TW438905B - Metal plating pertreatment agent and metal plating method using the same - Google Patents
Metal plating pertreatment agent and metal plating method using the same Download PDFInfo
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- TW438905B TW438905B TW088111492A TW88111492A TW438905B TW 438905 B TW438905 B TW 438905B TW 088111492 A TW088111492 A TW 088111492A TW 88111492 A TW88111492 A TW 88111492A TW 438905 B TW438905 B TW 438905B
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
438905 五、發明說明（1) [發明領域] 本發明有關一葙益山—办 *料、或粉末狀材鍍層在具有低導電性、鏡面 關供其使用之金屬鍍層前處理劑。 有 [背景技藝] 屬膜St鍵層：法係在不具有導電性之基材上形成金 # .及一般使用藉由預先黏著至基材作為觸 ^ . 絶）而活化有關之方法作為無電鍍層用之 :理Ϊ蕻Ϊ:、嗇已使用一種藉由在以Μ 12之氩氣酸溶液 ，理後藉由浸潰於PdCi2水溶液中而使pd吸附在基材上之 法’或「種藉由含有Sn及以之膠體溶液使pd被支撐於表 上之方法此等方法具有與使用Sn(複雜的處理步驟）等 關之許多問題°如此’近來已提出種種方法，其中使用 ，夠Λ此等貴/屬形成錯合物之具有官能基…偶合劑 ^日本專利么報第59_52701號、日本專利公報公開第 0-181 294號、日本專利公報公開第61 194183號、及日本 專利公報公開第3-44149號），以作為在表面上支撐使用作 為無電鍍層用之觸媒之貴金屬（如：pd)之方法。然而若 嘗試使其中所述之矽烷偶合劑均勻吸附於基材上，則習用 之胺基矽烷偶合劑或環氡矽烷偶合劑將易在水溶液令經由 脫水縮合作用而硬化成凝膠，所以此等凝膠在高濃度下益 法落解。進-#，因為水解之縮合作用在有機溶劑中難以 發生及其大部分係以單體之形式存在，所以溶液之黏度 低《因此，即使此種矽烷偶合劑均勻分佈在鏡面材料上，438905 V. Description of the invention (1) [Field of the invention] The present invention relates to a pre-treatment agent for a metal plating layer having a low conductivity and a mirror surface for coatings of powdered materials or powder materials. There is [Background technology] Metal film St bond layer: The method is to form gold on a substrate that does not have conductivity. And it is generally used as a method of electroless plating by pre-adhesion to the substrate as a contact. The layer is used for: Ϊ 蕻 Ϊ :, 啬 has used a method of absorbing the pd on the substrate by immersing in an aqueous solution of PdCi2 after the argon acid solution at M12, or "species Methods for supporting pd on a table by containing a colloidal solution with Sn These methods have many problems related to the use of Sn (complex processing steps), etc. So, recently, various methods have been proposed, among them, These expensive / complex-containing functional groups ... coupling agents ^ Japanese Patent No. 59_52701, Japanese Patent Publication No. 0-181 294, Japanese Patent Publication No. 61 194183, and Japanese Patent Publication No. 3-44149) as a method for supporting and using precious metals (such as pd) as catalysts for electroless plating on the surface. However, if you try to make the silane coupling agent described therein uniformly adsorbed on the substrate, Amine-based silane coupling agents or Cyclopentasilane coupling agents will easily harden into gels through dehydration and condensation in aqueous solution, so these gels will decompose efficiently at high concentrations. Enter-#, because the condensation of hydrolysis is difficult to occur in organic solvents and Most of them exist as monomers, so the viscosity of the solution is low. Therefore, even if this silane coupling agent is evenly distributed on the mirror material,
C:\Program Files\Patent\3l0707.ptd 第 5 頁 438905 五、發明說明（2) 但是因為難以控制臈厚’所以偶合劑亦僅能夠提供薄膜。 如此’因為於表面上僅能夠存在少量之獲取貴金屬之官能 基’所以在後步驟具有鍍層觸媒功能之貴金屬均勻的 於其上。結果，難以均勻形成無電鍍膜。因此，對於 在鏡面玻璃表面上之無電鍍層而言，目前仍以其中藉由氩 氟酸或熱強驗溶液之方式將表面粗較化之方法進行。進一 步二於處理粉末狀材料時，因為習用之胺基矽烷偶合劑及 ，氧矽烷偶合劑對於表面u黏著,所以處理液中之溶劑 需要完全蒸發，如此能強迫偶合劑黏著至粉末表面及其 後藉由水解縮合用之加熱而乾燥β [發明揭示] 於如此情況下’本發明之目的係提供一種新穎之無電 方式之金屬鍍層方法，其中能夠成功的將金屬鍍層塗敷於 以習用方式難以將無電鍍層塗敷之粉末材料或鏡像材料 上’及提供一種其金屬鍍層前處理劑。 本發明之發明人已致力研究，及已發現上述之問題能 夠藉由選擇特定之矽烷偶合劑作為具有與如上述之貴金屬 離子形成錯合物之能力之矽烷偶合劑而解決，因而達成本 發明。 即，本發明有關下列項目： (ο—種金屬鍍層前處理劑，包括藉由唑類化合物與環氧 矽烷類化合物反應所獲得之矽烷偶合劑，該唑^化合 物具有能與貴金屬離子形成錯合物之活性官能基。 (2) —種金屬鍍層方法，特徵在於以含有貴金屬離子之溶C: \ Program Files \ Patent \ 3l0707.ptd Page 5 438905 V. Description of the invention (2) However, because it is difficult to control the thickness, the coupling agent can only provide a thin film. Thus, 'because only a small amount of functional groups capable of acquiring precious metals can be present on the surface', the precious metals having a plating catalyst function in a later step are uniformly formed thereon. As a result, it is difficult to form an electroless plated film uniformly. Therefore, for the electroless plating layer on the surface of the mirror glass, the method of roughening the surface by means of argon fluoride or a thermal test solution is still performed. Further, when processing powdery materials, because the conventional amine-based silane coupling agent and oxysilane coupling agent adhere to the surface u, the solvent in the treatment solution needs to be completely evaporated, which can force the coupling agent to adhere to the powder surface and thereafter. Drying by heating for hydrolysis and condensation β [Invention of the invention] In this case, the object of the present invention is to provide a novel electroless metal plating method, in which the metal plating can be successfully applied to the conventionally difficult to apply The electroless plating layer is applied on a powder material or a mirror image material, and a metal plating pretreatment agent is provided. The inventors of the present invention have made intensive studies, and have found that the above-mentioned problems can be solved by selecting a specific silane coupling agent as a silane coupling agent having the ability to form a complex with a noble metal ion as described above, and thus have reached the cost of the invention. That is, the present invention relates to the following items: (o—a metal plating pre-treatment agent, including a silane coupling agent obtained by reacting an azole compound with an epoxy silane compound, the azole compound having a complex capable of forming a noble metal ion (2) —A method of metal plating, which is characterized by a solution containing precious metal ions.
4389 0 5 五、發明說明（3) 液處理已經使用藉由吐類化合物 裕祺值子坊π加人如 興環氣石夕院類化合物 反應所獲知之砍院偶合劑進行* ;占 材料，該唾類化合杨具有能與要被鍍層之 之活性官能基，及然後進行無=離子形成錯合物 (3) 如上述第（2)項之金屬鍍層方法， 唑。 古其令唑類化合物為咪 其中貴金屬離子為把 其中以銅或錄進行益 * » *»«、 (4) 如上述第（2)項之金屬鍍層方法 離子》 (5) 如上述第（2)項之金屬鍍層方法 電鍍層。 [進行本發明之最佳方法] 對於本發明而t，重|者為使用4有能與貴金屬形成 錯〇物之官能基之唑類化合物與環氧矽烷類化合物之反應 產物作為用以在無電鍍層中要被鍍層之表面上支撐貴金屬 如：Pd，（觸媒）之矽烷偶合劑，或作為具有能夠與貴金屬 形成錯合物之上示官能基之矽烷偶合劑。 如上述之唑類化合物，可述及吡咯、吲哚、咪唑、吡 吐、苯并味峻、吲唑等，但不限於此。如上述之環氧矽烷 類化合物，可述及在一個分子中具有環氧基與烷氧單矽烷 基之化合物，一般包含r —縮水甘油氧丙基烷氧基矽烷， 但不限於此。藉由唑類化合物與環氧矽烷類化合物之反應 所獲得之矽燒偶合劑為本身已眾所熟知者。例如，日本專 利申請案公開第6-256358號揭示味啥，石夕烧化合物可藉由 咪唾化合物與環氧矽烷之反應而獲得；然而，以相同之方4389 0 5 V. Explanation of the invention (3) The liquid treatment has been performed using the chopstick coupling agent obtained through the reaction of the vomiting compound Yuqi Value Zifang π plus Renxing Xingqi Shixiyuan compound reaction *; accounting for materials, The salivary compound has an active functional group capable of contacting with the layer to be plated, and then a metal plating method such as the above-mentioned item (2), azole, is performed without ion formation. Guchlingazole compounds are imid. Among them, noble metal ions are benefited by copper or metallurgical compounds. »» * »«, (4) Ion of metal plating method as described in item (2) above "(5) As described in item (2) above ) Item of the metal plating method plating layer. [The best method for carrying out the present invention] For the present invention, t, it is important to use the reaction product of an azole compound and an epoxy silane