斑 <耐濕性> 耐濕性試驗於5〇t大氣溫度、相對濕度最小98%下執 行500小時，評估生成鏽斑之程度。 ◎:無污點 〇：輕微污點 17 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 1T---------線座 510832 五 、發明說明（ A7 B7 △:中度污點 X:可觀的污點 XX ··全面的污點 錐離子 3〇〇 ppm 磷酸鹽離子 3〇〇 ppm 銘離子 〇ppm 有效氟離子 5 ppm pH 2〜 單寧酸 500 ppm 耐腐蝕性 耐濕性510832 ___B7 ___ 5. Description of the invention (^) 1 ~ 500 ppm of ion, preferably 1 to 10 ppm; organic acid with at least one phenolic hydroxyl group in the molecule 10 to 10,000 ppm, preferably 100 to 1,000 ppm pH 1.0 to 4.0, preferably 1.5 to 2.5. The zirconium ions mentioned above are obtained from fluorozirconic acid, lithium, sodium, potassium, ammonium and other fluorozirconic acid, zirconium sulfate, zirconium nitrate, zirconium hafnium nitrate, zirconium fluoride and the like. If the content of pin ions is less than 10 ppm, the zirconium content in the obtained chemical conversion coating is too low, which reduces the corrosion resistance and the adhesion of the hydrophilic coating. If it exceeds 10,000 ppm, it cannot be expected to further improve its functional characteristics, and it is disadvantageous in terms of cost. Phosphate ions can be added by adding phosphoric acid selected from the group consisting of phosphoric acid, ammonium phosphate, and alkali metal phosphates such as sodium phosphate, potassium phosphate, etc., alkaline earth metal phosphates such as calcium phosphate, magnesium phosphate, and the like and concentrated phosphoric acid. Compounds. If the amount of phosphate ions is less than 10 ppm, the corrosion resistance is lowered because the content of phosphate ions in the obtained chemical conversion coating is too low. If it exceeds 10,000 ppm, it cannot be expected to further improve its functional characteristics, and it is easy to form a precipitate. The aluminum ions mentioned above can be provided by aluminum fluoride, aluminum oxide, aluminum sulfate, aluminum silicate, aluminum silicate, aluminate such as sodium aluminate, etc., and fluoroaluminate acid such as sodium fluoroaluminate. Aluminum ions can also be obtained from aluminum heat sink materials. If the amount of aluminum ions is less than 100 ppm, the reaction of the chemical conversion coating layer cannot be promoted, resulting in a decrease in corrosion resistance; if the amount is more than 10,000 ppm, it will conversely prevent the formation of the chemical conversion coating layer and cause A precipitate was formed in the chemical conversion treatment solution. The effective fluoride ions mentioned above can be hydrofluoric acid, ammonium fluoride, hydrogen 8 1 Paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) ----- I-^ ------ I-- 510832 ___ B7___ V. Description of the invention (h) Ammonium fluoride, sodium fluoride, sodium hydrofluoride, etc. are provided. When used as described above When the zirconium ion supplier is a fluoride-containing compound, such as fluorozirconic acid or ammonium fluorozirconate, the zirconium ion supplier also provides a part of the fluoride ion. Effective fluoride ion means the free fluoride concentration in the treatment solution. The effective fluoride ion concentration can be obtained by measuring the processing solution with a device containing a fluoride ion electrode. If the effective fluoride ion is less than 1 ppm, the surface of the heat sink material cannot be sufficiently etched, so that a sufficient amount of chemical conversion coating cannot be formed. If it exceeds 500 ppm, the aluminum ion concentration in the chemical conversion treatment solution will exceed the range of the present invention due to excessive etching, and the reaction will be hindered, and a large amount of precipitates will be formed at the same time. In order to further improve the corrosion resistance and moisture resistance, the treatment solution of the present invention contains an organic acid having at