TW201819686A

TW201819686A - A water-based composition for post-treatment of metal surfaces

Info

Publication number: TW201819686A
Application number: TW106120995A
Authority: TW
Inventors: 新井千穂; 佛羅倫薩拉戈爾斯－布拉克; 羅伯特魯瑟; 歐拉夫寇特茲
Original assignee: 德國艾托特克公司
Priority date: 2016-06-23
Filing date: 2017-06-23
Publication date: 2018-06-01
Also published as: WO2017220790A1; EP3475466A1; KR20190021326A; JP2019520480A; ES2781310T3; JP6931010B2; EP3475466B1; US20190177859A1; CN109477226A; KR102351460B1; TWI746583B

Abstract

A water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface, comprising an alkanethiol an anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant with a HLB value of 12 to 18, a compound of the general formula I: wherein R1 is -H, -CH3, -C2H5, -(C2H4O)p-H, -(C2H4O)p-CH3, -(C2H4O)p-CH(CH3)2, -(C2H4O)p-C(CH3)3, wherein p is 1 to 20, R2 is H, or CH3n is an integer in the range of 0 to 20, m is an integer in the range of 0 to 10.

Description

Water-based composition for metal surface post-treatment

本發明係關於用於金屬表面後處理之水基組合物、其用途及金屬表面後處理之方法。The present invention relates to a water-based composition for post-treatment of metal surfaces, its use, and a method for post-treatment of metal surfaces.

銀及銀合金用於電子裝置中但不可避免地，成品將需要進一步清潔並拋光以暫時地去除不期望的鏽污產品。眾所周知，由於暴露於每天大氣條件，銀及銀合金產生破壞光澤的暗色膜，稱為鏽污。防止金屬及金屬合金之鏽污在眾多工業中係具有挑戰性之問題。金屬及金屬合金之鏽污已尤其在電子材料工業中成問題，其中鏽污可在電子裝置中之組件之間引起錯誤的電接觸。 US20070277906A1揭示用於處理金屬(例如，銀或銀之合金)之水基組合物，其包含選自烷烴硫醇、氫硫乙酸烷基酯、二烷基硫醚或二烷基二硫醚之處理劑及有效使處理劑溶解之濃度之兩性、非離子或陽離子表面活性劑之至少一者。較佳地，組合物至少包含非離子相對疏水性表面活性劑，例如椰油醯胺DEA。組合物尤其適用於處理Ag-Cu-Ge合金。Silver and silver alloys are used in electronic devices but inevitably, the finished product will need to be further cleaned and polished to temporarily remove unwanted rusty products. It is well known that due to exposure to daily atmospheric conditions, silver and silver alloys produce a dark film that destroys the luster, called rust. Preventing rust on metals and metal alloys is a challenging problem in many industries. Rust of metals and metal alloys has become a problem especially in the electronic materials industry, where rust can cause erroneous electrical contact between components in electronic devices. US20070277906A1 discloses a water-based composition for treating a metal (for example, silver or a silver alloy) comprising a treatment selected from the group consisting of an alkanethiol, an alkyl hydrothioacetate, a dialkyl sulfide, or a dialkyl disulfide At least one of an amphoteric, nonionic, or cationic surfactant at a concentration effective to dissolve the treating agent. Preferably, the composition comprises at least a non-ionic relatively hydrophobic surfactant, such as cocoamide DEA. The composition is particularly suitable for processing Ag-Cu-Ge alloys.

