201137177 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種退除基材表面碳化鈦及氮化鈦膜層之溶 液及利用該溶液退除碳化鈦及氮化鈦膜層之方法。 【先前技術】 [0002] 鍍膜工藝在工業領域有著廣泛之應用。然，通常在以下 兩種情況下需要對鍍膜進行退除：經過長期使用後 ，工件表面之鐘膜已經被損傷或者嚴重老化，從而需要 去除鍍層，重新鍍覆；（2)在生產中，所鍍覆之鍍層不 符合品質要求’為減少损失，節約成本，需要退掉錢層 ，讓工件返工重新鍍膜。故，如何在不損傷基材之情況 下’將鍍層從基材表面完全除去係工業生產中之—個重 要問題。 [0003] 碳化鈦（TiC)及氮化鈦（TiN)膜層具有很強之抗氧化 、抗腐蝕性，而且硬度高、韌性強，彳匕學穩定性佳，对 磨性能優良，在工業領域具有廣闊之前景'然，目前尚 未有一種能夠在不損傷基材之情丨況下，穩定、有效地退 除碳化鈦或氮化鈦膜層之溶液及方法。 【發明内容】 [0004] 有鑒於此，有必要提供一種不易損傷基材，且能穩定、 有效地退除碳化鈦及氮化欽膜層之退除液。 [0005] 另外，還有必要提供一種使用上述退除液退除碳化鈦及 氮化欽膜層之方法。 [0006] 一種碳化鈦及氮化鈦膜層之退除液，該退除液為含有酸 099113802 表單編號A0101 第4頁/共12頁 0992024315-0 201137177 及加速劑、促進劑及緩敍劑之水溶液，其中所述酸為有 機酸或無機酸，該酸之濃度為90〜1〇〇〇g/L ;該加速劑為 含氟離子之酸或者鹽，該加速劑之濃度為7〇〜50〇g/L ; 該促進劑為醇胺類有機化合物，該促進劑之濃度 15〜200g/L ;該緩钱劑為硫脲、硫脲之衍生物及尿素中 之一種或者幾種之組合，該緩蝕劑之濃度為2〜8g/L。 [0007] 一種碳化鈦及氮化鈦膜層之退除方法，包括將碳化鈦或 氮化欽膜層與退除液接觸，其中該退除液為本發明之上 述退除液。 [0008] 相較於習知技術，所述碳化鈦及氮化鈦膜層之退除液及 退除方法使退膜後基材表面沒有受到腐钱，且能穩定、 有效地退除破化鈦及氮化欽膜層。 【實施方式】 [0009] 本發明之退除液適用於退除形成於基材表面之碳化鈦及 氮化鈦膜層。所述基材包括鐵基合.金、(.銅:、銅合金及塑 膠。 [0010] 本發明之退除液為含有酸及加速劑、促進劑及緩蝕劑之 水溶液。其中所述酸可為能夠提供氫離子之有機酸或無 機酸’例如，可為硫酸、醋酸、擰檬酸及乳酸等酸中之 一種或幾種之混合物’優選為硫酸。該酸之濃度可為 90〜 1 000g/L，優選為90~75〇g/L。 [0011] 所述加速劑起促進碳化鈦及氮化鈦膜層中金屬離子溶解 之作用。該加速劑可為含氟離子之酸或者鹽等化合物， 比如可為氫氟酸、氟化氫銨、氟化鈉、氟化鉀、氟硼酸 099113802 表單編號A0101 第5頁/共12頁 0992024315-0 201137177 鈉及敦結酸料化合物中之—種或者幾種之混合物，優 選為氫氟酸及/或氟化氫錢。加速劑之濃度可為 70〜500g/L ’ 優選為75〜30〇g/L。 [0012] [0013] [0014] [0015] [0016] [0017] 所述促進劑在紐液巾_低⑽介面張力，輔助膜層 溶解’並且促魏料*轉透之細。該促進劑為醇 胺類有機物中能與鈦結合之化合物，如三乙醇胺、一乙 醇胺及二乙醇胺等’其可為以上化合物中之—種或幾種 之混合物，優選為三乙醇胺。促進劑之濃度為 15〜2〇〇g/L，優選為3〇〜8〇g/L。 所述緩ϋ劑在退除液巾起保護基材免受酸之腐姓之作用 么緩餘劑可為UL之衍生物及尿素巾之-種或者 之混〇物，優選為硫脲及其衍生物。緩蝕劑之濃度 為2~8g/L ’優選為3〜5g/L。 除液可以藉由將上述酸、加速劑、促進劑及缓蝕劑 溶於水製得。 "： ;·,：： 利用上述退除液退除基材上之碳化鈦及氮化鈦膜層之方 j L括，將形成有碳化鈦或氮化鈦膜層之基材與該退除 觸以使該碳化欽或氮化鈥膜層完全退除。所述接 觸方式包括浸泡及喷淋。接觸時退除液之溫度為20-30T： 、奏觸時間為〇, 5〜2小時。基材與退除液接觸後，將基材 進行洗滌及乾燥。 、藉由實施例對本發明進一步詳細說明。 實施例1 099113802 表單編號A0101 第6頁/共12頁 0992024315-0 201137177 [0018] 1.配製退除液 [0019] 取500ml去離子水，向去離子水中加入50ml重量濃度為 98%之硫酸，再加入5g硫脲，攪拌至硫脲完全溶解後，加 入200ml重量百分比濃度為40%之氫氟酸溶液及50ml重量 百分比濃度為80%三乙醇胺，最後補去離子水使溶液體積 為1 000ml，得到退除液。該退除液中，硫酸之濃度為 90. 16g/L，氫氟酸之濃度為90. 4g/L，三乙醇胺之濃度 為40.8g/L 。 [0020] 2.退除碳化鈦及/或氮化鈦膜層 [0021] 取不銹鋼基材表面形成有碳化鈦或氮化鈦膜層之樣品若 干個，該碳化鈦或氮化鈦膜層之厚度大約為2/zm。將樣 品完全浸入到25°C之上述退除液中浸泡1.5小時，退除碳 化鈦或氮化鈦膜層。取出樣品，用水清洗乾淨後烘乾。 [0022] 實施例2 [0023] 1.配製退除液 〇 [0024] 取500ml去離子水，向去離子水中加入55ml重量濃度為 98%之硫酸，再加入5g硫脲，攪拌至硫脲完全溶解後，加 入175ml重量百分比濃度為40%之氫氟酸溶液及55ml重量 百分比濃度為80%之三乙醇胺溶液，最後補去離子水使溶 液體積為1000ml，得到退除液。該退除液中，硫酸之濃 度為99. 18g/L，氫氟酸之濃度為79. llg/L，三乙醇胺 之濃度為44. 88g/L。 [0025] 2.退除膜層 099113802 表單編號A0101 第7頁/共12頁 0992024315-0 201137177 [0026] 取不錄鋼基材表面形成有碳化鈦或氮化鈦膜層之樣品若 干個，該碳化鈦或氮化鈦膜層之厚度大約為1.5/zm。將 樣品完全浸入到室溫下之上述退除液中浸泡1小時，退除 碳化欽或氮化鈦膜層。取出樣品，用水清洗乾淨後烘乾 〇 [0027] 實施例3 [0〇28] 1.配製退除液 [〇〇29]取5〇〇ml溫度為5(TC左右之去離子水，將4〇〇§氟化氫銨 及5 g硫脲溶解於去離子水中，然後加入4〇 〇m丨重量百分比 濃度為36%之醋酸溶液及2〇ml重量百分比濃度為8〇%之三 乙醇胺溶液’再加去離子水使溶液體積至1〇〇〇ml，得到 退除液。該退除液中’醋酸之濃度為145g/L，三乙醇胺 之濃度為16. 32g/L。 [0030 ] 2.退除膜層 _]取不錄鋼基材表面形成有碳化欽或氮化欽膜層之樣品若 干個’該碳化欽或氮化鈦膜層之厚度大約為2。將樣 品完全浸入到室溫下之上述配製得退除液中浸泡2小時， 退除碳化鈦或氮化鈦骐層。取出樣品，用水清洗乾淨後 烘乾。 [0032] 實施例4-6 [0033] A別按照實施例1-3中所述之方法配製退除液，不同之處 為，將實施例1-3中之不銹鋼基材用銅基材代替，分別與 實施例卜3之相同條件下進行退膜。 099113802 表單編號A0101 第8 胃/共12頁 0992024315-0 201137177 [0034] 將上述實施例1至實施例6中退除膜層後之樣品作X射線繞 射（X-RD)分析，均未發現Ti元素存在，證明膜層完全退 除；將退除膜層後之樣品進行掃描電鏡（SEM)試驗，發現 基材均沒有受到腐蝕。 