compound with a functional group capable of forming a complex with a precious metal as Noble metals such as Pd, (catalyst) silane coupling agents are supported on the surface of the plating layer to be plated, or as silane coupling agents with functional groups shown above that can form complexes with precious metals. Examples of the azole-based compound include, but are not limited to, pyrrole, indole, imidazole, pyritantine, benzosulfone, indazole, and the like. As the above-mentioned epoxysilane compound, the compound having an epoxy group and an alkoxymonosilane group in one molecule may be mentioned, but generally includes r-glycidyloxypropylalkoxysilane, but is not limited thereto. The sintered coupling agent obtained by the reaction of an azole compound and an epoxy silane compound is well known in itself. For example, Japanese Patent Application Laid-Open No. 6-256358 discloses that the shibayan compound can be obtained by the reaction of a saliva compound with an silane oxide; however, in the same way
C:\ProgramFiles\Patent\3I0707.ptd 第 7 頁 438905 五、發明說明（4) 式可進行與其他唑類化合物之反應。雖然可獲得含有分子 間與分子内縮合物之矽烷偶合劑（反應產物），卻不一定需 要彼此分離’而能夠以混合物之形式使用。此等矽烷偶合 劑具有高反應性，及能夠藉由控制水溶液之酸度而調配成 具有任何恣意之濃度之水溶液。進一步，諸劑提供溶解之 溶液若干黏度。如此，能夠藉由使用矽烷偶合劑在要被鍍 層之材料之基材表面上以特定之厚度均勻形成塗覆膜。此 外’尚能夠在包含難以藉由習用之偶合劑（如：胺基矽烷） 鑛層之鏡面材料或僅能夠在溶劑蒸發後被處理之粉末狀材 料之種種基材表面輕易進行無電鍍層。如上述之貴金屬， 可述及鈀、銀、鉑、金等，此等金屬在將金屬（如：銅或 鎳）自無電鍍層溶液沉積於要被鍍層之材料表面上之期間 呈現催化效應，鈀係特別佳。 如本發明之金屬鍍層方法中，要被鍍層之材料不限於 其性質。雖然該方法可應用於無機材料如：玻璃及陶瓷； 塑膠材料如：$ SI、聚酿胺、聚醒亞胺、及氟樹脂；絕緣 材料如：環氧樹脂等之藉由前述之無機或塑膠材料等所製 地之膜、、織維、及若需要的話，玻璃纖維基材所補強 之絕緣板；及具有低導電性之要被鍍層之材料，如·包含 Si晶圓之半導體，如本發明之方法能夠成功的實施於包含 鏡面表面材料（如：透明玻璃板、Si晶園、及苴他半導體 J材)及粉末狀材料之要被鑛層之材料。如此種粉末狀材 :’可述及玻璃珠、二硫化飽粉末、氧化鎂粉末、石墨粉 末、SiC粉末、乳化錯粉末、链氧粉末、氧化石夕粉末雲C: \ ProgramFiles \ Patent \ 3I0707.ptd Page 7 438905 V. Description of the invention Formula (4) can be used to react with other azole compounds. Although silane coupling agents (reaction products) containing intermolecular and intramolecular condensates can be obtained, they do not necessarily need to be separated from each other 'and can be used as a mixture. These silane coupling agents are highly reactive and can be formulated into an aqueous solution having any desired concentration by controlling the acidity of the aqueous solution. Further, the agents provide several viscosities of the dissolved solution. In this way, it is possible to uniformly form a coating film with a specific thickness on the surface of the substrate of the material to be plated by using a silane coupling agent. In addition, it is also possible to easily perform electroless plating on the surface of various substrates containing mirror-like materials that are difficult to use with conventional coupling agents (such as amine silanes) or powdery materials that can only be processed after solvent evaporation. As the above precious metals, palladium, silver, platinum, gold, etc. can be mentioned. These metals exhibit a catalytic effect during the deposition of a metal (such as copper or nickel) from an electroless plating solution on the surface of the material to be plated. Palladium is particularly preferred. As in the metal plating method of the present invention, the material to be coated is not limited to its properties. Although this method can be applied to inorganic materials such as: glass and ceramics; plastic materials such as: $ SI, polyamine, polyimide, and fluororesin; insulating materials such as epoxy resin, etc. through the aforementioned inorganic or plastic Materials such as films, fabrics, and insulation boards reinforced with glass fiber substrates if necessary; and materials