[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

TWI746583B - A water-based composition for post-treatment of metal surfaces - Google Patents

A water-based composition for post-treatment of metal surfaces Download PDF

Info

Publication number
TWI746583B
TWI746583B TW106120995A TW106120995A TWI746583B TW I746583 B TWI746583 B TW I746583B TW 106120995 A TW106120995 A TW 106120995A TW 106120995 A TW106120995 A TW 106120995A TW I746583 B TWI746583 B TW I746583B
Authority
TW
Taiwan
Prior art keywords
water
based composition
range
metal
treatment
Prior art date
Application number
TW106120995A
Other languages
Chinese (zh)
Other versions
TW201819686A (en
Inventor
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
德商德國艾托特克公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 德商德國艾托特克公司 filed Critical 德商德國艾托特克公司
Publication of TW201819686A publication Critical patent/TW201819686A/en
Application granted granted Critical
Publication of TWI746583B publication Critical patent/TWI746583B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/145—Amides; N-substituted amides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

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:
Figure 106120995-A0101-11-0002-2
wherein R1 is -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 , wherein p is 1 to 20, R2 is H, or CH3 n is an integer in the range of 0 to 20, m is an integer in the range of 0 to 10.

Description

用於金屬表面後處理之水基組合物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 methods 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 undesirable rusty products. As we all know, due to exposure to daily atmospheric conditions, silver and silver alloys produce a dark film that destroys luster, called rust. Preventing the rust of metals and metal alloys is a challenging problem in many industries. Rust contamination of metals and metal alloys has particularly become a problem in the electronic materials industry, where rust stains can cause erroneous electrical contacts between components in electronic devices. US20070277906A1 discloses a water-based composition for treating metals (for example, silver or silver alloys), which comprises a treatment selected from alkane mercaptan, alkyl hydrogen thioacetate, dialkyl sulfide or dialkyl disulfide At least one of amphoteric, nonionic or cationic surfactants at a concentration effective to dissolve the treatment agent. Preferably, the composition contains at least a nonionic 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：

