1329138 --,1329138 --,
099年05月2β日修正替換頁I 六、發明說明： 【發明所屬之技術領域】 ' [0001] 本發明係關於一種喷淋型鋁合金化學蝕刻液，尤其係關 於一種使钱孔光亮完整、姓刻效率命、生産成本低之喷 淋型鋁合金化學蝕刻液。 【先前技術】 [〇〇〇2] 鋁係一種輕金屬，密度小，係半導體製程中最主要之導 線材料，它具有低電阻、易於沈積及钱刻等優點。銘之 導電性僅次於銀及銅，居第三位’用於製造各種導線。 鋁具有良好導熱性，可用作各種散熱材料。鋁還具有良 ® 好抗腐姓性能及塑性，適合於各種壓力加工。 [〇〇〇3] 在鋁蝕刻中，化學反應主導著蝕刻之進行，增加氣化物 之含量則蝕刻速率可增加，但蝕刻速率卻與離子轟擊程 度無關。而鋁的蝕刻屬放熱反應，對於殘留物及保持光 阻完整性而言，控制表面溫度就顯得很重要了。 [0004]由於鋁在常溫下表面極易氧化成氡化鋁，而氧化鋁與氣 分子或原子發生反應，因此在鋁蝕刻製程中常會添加三 氯化’等氣體來去除這層寄生氧化層。再者三氣化蝴極 易與水乳及氧氣反應，故可吸收腔禮内之水氣及氧氣， 以減低氧化鋁再形成。 [0005] 表面之化學姓刻方法係對所需圖案攝製底片，在 塗有感光材料之絲網上成伤 χ X像，再用絲網漏印法將圖案印 在銘合金表面，用酸作選樓 性弱腐姓，再經陽極氧化及 表面噴塗保護膜等工序來製 菽薛s 裂成刻论鋁板之方法，具有 093136483 藝簡單'圖案可按需任選'表單編ΚΛΟΙΟΙ 第3 S/it果觀、抗蝕、可以大批量生 n并29頁 0993183455-1 1329138 [0006] 099年05月26日修正替換頁 產及成本低廉·#特1¾，时制*丨— ‘·所製刻化叙板廣泛應用於電冰箱 、冷櫃製造業、電梯、密如 ^ 包稞讀、電器、家具等裝潢業，尤 其應用於手機面板之表面蝕刻。 在餘刻工藝中，經常會發生如下_不良情況。首先係 侧钮’又稱側部钱刻，第一圖所示係發生在抗㈣i下面 導線2側壁之蚀刻原理圖。圖中A所表示的寬度為成像底 版上的導線寬度，v表示導線厚度，而X表示舰量。側 姓程度係以侧向钱刻之寬度來表示，其與㈣液種類、 • 組成及所使用之綱卫藝及設備有關。 [0007] 其次係麟增寬及料^，第二圖所示。在圖形電鍵 時’由於電鍵金屬層3之厚度超過電鍍抗姓層（圖未示）之 厚度’而使導線寬度A増加，稱為鎮層增寬γ。鍵層增寬Y 與電鑛錢層（®未示）之厚度及電朗3之總厚度有直接 關係’實生產時應儘量避免產生锻層増寬。金屬鍵層 增寬Υ與側钱量X之總和稱為鍵層突沿Ζ H支有鍵層增 寬，鐘層突沿就等於側银量。 鲁 . [0008] 蝕刻速率係以蝕刻液在單位時間内溶解金屬的深度或溶 解一定厚度之金屬所需時間表示。 [0009] 目則，應用於銘合金圖案姓刻的喷淋型钮刻液，都是使 用線路板蝕刻銅的藥劑，並非鋁蝕刻專用藥劑。在該種 酸性蝕銅液中，銅離子含量為150£/1，氣離子含量為 2l〇g/l ’該種酸性蝕銅液之ρΗ值為〇 65，溫度為⑽艺， 壓力為3kg/cm2，姓刻時間為3分鐘，在該飯銅液中還含 有添加劑β第三圖係經該種酸性蝕銅液蝕刻之鋁合金之 093136483 表單编號Α0101 第4頁/共29頁 0993183455-0 [0010] [0011] [0012] [0013] [0014] [0015] I 099年 05月 26 孔邊形情況照片，該照片係金相顯微鏡下觀察得到的 電腦掃描照片。由第三圖所示的蝕孔可以看出，採用該 稜酸性蝕銅液蝕刻之鋁合金產品在蝕孔的深度和陽極處 埋後的光澤以及外觀要求均較高的情況下，存在下列問 趄：蝕孔變形嚴重，不美觀；大小孔蝕刻不均勻；蝕刻 迷度慢，側蝕嚴重；蝕孔表面粗糙，蝕刻後，為得到光 兜蝕孔，需增加三次化學拋光處理，陽極處理工藝複雜 ’導致良率降低。 有鑑於此，提供一種使蝕孔光亮完整、蝕刻效率高、生 産成本低之喷淋型鋁合金化學蝕刻液實為必需。 · 【發明内容】 本發明之目的在於提供一種使蝕扎光亮完整、蝕刻致率 向、生産成本低之喷淋型鋁合金化學蝕刻液。 本發明解決技術問題的技術方案為：提供一種噴淋型在呂 合金化學蝕刻液，其組成包括含量為2〇_8〇g/1之鋼離子 、含量為20-160g/l之氯離子、含量為uog/i之氧化 劑及含量為0· l-l〇〇mg/l之表面活性劑。 · 該蝕刻液的pH值範圍爲0.4-1. 2。 該表面活性劑包括壬基紛聚氧乙稀醚和脂肪醇聚氧乙稀 醚等非離子表面活性劑和十二烷基苯磺酸鈉和脂肪醇妒 酸鹽等陰離子表面活性劑。 相較於先前技術，本發明噴淋型化學蝕刻液採用合適的 氧化劑和表面活性劑，經蝕刻、化學抛光的鋁合金餘孔 邊沿光滑、完整 '無變形，且小孔蝕刻速度快，良率上 093136483 表單編號A0101 第5頁/共29頁 0993183455-0 1329138 099年05月26日梭正替換頁j 升，成本降低β 【實施方式】 _6]轉明之噴淋型化學餘刻液為銘合金專用钱刻液，應用 於經過油墨及其他塗層保護銘合金件，喷淋钱刻產生通 孔、盲孔、標識及各種圖案。可應用於手機件、電腦機 ' 相、PDA、DVD、數碼相機等電器產品的外殼、銘牌及其 他鋁合金外觀件等產品。 剛树_喷淋型化學_液巾，_子的含量為 籲 20 80g/l ’最佳含量為6〇g/1，氯離子的含量為 20 160g/l ’最佳含量為8〇g/1，在該蚀刻液中還含有氧 化劑’其含量為卜30g/1，最佳含量為14g/卜表面活性 劑含量為〇.卜io〇mg/卜最佳含量為2〇mg/1，該關液 的PH值範圍為〇.4十2，其中最佳值為〇 7。在使用本發 明喷淋型化學触刻液進行銘合金姓刻時，該侧液的溫 度為15-55°C ’最佳值為35〇c，喷淋壓力範圍為 1. 0-4. 0Kg/cm2，最佳值為3 〇Kg/cm2。 * _]在祕刻液中，鋼離子可通過硫酸銅、氣化銅及其它含 銅的金屬鹽加入，氣離子可通過鹽酸、氣化納、氣化鉀 '氣化銅含氣的金屬鹽加人。氧化劑包含箱酸鹽 、鉻酸鹽、氯酸鹽及其它含氧的氡化酸鹽、雙氧水等一 帛或幾種的組合’表面活性劑包含所有非離子表面活性 劑和陰離衫表面活性射的—種或者幾種的組合非 離子表面活性劑如壬基驗聚氧乙_(〇ίΜ〇)、脂肪醇聚 氧乙稀醚（又名平平加）等，_子型表面活性劑如十二 院基笨橫酸納、脂肪醇硫酸鹽等。本發明餘刻液的印值 093136483 表單編號Α0101 第6頁/共29百 、 Ά 0993183455-0 1329138 099年05月26日修正替換頁 可以用鹽酸和硫酸等無機酸調整連到。 _]本發明噴淋型化學_液之第—實施例為：銅離子含量 ’ 為50g/l ’氣離子含量為70g/：i，鉬酸铵含量為15g/l， 表面活性劑OHO的含量為心的，值為〇 9,温度 為30t，噴淋壓力為3kg/cm2，触刻時間為6〇秒鐘。 圃料閱第四圖’係採用上述喷淋型化學钱刻祕刻銘合 金的钱孔變形情況的金相顯微鏡掃描照片。相較於先前 技術採諸性#銅祕_㉝合金的飢變形情況金相 顯微鏡掃描照片，採用本發明噴淋型化學㈣祕_ 鋁合金對钮孔外觀有明顯改善，钱孔邊沿光滑、完整、零 無變形且光亮。 剛帛U圖及第五心合金祕職之航表面光滑度 對比圖。第五八圖為採用本發明化學钱刻液、經一次化學 拋光、陽極處理後的照片，第五B圖為採用先前技術酸: 钱銅祕刻、-次化學抛光、陽極處理後的照片。在照 片中’較黑的部份為表面凹陷處反光差。通過比較兩圖 可以看出，採用本發明噴淋型化學㈣液鞋刻的紹合金 鲁 的银孔表面光滑’採用先前技術酸性蚀銅液㈣的叙合 金的餘孔表面粗縫'黑色的溝槽較多、反光差大。