least one hydroxy group of phenol in the molecule at a concentration of 10 to 10,000 ppm. If its concentration is less than 10 ppm, the functional properties will be limited due to insufficient addition. If it exceeds 10, ⑻0 ppm, its functional characteristics cannot be further improved. Preferred organic acids include phenol, tannic acid and phenolic sulfuric acid. If the pH of the chemical conversion treatment solution is lower than 1.0, excessive corrosion will be caused, making it difficult to form a chemical conversion coating layer, and reducing the corrosion resistance. If it exceeds 4.0, it is also difficult to form a chemical conversion coating layer and reduce the corrosion resistance. The components of the chemical conversion treatment solution are analyzed, and the components of the solution are adjusted using a concentrated solution in accordance with the scope of the present invention. The treatment solution may contain other additives such as known inhibitors such as molybdic acid and tungstic acid, metal ions such as titanium, nickel, vanadium, hydrogen, iron and zinc, chemical conversion accelerators such as nitrite and hydrogen peroxide, and Clamping agent to maintain the aluminum ionization scale of 9 B. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm). One (Please read the precautions on the back before filling this page) -------- Order --------- line ^^-510832 A7 ___B7______ V. Description of the invention ("]). After the aluminum heat sink material is subjected to the aforementioned chemical conversion treatment, it can be washed with water for 2 to 10 seconds, or extruded with a rubber roller, or the water can be similarly removed. The chemical conversion treatment solution used in the present invention is sufficient for rubber roller extrusion or a similar manner to exclude water without cleaning with an aqueous solution. The remaining chemical conversion treatment solution has no adverse effects on subsequent steps and is relatively feasible. Improve corrosion resistance. This means that the wastewater treatment load can be easily maintained and reduced. The better chemical conversion coating formed in this step also contains zirconium and phosphorus, each containing a content ranging from 1 to 100 mg / m2. If the amount is less than 1 mg / m2, the corrosion resistance will decrease unexpectedly. If it exceeds 100 mg / m2, the adhesion is unexpectedly reduced. In the next step, on the aforementioned chemical conversion coating layer, a corrosion resistant coating composed of a hydrophilic coating layer using a resin and / or a hydrophilic treatment aqueous solution containing a water-borne resin as a main component is formed. Coating. On the aforementioned chemical conversion coating layer, the corrosion-resistant coating layer may be formed without forming the hydrophilic coating layer, or the hydrophilic coating layer may be formed without forming the corrosion-resistant coating layer. Furthermore, both the corrosion-resistant coating layer and the hydrophilic coating layer can be formed at the same time. In order to provide lubricity, a lubricating coating layer obtained from a water-floatable resin can be further formed on the hydrophilic coating layer by the method described above. Therefore, any one of (1) a hydrophilic coating layer made of a resin that floats on water can be formed on the chemical conversion coating (2), and (2) a hydrophilic property formed of a resin that floats on water Coating layer, and a lubricious coating layer formed on it by a resin that can float on the water (3 layers treatment), (3) 10 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- -I -------------- II ^ ------ I-- (Please read the notes on the back before filling out this page) 510832 A7 _B7 _ ^ _ V. Description of the invention ( g) forming a corrosion-resistant