Figure 02_image006
， 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：
Figure 02_image008
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。Object of the Invention The object of the present invention is to provide a composition for effective post-treatment of metal (especially silver or silver alloy) surfaces to prevent rust stains on these surfaces. The present invention provides a water-based composition for post-treatment of metal surfaces (preferably silver or silver alloy surfaces), its use and methods. The preferred embodiments are described in the scope of the dependent patent application. The metal surface is especially one of the technical and decorative surfaces of metal substrates or plastic materials (for example, connectors or IC/lead frame applications) and the surfaces of automobiles, aerospace, construction, communications, furniture, hygiene and consumer products surface. In particular, the present invention provides a water-based composition for post-treatment of metal surfaces (preferably silver or silver alloy surfaces), which comprises: alkanethiol anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, wherein HLB The value is 12 to 18, preferably 15, wherein the water-based composition further contains a compound of general formula I:
Figure 02_image006
, 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, even more preferably 1 or 2, and m is an integer in the range of 0, 1, or 2, preferably 0. The HLB value is determined according to the method of WC Griffin. For the present invention, generally or in one of the following other embodiments, one or more of the following benefits are obtained:-Enhancement of anti-rust properties (especially proven by the K 2 S test)-Transparent protective coating provides high hydrophobicity Surface properties-Repelling oxidants-Transparent composition to prevent negative effects on the appearance of the surface treated by the composition-Enhanced formation of a self-assembled thiol monolayer on the immersed silver surface to provide a non-polar film-After silver surface treatment , Improved washing ability of hydrophobic alkane mercaptan residues, effectively eliminating oily residues. The composition can be used as an emulsion. Alkane mercaptans form a self-assembled monolayer of mercaptan on the immersed silver surface, which prevents or retards rust stains. The compound of formula I is also called "gemini surfactant", which has a more general structure as follows:
Figure 02_image008
Gemini surfactants include two polar heads (hydrophilic groups) flanked by a spacer to which a hydrophobic tail is attached; the spacer can be rigid or flexible, polar or non-polar. The present 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, especially by adding a component of formula I, improved anti-rust 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, where p is in the range of 2 to 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 dipolyoxyethylene ether. Anionic, cationic, nonionic, amphoteric or zwitterionic surfactants can have hydrophobic tails that can be linear or branched. Anionic, cationic, nonionic, amphoteric or zwitterionic surfactants can be ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amines, ethoxylated or propoxylated amines , Ethoxylated or propoxylated alcohols or mixtures thereof. The 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 chain or branched chain with 6 to 15 carbon atoms, preferably 8 to 12 carbon atoms In the alkyl group, x is an integer in the range of 3-15, preferably 7-11. Preferably, the surfactant is polyethylene glycol, more preferably PEG-11 C10-11 oxo 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." The co-emulsifier 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 Base, y is an integer in the range of 2-10, preferably 3-6. The co-emulsifier is preferably polyalkylene glycol ether. Preferably, the co-emulsifier is an ethoxylated propoxylated C16-18 alcohol (CAS Nr. 68002-96-0). Alkane mercaptans are preferably branched or unbranched C 10 -to C 20 -alkane mercaptans, more preferably unbranched C 10 -to C 20 -alkane mercaptans, such as decane mercaptan, undecyl mercaptan, Dodecyl mercaptan, cetyl mercaptan, heptathiol, stearyl mercaptan, nonadecane mercaptan, aracoscaptan, the best heptathiol, stearyl mercaptan, nonadeca thiol, and docosathiol alcohol. In a preferred embodiment, the alkane mercaptan is stearyl mercaptan. In a preferred embodiment, the water-based composition does not contain chromate and/or does not contain 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 the buffer system. Suitable buffer systems are citric acid/citrate, acetic acid/acetate, tartaric acid/tartrate, phosphoric acid/phosphate or any suitable combination of acids and salts. The water-based composition may contain the mentioned ingredients in the following amounts: Alkane mercaptan: 0.1 g/L-5 g/L, preferably 0.5 g/L-4 g/L Surfactant: 2 g/L-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 use of the above water-based composition for post-treatment of metal surfaces (especially silver or silver alloy surfaces) Purpose, it is used to avoid rust stains after metal deposition, especially after silver or silver alloy deposition. In yet another aspect, the present invention relates to a method for post-treatment of a metal surface (especially silver or silver alloy surface), which includes the following steps in this order: a. providing a metal surface, especially a silver or silver alloy surface, b. making The metal surface (especially the silver or silver alloy surface) is in contact with the water-based composition described above. Any of the water-based compositions described above can be used. The contact can be accomplished by any suitable method. The contact in step b. can in particular be accomplished by immersion into the water-based composition and/or by spraying the water-based composition onto the surface. The contact in step b. can also be completed under no electricity conditions, that is, no current is supplied between the metal surface and the electrode. In another embodiment, the contact in step b. occurs when a current is applied between the metal surface (especially the silver or silver alloy surface) and the at least one electrode when the metal surface is immersed in the water-based composition. The metal surface can be used as a cathode and the other electrode (which is the opposite electrode) can be used as an anode or vice versa. Preferably, the metal surface is cathodic. The present invention preferably works with the 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 UnicleanTM 260 (電泳鹼性清潔器)陰極7V / 45℃ / 30 sec 2. 活化： UnicleanTM 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ArgaluxTM 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ArgaluxTM 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ArgaluxTM 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。