並: 採用酸性賴工藝钱刻後需四次化學抛光，才能達 用本發明喷淋型化學餘刻工藝钱刻後一次化學抛光的 果〇 攻 [_树时Μ化學_液第二實施例爲 :銅離子含量爲 20g/l氣離子3量爲2〇g/1，氯酸鉀含量爲1&/1，表面 093136483 表單编號A0HH 帛7頁/共29頁 °"3183455~〇 1329138[010001] The invention relates to a spray-type aluminum alloy chemical etching liquid, and more particularly to a method for making a money hole bright and complete, A spray-type aluminum alloy chemical etching solution with a high efficiency and low production cost. [Prior Art] [〇〇〇2] Aluminum is a light metal with a low density and is the most important wire material in the semiconductor process. It has the advantages of low resistance, easy deposition and money engraving. Ming is second only to silver and copper, and is used in the manufacture of various wires. Aluminum has good thermal conductivity and can be used as a variety of heat dissipating materials. Aluminum also has good properties and plasticity, suitable for a variety of pressure processing. [〇〇〇3] In aluminum etching, the chemical reaction dominates the etching process. Increasing the vapor content increases the etching rate, but the etching rate is independent of the ion bombardment. The etching of aluminum is an exothermic reaction, and controlling the surface temperature is important for the residue and for maintaining the integrity of the photoresist. [0004] Since aluminum is easily oxidized to aluminum telluride at a normal temperature, and alumina reacts with gas molecules or atoms, a gas such as trichlorination is often added to remove the parasitic oxide layer in the aluminum etching process. In addition, the three gasification butterfly easily reacts with the water emulsion and oxygen, so it can absorb the moisture and oxygen in the chamber to reduce the formation of alumina. [0005] The surface chemical engraving method is to take a negative film on a desired pattern, form a scar X image on a screen coated with a photosensitive material, and then print the pattern on the surface of the alloy by screen printing, using acid The selection of the property is weak and rot, and the process of anodizing and surface-spraying protective film is used to make the s s cleavage into the aluminum plate. It has an image of '093136483' and can be edited as needed. 3rd S/ It is fruit, resist, can be mass produced n and 29 pages 0993183455-1 1329138 [0006] May 26, 099 revised replacement page production and low cost · #特13⁄4, time system *丨 - '· It is widely used in the decoration industry of refrigerators, refrigerators, elevators, elevators, electrical appliances, furniture, etc., especially in the surface etching of mobile phone panels. In the remaining process, the following _ bad conditions often occur. First, the side button ‘ is also called the side money. The first figure shows the etching principle of the side wall of the wire 2 under the anti-(4)i. The width indicated by A in the figure is the width of the wire on the imaging plate, v is the wire thickness, and X is the ship's volume. The degree of side surname is expressed by the width of the lateral money engraving, which is related to the type of liquid (4), the composition, and the type of art and equipment used. [0007] Secondly, Lin Lin widened and material ^, as shown in the second figure. In the case of the graphic key, the wire width A is increased because the thickness of the metal layer 3 of the key exceeds the thickness of the plating anti-surname layer (not shown), which is called the town layer widening γ. The widening of the bond layer Y is directly related to the thickness of the electric mineral layer (® not shown) and the total thickness of the electric ridge 3, which should be avoided as much as possible in the production. The sum of the metal bond layer and the side money amount X is called the bond layer. The H branch has a bond layer widening, and the clock layer edge is equal to the side silver amount. Lu [0008] The etch rate is expressed by the time required for the etchant to dissolve the depth of the metal per unit time or to dissolve a certain thickness of the metal. [0009] For the purpose, the shower-type button engraving applied