發明目標本發明之目標係提供用於金屬(尤其銀或銀合金)表面有效後處理以防止此等表面之鏽污之組合物。本發明提供用於金屬表面(較佳銀或銀合金表面)後處理之水基組合物、其用途及方法。較佳實施例在從屬申請專利範圍內闡述。金屬表面尤其係金屬基材或塑膠材料(例如，連接器或IC /引線架應用)之技術級及裝飾性表面以及汽車、航空太空、建築、通信、家具、衛生及消費品之表面之領域中之表面。本發明特定而言提供用於金屬表面(較佳銀或銀合金表面)後處理之水基組合物，其包含：烷烴硫醇陰離子、陽離子、非離子、兩性或兩性離子表面活性劑，其中HLB值為12至18、較佳15，其中水基組合物進一步含有通式I之化合物：，其中 R₁ 係-H、-CH₃ 、-C₂ H₅ 、-(C₂ H₄ O)_p -H、-(C₂ H₄ O)_p -CH₃ 、-(C₂ H₄ O)_p -CH(CH₃ )₂ 、-(C₂ H₄ O)_p -C(CH₃ )₃ ，其中p係1至20、較佳1至10、更佳2至6範圍內之整數， R₂ 係H或CH₃ ，較佳CH₃ ， n係0至3、較佳1至3、甚至更佳1或2範圍內之整數， m係0、1或2範圍內之整數，較佳0。 HLB值係根據W.C. Griffin之方法測定。對於本發明，通常或在以下其他實施例中之一者中，獲得一或多個以下益處： - 抗鏽污性質之增強(尤其由K₂ S測試證明) - 透明保護性塗層提供高度疏水表面性質 - 排斥氧化劑 - 透明組合物，防止對經組合物處理之表面之外觀的負面效應 - 增強之自裝配硫醇單層在浸沒銀表面上之形成，從而提供非極性膜 - 銀表面處理後，改良之疏水烷烴硫醇剩餘物之沖洗能力，有效消除油性殘餘物該組合物可係乳液。烷烴硫醇在浸沒銀表面上形成自裝配硫醇單層，其防止或延緩鏽污。式I之化合物亦稱為「雙子表面活性劑」，其具有更一般之以下結構：雙子表面活性劑包括兩個極性頭(親水基團)，其側接有疏水尾連接至其之間隔基；間隔基可為剛性或撓性、極性或非極性。本發明亦揭示在用於金屬表面後處理之組合物中使用此等一般表面活性劑。已顯示，藉由添加具有上述結構之表面活性劑，尤其藉由添加式I之組分，可達成組合物改良之抗鏽污性質。在式I化合物之較佳實施例中，m = 0，n在0至3之範圍內，較佳n在1至3之範圍內，更佳n係1或2，且R₁ 獨立地選自由以下組成之群：-H、-CH₃ 、-C₂ H₅ 及-(C₂ H₄ O)_p -H，其中p在2至6之範圍內。更佳式I之化合物係選自由以下組成之群：2,3,6,7-四甲基-4-辛炔-3,6-二醇、2,5,8,11-四甲基-6-十二炔-5,8-二醇乙氧基化物、2,4,7,9-四甲基-5-癸炔-4,7-二醇乙氧基化物、2,4,7,9-四甲基-5-癸炔-4,7-二醇、2,2’-[(2,4,7,9-四甲基-5-癸炔-4,7-二基)雙(氧基)]二乙醇及2,4,7,9-四甲基-5-癸炔-4,7-二醇雙聚氧乙烯-醚。陰離子、陽離子、非離子、兩性或兩性離子表面活性劑可具有可為直鏈或具支鏈之疏水尾。陰離子、陽離子、非離子、兩性或兩性離子表面活性劑可係乙氧基化或丙氧基化烷基、乙氧基化或丙氧基化胺、乙氧基化或丙氧基化醯胺、乙氧基化或丙氧基化醇或其混合物。有益的表面活性劑係3-乙氧基-2-甲基壬烷。表面活性劑可具有通式II： R₃ O(CH₂ CH₂ O)_x H 式II 其中 R₃ 係具有6至15個碳原子、較佳8至12個碳原子之直鏈或具支鏈烷基， x係3至15、較佳7至11範圍內之整數。較佳地，表面活性劑係聚乙二醇、更佳PEG-11 C10-11羰基合成醇乙氧基化物(CAS Nr：78330-20-8)。水基組合物可包含共乳化劑，其亦可稱為「第二表面活性劑」。共乳化劑可具有通式III R₄ O(CH₂ CH₂ O)_y H 式III 其中 R₄ 係具有16至20個碳原子、較佳16至18個碳原子之直鏈或具支鏈烷基， y係2至10、較佳3至6範圍內之整數。共乳化劑較佳係聚伸烷基二醇醚。較佳地，共乳化劑係乙氧基化丙氧基化C16-18醇(CAS Nr. 68002-96-0)。烷烴硫醇較佳係具支鏈或無支鏈C₁₀ -至C₂₀ -烷烴硫醇，更佳無支鏈C₁₀ -至C₂₀ -烷烴硫醇，例如癸硫醇、十一硫醇、十二硫醇、十六硫醇、十七硫醇、十八硫醇、十九硫醇、二十硫醇，最佳十七硫醇、十八硫醇、十九硫醇、二十硫醇。在一個較佳實施例中，烷烴硫醇係十八硫醇。在較佳實施例中，水基組合物不含鉻酸鹽及/或不含有機溶劑。水基組合物可具有1至6、較佳2至4範圍內之pH。pH可藉由緩衝系統調整。適宜緩衝系統係檸檬酸/檸檬酸鹽、乙酸/乙酸鹽、酒石酸/酒石酸鹽、磷酸/磷酸鹽或任何適宜的酸及鹽組合。水基組合物可包含以下量之所提及成分：烷烴硫醇： 0.1 g/L- 5 g/L、較佳0.5 g/L- 4 g/L 表面活性劑： 2 g/L- 30 g/L、較佳5 g/L- 20 g/L 式I化合物： 1 g/L- 10 g/L、較佳1 g/L- 5 g/L；及視情況共乳化劑： 0.1 g/L- 5 g/L、較佳0.5 g/L- 2 g/L 在另一態樣中，本發明係關於上文水基組合物用於金屬表面(尤其銀或銀合金表面)後處理之用途，其用於在金屬沈積後，尤其在銀或銀合金沈積後避免鏽污。在又一態樣中，本發明係關於金屬表面(尤其銀或銀合金表面)後處理之方法，其以此順序包含以下步驟： a. 提供金屬表面、尤其銀或銀合金表面， b. 使金屬表面(尤其銀或銀合金表面)與上文所述之水基組合物接觸。可用上文所述之任一水基組合物。接觸可藉由任何適宜方法完成。步驟b.中之接觸特定而言可藉由浸沒至水基組合物中及/或藉由用水基組合物噴射至表面上完成。步驟b.中之接觸可另外在無電條件下，亦即不在金屬表面與電極之間供應電流之情形下完成。在另一實施例中，步驟b.中之接觸係在當金屬表面浸沒於水基組合物中時在金屬表面(尤其銀或銀合金表面)與至少一個電極之間施加電流下發生。金屬表面可用作陰極且另一電極(其係相對電極)可用作陽極或反之亦然。較佳地，金屬表面係陰極的。本發明較佳以室溫(22±2℃)或更高、更佳30℃或更高之範圍內、最佳35℃至65℃範圍內之組合物溫度工作。OBJECTS OF THE INVENTION The object of the present invention is to provide a composition for effective post-treatment of the surfaces of metals, especially silver or silver alloys, to prevent rusting of these surfaces. The present invention provides a water-based composition for post-treatment of a metal surface (preferably a surface of silver or a silver alloy), its use and method. Preferred embodiments are described within the scope of the dependent patent applications. Metallic surfaces are in particular technical and decorative surfaces of metal substrates or plastic materials (e.g. connectors or IC / lead frame applications) and in the fields of automotive, aerospace, construction, communications, furniture, sanitary and consumer products surface. The present invention specifically provides a water-based composition for post-treatment of a metal surface (preferably a silver or silver alloy surface), which comprises: an alkanethiol anionic, cationic, nonionic, amphoteric or zwitterionic