coating layer from a resin (two-layer treatment), (4) forming a corrosion-resistant coating layer from a resin, and a hydrophilic coating layer (three-layer treatment) formed thereon by a resin floatable on water, (5) a hydrophilic coating formed by water glass and a resin floating on water (two-layer treatment), (6) a hydrophilic coating formed by water glass and a resin floating on water, and A lubricious coating layer is formed by a resin floating on water (3 layers), (7) is formed by colloidal silica and a resin floating on water Hydrophilic coating layer (two-layer treatment), or (8) a hydrophilic coating layer composed of colloidal silica and a resin that floats on water, and a lubricious coating that is formed of a resin that floats on water Layers (3 layers processing). The water-repellent resin used to form the hydrophilic coating layer may be a resin generally used. For example, (a) unsaturated polymerizable polymer compounds containing carbonyl groups and / or carbonyl groups, (b) natural polymer compounds containing carbonyl groups and / or hydroxyl groups or derivatives thereof, and (c) floating Alkyd resin on water, (d) maleiated oil that can float on water, (e) polyester resin that can float on water, (f) polybutadiene resin that can float on water, (g ) Polyamino compound resin that can float on water, (h) epoxy resin that can float on water, (i) polyaminopotassium resin that can float on water, (j) phenol resin that can float on water, ( k) Amino resins that can float on water, and mixtures thereof. If necessary, a crosslinking agent may be used in a combination of these resins. As disclosed in Japanese Kokai Publication Hei-7-102189, it is also a better method to combine at least one of the above-mentioned floating resins (a) to (k) to form a polymer compound that can float on water. No. 11 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notice on the back before filling this page) ^ -------- ^ ------ --- 510832 A7 __B7_______ 5. Description of the invention (y) is less than 10% by weight of the polyoxycycloolefin chain on a solid basis. (Please read the precautions on the back before filling this page) Take the unsaturated polymerizable polymer compound (a) with carbonyl and / or hydroxyl group as an example, which includes poly (meth) acrylic acid, (a Base) acrylic acid mono (meth) acrylate copolymer, styrene mono (meth) acrylate copolymer, polyvinyl alcohol and polyethylene tetrahydropyrrolidone obtained by saponification of a part of polyvinyl acetate resin, (a Acrylamide-derived polymers such as N-methylol (meth) acrylamide and the like. Natural polymer compounds (b) containing a carbonyl group and / or a hydroxyl group or a derivative thereof, examples of which are cellulose derivatives such as carbonyl methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl Cellulose (HPC), methyl cellulose (CM), ethyl cellulose (EC), ethyl hydroxyethyl cellulose (EHEC), etc .; methyl cellulose derivatives, and their sodium, potassium, and ammonium salts and many more. Floatable alkyd resin (the compound mentioned here is obtained from dehydrated polyhydroxy, such as glycerol, pentaerythritol, ethylene glycerol, trimethylhydroxyethane, etc., accompanied by an oil- Derived higher fatty acids, such as dibasic acids, such as palmitic acid, phthalic anhydride, maleic anhydride, etc. Polyester resins that can float on water (e) The compounds mentioned here are compounds made by a polyester resin It is obtained by the semi-esterification reaction of hydroxyl and trimellitic anhydride. The residual carboxyl group is neutralized with amines, and it is a hydrophilic relaxation product. The compound is obtained by the reaction of polyvinyl glycerol and polybasic acid, and is hydrophilic. Blend the polyester product. Polybutadiene resin that can float on the water (f) It is referred