to the name of the alloy pattern is a chemical for etching copper using a circuit board, and is not a special agent for aluminum etching. In this kind of acid copper solution, the copper ion content is 150£/1, and the gas ion content is 2l〇g/l 'The acid etched copper liquid has a ρΗ value of 〇65, the temperature is (10) art, and the pressure is 3kg/ Cm2, the last time is 3 minutes, and the additive copper is also contained in the copper liquid. The third figure is the 093136483 of the aluminum alloy etched by the acid etching solution. Form No. 1010101 Page 4 / Total 29 Page 0993183455-0 [0012] [0012] [0015] [0115] May 05, 2009, the photo of the hole-shaped shape, the photo is a computer scan taken under a metallographic microscope. It can be seen from the etched holes shown in the third figure that the aluminum alloy product etched by the etched etched copper solution has the following problems in the case of the depth of the etched holes and the gloss and appearance requirements after burying at the anode.趄: The etched hole is severely deformed and unsightly; the size hole is not uniformly etched; the etching is slow and the side etch is severe; the surface of the etched hole is rough, and after etching, in order to obtain the light hole, three times of chemical polishing treatment is required, and the anode treatment process is performed. Complex 'causes a drop in yield. In view of the above, it is necessary to provide a shower-type aluminum alloy chemical etching solution which makes the etching hole bright and complete, has high etching efficiency, and has low production cost. SUMMARY OF THE INVENTION An object of the present invention is to provide a shower-type aluminum alloy chemical etching solution which is excellent in etching, etching rate, and low production cost. The technical solution of the invention solves the technical problem is: providing a spray type Lu alloy electroless etching liquid, the composition comprising a steel ion having a content of 2〇_8〇g/1, a chloride ion having a content of 20-160g/l, An oxidizing agent having a content of uog/i and a surfactant having a content of 0·ll〇〇mg/l. The pH of the etchant is in the range of 0.4 to 1.2. The surfactant includes a nonionic surfactant such as a mercapto ethoxylate and a fatty alcohol polyoxyethylene ether, and an anionic surfactant such as sodium dodecylbenzenesulfonate and a fatty alcohol phthalate. Compared with the prior art, the spray type chemical etching liquid of the invention adopts a suitable oxidizing agent and a surfactant, and the edge of the etched and chemically polished aluminum alloy has smooth, complete 'no deformation, and the small hole etching speed is fast, and the yield is good.上093136483 Form No. A0101 Page 5 / Total 29 Page 0993183455-0 1329138 On May 26, 099, the shuttle is replacing page j, the cost is reduced by β [Embodiment] _6] The sprayed chemical remnant of Mingming is Ming alloy Special money engraving solution is applied to protect the alloy parts by ink and other coatings. The spray money is used to produce through holes, blind holes, signs and various patterns. It can be applied to the outer casing, nameplate and other aluminum alloy appearance parts of mobile phone parts, computer parts, PDA, DVD, digital camera and other electrical products. Gangshu_spray type chemical_liquid towel, the content of _ sub is 20 80g / l 'the best content is 6〇g / 1, the chloride ion content is 20 160g / l 'the best content is 8〇g / 1, the etchant further contains an oxidant' content of 30g / 1, the optimum content of 14g / b surfactant content is 〇. io 〇 mg / Bu optimal content is 2 〇 mg / 1, the The pH of the shut-off liquid ranges from 〇.4 to 12, with the best value being 〇7. 