surfactant, wherein HLB The value is 12 to 18, preferably 15, wherein the water-based composition further contains a compound of general formula I: , Where R ₁ is -H, -CH ₃ , -C ₂ H ₅ ,-(C ₂ H ₄ O) _p -H,-(C ₂ H ₄ O) _p -CH ₃ ,-(C ₂ H ₄ O ) _p -CH (CH ₃ ) ₂ ,-(C ₂ H ₄ O) _p -C (CH ₃ ) ₃ , where p is an integer in the range of 1 to 20, preferably 1 to 10, more preferably 2 to 6, R ₂ is H or CH ₃ , preferably CH ₃ , n is an integer in the range of 0 to 3, preferably 1 to 3, or even more preferably 1 or 2, and m is an integer in the range of 0, 1 or 2, preferably 0. The HLB value was measured according to the method of WC Griffin. For the present invention, one or more of the following benefits are generally obtained or in one of the following other examples:-enhanced rust resistance (especially as evidenced by the K ₂ S test)-transparent protective coating provides a high degree of hydrophobicity Surface properties-Repellent oxidant-Transparent composition to prevent negative effects on the appearance of the treated surface of the composition-Enhanced formation of self-assembled thiol monolayer on immersed silver surface to provide non-polar film-After silver surface treatment The improved flushing ability of the hydrophobic alkanethiol residue can effectively eliminate the oily residue. The composition can be an emulsion. The alkanethiol forms a self-assembled thiol monolayer on the surface of the immersed silver, which prevents or delays rusting. Compounds of formula I are also known as "gemini surfactants" and have a more general structure: Gemini surfactants include two polar heads (hydrophilic groups) that are flanked by spacers to which hydrophobic tails are attached; spacers can be rigid or flexible, polar or non-polar. The invention also discloses the use of these general surfactants in compositions for post-treatment of metal surfaces. It has been shown that by adding a surfactant having the above-mentioned structure, and in particular by adding a component of formula I, improved rust resistance properties of the composition can be achieved. In a preferred embodiment of the compound of formula I, m = 0, n is in the range of 0 to 3, preferably n is in the range of 1 to 3, more preferably n is 1 or 2, and R _{1 is} independently selected from the group consisting _{_{of: -H, -CH 3, -C 2}} H 5 and _{_{- (C 2 H 4 O)}} p -H, wherein p is in the range of 2-6. More preferably the compound of formula I is selected from the group consisting of: 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 2,5,8,11-tetramethyl- 6-dodecyne-5,8-diol ethoxylate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate, 2,4,7 , 9-tetramethyl-5-decyne-4,7-diol, 2,2 '-[(2,4,7,9-tetramethyl-5-decyne-4,7-diyl) Bis (oxy)] diethanol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol bispolyoxyethylene-ether. Anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants may have hydrophobic tails which may be straight or branched. Anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants can be ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amines, ethoxylated or propoxylated amidines , Ethoxylated or propoxylated alcohols, or mixtures thereof. A beneficial surfactant is 3-ethoxy-2-methylnonane. The surfactant may have the general formula II: R ₃ O (CH ₂ CH ₂ O) _x H Formula II wherein R ₃ is a straight or branched chain having 6 to 15 carbon atoms, preferably 8 to 12 carbon atoms Alkyl, x is an integer in the range of 3 to 15, preferably 7 to 11. Preferably, the surfactant is polyethylene glycol, more preferably PEG-11 C10-11 carbonyl