to be plated with low conductivity, such as semiconductors containing Si wafers, such as this The method of the invention can be successfully implemented on a material to be mineralized including a mirror surface material (such as a transparent glass plate, a Si crystal garden, and a solar semiconductor J material) and a powdery material. Such a powdery material: 'can be mentioned glass beads, disulfide saturated powder, magnesium oxide powder, graphite powder, SiC powder, emulsified powder, chain oxygen powder, stone oxide powder cloud
438905 五、發明說明（5) 母薄片、玻璃織維、氮化碎、或特夫綸粉末等。 於使用上述之峻類化合物與環氧矽烷類化合物之反應 產物之梦烧偶合劑處理之無電鍍層用之基材表面時石夕烷 偶合劑能夠溶解於適合之溶劑如：水、甲醇、乙醇、2丙 醇丙f苯、乙一醇、》乙二醇、或其混合溶而 形成溶液。對於板狀之基材表面而言，一般使用—種藉由 浸潰處理或刷塗，其後將溶劑蒸發而塗覆基材表面之方 法，但不限於此。能使用可將矽烷偶合劑均勻黏著至表面 之任何方法。再者，對於粉末狀材料而言，除了在浸潰處 理後使溶劑蒸發以強迫溶液中所含有之矽烷偶合劑黏著至 表面之方法之外’因為在浸漬狀態下由於其均勾成膜 性質而能夠將矽烷偶合劑吸附在基材表面上，所以尚可有 在以鍍層溶液處理後藉由過濾之方式移除溶劑而使濕粉末 材料乾燥之方法。 總之，處理液中之矽烷偶合劑之濃度並無限制，但實 用時一般為0.001至10重量％。若少於〇 〇〇1重量％時’黏 著至基材表面之偶合劑之量易變低，如此難以獲得盆效 ，。進一步，若量高於10重量％，則黏著之量變太多'，使 什乾燥固難，U形成粉末聚集。對於在表面處理後 之溶劑蒸發而言，則至少在溶劑之揮發溫度下加熱 /、表面乾燥即為充分，但較佳為在60至120下 乾燥達10至60分鐘。 「加熟與 如上述處理之材料表面上進行化學鍍層之方法 為眾所熟知之方法。即，藉由與含有貴金屬離子(例如把去438905 V. Description of the invention (5) Mother sheet, glass weave, nitrided powder, or Teflon powder. When the surface of the substrate for the electroless plating layer treated with the dream product of the reaction product of the above-mentioned compound and the epoxy silane compound is used, the lithoxane coupling agent can be dissolved in a suitable solvent such as water, methanol, and ethanol , 2 propanol, propyl benzene, ethylene glycol, ethylene glycol, or a mixture thereof to form a solution. For a plate-like substrate surface, a method of coating the substrate surface by dipping or brushing and then evaporating the solvent is generally used, but is not limited thereto. Any method that can uniformly adhere the silane coupling agent to the surface can be used. Moreover, for powdery materials, in addition to the method of evaporating the solvent after the impregnation treatment to force the silane coupling agent contained in the solution to adhere to the surface, 'because it is a film-forming property in the impregnated state. The silane coupling agent can be adsorbed on the surface of the substrate, so there is still a method for drying the wet powder material by removing the solvent by filtering after the treatment with the plating solution. In short, the concentration of the silane coupling agent in the treatment liquid is not limited, but it is generally 0.001 to 10% by weight in practical use. If it is less than 0.0001% by weight, the amount of the coupling agent that is adhered to the surface of the substrate tends to be low, so that it is difficult to obtain a pot effect. Further, if the amount is more than 10% by weight, the amount of adhesion becomes too large, making it difficult to dry and solidify, and U forms powder aggregates. For solvent evaporation after surface treatment, it is sufficient to heat / dry the surface at least at the volatilization temperature of the solvent, but it is preferred to dry at 60 to 120 for 10 to 60 minutes. "The method of curing and electroless plating on the surface of a material treated as described above is a well-known method. That is, by combining with precious metal ions (such as
438905438905