0 0. 0Kg 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 /cm2, the best value is 3 〇Kg/cm2. * _] In the secret engraving solution, steel ions can be added through copper sulfate, vaporized copper and other copper-containing metal salts. The gas ions can be used to vaporize copper-containing metal salts through hydrochloric acid, gasified sodium and vaporized potassium. add people. The oxidant comprises a combination of a tank salt, a chromate, a chlorate and other oxygenated bismuth hydride, hydrogen peroxide, etc. The surfactant comprises all nonionic surfactants and a smear surface active shot. a combination of one or several kinds of nonionic surfactants such as fluorenyl polyoxyethylene _ (〇ίΜ〇), fatty alcohol polyoxyethylene ether (also known as Pingping), _ subtype surfactant such as ten The second hospital is a bit of a sulphate, a fatty alcohol sulfate, and the like. The printing value of the residual liquid of the present invention 093136483 Form No. Α0101 Page 6 / Total 29, Ά 0993183455-0 1329138 Correction replacement page of May 26, 099 It can be adjusted by using inorganic acid such as hydrochloric acid and sulfuric acid. _] The spray type chemistry of the present invention - the example is: copper ion content '50g / l 'gas ion content is 70g /: i, ammonium molybdate content is 15g / l, surfactant OHO content For the heart, the value is 〇9, the temperature is 30t, the spray pressure is 3kg/cm2, and the etch time is 6 〇 seconds. In the fourth picture, we use the above-mentioned spray-type chemical money to engrave the metallographic microscope scan of the gold hole deformation. Compared with the metallographic microscope scan of the hunger deformation of the previous technology, the copper chemistry of the copper secret _33 alloy, the spray type chemistry (4) secret _ aluminum alloy has obvious improvement on the appearance of the buttonhole, and the edge of the money hole is smooth and complete. , zero distortion and light. The comparison of the smoothness of the surface of the U-picture and the fifth-heart alloy. The fifth figure is a photograph of the chemical engraving liquid of the present invention, after one chemical polishing and the anode treatment, and the fifth drawing B is a photograph of the prior art acid: money copper secret engraving, - secondary chemical polishing, and anodizing treatment. In the photo, the darker portion is the difference in reflection at the surface depression. By comparing the two figures, it can be seen that the surface of the silver hole of the Shaolu Lu, which is engraved by the spray type chemical (four) liquid shoe of the present invention, is smooth. The prior surface of the acid etching copper solution (four) is the surface of the residual hole of the alloy. There are many slots and the difference in reflection is large. And: After using the acid-based process, it takes four times of chemical polishing to achieve the effect of the chemical polishing process of the spray-type chemical remnant process of the present invention. [The second embodiment of the tree-time chemical _ liquid is : Copper ion content is 20g / l gas ion 3 amount is 2〇g / 1, potassium chlorate content is 1 & / 1, surface 093136483 Form No. A0HH 帛 7 pages / Total 29 pages ° "3183455~〇1329138