synthesis alcohol ethoxylate (CAS Nr: 78330-20-8). The water-based composition may include a co-emulsifier, which may also be referred to as a "second surfactant." Co-emulsifiers may have the general formula III R ₄ O (CH ₂ CH ₂ O) _y H Formula III wherein R ₄ is a straight or branched chain alkane having 16 to 20 carbon atoms, preferably 16 to 18 carbon atoms. The base, y is an integer in the range of 2 to 10, preferably 3 to 6. The co-emulsifier is preferably a polyalkylene glycol ether. Preferably, the co-emulsifier is an ethoxylated propoxylated C16-18 alcohol (CAS Nr. 68002-96-0). The alkanethiol is preferably a branched or unbranched C ₁₀ -to C ₂₀ -alkanethiol, more preferably an unbranched C ₁₀ -to C ₂₀ -alkanethiol, such as decanethiol, undecanethiol, Dodecylmercaptan, hexadecanethiol, heptathiol, octadecylthiol, nonadecanethiol, eicosylthiol, the best heptathiol, octadecylthiol, nonadecanylthiol, eicosylthiol alcohol. In a preferred embodiment, the alkanethiol is octadecanethiol. In a preferred embodiment, the water-based composition is free of chromate and / or free of organic solvents. The water-based composition may have a pH in the range of 1 to 6, preferably 2 to 4. The pH can be adjusted by a buffer system. Suitable buffer systems are citric acid / citrate, acetic acid / acetate, tartaric acid / tartrate, phosphoric acid / phosphate or any suitable acid and salt combination. The water-based composition may contain the mentioned ingredients in the following amounts: Alkane thiol: 0.1 g / L to 5 g / L, preferably 0.5 g / L to 4 g / L Surfactant: 2 g / L to 30 g / L, preferably 5 g / L-20 g / L Compound of formula I: 1 g / L-10 g / L, preferably 1 g / L-5 g / L; and optionally co-emulsifier: 0.1 g / L- 5 g / L, preferably 0.5 g / L- 2 g / L In another aspect, the present invention relates to the above-mentioned water-based composition for post-treatment of metal surfaces, especially silver or silver alloy surfaces. Uses to prevent rusting after metal deposition, especially after silver or silver alloy deposition. In yet another aspect, the present invention relates to a method for post-processing a metal surface (especially a silver or silver alloy surface), which in this order includes the following steps: a. Providing a metal surface, especially a silver or silver alloy surface, b. Using Metal surfaces, especially silver or silver alloy surfaces, are in contact with the water-based composition described above. Any of the water-based compositions described above can be used. Contacting can be accomplished by any suitable method. The contacting in step b. Can be done in particular by immersion into the water-based composition and / or by spraying the water-based composition onto the surface. The contacting in step b. May be additionally performed under no-current conditions, that is, without supplying a current between the metal surface and the electrode. In another embodiment, the contacting in step b. Occurs when an electrical current is applied between the metal surface (especially a silver or silver alloy surface) and the at least one electrode when the metal surface is immersed in the water-based composition. A metal surface can be used as the cathode and another electrode (which is the opposite electrode) can be used as the anode or vice versa. Preferably, the metal surface is cathodic. The present invention preferably operates at a composition temperature in the range of room temperature (22 ± 2 ° C) or higher, more preferably 30 ° C or higher, and most preferably in the range of 35 ° C to 65 ° C.