to as butadiene 12 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 510832 A7 ____B7_ V. Description of the Invention (ίϋ) Hydrophilic group-containing copolymeric monomers of olefins. Polyamino resins that can float on water (g) The mention here is made by ε-caprolactam or polymer-containing concentrated hexamethylene Ring-opening pol ymerization) is obtained after the polyamine is dissolved. Floatable epoxy resin (h), mentioned herein can be floated epoxy resin such as aliphatic polyhydroxy, di or polyacrylic acid First, one of dicarbonyl acid, diacrylic acid, nitrogen-containing isocyclic epoxy compound, etc., water-dispersed epoxy resin can be added by adding an emulsifier to water or a mixed solution of water and an organic solvent, and then adding A certain epoxy resin dispersed or emulsified therein, or a certain epoxy resin is blended in order to dissolve or disperse / emulsify the resin in water. The polyaminopotassium resin (i), which can float on water, is provided here. The compound is obtained by dissolving the anion or cationic group in the molecule. The resin mentioned here can also be obtained by adding bisulfite to the final isocyanato group of the potassium urethane prepolymer. group) to block the isocyanato group and dissolve the resin by the hydrophilicity of the sulfonate. The resin mentioned here can also block the urethane prepolymer with a blocking agent And then emulsify it with force / Disperse. Floatable phenol resin (j), the multi-concentrated product of phenolic hydroxyl-containing compounds mentioned here, such as phenol, xylenol, p-alkylphenol, p-phenyl acid (P-phenylphenc ^) 'chlorophenol, 2,2-bis-p-phenol methane, phenolsulfonic acid, resorcinol and other acetaldehyde, such as formaldehyde, furfural or similar compounds. Well known as phenol-formaldehyde Resin, cresol-formaldehyde resin, phenol-furfural resin, resorcinol resin 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) · .. --------- ---.------- ^ --------- (Please read the notes on the back before filling out this page) 510832 A7 ___ B7___ _ 5. Description of the invention (M) and so on. Floatable amino resins (ι〇, mentioned herein are melamine resins, such as n-butylated melamine resin, isobutylated melamine resin and similar compounds, and urea resin All of the above have become water-soluble. When the floatable polymer compound is contained on a solid basis, not less than 10% by weight of a polyoxycycloolefin chain, mentioned herein is polyethylene oxide (PE0 ), Ethylene oxide-propylene oxide copolymer, ethylene oxide-methylene oxide copolymer, etc. The above-mentioned hydrophilic treatment aqueous solution is usually used after diluting the concentrated aqueous solution with water, and the preferred dilution is The concentration of the resin that can be floated on the water is 1 to 50% by weight, and more preferably 2 to 20% by weight. The aforementioned crosslinker can be a floatable crosslinker, which is a metal compound, which can interact with each A resin that floats on water forms complex compounds. For example, the compounds mentioned herein include oxides, oxide salts, halides, nitrates, sulfates, major or minor phosphates, silicates, Carbonate, Organic acid salts or double salts of chromium, titanium, aluminum, zinc, zirconium, etc. Floating resins used to form the hydrophilic coating can use various additives in different ranges without causing floating to water. The formation of the resin film has adverse effects. For example, those mentioned here are lubricants, preservatives, antibacterial agents, antibacterial agents, surfactants, pigments, and dyeing. To impart higher levels of hydrophilicity, add Colloidal silicon dioxide or water glass is preferred. The coating method for the above-mentioned floating treatment solution includes roller coating. 