【圖式簡單說明】 【主要元件符號說明】 〇 0992024315-0 099113802 表單編號A0101 第9頁/共12頁201137177 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a solution for removing a titanium carbide and a titanium nitride film layer on a surface of a substrate and using the solution to remove titanium carbide and a titanium nitride film layer method. [Prior Art] [0002] The coating process has a wide range of applications in the industrial field. However, the coating is usually removed in the following two cases: after long-term use, the film on the surface of the workpiece has been damaged or severely aged, which requires removal of the coating and re-plating; (2) in production, The plating plating does not meet the quality requirements. In order to reduce losses and save costs, it is necessary to retreat the money layer and rework the workpiece. Therefore, how to completely remove the plating layer from the surface of the substrate without damaging the substrate is an important problem in industrial production. [0003] Titanium carbide (TiC) and titanium nitride (TiN) coatings have strong resistance to oxidation and corrosion, high hardness, high toughness, good dropout stability, excellent grinding performance, and industrial fields. It has a broad prospect. However, there is currently no solution or method for stably and effectively removing the titanium carbide or titanium nitride film layer without damaging the substrate. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a retreating liquid which is less likely to damage a substrate and which can stably and efficiently remove titanium carbide and a nitride film. Further, it is also necessary to provide a method of removing titanium carbide and a nitrided film layer using the above-mentioned withdrawal liquid. [0006] A titanium carbide and titanium nitride film layer retreating liquid, the replenishing liquid containing acid 099113802 Form No. A0101 Page 4 / 12 pages 0992024315-0 201137177 and accelerator, accelerator and retardant An aqueous solution, wherein the acid is an organic acid or a mineral acid, and the concentration of the acid is 90 to 1 〇〇〇g/L; the accelerator is a fluoride-containing acid or a salt, and the accelerator has a concentration of 7 〇 50 50 〇g/L; the accelerator is an alcohol amine organic compound, the accelerator concentration is 15~200g/L; the smoky agent is one or a combination of thiourea, thiourea derivative and urea, The concentration of the corrosion inhibitor is 2 to 8 g/L. [0007] A method for removing titanium carbide and a titanium nitride film layer, comprising contacting a titanium carbide or a nitride film with a withdrawal liquid, wherein the withdrawal liquid is the above-mentioned withdrawal liquid. [0008] Compared with the prior art, the retreating liquid and the removing method of the titanium carbide and titanium nitride film layer make the surface of the substrate after the film is not rotted, and can stably and effectively remove the cracking. Titanium and nitrided film. [Embodiment] The retreating liquid of the present invention is suitable for removing the titanium carbide and titanium nitride film layers formed on the surface of a substrate. The substrate comprises iron-based gold, (.copper:, copper alloy, and plastic. [0010] The withdrawal liquid of the present invention is an aqueous solution containing an acid and an accelerator, an accelerator, and a corrosion inhibitor. It may be an organic acid or a