在下文中，本發明藉由工作實例闡釋。發明實例 1 ：提供水基組合物，其中分別通式I之c.)化合物(化合物c1))之濃度變化，而其他組分之濃度固定。水基組合物係藉由將以下組分溶解於水中製得： a.烷烴硫醇：十八硫醇。(CAS Nr. 2885-00-9) 量：2.5 g/L b.表面活性劑：PEG-11 C10 - 11 羰基合成醇乙氧基化物 (CAS Nr: 78330-20-8) 量：17.5 g/l c.通式 I 之化合物 ：c1)2,5,8,11- 四甲基 -6- 十二炔 -5,8- 二醇乙氧基化物 ，(CAS Nr. 169117-72-0)，量：2 g/l、3 g/l或4 g/l d. 共乳化劑：C16-18醇聚伸烷基二醇醚，(CAS Nr. 68002-96-0) 量：2.5 g/L。發明實例 2 ：提供水基組合物，其中通式I之c.)化合物之以下化合物c2) 2,4,7,9-四甲基-5-癸炔-4,7-二醇乙氧基化物(CAS Nr. 9014-85-1)及c3) 2,4,7,9-四甲基-5-癸炔-4,7-二醇(CAS Nr. 126-86-3)係以相同濃度單獨使用：水基組合物係藉由將以下組分溶解於水中製得： a.烷烴硫醇：十八硫醇。(CAS Nr. 2885-00-9) 量：2.5 g/L b.表面活性劑：PEG-11 C10 - 11 羰基合成醇乙氧基化物 (CAS Nr: 78330-20-8) 量：17.5 g/l c.通式 I 之化合物 (c2 或 c3) ：量：2 g/l d. 共乳化劑：C16-18醇聚伸烷基二醇醚，(CAS Nr. 68002-96-0) 量：2.5 g/L。比較實例 ：提供比較水基組合物，其包含a.、b.及d.，其中通式I之化合物(c1-c3)之濃度係零且其他濃度係如上文所說明。 1.方法在鍍銀銅板上實施後處理。具有銅表面之該等板可自以下步驟提供：提供銅板 1. 脫脂 Uniclean^TM 260 (電泳鹼性清潔器)陰極7V / 45℃ / 30 sec 2. 活化： Uniclean^TM 675 (溫和酸性活化劑)浸沒/ RT / 30 sec 3. 鍍銀前鍍銀前(低銀濃縮溶液)陰極3V / RT / 15 sec 4. 鍍銀 Silverlume Plus (亮銀沈積溶液)陰極1 ASD / RT / 5 min 或AgO-56 (技術級銀沈積溶液)陰極1 ASD / RT / 5 min 或Argalux^TM NCmod. (無氰化物之亮銀沈積溶液)陰極0.8 ASD / RT / 5 min 其中RT係介於22±2℃之間之室溫；DI水係去離子水；ASD係安培(Ampere) /平方公寸(A/dm²)且V係伏特(volt/voltage)。在本發明之意義上，在使用技術級或裝飾性(有氰化物或無氰化物)銀沈積溶液用於鍍銀以避免在此鍍銀後鏽污之領域中，後處理組合物亦可對以其他方式獲得之鍍銀表面起作用。根據本發明用於後處理之本發明水基組合物及比較水基組合物在多種條件下使用(參見以下測試)。在水基組合物中後處理後，用以下各項沖洗所有試樣： -熱DI水沖洗 -冷DI水沖洗及 -用壓縮空氣乾燥。 ▪ 用本發明組合物及比較組合物後處理後之光學評估及隨後硫化物測試，其係由於： - 緊接後處理及沖洗後之殘餘物 - 硫化物測試後之著色及鏽污熟習此項技術者在無任何儀器之情形下實施觀測。 ▪ 硫化物測試 ▪ 材料：玻璃燒杯 ▪ 化學品：硫化鉀44% K₂ S，2% w/w於水中 ▪ 溫度：22 ± 2℃ ▪ 浸漬時間：5 - 10 min ▪ 由熟習此項技術者評估 ▪ 根據色彩強度 2.結果 2.1 沖洗能力測試本發明水基組合物與比較水基組合物相比顯示改良之沖洗能力並完全消除油性殘餘物問題。用比較水基組合物處理Silverlume Plus、AgO-56及Argalux^TM NC mod.鍍銀表面，表面顯示差的沖洗能力，而本發明水基組合物顯示極佳沖洗能力。 2.2 抗鏽污測試與無通式I之化合物(c1-c3)之比較水基組合物相比，本發明水基組合物顯示改良之抗鏽污保護。自諸如Silverlume Plus、AgO-56及Argalux^TM NC mod.之鍍銀溶液獲得之未經處理之銀表面展現極差的抗鏽污保護。經比較水基組合物處理之該等鍍銀表面在硫化物測試後顯示較少變色，而經本發明水基組合物處理之表面顯示極少變色至無變色。測試材料：亮銀鍍覆之表面(Silverlume Plus) 水基組合物條件：pH 2.5 -溫度55℃-攪動200 RPM -浸沒過程持續1 min，沖洗並乾燥。測試材料：亮銀鍍覆之表面(Argalux NC^TM mod)，無氰化物水基組合物條件：pH 2.5 -溫度55℃ -攪動200 RPM -1 min浸沒過程，沖洗及乾燥。測試材料：技術級銀鍍覆之表面(AgO-56^TM ) 水基組合物條件：pH 2.5 -溫度55℃ -攪動200 RPM -浸沒過程持續1 min，沖洗及乾燥。 2.3 陰極用途測試材料：技術級銀鍍覆之表面(AgO-56^TM ) 水基組合物條件：pH 2.5 -溫度55℃ -攪動200 RPM -浸沒持續1 min或陰極0.5 A/dm²持續1min，沖洗及乾燥 3. 結論 ▪ 本發明水基組合物確實改良： - 浸沒金屬表面(尤其銀)之潤濕性 - 自裝配硫醇單層在浸沒銀表面上之形成，從而得到非極性膜並增強抗鏽污性質 - 在利用本發明之水基溶液之銀表面處理後，疏水烷烴硫醇剩餘物之沖洗。 ▪ 浸沒及電泳用途適於避免金屬電鍍後鍍金屬表面之鏽污。In the following, the invention is explained by working examples. Inventive Example 1 : Provide a water-based composition in which the concentration of the compound (compound c1)) of c.) Of the general formula I is changed, while the concentrations of other components are fixed. Water-based compositions are prepared by dissolving the following components in water: a. Alkanethiol : octadecanethiol. (. CAS Nr 2885-00-9) quantity: 2.5 g / L b Surfactant: PEG-11 C10 - 11 oxo alcohol ethoxylate (CAS Nr: 78330-20-8). Amount: 17.5 g / l c of the compounds of formula I:. c1) 2,5,8,11- tetramethyl-6-dodecene-5,8-diol ethoxylate, (CAS Nr 169117-72-0). , Amount: 2 g / l, 3 g / l or 4 g / l d. Co-emulsifier: C16-18 alcohol polyalkylene glycol ether, (CAS Nr. 68002-96-0) Amount: 2.5 g / L. Inventive Example 2 : Provide a water-based composition in which the following compound c2) of the compound of general formula I is c2) 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxy (CAS Nr. 9014-85-1) and c3) 2,4,7,9-tetramethyl-5-decyne-4,7-diol (CAS Nr. 126-86-3) are the same The concentration is used alone: The water-based composition is prepared by dissolving the following components in water: a. Alkane thiol : octadecanethiol. (. CAS Nr 2885-00-9) quantity: 2.5 g / L b Surfactant: PEG-11 C10 - 11 oxo alcohol ethoxylate (CAS Nr: 78330-20-8). Amount: 17.5 g / l c a compound of formula (c2 or c3) I of: amount: 2 g / l d coemulsifiers: alkylene of C16-18 alcohol polyethylene glycol ether, (CAS Nr 68002-96-0.) an amount of: 2.5 g / L. Comparative Example : A comparative water-based composition is provided, which comprises a., B., And d., Wherein the concentration of the compound (c1-c3) of the general formula I is zero and the other concentrations are as described above. 1. Method Post-treatment is performed on a silver-plated copper plate. These plates with copper surface can be provided from the following steps: Provide copper plates 1. Degreased Uniclean ^TM 260 (electrolytic alkaline cleaner) cathode 7V / 45 ° C / 30 sec 2. Activation: Uniclean ^TM 675 (mild acid activator) immersion / RT / 30 sec 3. Before silver plating (silver concentrated solution) cathode 3V / RT / 15 sec 4. Silverlume Plus (bright silver deposition solution) cathode 1 ASD / RT / 5 min or AgO-56 (Technical grade silver deposition solution) cathode 1 ASD / RT / 5 min or Argalux ^TM NCmod. (Cyanide-free bright silver deposition solution) cathode 0.8 ASD / RT / 5 min where RT is between 22 ± 2 ℃ Room temperature; DI water is deionized water; ASD is Ampere / square inch (A / dm²) and V is volt / voltage. In the sense of the present invention, in the field of using technical grade or decorative (with or without cyanide) silver deposition solution for silver plating to avoid rusting after this silver plating, the post-treatment composition can also be applied to Silver plated surfaces obtained in other ways work. The water-based composition of the present invention and the comparative water-based composition for post-treatment according to the present invention are used under various conditions (see test below). After post-treatment in the water-based composition, all samples were rinsed with:-hot DI water rinse-cold DI water rinse and-dried with compressed air. ▪ Optical evaluation and subsequent sulfide test after treatment with the composition of the present invention and comparative composition