Figure 106120995-A0304-0001
測試材料：亮銀鍍覆之表面(Argalux NCTM 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。
Figure 106120995-A0304-0002
 測試材料：技術級銀鍍覆之表面(AgO-56TM ) 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。
Figure 106120995-A0304-0003
 2.3 陰極用途 測試材料：技術級銀鍍覆之表面(AgO-56TM ) 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
Figure 106120995-A0304-0004
 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 present invention is explained by working examples. Invention Example 1 : Provide a water-based composition, wherein the concentration of the compound c.) of the general formula I (compound c1)) is changed, and the concentration of the other components is fixed. The water-based composition is prepared by dissolving the following components in water: a. Alkane mercaptan : Stearyl mercaptan. (. 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). , Quantity: 2 g/l, 3 g/l or 4 g/l d. Co-emulsifier: C16-18 alcohol polyalkylene glycol ether, (CAS Nr. 68002-96-0) Quantity: 2.5 g/ L. Invention Example 2 : Provide a water-based composition, wherein the following compound c2) 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxy of the compound of general formula I c.) 9014-85-1 and c3) 2,4,7,9-tetramethyl-5-decyne-4,7-diol (CAS Nr. 126-86-3) are the same Concentration used alone: Water-based composition is prepared by dissolving the following components in water: a. Alkane mercaptan : Stearyl mercaptan. (. 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 includes a., b. and d., wherein the concentration of the compound of formula I (c1-c3) is zero and the other concentrations are as described above. 1. Method Perform post-treatment on the silver-plated copper plate. These boards with copper surfaces can be provided from the following steps: Provide copper boards 1. Degreasing Uniclean TM 260 (electrophoresis alkaline cleaner) cathode 7V / 45°C / 30 sec 2. Activation: Uniclean TM 675 (mild acid activator) immersion / RT / 30 sec 3. Before silver plating (low silver concentrated solution) cathode 3V / RT / 15 sec 4. Silver plating 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 system deionized water; ASD system ampere (Ampere) / square meter (A/dm²) and V system volt/voltage. In the sense of the present invention, in the field of using technical grade or decorative (cyanide or non-cyanide) silver deposition solution for silver plating to avoid rust stains after silver plating, the post-treatment composition can also be used for Silver-plated surfaces obtained in other ways work. The water-based composition of the present invention and the comparative water-based composition used for post-treatment according to the present invention were used under various conditions (see the following test). After post-treatment in the water-based composition, rinse all samples with the following:-rinse with hot DI water-rinse with cold DI water and-dry with compressed air. ▪ The optical evaluation and subsequent sulfide test after post-treatment with the composition of the present invention and the comparative composition are due to:-residues immediately after post-treatment and washing-coloration and rust staining after sulfide test Technicians perform observations without any instruments. ▪ Sulfide test ▪ Material: glass beaker ▪ Chemical: Potassium sulfide 44% K 2 S, 2% w/w in water ▪ Temperature: 22 ± 2℃ ▪ Immersion time: 5-10 min ▪ By those who are familiar with this technique Evaluation ▪ According to color intensity 2. Results 2.1 Rinsing ability test The water-based composition of the present invention shows improved flushing ability compared with the comparative water-based composition and completely eliminates the problem of oily residue. The silver-plated surfaces of Silverlume Plus, AgO-56 and Argalux TM 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 comparative water-based composition without the compound of formula I (c1-c3), 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 TM NC mod. exhibit extremely poor protection against rust. The silver-plated surfaces treated with the comparative water-based composition showed less discoloration after the sulfide test, while the surface treated with the water-based composition of the present invention showed little to no discoloration. Test material: Bright silver-coated surface (Silverlume Plus) Water-based composition conditions: pH 2.5-temperature 55°C-agitation 200 RPM-immersion process lasts 1 min, rinse and dry.
Figure 106120995-A0304-0001
 Test material: bright silver-plated surface (Argalux NC TM mod), cyanide-free water-based composition. Conditions: pH 2.5-temperature 55°C-agitation 200 RPM -1 min immersion process, rinse and dry.
Figure 106120995-A0304-0002
 Test material: technical grade silver-coated surface (AgO-56 TM ) Water-based composition conditions: pH 2.5-temperature 55°C-agitation 200 RPM-immersion process lasts 1 min, rinse and dry.
Figure 106120995-A0304-0003
 2.3 Cathode use test material: technical grade silver-coated surface (AgO-56 TM ) water-based composition conditions: pH 2.5-temperature 55 ℃-agitation 200 RPM-immersion for 1 min or cathode 0.5 A/dm² for 1 min, rinse And dry
Figure 106120995-A0304-0004
 3. Conclusion ▪ The water-based composition of the present invention does improve:-The wettability of the immersed metal surface (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 silver surface treatment with the water-based solution of the present invention, the hydrophobic alkane mercaptan residue is washed. ▪ Immersion and electrophoresis applications are suitable for avoiding rust stains on the plated metal surface after metal electroplating.