mineral acid capable of providing a hydrogen ion, for example, a mixture of one or more of an acid such as sulfuric acid, acetic acid, citric acid, and lactic acid, preferably sulfuric acid. The concentration of the acid may be 90 to 1 000g/L, preferably 90~75〇g/L. [0011] The accelerator acts to promote dissolution of metal ions in the titanium carbide and titanium nitride film layers. The accelerator may be an acid or a salt containing fluorine ions. Such compounds, for example, may be hydrofluoric acid, ammonium hydrogen fluoride, sodium fluoride, potassium fluoride, fluoroboric acid 099113802 Form No. A0101 Page 5 / Total 12 pages 0992024315-0 201137177 Sodium and Dunnic acid compounds - or A mixture of several, preferably hydrofluoric acid and/or hydrogen fluoride. The concentration of the accelerator may be 70 to 500 g/L 'preferably 75 to 30 g/L. [0012] [0015] [0017] [0017] The accelerator in the New Liquid Towel _ low (10) interface tension, the auxiliary film layer dissolves 'and promotes the material * The promoter is a compound capable of binding to titanium in an alcohol amine-based organic substance, such as triethanolamine, monoethanolamine, diethanolamine, etc., which may be a mixture of the above compounds or a mixture of several, preferably three The concentration of the accelerator is 15~2〇〇g/L, preferably 3〇~8〇g/L. The buffering agent protects the substrate from the acid rot in the liquid towel. The retarding agent may be a mixture of a UL derivative and a urea towel, preferably a thiourea and a derivative thereof, and the concentration of the corrosion inhibitor is 2 to 8 g/L', preferably 3 to 5 g/L. The liquid removal can be obtained by dissolving the above acid, accelerator, accelerator and corrosion inhibitor in water. ": ;·,:: Using the above-mentioned withdrawal liquid to remove the titanium carbide and titanium nitride film on the substrate The layer j L includes a substrate on which a titanium carbide or titanium nitride film layer is formed and the retreat touches to completely remove the carbonized or tantalum nitride film layer. The contact manner includes soaking and spraying. The temperature of the withdrawal liquid at the time of contact is 20-30T: The contact time is 〇, 5~2 hours. After the substrate is in contact with the withdrawal liquid, the substrate is washed and dried. The present invention will be further described in detail by way of examples. Example 1 099113802 Form No. A0101 Page 6 / Total 12 Page 0992024315-0 201137177 [0018] 1. Preparation of withdrawal liquid [0019] Take 500ml of deionized water, go Add 50ml of sulfuric acid with a concentration of 98% sulfuric acid to the ionic water, add 5g of thiourea, stir until the thiourea is completely dissolved, add 200ml of a 40% by weight hydrofluoric acid solution and 50ml of a concentration of 80% triethanolamine. Finally, the ionized water was added to make the volume of the solution 1 000 ml, and a withdrawal liquid was obtained. The concentration of sulfuric acid was 90.16 g/L, the concentration of hydrofluoric acid was 90.4 g/L, and the concentration of triethanolamine was 40.8 g/L. [0020] 2. Retreat the titanium carbide and/or titanium nitride film layer [0021] Take a sample of the surface of the stainless steel substrate formed with a titanium carbide