五、發明說明（6) 離子）之溶液接觸，而將貴金屬捕獲在處理基底表面用之 偶合劑之唑基上。在洗除過量之可溶性貴金屬鹽如：幽 物與溶解化劑如：氩氣酸後’進行化學鍍層處理，例如無 進一步，可首先進行無電鍍層以將金屬薄膜鍍在非導 電性之基材表面上’使其成為導電性，及然後可使用基底 金屬進行電鍍或取代鍍層。 如本發明，能夠藉由無電鍍層鍍如•銅、鎮、銘、 錫、或金之金屬，及如下列敘述本發明中所使用之舉例性 之無電鍍層溶液。 ①高速與厚鍍層用之無電鍍銅組成物之典型實例：5. Explanation of the invention (6) Ion) solution is contacted, and the precious metal is captured on the azole group of the coupling agent used for treating the surface of the substrate. After washing away excess soluble precious metal salts, such as: foul matter and dissolving agents, such as: argon acid, the chemical plating process is performed. For example, without further steps, an electroless plating layer may be performed first to plate the metal thin film on a non-conductive substrate. The surface 'makes it conductive, and then the base metal can be used for plating or to replace the plating. According to the present invention, it is possible to plate a metal such as copper, town, inscription, tin, or gold by an electroless plating layer, and an exemplary electroless plating solution used in the present invention as described below. ① Typical examples of electroless copper composition for high speed and thick plating:
CuS04 · 5H20 0. 04 至0. 〇 6 莫耳/ 升 EDTA . 2Na 〇♦ 04 至0 1 2 莫耳/ 升 HCHOC37%) 0_ 08 至0.5 莫耳/ 升CuS04 · 5H20 0. 04 to 0. 〇 6 moles / liter EDTA. 2Na 〇 ♦ 04 to 0 1 2 moles / liter HCHOC37%) 0_ 08 to 0.5 moles / liter
Ph 12 至 12. 5Ph 12 to 12. 5
鍍層溫度 70至90 °C 0低溫無電鍍銅組成物之典型實例： CuS04 * 5H20 12. 5 至 14· 5 克/ 升 HCHO(37%) 20 至25 克/升 羅謝爾鹽（Rochelle salt) 25至40克/升 pH 12. 2 至1 2. 5 鍍層溫度 20至30 t ③作為高溫酸性池之無電锻N i組成物之典型實例： 硫酸鎳 2G至22克/升Coating temperature 70 to 90 ° C 0 Typical examples of low temperature electroless copper composition: CuS04 * 5H20 12. 5 to 14.5 g / l HCHO (37%) 20 to 25 g / l Rochelle salt 25 to 40 g / L pH 12. 2 to 1 2. 5 Coating temperature 20 to 30 t ③ Typical example of electroless forging Ni composition as high temperature acid bath: Nickel sulfate 2G to 22 g / L
4389 0 5 五、發明說明（7) 乳酸 丙酸 次磷酸鈉4389 0 5 V. Description of the invention (7) Lactic acid Propionic acid Sodium hypophosphite
pH 溫度pH temperature
25至30克/升 2至3克/升 20至22克/升 4. 5 至5_ 5 80 至 90 〇C25 to 30 g / l 2 to 3 g / l 20 to 22 g / l 4.5 to 5_ 5 80 to 90 ° C
鹼性Alkaline
④作為低溫氨 硫酸鎳 焦磷酸鈉 次鱗酸納 pH 鍍層溫度 池之無電鍍Ni 24至26克/升 48至52克/升 24至26克/升 10 至 11④ As low-temperature ammonia nickel sulfate sodium pyrophosphate sodium hyposcale acid pH coating temperature electroless Ni 24 to 26 g / L 48 to 52 g / L 24 to 26 g / L 10 to 11
55 至65 °C 組成物之典型實例： [實例] [實例1 ] 1 mm厚度之載玻片以鹼脫脂液處理後，藉由使用含 0.4重量％之矽烷偶合劑之2 -丙醇溶液，於玻片表面上从 500 RPM進行旋轉塗佈，該碎烧偶合劑為咪嗤與縮水甘 油氧丙基三甲氧基矽烷之等莫耳反應產物。其後，使破 片在105 C下乾燥30分鐘。在將該玻片進一步浸潰於室溫 下之Pd活化之溶液（CG-535A，一種活化劑，Nikko金屬鍵 層股份有限公司製造）中達1分鐘後，使用約1〇〇 之去離 子水洗滌，及於105 eC下乾燥30分鐘，以在玻片表面上使 用貴金屬進行活化處理。然後，將如此活化之玻片浸漬於 80°C下之無電鍍鎳溶液（NIKOMU 7N，Nikko金屬鍍層股份 有限公司製造）中達4分鐘。發現藉由無電鍍鎳溶液在整個Typical examples of the composition at 55 to 65 ° C: [Example] [Example 1] After a 1 mm thick glass slide was treated with an alkaline degreasing solution, by using a 2-propanol solution containing 0.4% by weight of a silane coupling agent, Spin coating was performed on the surface of the glass slide from 500 RPM. The crushed-coupling coupling agent was a mole reaction product such as imidazole and glycidyloxypropyltrimethoxysilane. Thereafter, the fragments were dried at 105 C for 30 minutes. After the slide was further immersed in a Pd-activated solution (CG-535A, an activator, manufactured by Nikko Metal Bond Co., Ltd.) at room temperature for 1 minute, about 100 deionized water was used. Wash and dry at 105 eC for 30 minutes to activate the surface with a precious metal on the glass slide. Then, the thus activated glass slide was immersed in an electroless nickel plating solution (NIKOMU 7N, manufactured by Nikko Metallization Co., Ltd.) at 80 ° C for 4 minutes. Found by electroless nickel solution throughout