[^99年05月26日修正雜頁I 活性劑0P —10的含量爲〇. lmg/1，pH值爲〇. 4，溫度爲15 C ’喷淋塵力爲ikg/cm2，蝕刻時間爲160秒鐘。 []採用本發明第一實施例的喷淋型铭合金化學姓刻液银刻 紹合金的银孔變形情況的金相顯微鏡掃描照片如第六圖 所不，其採用本發明第二實施例的化學蝕刻液、經—次 化學抛光、陽極處理後的照片如第七圖所示。 [0024]本發明喷淋型化學蝕刻液第三實施例爲：銅離子含量爲 8〇g/l，乳離子含量爲igOg/l，氧化劑銦酸錄含量爲 3〇g/l，表面活性劑十二烷基苯磺酸鈉的含量爲1〇〇mg/i ,PH值爲1.2，溫度爲55〇C，喷淋壓力爲4kg/cm2，蝕刻 時間爲5 0秒鐘。 [0025]才采用本發明第三實施例的喷淋型铭合金化學飯刻液钱刻 鋁合金的蝕孔變形情況的金相顯微鏡掃描照片如第八圖 所不，其採用本發明第三實施例的化學蝕刻液、經—次 化學拋光、陽極處理後的照片如第九圖所示。 隹 [0026]本發明喷淋型化學蝕刻液第四實施例（也是最佳實施例 )爲：銅離子含量爲6〇g/l，氣離子含量爲8〇g/1，氧化 劑鉬酸銨含量爲14g/l ’表面活性劑op-io的含量爲 2〇mg/l ’ PH值爲〇. 7，溫度爲35°C，噴淋麼力爲 3kg/cm2，蝕刻時間爲60秒鐘。 [0027]採用本發明第四實施例的噴淋型鋁合金化學蝕刻液蝕刻 鋁合金的蝕孔變形情況的金相顯微鏡掃描照片如第十圖-所示，其採用本發明第四實施例的化學钱刻液、經一欠 化學拋光、陽極處理後的照片如第十一圖所示。 093136483 表單編號A0101 第8頁/共29頁 0993183455-0 1329138 099年05月26日後正替換頁 [0028] 對比採用本發明第二、第三、第四實施例时淋型銘合 金化學蝕刻液、經一次化學抛光、陽極處理後之照片， 如第七圖、第九圖、第十一圖所示，可以看出，採用本 發明第四實施例的侧液㈣處理後㈣孔表面光滑度 取好。對比第六®、H、第十圖所示的金相顯微鏡 掃描照片可以看出，第十圖所示之照片中，钱孔光亮且 變形最小’蝕孔邊沿光滑、完整。 [0029] 本發明喷淋型化學ϋ刻液中的氧化劑及表面活性劑是必 要組份’ Α說明言玄兩種物質的作用，特做對比實施例如 下：在該對比實施例配方中，銅離子含量為50§/1，氯離 子含量為70g/卜pH值為〇 7，溫度為3(rc，喷淋壓力為 3kg/cm2，噴淋時間12〇秒鐘。該對比實施例中不含氧化 劑及表面活性劑〇經該對比實施例配方_舰姓刻的 鋁合金的蝕孔變形情況金相顯微鏡掃描照片，如第十二 圖所不。與第四㈣比可以看出’採用合適的氧化劑和 表面活性劑的蝕刻液蝕刻的鋁合金的蝕孔外觀，相較於 採用未加氧化跡表面活性劑的㈣祕刻的效果好， 外觀較完美。 [0030] 將本發明第-、第二、第三、第四實施例姓刻液與先前 技術以及對比實施例的配方（與第一實施例對比）以及測 試資料對比如表1所示。其中對比實施例係與本發明第一 實施例對比之未加氧化劑及表面活性劑之配方，L1表示 〇.4mm孔徑的姓孔深度，L2表示l〇mm孔徑的姓孔深度， 孔深用螺旋測厚儀測試’孔徑用投影儀測試。其中L2/L1 越小，就表示不同孔徑處的蝕孔深度越接近，表示蝕孔 093136483 表單编號A0101 第9頁/共29頁 0993183455-0 1329138 __ 099年05月26日修正替換頁 的均勻性越好。 [0031]表 1[^99年05月26日修正# I active agent 0P-10 content is 〇. lmg/1, pH value 〇. 4, temperature is 15 C 'spray dust force is ikg/cm2, etching time is 160 seconds. [] A metallographic microscope scan image of the silver hole deformation of the spray-type alloy alloy chemically engraved silver engraved alloy according to the first embodiment of the present invention is as shown in the sixth drawing, which adopts the second embodiment of the present invention. Photographs of chemical etching solution, chemical polishing, and anodizing are shown in the seventh figure. [0024] The third embodiment of the spray type chemical etching solution of the present invention is: copper ion content is 8 〇g / l, milk ion content is igOg / l, oxidant indium acid content is 3 〇 g / l, surfactant The sodium dodecylbenzenesulfonate content was 1 〇〇mg/i, the pH was 1.2, the temperature was 55 〇C, the spray pressure was 4 kg/cm2, and the etching time was 50 seconds. [0025] The metallographic microscope scan image of the corrosion deformation of the aluminum alloy of the spray-type alloy etched in the third embodiment of the present invention is as shown in the eighth figure, which adopts the third embodiment of the present invention. The photographs of the chemical etching solution, the chemical polishing, and the anodizing are shown in the ninth figure.第四 [0026] The fourth embodiment of the spray type chemical etching solution of the present invention (also a preferred embodiment) is: copper ion content of 6 〇g / l, gas ion content of 8 〇 g / 1, oxidant ammonium molybdate content It is 14 g / l 'the surfactant op-io content is 2 〇 mg / l ' PH value 〇. 7, the temperature is 35 ° C, the spray force is 3 kg / cm 2 , the etching time is 60 seconds. [0027] A metallographic microscope scan photograph of the etching of the aluminum alloy by the spray-type aluminum alloy chemical etching solution according to the fourth embodiment of the present invention is shown in FIG. 10, which adopts the fourth embodiment of the present invention. Photographs of chemical money engraving, after chemical polishing, and anodizing are shown in Figure 11. 