14 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --- ----- Order --------- (Please read the precautions on the back before filling out this page) 510832 A7 __B7 ___ V. Roll coater method and strip plating method (Bar coater method), dip plating method, spray method, brush plating method, and other similar methods. In this coating method, when a roller coating method is used, for example, a hydrophilic coating layer may be used at 150 to 270 ° C. It is obtained after drying the coating layer for 10 seconds to 1 minute. It can float on use When the baking temperature is lower than 150 ° C, the film formation will not meet the requirements, and when it exceeds 270 ° C, the hydrophilicity will be lost due to excessive baking. Thickness of the hydrophilic coating It is preferably less than 0.05 g / m2, and more preferably 0.1 to 2 g / m2. If the thickness of the coating film is less than 0.05 g / m2, the hydrophilic life and processability of the heat sink material will be poor. When the resin is used for the formation of the corrosion-resistant coating layer, those resins generally used to improve the corrosion resistance can be used. The water-soluble resin used to form the lubricious coating layer is not particularly limited, but in this Among the resins floating on water, those which are soluble in water can be used. The aluminum heat sink material produced according to the above method of the present invention is an aluminum heat sink material on which a chemical conversion coating layer is formed, and on the top of the above chemical conversion coating layer, a corrosion-resistant coating layer and / or a hydrophilic material are simultaneously formed. Sex coating. Preferably, the chemical conversion coating layer contains both phosphorus and phosphorus, and the content of each species is 1 to mg / m2. The aluminum heat sink material produced according to the present invention is mainly composed of a chemical conversion treatment using a treatment solution containing aluminum ions in a specific range, and a hydrophilic treatment is applied thereon. Because the above-mentioned aluminum ions and effective gas ions can form a tough chemical conversion coating, when the corrosion-resistant coating and / or pro 15 (Please read the precautions on the back before filling this page) -------- Order --------- Wire size This paper applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ---- 510832 V. Description of the invention (IV) Water-based coating is used for chemical conversion coating When formed on the layer, it will produce a heat sink material that is equivalent to the traditional chromate-treated heat-dissipating material, or has weather resistance, humidity resistance, and adsorption properties. The aluminum heat sink material produced by the above production method in the middle of the month has excellent weather resistance, humidity resistance, and adsorption, so it can be widely used in thermal systems such as air-conditioning systems and similar equipment. EXAMPLES Next, the present invention will be described in more detail by way of examples and comparative examples. Example 1 A chemical conversion treatment solution was prepared by adding fluoro acid, phosphoric acid and hydrofluoric acid in the same total amount. Individual concentrations are shown in Table 丨, and then 500 ppm of tannic acid and ammonia were added to adjust the pH 値 to 2. Zirconium, phosphoric acid, and aluminum ions were measured using Kyoto Koken's ICP; effective fluoride ions were measured using fluoride ions; and tannic acid was measured using TOC of Shimadzu Corporation to establish a calibration curve. Then, the aluminum heat sink material (JIS-A1100) was cut into 200 × 250 mm test specimens. These test pieces were sprayed with a degreaser (Surf Cleaner 340, product of Nippon Paint Co.) at a concentration of 1% by weight for 