C:\ProgramFiles\Patent\310707.ptd 第 11 頁 438905 五、發明說明（8) 破璃表面上沉積均勻光澤之膜，以便具有良好之黏著，；f 會因玻璃紙膠帶而剝落。 [比較例1 ] 在將具有1 mm厚度之載玻片以鹼脫脂液處理後，將该 玻片浸潰於室溫下之Pd活化之溶液（CG-535A)中達1分键’ 不在表面上以偶合劑做任何處理，及其後使用約1〇〇 之 去離子水洗滌’及於1〇5 °c下乾燥3〇分鐘，以在玻片表面 上使用貴金屬進行活化處理。然後，將活化之玻片浸漬於 8 0 °C下之無電鍍鎳溶液（NIKOMU 7Ν)中達4分鐘。玻片上沉 積稀少之無電鎳鍍膜。 [比較例2] 在藉由將具有1 mni厚度之載玻片浸漬於25t下之氫象 酸與硝酸之混合溶液（100 ml/L之氫氟酸與1〇〇 mi/L之硝 酸）達10分鐘而進行表面粗糙化學處理後。該玻片以鹼脫 脂液處理及浸潰於室溫下之Pd活化之溶液（CG-5 35A)中達1 分鐘後’使用約1〇〇 ml之去離子水洗滌，及於105 °c下乾 燥30分鐘，以在玻片表面上使用貴金屬進行活化處理。然 後’將如此活化之玻片浸潰於80 °C下之無電鍍鎳溶液 (ΝίΚΟΜϋ 7N)中達4分鐘。玻片上沉積稀少之無電鎳鍍膜。 [比較例3 ] 在將具有1 mm厚度之載玻片以鹼脫脂液處理後，藉由使用 含有0. 4重量％之胺基矽烷偶合劑（KBM-903，Shinetsu Kagaku Kogyo股份有限公司製造，γ -胺基丙基三甲氧基 矽烷）之2 -丙醇溶液，於玻片表面上以500 RPM進行旋轉塗C: \ ProgramFiles \ Patent \ 310707.ptd Page 11 438905 V. Description of the invention (8) A uniform and shiny film is deposited on the broken glass surface so as to have good adhesion; f will be peeled off by cellophane tape. [Comparative Example 1] After a glass slide having a thickness of 1 mm was treated with an alkaline degreasing solution, the glass slide was immersed in a Pd-activated solution (CG-535A) at room temperature to achieve a 1-point bond. The coupling agent was used for any treatment, and then washed with about 100 'deionized water' and dried at 105 ° C for 30 minutes, to perform activation treatment on the surface of the slide with precious metals. Then, the activated slide was immersed in an electroless nickel solution (NIKOMU 7N) at 80 ° C for 4 minutes. Rarely deposited electroless nickel coating on the glass slide. [Comparative Example 2] A glass slide having a thickness of 1 mni was immersed in a mixed solution of hydrogen-like acid and nitric acid (100 ml / L of hydrofluoric acid and 100 mi / L of nitric acid) at 25 t 10 minutes after surface roughening chemical treatment. The slide was treated with an alkaline degreasing solution and immersed in a Pd-activated solution (CG-5 35A) at room temperature for 1 minute, and then 'washed with about 100 ml of deionized water and at 105 ° C. Dry for 30 minutes to activate the surface with a precious metal on the glass slide. Then, the thus activated glass slide was immersed in an electroless nickel solution (NίΚΟΟ 7N) at 80 ° C for 4 minutes. A rare electroless nickel coating is deposited on the glass slide. [Comparative Example 3] After a glass slide having a thickness of 1 mm was treated with an alkali degreasing solution, by using an aminosilane coupling agent (KBM-903, manufactured by Shinetsu Kagaku Kogyo Co., Ltd., containing 0.4% by weight, γ-aminopropyltrimethoxysilane) 2-propanol solution, spin-coated on the surface of the slide at 500 RPM
C:\ProgramFiles\PatenU3l0707.ptcl 第 12 頁C: \ ProgramFiles \ PatenU3l0707.ptcl page 12
43 890 5 五、發明說明（9) 佈。其後’使玻片在105 °C下乾燥30分鐘°在將該玻片進 一步浸潰於室溫下之Pd活化之溶液（CG-535A)中達1分鐘 後’使用約100 ml之去離子水洗滌，及於l〇5°C下乾燥30 分鐘，以在玻片表面上使用貴金屬進行活化處理β然後， 浸溃於80°C下之無電鍍鎳溶液（NIKOMU 7Ν)中達4分鐘。無 電鎳鍍層僅沉積於部份之玻片處。 [比較例4與5 ] 為了促進水解縮合，藉由添加少量之氫氯酸至等量之 水與2-丙醇之混合溶液，及然後溶解〇. 4重量％或其10倍 (即’4重量％)(比較例5)之胺基矽烷偶合劑KBM-90 3於溶 液中，而製備溶液。在進行如比較例3所示之相同貴金屬 活化處理後，在各活化玻片上進行無電鍍鎳β於二例中， 無電鍍層僅在實質上一半之玻片上不均勻的進行D [實例2] 在使pet膜（商品名：Diafoil)於2 -丙醇中進行超音波 洗滌達5分鐘以在表面上進行脫脂處理後，於1〇5 eC下乾燥 達10分鐘。在將膜浸潰於含有4重量％之矽烷偶合劑（即， 咪唑與r_縮水甘油氧丙基三乙氧基矽烷之等莫耳反應產 物）之2 -丙醇溶液中達1分鐘後，於105 °c下乾燥達1〇分 鐘。在將該片進一步浸漬於室溫下之Pd活化之溶液 (CG-535A)中達1分鐘後，使用去離子水洗滌，及於i〇5°c 下乾燥10分鐘’以在pet膜之表面上使用貴金屬進行活化 處理。然後’浸潰於72 °C下之無電鍍銅溶液（KC ~500， Nikko金屬鍵層股份有限公司製造）中達20分鐘。