093136483 Form No. A0101 Page 8 of 29 0993183455-0 1329138 After May 26, 2009, the replacement page [0028] comparing the second, third, and fourth embodiments of the present invention, the etched alloy chemical etching solution, After a chemical polishing and anodic treatment, as shown in the seventh, ninth, and eleventh drawings, it can be seen that the smoothness of the surface of the (four) hole is treated by the side liquid (four) of the fourth embodiment of the present invention. it is good. Comparing the metallographic microscope scans shown in the sixth, H, and tenth figures, it can be seen that in the photograph shown in the tenth figure, the money hole is bright and the deformation is minimal, and the edge of the etched hole is smooth and complete. [0029] The oxidizing agent and surfactant in the spray type chemical engraving liquid of the present invention are the necessary components ' Α 言 言 玄 玄 两种 两种 两种 两种 两种 , , , , , , , 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种 两种The ion content is 50 §/1, the chloride ion content is 70 g/bu, the pH value is 〇7, the temperature is 3 (rc, the spray pressure is 3 kg/cm2, and the shower time is 12 〇 seconds. This comparative example does not contain The oxidant and the surfactant are scanned by the metallographic microscope of the corrosion deformation of the aluminum alloy in the formulation of the comparative example, as shown in the twelfth figure. Compared with the fourth (four), it can be seen that The appearance of the etched hole of the etched liquid of the oxidizing agent and the surfactant is better than that of the (4) secret film using the unoxidized surfactant, and the appearance is perfect. [0030] 2. The third and fourth embodiments of the surname engraving and the prior art and the formulation of the comparative example (compared with the first embodiment) and the test data pair are shown in Table 1. The comparative embodiment is the first embodiment of the present invention. Example comparison without oxidant and surface Formula of the agent, L1 represents the depth of the hole of the 4mm aperture, L2 represents the depth of the hole of the aperture of l〇mm, and the depth of the hole is tested by a spiral thickness gauge. The aperture is tested with a projector. The smaller the L2/L1 is, the smaller the L2/L1 is. Indicates that the closer the depth of the etch holes at different apertures is, the etched holes 093136483 Form No. A0101 Page 9 / Total 29 Pages 0993183455-0 1329138 __ On May 26, 2008, the uniformity of the replacement page is corrected. [0031] 1
第一 實施例 對比 實施例 第二 實施例 第三 實施例 第四 實施例 現有技 術 銅離子 含量 (g/1) 50 50 20 80 60 150 氣離子 含量 (g/1) 70 70 20 160 80 210 鉬酸敍 (g/1) 15 0 一 30 14 0 氯酸鉀 (g/1) — — 1 一 一 一 ΟΡ-ΙΟ (mg/ 1 ) 15 0 0. 1 20 0 十二烷 基苯磺 酸鈉 (g/1) 100 溫度（ °〇 30 30 15 55 35 30 pH值 0. 9 0. 8 0. 4 1.2 0.7 0.65 壓力 3 3 1 4 3 3 表單編號A0101 第10頁/共29頁 0993183455-0 093136483 1329138 099年05月26日修正替換頁 (kg/c 2n m ) 時間（ 秒） 60 60 160 50 60 60 0. 4ram 孔徑之 孔深 (ram Li> 0. 182 0.17 0. 19 0.216 0. 202 0. 07 J 0. 4mm 孔徑之 擴孔 (mm) 0. 085 0.095 0.096 0.091 0.076’ 0. 4mm 孔徑之 孔深/ 擴孔 2. 1 1.4 2 2. 25 2. 22 0. 92 _i 0. 4mm 孔徑之 側钮 小 较大 小 較小 較小 \ 大 1 0mm 孔徑之 孔深 (mm V 0. 201 0. 22 0. 225 0. 263 0. 214 0. 42 L2/Ll 1.1 1.3 1.18 1. 22 1.06 6 表單編號A0101 第11頁/共29頁 0993183455-0 093136483 1329138First Embodiment Comparative Example Second Embodiment Third Embodiment Fourth Embodiment Prior Art Copper ion content (g/1) 50 50 20 80 60 150 Gas ion content (g/1) 70 70 20 160 80 210 Molybdenum Acidity (g/1) 15 0 - 30 14 0 Potassium chlorate (g/1) — — 1 一 ΟΡ-ΙΟ (mg/ 1 ) 15 0 0. 1 20 0 Sodium dodecyl benzene sulfonate (g /1) 100 Temperature ( °〇30 30 15 55 35 30 pH 0. 9 0. 8 0. 4 1.2 0.7 0.65 Pressure 3 3 1 4 3 3 Form No. A0101 Page 10 of 29 0993183455-0 093136483 1329138 Correction replacement page (kg/c 2n m ) time (seconds) on May 26, 099 60 60 160 50 60 60 0. 4ram Hole depth of aperture (ram Li) 0. 182 0.17 0. 19 0.216 0. 202 0. 07 J 0. 4mm Reaming of the hole diameter (mm) 0. 085 0.095 0.096 0.091 0.076' 0. 4mm Hole depth of the hole / Reaming 2. 1 1.4 2 2. 25 2. 22 0. 92 _i 0. 4mm Aperture Side button small larger small smaller smaller \ large 1 0mm hole depth (mm V 0. 201 0. 22 0. 225 0. 263 0. 214 0. 42 L2/Ll 1.1 1.3 1.18 1. 22 1.06 6 form No. A0101 Page 11 of 29 0993183 455-0 093136483 1329138