or titanium nitride film layer, the titanium carbide or titanium nitride film layer The thickness is approximately 2/zm. The sample was completely immersed in the above-mentioned withdrawal liquid at 25 ° C for 1.5 hours, and the titanium carbide or titanium nitride film layer was removed. The sample was taken out, washed with water and dried. Example 2 [0023] 1. Prepare the withdrawal liquid [0024] Take 500 ml of deionized water, add 55 ml of 98% by weight sulfuric acid to deionized water, then add 5 g of thiourea, stir until the thiourea is completely After dissolution, 175 ml of a 40% by weight hydrofluoric acid solution and 55 ml of a 80% by weight solution of triethanolamine were added, and finally the ionized water was added to make the solution volume 1000 ml, and a withdrawal liquid was obtained. The concentration of the hydrofluoric acid was 79. llg / L, and the concentration of triethanolamine was 44. 88 g / L. [0025] 2. Removal film layer 099113802 Form No. A0101 Page 7 / Total 12 page 0992024315-0 201137177 [0026] Take a number of samples of the surface of the steel substrate formed with titanium carbide or titanium nitride film layer, the The thickness of the titanium carbide or titanium nitride film layer is approximately 1.5/zm. The sample was completely immersed in the above-mentioned withdrawal liquid at room temperature for 1 hour, and the carbonization or titanium nitride film layer was removed. The sample was taken out, washed with water and dried. [0027] Example 3 [0〇28] 1. Prepare the withdrawal liquid [〇〇29] Take 5 〇〇ml at a temperature of 5 (about TC of deionized water, 4 〇〇§Ammonium hydrogen fluoride and 5 g of thiourea are dissolved in deionized water, then add 4 〇〇m 丨 concentration of 36% acetic acid solution and 2 〇ml of 8% by weight of triethanolamine solution' The concentration of the acetic acid was 145 g/L, and the concentration of triethanolamine was 16.32 g/L. [0030] 2. Withdrawal of the solution to a volume of 1 〇〇〇ml. The film layer _] takes no sample of the surface of the steel substrate to form a carbonized or nitrided film. The thickness of the carbonized or titanium nitride film layer is about 2. The sample is completely immersed in the room temperature. The above-mentioned prepared withdrawal liquid was immersed for 2 hours to remove the titanium carbide or titanium nitride layer. The sample was taken out, washed with water and dried. [0032] Example 4-6 [0033] A according to Example 1 The method described in 3 is used to prepare a withdrawal liquid, except that the stainless steel substrate in the examples 1-3 is replaced with a copper substrate, respectively, and implemented. The film was peeled off under the same conditions as in Fig. 3. 099113802 Form No. A0101 No. 8 Stomach/Total 12 Page 0992024315-0 201137177 [0034] The samples obtained by removing the film layers in the above Examples 1 to 6 were subjected to X-ray diffraction ( In the X-RD analysis, no Ti element was found, which proved that the film layer was completely removed. The sample after the film layer was removed was subjected to scanning electron microscopy (SEM) test, and it was found that the substrate was not corroded. [Simplified illustration] [Main component symbol description] 〇0992024315-0 099113802 Form number A0101 Page 9 of 12