due to:-Residues immediately after treatment and processing-Color and rust after sulfide test familiarize yourself with this The technician performs the observation without any instrument. ▪ Sulfide test ▪ Material: glass beaker ▪ Chemicals: potassium sulfide 44% K ₂ S, 2% w / w in water ▪ Temperature: 22 ± 2 ℃ ▪ Immersion time: 5-10 min Evaluation ▪ Based on color intensity 2. Results 2.1 Rinse ability test The water-based composition of the present invention showed improved rinse ability and completely eliminated the problem of oily residues compared to the comparative water-based composition. The silver-plated surfaces of Silverlume Plus, AgO-56, and Argalux ^™ NC mod. Were treated with the comparative water-based composition, and the surface showed poor rinsing ability, while the water-based composition of the present invention showed excellent rinsing ability. 2.2 Anti-rust test Compared with the comparison water-based composition of the compound (c1-c3) without the general formula I, the water-based composition of the present invention shows improved anti-rust protection. Untreated silver surfaces obtained from silver plating solutions such as Silverlume Plus, AgO-56 and Argalux ^™ NC mod. Exhibit extremely poor anti-rust protection. The silver-plated surfaces treated with the comparative water-based composition showed less discoloration after the sulfide test, while the surfaces treated with the water-based composition of the present invention showed little to no discoloration. Test material: Bright silver plated surface (Silverlume Plus) Water-based composition conditions: pH 2.5-temperature 55 ° C-agitation 200 RPM-immersion process lasts 1 minute, rinse and dry. Test material: bright silver plated surface (Argalux NC ^TM mod), cyanide-free water-based composition conditions: pH 2.5-temperature 55 ° C-agitate 200 RPM -1 min immersion process, rinse and dry. Test material: technical silver-plated surface (AgO-56 ^TM ) Water-based composition conditions: pH 2.5-temperature 55 ° C-agitation 200 RPM-immersion process lasts 1 minute, rinse and dry. 2.3 Cathode test material: technical grade silver-plated surface (AgO-56 ^TM ) Water-based composition conditions: pH 2.5-temperature 55 ° C-agitation 200 RPM-immersion for 1 min or cathode 0.5 A / dm² for 1 min, rinse And dry 3. Conclusion ▪ The water-based composition of the present invention does improve:-the wettability of immersed metal surfaces (especially silver)-the formation of a self-assembled thiol monolayer on the immersed silver surface, thereby obtaining a non-polar film and enhancing rust resistance Properties-After the surface treatment of silver with the water-based solution of the present invention, the residue of the hydrophobic alkanethiol is rinsed. ▪ Immersion and electrophoresis are suitable for avoiding rust on the metal surface after metal plating.