Figure 106120995-A0101-11-0003-3
Figure 106120995-A0101-11-0003-3

Claims (15)

一種用於金屬表面後處理之水基組合物，其包含0.1g/L至5g/L之量的烷烴硫醇，2g/L至30g/L之量的陰離子、陽離子、非離子、兩性或兩性離子表面活性劑，其中親水親油平衡(HLB)值為12至18，其特徵在於，該水基組合物另外含有1g/L至10g/L之量的通式I之化合物：
Figure 106120995-A0305-02-0016-1
 其中R1係-H、-CH3、-C2H5、-(C2H4O)p-H、-(C2H4O)p-CH3、-(C2H4O)p-CH(CH3)2、-(C2H4O)p-C(CH3)3，其中p係1至20範圍內之整數，R2係H或CH3，n係0至3範圍內之整數，m係0、1或2範圍內之整數。 A water-based composition for post-treatment of metal surfaces, which contains alkane mercaptan in an amount of 0.1g/L to 5g/L, an anion, cationic, nonionic, amphoteric or amphoteric in an amount of 2g/L to 30g/L An ionic surfactant, wherein the hydrophile-lipophile balance (HLB) value is 12 to 18, characterized in that the water-based composition additionally contains a compound of general formula I in an amount of 1 g/L to 10 g/L:
Figure 106120995-A0305-02-0016-1
 Among them, 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 3 An integer within the range, m is an integer within the range of 0, 1, or 2. 如請求項1之水基組合物，其中在該式I之化合物中，m=0，n在0至3之範圍內且R1係獨立地選自由以下組成之群：-H、-CH3、-C2H5及-(C2H4O)p-H，其中p在2至6之範圍內。 The water-based composition of 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. 如請求項1之水基組合物，其中該式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-雙聚氧乙烯醚及2,4,7,9-四甲基-5-癸炔-4,7-二醇。 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-dipolyoxyethylene ether and 2,4,7,9-tetramethyl-5-decene Alkyne-4,7-diol. 如請求項1至3中任一項之水基組合物，其中該表面活性劑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。 The water-based composition according to any one of claims 1 to 3, wherein the surfactant is an ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amine, ethoxylated or Propoxylated amide, ethoxylated or propoxylated alcohol or mixtures thereof. 如請求項1至3中任一項之水基組合物，其中該表面活性劑具有通式II R3O(CH2CH2O)xH (II)其中R3係具有6至15個碳原子之直鏈或具支鏈烷基，x係3至15範圍內之整數。 The water-based composition of 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-chain or branched alkyl group of atoms, x is an integer in the range of 3-15. 如請求項1至3中任一項之水基組合物，其中該烷烴硫醇係C10-至C20-烷烴硫醇。 The water-based composition according to any one of claims 1 to 3, wherein the alkane thiol is C 10 -to C 20 -alkane thiol. 如請求項1至3中任一項之水基組合物，其中該組合物包含共乳化劑。 The water-based composition according to any one of claims 1 to 3, wherein the composition comprises a co-emulsifier. 如請求項7之水基組合物，其中該共乳化劑具有通式III R4O(CH2CH2O)yH (III)其中R4係具有16至20個碳原子之直鏈或具支鏈烷基，y係2至10範圍內之整數。 The water-based composition of claim 7, wherein the co-emulsifier has the general formula III R 4 O(CH 2 CH 2 O) y H (III), wherein R4 is a linear or branched chain with 16 to 20 carbon atoms Alkyl, y is an integer in the range of 2-10. 如請求項7之水基組合物，其中該共乳化劑係聚伸烷基二醇醚。 The water-based composition of claim 7, wherein the co-emulsifier is polyalkylene glycol ether. 如請求項1至3中任一項之水基組合物，其中該組合物不含鉻酸鹽及/或不含有機溶劑。 The water-based composition according to any one of claims 1 to 3, wherein the composition does not contain chromate and/or does not contain organic solvents. 如請求項1至3中任一項之水基組合物，其具有1至10範圍內之pH。 The water-based composition according to any one of claims 1 to 3, which has a pH in the range of 1 to 10. 一種如前述請求項1至10中任一項之水基組合物之用途，其用於金屬表面後處理以避免金屬鏽污。 A use of the water-based composition according to any one of the aforementioned claims 1 to 10, which is used for post-treatment of metal surfaces to avoid metal rust stains. 一種用於金屬表面後處理之方法，其以此順序包含以下步驟：a.提供金屬表面，b.使該金屬表面與如請求項1至11中任一項之水基組合物接觸。 A method for post-treatment of a metal surface, which comprises the following steps in this order: a. providing a metal surface, b. contacting the metal surface with the water-based composition according to any one of claims 1 to 11. 如請求項13之方法，其中該步驟b.中之接觸係以浸沒及/或按照噴射及/或按照使金屬與所主張溶液之間接觸之任何其他適宜方法施加。 The method of claim 13, wherein the contact in step b. is applied by immersion and/or by spraying and/or by any other suitable method for contacting the metal with the claimed solution. 如請求項13或14之方法，其中該步驟b.中之接觸係在將該金屬浸沒至所主張溶液中時在該金屬表面與至少一個電極之間施加之電流下發生。The method of claim 13 or 14, wherein the contact in step b. occurs under an electric current applied between the metal surface and at least one electrode when the metal is immersed in the claimed solution.
TW106120995A 2016-06-23 2017-06-23 A water-based composition for post-treatment of metal surfaces TWI746583B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP16175905.5 2016-06-23
EP16175905 2016-06-23
??16175905.5 2016-06-23