5 seconds at 70 ° C, and then rinsed with water. Using the above-mentioned chemical conversion treatment solution, the test piece was continuously subjected to chemical conversion treatment one by one at a temperature of 55 ° C, and the spraying time was 5 seconds. During the continuous chemical conversion treatment, the composition concentration of the treatment solution was gradually diluted. Therefore, in order to maintain the concentration of each component of the chemical conversion treatment solution, the solution was analyzed by composition16 (Please read the precautions on the back before filling this page) ----- III- · 11111111- This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 public love) 510832 A7 _____J7____ 5. Description of the invention (/ f) to monitor and adjust with concentrated liquid. As a result, aluminum ions were eluted from the test piece, gradually accumulated in the chemical conversion treatment solution, and finally reached a concentration of 1,000 ppm. To further increase the aluminum ion concentration, aluminum nitrate was dissolved therein, and the concentration of the constituent solution was 2,000 ppm. The test piece was treated with a solution having an initial composition and an aluminum ion concentration of 50, 200, 1,000, and 2,000 ppm, respectively, and then treated with a hydrophilic organic / inorganic composite modifier (Surf Alcoat 131, Nippon Paint Co.). In order to obtain hydrophilicity to prepare aluminum heat sink material, the method described below was used to evaluate the corrosion resistance and moisture resistance. As a result, satisfactory results were obtained in both corrosion resistance and humidity resistance at a concentration of aluminum ion not exceeding 200 ppm. The results are shown in Table 1. < Corrosion resistance > Salt spray test: The test piece was sprayed with a 5% sodium chloride aqueous solution at 35 ° C to evaluate the degree of white rust formation after 500 hours. ◎ No rust formation. Slight rust formation. Moderate rust formation. X Significant formation of rust spots XX: Overall formation of rust spots < Moisture resistance > The moisture resistance test was performed for 500 hours at 50 t atmospheric temperature and a minimum relative humidity of 98% to evaluate the degree of rust spots. ◎: No stains 0: Slight stains 17 _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 1T ------- --Sleeve 510832 V. Description of the invention (A7 B7 △: Moderate stain X: Considerable stain XX · Comprehensive stain cone ion 300 ppm Phosphate ion 300 ppm Ming ion 0 ppm Effective fluoride ion 5 ppm pH 2 ~ Tannin 500 ppm Corrosion resistance Humidity resistance
^〇PPm 5_ΡΡΠ1 了 50^pm Δ^ a" 陪離子濃度（ppm) 200 1000 2000 300 ppm 300 ppm 300 ppm 300 ppm 300 ppm 300 ppm 200 ppm 1000 ppm 2000 ppm 5 ppm 5 ppm 5 ppm 2 2 2 500 ppm 500 ppm 500 ppm ，~〇~ ◎ ◎ ◎ ◎ (請先閱讀背面之注意事項再填寫本頁) 竹枓亦以下列方法評估其附著性。其 洁果如表2所示。 <附著性> 試驗片浸入流動的水中25〇小時，以擦去的方式實施 刻離試驗。 〇：無異常 △:輕微剝離 X :剝離 再者，由鋁離子濃度爲1，〇〇〇 ppm中處理之試驗片所 生產之鋁散熱片材料的化學轉換被覆層，其锆或磷之重量 (mg/m2)由螢光 X-Ray 分析儀 3070 (Rigaku-sha 製造） 之螢光X-Ray分析測定。結果如表4所示。 實施例2-18，比較例1-1〇，及參考實施例 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公爱） 510832 A7 B7 五、發明說明（β) 以與實施例1相同的程序生產散熱片材料，除了個別 之離子濃度、單寧酸濃度、pH、噴灑溶液溫度噴灑時間、 化學轉換後之水溶液淸洗或忽略，及改變親水性處理溶液 之種類，並評估各試驗片之耐腐蝕性，耐濕性及附著性。 鋁離子濃度以添加硝酸鋁來調整。對於參考實施例，化學 轉換被覆層以傳統含鉻磷酸鹽來形成。結果如表2所示。 表2 由比較例1、2及 8，鋁散熱片材料 之化學轉換被覆 層中之锆或磷之 重量（mg/m2)以 如實施例1之方 法來測定。結果 如表4所示。 