無電鑛銅43 890 5 V. Description of Invention (9) Cloth. Thereafter, 'the slide was dried at 105 ° C for 30 minutes. After further immersing the slide in a Pd-activated solution (CG-535A) at room temperature for 1 minute', about 100 ml of deionization was used. It was washed with water, and dried at 105 ° C for 30 minutes to perform the activation treatment with a precious metal on the surface of the slide β, and then immersed in an electroless nickel solution (NIKOMU 7N) at 80 ° C for 4 minutes. Electroless nickel plating is only deposited on a portion of the glass slide. [Comparative Examples 4 and 5] In order to promote the hydrolytic condensation, by adding a small amount of hydrochloric acid to a mixed solution of an equal amount of water and 2-propanol, and then dissolving 0.4% by weight or 10 times (ie, '4 % By weight) (Comparative Example 5) of an aminosilane coupling agent KBM-90 3 in a solution to prepare a solution. After performing the same precious metal activation treatment as shown in Comparative Example 3, electroless nickel plating was performed on each activated glass slide. In the two cases, the electroless plating layer was unevenly performed only on substantially half of the glass slide [Example 2] After a pet film (trade name: Diafoil) was subjected to ultrasonic washing in 2-propanol for 5 minutes to degrease the surface, it was dried at 105 eC for 10 minutes. After immersing the membrane in a 2-propanol solution containing 4% by weight of a silane coupling agent (ie, a mole reaction product of imidazole and r-glycidyloxypropyltriethoxysilane), for 1 minute, Dry at 105 ° C for 10 minutes. After the sheet was further immersed in a Pd-activated solution (CG-535A) at room temperature for 1 minute, it was washed with deionized water and dried at 105 ° C for 10 minutes' to the surface of the pet film. Noble metals are used for activation. Then, it was immersed in an electroless copper solution (KC ~ 500, manufactured by Nikko Metal Bond Co., Ltd.) at 72 ° C for 20 minutes. Electroless copper
C:\ProgramFiIes\Patent\3i0707.ptd 第 13 頁 4389 0 5 五、發明說明（ίο) - 允許在整個pet膜表面上沉積均勻光澤之膜。 [實例3] ' 在將具有玻璃織品基材之環氧樹脂絕緣片（藉由將銅 以化學姓刻之方式自Matsushita Denko股份有限公司所製 之塗佈銅之層壓片FR-4移除所獲得之片材）浸潰於含有〇4 重量％之矽烷偶合劑（其為咪唑與縮水甘油氧丙基三甲 氧基矽燒之等莫耳反應產物）之2 -丙醇溶液中達1分鐘後， 於1 05 °C下乾燥達60分鐘。然後，在將該積層片浸潰於室 溫下之Pd活化之溶液（CG-53 5A)中達1分鐘後，使用去離子 水洗滌’及於105 °C下乾燥60分鐘，以在層壓片之表面上 使用貴金屬進行活化處理。在將層壓片浸潰於8(rc下之無 電链錄溶液（NIKOMU 7N)中達2分鐘後，在層魔片上均句沉 積無電鎳鍍膜。進一步’當將以責金屬進行過類似之活化 處理之層壓片浸潰於70。(：下之無電鍍銅溶液（KC- 500)達 30分鐘時，於表面上均勻沉積銅。 [比較例6 ] 在將類似於實例3之具有玻璃織品基材之環氧樹脂絕 緣片浸潰於藉由將少量之氫氯酸添加至等量之水與2_丙醇 所形成之混合溶液所製備之溶液中，及然後將〇 4重量％ 之胺基矽烷偶合劑（KBM- 903 )溶解於溶液中達1分鐘後，於 105 °C下乾燥達60分鐘。在將該片材進一步浸漬於室溫下 之Pd活化之溶液（CG-53 5 Α)中達1分鐘後，使用去離子水洗 滌，及於105 °C下乾燥60分鐘，以在層壓片之表面上使用 貴金屬進行活化處理。在將片材浸潰於80 °C下之無電鑛錄C: \ ProgramFiIes \ Patent \ 3i0707.ptd Page 13 4389 0 5 5. Description of the Invention (ίο)-Allows to deposit a uniform and shiny film on the entire pet film surface. [Example 3] 'The epoxy resin insulating sheet having a glass fabric substrate (by engraving copper with a chemical surname was removed from a copper-coated laminated sheet FR-4 made by Matsushita Denko Co., Ltd. The obtained sheet was immersed in a 2-propanol solution containing 0. 4% by weight of a silane coupling agent (which is a Mohr reaction product such as imidazole and glycidyloxypropyltrimethoxysilane) for 1 minute. Then, it was dried at 105 ° C for 60 minutes. Then, the laminated sheet was immersed in a Pd-activated solution (CG-53 5A) at room temperature for 1 minute, washed with deionized water ', and dried at 105 ° C for 60 minutes to laminate. The surface of the sheet is activated with a precious metal. After the laminate was immersed in 8 (non-electric chain recording solution (NIKOMU 7N) at rc) for 2 minutes, electroless nickel plating was deposited on the layer magic sheet. Further, when similar activation of the metal was