Publications (2)

Publication Number Publication Date
TW201819686A TW201819686A (en) 2018-06-01
TWI746583B true TWI746583B (en) 2021-11-21

Family

ID=56363712

Family Applications (1)

Application Number Title Priority Date Filing Date
TW106120995A TWI746583B (en) 2016-06-23 2017-06-23 A water-based composition for post-treatment of metal surfaces

Country Status (8)

Country Link
US (1) US20190177859A1 (en)
EP (1) EP3475466B1 (en)
JP (1) JP6931010B2 (en)
KR (1) KR102351460B1 (en)
CN (1) CN109477226A (en)
ES (1) ES2781310T3 (en)
TW (1) TWI746583B (en)
WO (1) WO2017220790A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110424030B (en) * 2019-08-30 2020-06-30 广州三孚新材料科技股份有限公司 Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board
JP2021042326A (en) * 2019-09-12 2021-03-18 日華化学株式会社 Electrolytic detergent and method for cleaning metal
JP2021143325A (en) * 2020-02-14 2021-09-24 エボニック オペレーションズ ゲーエムベーハー Solvent-free composition based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4885064A (en) * 1989-05-22 1989-12-05 Mcgean-Rohco, Inc. Additive composition, plating bath and method for electroplating tin and/or lead

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59215490A (en) * 1983-05-23 1984-12-05 Alps Electric Co Ltd Discoloration inhibitor for metal
JPS60251285A (en) * 1984-05-25 1985-12-11 Showa Denko Kk Surface treating agent for plating on electrical contact
JPS61270382A (en) * 1985-05-23 1986-11-29 Nippon Shokubai Kagaku Kogyo Co Ltd Aqueous surface treating composition for metal capable of treating oil stuck surface
JP2905658B2 (en) * 1993-01-11 1999-06-14 信越化学工業株式会社 Underwater non-separable concrete composition and defoamer for concrete composition
US5525206A (en) * 1995-02-01 1996-06-11 Enthone-Omi, Inc. Brightening additive for tungsten alloy electroplate
JP2001276705A (en) * 2000-01-24 2001-10-09 Daikin Ind Ltd Method for coating base material, coated article and coating apparatus
JP2002356602A (en) * 2000-07-28 2002-12-13 Sekisui Chem Co Ltd Colored resin emulsion, ink for ink-jet printing, electrodeposition liquid and color filter
JP4386156B2 (en) * 2001-05-30 2009-12-16 日信化学工業株式会社 Water-soluble surfactant composition
GB0307290D0 (en) * 2003-03-31 2003-05-07 Cole Paul G Enhancing silver tarnish-resistance
GB2412666B (en) * 2004-03-30 2008-10-08 Paul Gilbert Cole Water-based metal treatment composition
US7771588B2 (en) * 2005-11-17 2010-08-10 General Electric Company Separatory and emulsion breaking processes
JP2007246978A (en) * 2006-03-15 2007-09-27 Jsr Corp Electroless plating liquid
CN101353800B (en) * 2007-07-26 2011-09-21 深圳市华傲创表面技术有限公司 Water-soluble silver protecting agent and preparation thereof
CN102145267A (en) * 2010-02-09 2011-08-10 天津赛菲化学科技发展有限公司 Multifunctional surfactant composition for water-based system and preparation method thereof
IT1398698B1 (en) * 2010-02-24 2013-03-08 Mesa S A S Di Malimpensa Simona E Davide E C METHOD FOR THE PROTECTION OF SILVER SURFACES AND ITS UNDERSTANDING ALLOYS.
CN101967631A (en) * 2010-11-04 2011-02-09 西北工业大学 Water-soluble silver anti-blushing agent and preparation method and using method thereof
JP5666940B2 (en) * 2011-02-21 2015-02-12 株式会社大和化成研究所 SEALING AGENT SOLUTION AND SEALING TREATMENT METHOD USING THE SAME
JP5599762B2 (en) * 2011-06-17 2014-10-01 富士フイルム株式会社 Ink composition, ink set, and image forming method
US9293571B2 (en) * 2012-08-09 2016-03-22 City University Of Hong Kong Metal nanoparticle monolayer
JP6004469B2 (en) * 2012-08-31 2016-10-05 Ｊｘ金属株式会社 Metal surface treatment agent and surface treatment method
TW201509245A (en) * 2013-03-15 2015-03-01 Omg Electronic Chemicals Llc Process for forming self-assembled monolayer on metal surface and printed circuit board comprising self-assembled monolayer
CN103726056B (en) * 2013-12-26 2015-10-21 张文博 The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4885064A (en) * 1989-05-22 1989-12-05 Mcgean-Rohco, Inc. Additive composition, plating bath and method for electroplating tin and/or lead