Claims

A water-based composition for post-treatment of metal surfaces, preferably silver or silver alloy surfaces, comprising an alkanethiol, anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant, wherein the HLB value is 12 to 18, It is characterized in that the water-based composition further comprises a compound of the general formula I: , Where R ₁ is -H, -CH ₃ , -C ₂ H ₅ ,-(C ₂ H ₄ O) _p -H,-(C ₂ H ₄ O) _p -CH ₃ ,-(C ₂ H ₄ O ) _p -CH (CH ₃ ) ₂ ,-(C ₂ H ₄ O) _p -C (CH ₃ ) ₃ , where p is an integer in the range of 1 to 20, R ₂ is H or CH ₃ , and n is 0 to Integers in the range 3, m is an integer in the range 0, 1, or 2.

The water-based composition as claimed in claim 1, wherein in the compound of formula I, m = 0, n is in the range of 0 to 3 and R ₁ is independently selected from the group consisting of -H, -CH ₃ -C ₂ H ₅ and-(C ₂ H ₄ O) _p -H, where p is in the range of 2 to 6.

The water-based composition of claim 1, wherein the compound of formula I is selected from the group consisting of: 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 2, 5,8,11-tetramethyl-6-dodecyne-5,8-diol ethoxylate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol Ethoxylate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol-bispolyoxyethylene ether and 2,4,7,9-tetramethyl-5-decane Alkyne-4,7-diol.

The water-based composition according to any one of claims 1 to 3, wherein the surfactant is an ethoxylated or propoxylated alkyl group, an ethoxylated or propoxylated amine, an ethoxylated or Propoxylated ammonium, ethoxylated or propoxylated alcohols or mixtures thereof.

The water-based composition according to any one of claims 1 to 3, wherein the surfactant has the general formula II R ₃ O (CH ₂ CH ₂ O) _x H (II) wherein R ₃ has 6 to 15 carbons. A straight or branched chain alkyl group of 8 to 12 carbon atoms, x is an integer in the range of 3 to 15, preferably 7 to 11.

The water-based composition according to any one of claims 1 to 3, wherein the alkanethiol is a C ₁₀ -to C ₂₀ -alkanethiol.

The water-based composition of any one of claims 1 to 3, wherein the composition comprises a co-emulsifier.

The water-based composition according to claim 7, wherein the co-emulsifier has the general formula III R ₄ O (CH ₂ CH ₂ O) _y H (III) wherein R ₄ has 16 to 20 carbon atoms, preferably 16 to 18 A straight or branched alkyl group of one carbon atom, y is an integer in the range of 2 to 10, preferably 3 to 6.

The water-based composition according to claim 7, wherein the co-emulsifier is a polyalkylene glycol ether.

The water-based composition according to any one of claims 1 to 3, wherein the composition is free of chromate and / or free of organic solvents.

The water-based composition according to any one of claims 1 to 3, which has a pH in the range of 1 to 10.

A use of a water-based composition according to any one of the preceding claims 1 to 10 for post-treatment of metal surfaces, especially silver or silver alloy surfaces, to avoid metal rusting.

A method for post-processing a metal surface, especially a silver or silver alloy surface, comprising the following steps in this order: a. Providing a metal surface, especially a silver or silver alloy surface, b. Subjecting the metal surface, especially a silver or silver alloy The surface is in contact with a water-based composition as claimed in any one of claims 1 to 11.

The method of claim 13, wherein the contacting in step b. Is applied by immersion and / or by spraying and / or by any other suitable method of bringing the metal into contact with the claimed solution.

The method of claim 13 or 14, wherein the contact in step b. Is under a current applied between the surface of the metal, especially the surface of silver or a silver alloy, and at least one electrode when the metal is immersed in the claimed solution occur.