099年05月26日核正替換頁 蝕刻均 勻性 好 差 好 好 較好 很差 蝕孔變 形 小 大 小 小 小 大 一次抛 光/陽 極處理 後的小 孔光澤 好 差 好 較好 較好 差 表中的蝕孔變形與一次化學拋光/陽極處理後的小孔光澤 係由金相顯微鏡掃描照片觀察得到。並且在蝕刻實驗過 程中發現：採用本發明化學蝕刻液蝕刻的鋁合金，側蝕 減少為先前技術的50%，且對於0. 4mm孔徑圓孔的蝕刻速 度為先前技術的3倍，提高了蝕刻效率；並且對於不同尺 寸小孔蝕刻速度的差異明顯減小，對於先前技術的酸性 蝕銅液蝕刻來說，大孔徑的圓孔蝕刻速度較快，小孔徑 的圓孔钱刻速度較慢，例如1 Omm孔徑的圓孔钮刻速度約 為0. 4mm孔徑圓孔蝕刻速度的六倍，這不利於工業應用， 而採用本發明的化學蝕刻液蝕刻的不同尺寸小孔的蝕刻 速度差異不大，減小到10%，蝕刻速度大體接近，這增加 了工藝的應用範圍，有利於工業應用。 [0033] 因此，本發明喷淋型化學蝕刻液針對鋁合金的特點，對 蝕刻液進行了如下方面的改進： [0034] (1)確定了最佳的銅離子和氣離子的含量範圍； [0035] (2)選擇了合適的氧化劑； 093136483 表單编號A0101 苐12頁/共29頁 0993183455-0 1329138 099年05月26日修正替換頁 [0036] (3)選擇了合適的表面氧化劑。 [0037] 從實驗對比可以看出，採用本發明的喷淋型化學蝕刻液 具有以下優點：蝕孔變形小，蝕孔面較平滑，蝕刻後處 理蝕孔，易得到光亮的陽極處理效果，且陽極工藝簡單 ，小孔蝕刻速度快，蝕刻均勻性好。 [0038] 綜上所述，本發明確已符合發明專利之要件，爰依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，本發明之範圍並不以上述實施方式為限，舉凡熟習 本案技藝之人士援依本發明之精神所作之等效修飾或變 化，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 [0039] 第一圖係側蝕產生的原理圖。 [0040] 第二圖係鍍層增寬與鍍層突沿產生的原理圖。 [0041] 第三圖係先前技術酸性蝕銅液蝕刻鋁合金的蝕孔變形情 況金相顯微鏡掃描照片。 [0042] 第四圖係採用本發明喷淋型化學蝕刻液蝕刻鋁合金的蝕 孔變形情況的金相顯微鏡掃描照片。 [0043] 第五A圖係採用本發明第一實施例喷淋型化學蝕刻液、經 一次化學抛光、陽極處理後的蝕孔表面光滑度照片。 [0044] 第五B圖係採用現有技術酸性蝕銅液、經一次化學抛光、 陽極處理後的蝕孔表面光滑度照片。 [0045] 第六圖係採用本發明第二實施例喷淋型化學蝕刻液蝕刻 鋁合金的蝕孔變形情況的金相顯微鏡掃描照片。 093136483 表單编號A0101 第13頁/共29頁 0993183455-0 1329138 _^ 099年05月26日核正替换頁 [0046] 第七圖係採用本發明第二實施例噴淋型化學蝕刻液、經 一次化學拋光、陽極處理後的蝕孔表面光滑度照片。 [0047] 第八圖係採用本發明第三實施例噴淋型化學蝕刻液蝕刻 鋁合金的蝕孔變形情況的金相顯微鏡掃描照片。 [0048] 第九圖係採用本發明第三實施例喷淋型化學蝕刻液、經 ' 一次化學抛光、陽極處理後的蝕孔表面光滑度照片。 [0049] 第十圖係本發明第四實施例喷淋型化學蝕刻液蝕刻鋁合 金的蝕孔變形情況的金相顯微鏡掃描照片。 [0050] 第十一圖係採用本發明第四實施例喷淋型化學蝕刻液、 經一次化學抛光、陽極處理後的蝕孔表面光滑度照片。 [0051] 第十二圖係經對比實施例蝕刻液蝕刻的鋁合金的蝕孔變 形情況金相顯微鏡掃描照片。 【主要元件符號說明】 093136483 表單編號A0101 第14頁/共29頁 0993183455-0On May 26, 099, the replacement of the page is good, the etching uniformity is good, the difference is good, the difference is very poor, the deformation of the hole is small, the small size is small, the polishing after the anodizing is good, the gloss is good, and the etch is better. The pore deformation and the pore gloss after one chemical polishing/anodizing treatment were observed by a metallographic microscope scanning photograph. And during the etching experiment, it was found that the aluminum alloy etched by the chemical etching solution of the present invention reduced the side etching to 50% of the prior art, and the etching speed for the 0. 4 mm aperture round hole was three times that of the prior art, and the etching was improved. Efficiency; and the difference in etching speed of small holes for different sizes is significantly reduced. For the prior art acid etching copper etching, the large hole diameter etching speed is faster, and the small hole diameter is slower, for example, 1 Omm aperture round hole button engraving speed is about 0. 4mm aperture round hole etching speed six times, which is not conducive to industrial applications, and the etching speed of different size holes etched by the chemical etching liquid of the invention is not much difference, By reducing it to 10%, the etching rate is generally close, which increases the range of applications of the process and is advantageous for industrial applications. [0033] Therefore, the spray type chemical etching liquid of the present invention is improved on the etching liquid according to the characteristics of the aluminum alloy: [0034] (1) determining the