Also Published As

Publication number Publication date
EP3475466B1 (en) 2020-03-04
TW201819686A (en) 2018-06-01
CN109477226A (en) 2019-03-15
JP2019520480A (en) 2019-07-18
JP6931010B2 (en) 2021-09-01
US20190177859A1 (en) 2019-06-13
KR20190021326A (en) 2019-03-05
ES2781310T3 (en) 2020-09-01
WO2017220790A1 (en) 2017-12-28
KR102351460B1 (en) 2022-01-13
EP3475466A1 (en) 2019-05-01

Similar Documents

Publication Publication Date Title
TWI746583B (en) A water-based composition for post-treatment of metal surfaces
TWI688679B (en) Tin plating bath and tin coating
BR112017021409B1 (en) METHOD FOR PHOSPHATATION OF A METALLIC SURFACE, AND, METALLIC SURFACE COATED WITH PHOSPHATE
JPH0633503B2 (en) Anodized sealant composition for aluminum
TW201343980A (en) Method of preventing silver tarnishing
US6555170B2 (en) Pre-plate treating system
KR101286661B1 (en) Silver-containing alloy plating bath and method for electrolytic plating using same
EP3178968A1 (en) Copper-nickel alloy electroplating bath
US11505874B2 (en) Methods and apparatuses for mitigating tin whisker growth on tin and tin-plated surfaces by doping tin with germanium
CN102282294B (en) Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface
JP6192181B2 (en) Electronic component and manufacturing method thereof
TWI417429B (en) An electroplating bath using the electroplating bath, and a substrate deposited by the electrolytic plating
TWI577831B (en) Surface treatment solution
JP2008144228A (en) Chemical dissolution control agent for metal, chemically dissolving solution for metal, and chemically dissolving method for metal
KR101033913B1 (en) Method for the carboxylation treatment of metal surfaces, use of said method in order to provide temporary protection against corrosion and method for producing shaped sheet metal thus carboxylated
JP6006475B2 (en) Liquid for forming microstructural film on metal surface
KR100802878B1 (en) Metal surface treating agent, surface treating method and use thereof
JP2015067853A (en) Electronic component and manufacturing method thereof
CN115044894B (en) Water-based protective agent shared by gold and tin plating layers and preparation method thereof
JP2005041989A (en) Detergent composition for component made of tin-containing alloy, and washing method
JP2020111765A (en) Hydrophilization treatment agent for metal plate, and hydrophilization treatment method using the same
KR20200007584A (en) Composition for cleaning mask and method for cleaning mask using the same
JP2796213B2 (en) Continuous surface treatment method for copper and copper alloy
EP3889318A1 (en) Method for forming a black-passivation layer on a zinc-iron alloy and black-passivation composition
CN114657618A (en) Electroplating pretreatment process for aluminum base material PCB circuit board and application thereof