離子濃度（ppm) pH 有機酸 (ppm) 化學轉換條件 化學轉換 後之水溶 液淸洗 親水性 調質劑 試驗結果 锆 磷酸鹽 鋁 有效氟 溫度 時間 耐腐蝕性 耐濕性 附著性 實施例 1 300 300 1000 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 2 100 300 1000 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 3 1000 300 1000 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 4 300 100 1000 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 5 300 1000 1000 5 2 500 5S〇C 5秒 No A ◎ ◎ 〇 6 300 300 500 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 7 300 300 2000 5 2 500 55〇C 5秒 No A ◎ ◎ 〇 8 300 300 1000 2 2 500 55〇C 5秒 No A ◎ ◎ 〇 9 300 300 1000 5 2.5 500 55〇C 5秒 No A ◎ ◎ 0 10 300 300 1000 1.5 2 500 55〇C 5秒 No A ◎ ◎ 〇 11 300 300 1000 5 2 250 55〇C 5秒 No A ◎ ◎ 〇 12 300 300 1000 5 2 500 45〇C 5秒 No A ◎ ◎ 〇 13 300 300 1000 5 2 500 65〇C 5秒 No A ◎ ◎ 〇 14 300 300 1000 5 2 500 55〇C 3秒 No A ◎ ◎ 〇 15 300 300 1000 5 2 500 55〇C 10秒 No A ◎ ◎ 〇 16 300 300 1000 5 2 500 55〇C 浸5秒 No A ◎ ◎ 〇 17 300 300 1000 5 2 500 55〇C 5秒 YES A 〇 〇 〇 18 300 300 1000 5 2 500 55〇C 5秒 No B ◎ ◎ 〇 19 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) n n I n n^OJ· ϋ n I n ϋ ϋ 線_· 510832^ 〇PPm 5_ΡΡΠ1 50 ^ pm Δ ^ a " Concentration of ion (ppm) 200 1000 2000 300 ppm 300 ppm 300 ppm 300 ppm 300 ppm 300 ppm 200 ppm 1000 ppm 2000 ppm 5 ppm 5 ppm 5 ppm 2 2 2 500 ppm 500 ppm 500 ppm, ~ 〇 ~ ◎ ◎ ◎ ◎ (Please read the precautions on the back before filling this page) Penny also evaluates its adhesion by the following methods. Its clean fruit is shown in Table 2. < Adhesiveness > The test piece was immersed in flowing water for 25 hours, and the peeling test was performed by wiping. 〇: No abnormality △: Slight peeling X: peeling Further, the chemical conversion coating layer of the aluminum heat sink material produced from the test piece treated in the aluminum ion concentration of 1,000 ppm, the weight of zirconium or phosphorus ( mg / m2) was measured by fluorescent X-Ray analysis using a fluorescent X-Ray analyzer 3070 (manufactured by Rigaku-sha). The results are shown in Table 4. Examples 2-18, Comparative Examples 1-10, and Reference Example 18 This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 public love) 510832 A7 B7 V. Description of the invention (β) The same procedure as in Example 1 was used to produce the heat sink material, except for the individual ion concentration, tannic acid concentration, pH, spray solution temperature spray time, washing or neglect of the aqueous solution after chemical conversion, and changing the type of hydrophilic treatment solution, and evaluated Corrosion resistance, humidity resistance and adhesion of each test piece. The aluminum ion concentration was adjusted by adding aluminum nitrate. For the reference example, the chemical conversion coating was formed using a conventional chromium-containing phosphate. The results are shown in Table 2. Table 2 From Comparative Examples 1, 2 and 8, the weight (mg / m2) of zirconium or phosphorus in the chemical conversion coating layer of the aluminum heat sink material was measured in the same manner as in Example 1. The results are shown in Table 4. Ion concentration (ppm) pH Organic acid (ppm) Chemical conversion conditions Aqueous solution washing after chemical conversion Hydrophilic conditioner test results Zirconium phosphate aluminum Effective fluorine temperature time Corrosion resistance Moisture resistance Adhesion Example 1 300 300 1000 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 2 100 300 1000 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇3 1000 300 1000 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 4 300 100 1000 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 5 300 1000 1000 5 2 500 5S〇C 5 seconds No A ◎ ◎ 〇 6 300 300 500 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 300 300 2000 5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇8 300 300 1000 2 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 9 300 300 1000 5 2.5 500 55 ° C 5 seconds No A ◎ ◎ 0 10 300 300 1000 1.5 2 500 55 ° C 5 seconds No A ◎ ◎ 〇 11 300 300 1000 5 2 250 55 ° C 5 seconds No A ◎ ◎ 〇 12 300 300 1000 5 2 500 45 ° C 5 seconds No A ◎ ◎ ○ 13 300 300 1000 5 2 500 65 ° C 5 seconds No A ◎ ◎ 〇 14 300 300 1000 5 2 500 55 ° C 3 seconds No A ◎ ◎ ○ 15 300 300 1000 5 2 500 55 ° C 10 seconds No A ◎ ◎ 〇 16 300 300 1000 5 2 500 55 ° C Immersion for 5 seconds No A ◎ ◎ 〇 17 300 300 1000 5 2 500 55 ° C 5 seconds YES A 〇〇〇18 300 300 1000 5 2 500 55 ° C 5 seconds No B ◎ ◎ 〇19 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) nn I nn ^ OJ · ϋ n I n ϋ ϋ line 510832