optimum range of copper ions and gas ions; [0035] (2) The appropriate oxidant was selected; 093136483 Form No. A0101 苐12 pages/Total 29 pages 0993183455-0 1329138 Modified on May 26, 099 [0036] (3) A suitable surface oxidant was selected. [0037] It can be seen from the experimental comparison that the spray type chemical etching liquid of the present invention has the following advantages: the etching hole is small in deformation, the etching surface is smooth, and the etching hole is treated after etching, so that a bright anode treatment effect is easily obtained, and The anode process is simple, the small hole etching speed is fast, and the etching uniformity is good. [0038] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only the preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make equivalent modifications or changes in accordance with the spirit of the present invention. It should be covered by the following patent application. [Simple Description of the Drawings] [0039] The first figure is a schematic diagram of the generation of side etching. [0040] The second figure is a schematic diagram of the plating broadening and the plating edge. [0041] The third figure is a photograph of a metallographic microscope scan of the etched hole of the prior art acid etched copper etched aluminum alloy. [0042] The fourth figure is a metallographic microscope scan photograph of the etching deformation of the aluminum alloy by the spray type chemical etching solution of the present invention. [0043] Fig. 5A is a photograph showing the surface smoothness of the etched hole after the primary chemical polishing and the anodic treatment using the spray type chemical etching solution of the first embodiment of the present invention. [0044] The fifth B is a photograph of the surface smoothness of the etched holes after the prior art acid etched copper solution, after one chemical polishing and anodic treatment. [0045] The sixth drawing is a metallographic microscope scanning photograph of the etching deformation of the aluminum alloy by the spray type chemical etching solution of the second embodiment of the present invention. 093136483 Form No. A0101 Page 13 of 29 0993183455-0 1329138 _^ May 26, 2017, Nuclear Replacement Page [0046] The seventh figure is a spray type chemical etching solution according to the second embodiment of the present invention. Photograph of the surface smoothness of the etched holes after a chemical polishing and anodization. The eighth drawing is a metallographic microscope scanning photograph of the etching deformation of the aluminum alloy by the spray type chemical etching solution of the third embodiment of the present invention. [0048] The ninth drawing is a photograph of the surface smoothness of the etched hole after the first chemical polishing and the anodic treatment using the spray-type chemical etching solution of the third embodiment of the present invention. [0049] The tenth photograph is a metallographic microscope scanning photograph of the etching deformation of the aluminum alloy in the spray type chemical etching liquid according to the fourth embodiment of the present invention. [0050] The eleventh drawing is a photograph of the surface smoothness of the etched hole after the primary chemical polishing and the anodic treatment using the spray type chemical etching solution of the fourth embodiment of the present invention. Fig. 12 is a photograph of a metallographic microscope scan of an etched liquid etched aluminum alloy by a comparative example. [Main component symbol description] 093136483 Form No. A0101 Page 14 of 29 0993183455-0