7 7 A B 五、發明說明（ 表3 離子濃度（ppm) pH 有機酸 (ppm) 化學轉換條件 化學轉換 後之水溶 液淸洗 親水性 調質劑 試驗結果 锆 磷酸鹽 鋁 有效氟 溫度 時間 耐腐蝕性 耐濕性 附著性 比較例 1 5 300 1000 5 2 500 55〇C 5秒 No A XX XX 〇 2 300 5 1000 5 2 500 55〇C 5秒 No A Δ X Δ 3 300 300 10 5 2 500 55〇C 5秒 No A Δ Δ 〇 4 300 100 20000 5 2 500 55〇C 5秒 No A XX XX Δ 5 300 1000 1000 500 5 500 55〇C 5秒 No A XX XX Δ 6 300 300 1000 0.1 2 500 55 V 5秒 No A X Δ 〇 7 300 300 1000 5 2 500 25〇C 5秒 No A X X Δ 8 300 300 1000 5 2 500 55〇C 0.5秒 No A XX XX 〇 9 300 300 1000 5 2 500 55〇C 5秒 No No Δ Δ 10 300 300 1000 5 2 0 55〇C 5秒 No A Δ 〇 Ο 參考實施例 含絡碟酸鹽 55〇C 5秒 No A Δ Δ 〇 锆離子...........由氟锆酸提供 磷酸根離子.....由磷酸提供 鋁離子...........由硝酸鋁提供 有效氟離子.....由氫氟酸提供 pH.................以氛水來調整 有機酸............單寧酸 親水性調質劑 A.........有機/無機複合系統（Surf Alcoat 131，Nippon7 7 AB V. Description of the invention (Table 3 Ion concentration (ppm) pH Organic acid (ppm) Chemical conversion conditions Washing of hydrophilic modifiers in aqueous solution after chemical conversion Test results of zirconium phosphate aluminum effective fluorine temperature time corrosion resistance Wet adhesion comparative example 1 5 300 1000 5 2 500 55 ° C 5 seconds No A XX XX 〇2 300 5 1000 5 2 500 55 ° C 5 seconds No A Δ X Δ 3 300 300 10 5 2 500 55 ° C 5 seconds No A Δ Δ 〇4 300 100 20000 5 2 500 55 ° C 5 seconds No A XX XX Δ 5 300 1000 1000 500 5 500 55〇C 5 seconds No A XX XX Δ 6 300 300 1000 0.1 2 500 55 V 5 seconds No AX Δ 〇 300 300 1000 5 2 500 25 ° C 5 seconds No AXX Δ 8 300 300 1000 5 2 500 55 ° C 0.5 seconds No A XX XX 〇 300 300 1000 5 2 500 55 ° C 5 seconds No No Δ Δ 10 300 300 1000 5 2 0 55 ° C 5 seconds No A Δ 〇 Reference Example Contains complexate 55 ° C 5 seconds No A Δ Δ 〇Zirconium ions ......... ..Phosphate ion provided by fluorozirconic acid ... Aluminum ion provided by phosphoric acid ... Effective fluoride ion provided by aluminum nitrate ... pH provided by hydrofluoric acid ...... Adjusted with water ............ acids tannic acid hydrophilic texturizing agent A ......... organic / inorganic composite system (Surf Alcoat 131, Nippon
Paint Co.的產品） B..........有機系統（Surf Alcoat 240，Nippon Paint Co· 的產品） 含鉻隣酸鹽........混合3.0重量％之Alsurf 407 (日本 塗料公司生產）及〇·4重量％之Alsurf 47 (Nippon Paint 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) ^裝 ϋ n n -^1 n n · n ·ϋ ϋ l in 510832 _B7 f\ 五、發明說明（f Y )Product of Paint Co.) B ...... Organic system (Surf Alcoat 240, product of Nippon Paint Co.) Containing chromium ortho acid salt ..... Mixing 3.0% by weight of Alsurf 407 (manufactured by Japan Coatings Co., Ltd.) and 0.4% by weight of Alsurf 47 (Nippon Paint 20) This paper size is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) (Please read the precautions on the back before filling in this Page) ^ 装 ϋ nn-^ 1 nn · n · ϋ ϋ l in 510832 _B7 f \ 5. Description of the invention (f Y)
Co.的產品）之水溶液。 表4 化學轉換被覆層重量（mg/m2) 鉻 磷 實施例1 15 6 比較例1 0.2 3 比較例2 14 0.1 比較例8 0.8 0.5 上列之結果指出，在耐腐蝕生、耐濕性及附著性與親 水性的比較，實施例中試驗片的製備優於於參考實施例中 以含鉻磷酸鹽所製備之試驗片。因此，很顯然其用於散熱 片材料可獲得令人滿意的結果。 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------·Co. product). Table 4 Chemical conversion coating weight (mg / m2) Chromium-phosphorus Example 1 15 6 Comparative Example 1 0.2 3 Comparative Example 2 14 0.1 Comparative Example 8 0.8 0.5 The results listed above indicate that corrosion resistance, moisture resistance, and adhesion Compared with the hydrophilicity, the test piece prepared in the example is superior to the test piece prepared with the chromium-containing phosphate in the reference example. Therefore, it is clear that satisfactory results can be obtained by using it for a heat sink material. 21 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order -------- -·