performed The treated laminate was immersed in 70. (: The copper-free electroless copper solution (KC-500) below for 30 minutes, copper was uniformly deposited on the surface. [Comparative Example 6] A glass fabric similar to Example 3 was used. The epoxy resin insulating sheet of the substrate was immersed in a solution prepared by adding a small amount of hydrochloric acid to a mixed solution of an equal amount of water and 2-propanol, and then 0.4% by weight of amine Silane coupling agent (KBM-903) was dissolved in the solution for 1 minute, and then dried at 105 ° C for 60 minutes. The sheet was further immersed in a Pd-activated solution (CG-53 5 Α) at room temperature. ) For 1 minute, wash with deionized water, and dry at 105 ° C for 60 minutes to activate the precious metal on the surface of the laminated sheet. The sheet is impregnated at 80 ° C without electricity Mine record
C:\Program Files\Patent\310707.ptd 第 14 頁 4389 0 5 五、發明說明（11) 溶液（NIKOMU 7N)中達2分鐘後，僅在層壓片之約8〇%之整 個表面上均句沉積無電鎳鍍膜/ [實例4] ' 將20克具有約1.5 mm直徑之玻璃珠浸潰於50 ml之含 有0. 08 g之溶解之矽烷偶合劑（其為咪唑與7-縮水甘油氧 丙基甲基二乙氡基矽烷之等莫耳反應產物）之2-丙醇溶液 中達1分鐘。在將溶液過濾後，於105°C下乾燥達30分鐘。 在將玻璃珠浸潰於室溫下之Pd活化之溶液（CG-535A)中達1 分鐘後，將活化溶液過濾，及進一步使用50 ml去離子水 洗滌’及於1 05 °C下乾燥30分鐘，以在玻璃珠之表面上使 用貴金屬進行活化處理。在將玻璃珠浸潰於80 °C下之無電 鍵錄溶液（NIKOMU 7N)中達4分鐘後，在玻璃珠之整個表面 上均勻沉積無電鎳鍍層。 [比較例7 ] 將具有約1.5 mm直徑之玻璃珠浸潰於50 ml之含有0.4 重量％之胺基矽烷偶合劑（KBM-9 03)之2 -丙醇溶液中達1分 鐘。在將溶液過濾後，使珠子於105 °C下乾燥達30分鐘。 在將玻璃珠浸潰於室溫下之50 ml之Pd活化之溶液 (CG-53 5A)中達1分鐘後，將活化溶液過濾，及進一步使用 50 ml去離子水洗滌，及於l〇5°C下乾燥30分鐘，以在玻璃 珠之表面上使用貴金屬進行活化處理。在將玻璃珠浸潰於 80 t下之無電鍍鎳溶液（NIKOMU 7N)中達4分鐘後，在玻璃 珠之表面上沉積無電鎳鍍膜，留下大於約30%之玻璃珠表 面未被鍍層。C: \ Program Files \ Patent \ 310707.ptd Page 14 4389 0 5 V. Description of the invention (11) After 2 minutes in the solution (NIKOMU 7N), only about 80% of the entire surface of the laminate is Sentence Electroless Nickel Plating / [Example 4] '20 grams of glass beads with a diameter of about 1.5 mm were immersed in 50 ml of a dissolved silane coupling agent containing 0.08 g (which is imidazole and 7-glycidyloxypropyl) Mole reaction products such as methylmethyldiethylsulfanyl silane) in a 2-propanol solution for 1 minute. After the solution was filtered, it was dried at 105 ° C for 30 minutes. After immersing glass beads in a Pd-activated solution (CG-535A) at room temperature for 1 minute, the activation solution was filtered and further washed with 50 ml of deionized water 'and dried at 1 05 ° C for 30 minutes. Minutes to activate the surface with glass beads using precious metals. After immersing the glass beads in an electroless key recording solution (NIKOMU 7N) at 80 ° C for 4 minutes, an electroless nickel plating was uniformly deposited on the entire surface of the glass beads. [Comparative Example 7] Glass beads having a diameter of about 1.5 mm were immersed in 50 ml of a 2-propanol solution containing 0.4% by weight of an aminosilane coupling agent (KBM-9 03) for 1 minute. After filtering the solution, the beads were dried at 105 ° C for 30 minutes. After immersing glass beads in 50 ml of Pd-activated solution (CG-53 5A) at room temperature for 1 minute, the activated solution was filtered, and further washed with 50 ml of deionized water, and at 105 Dry at 30 ° C for 30 minutes to activate the glass beads with precious metals. After immersing the glass beads in an electroless nickel solution (NIKOMU 7N) at 80 t for 4 minutes, an electroless nickel plating film was deposited on the surface of the glass beads, leaving more than about 30% of the surface of the glass beads unplated.
ΙΗϋη HR C:\ProgramFiles\Patent\3I0707.ptd 第 15 買 4389 0 5 五、發明說明（12) [實例5 ] 將25克具有50微米之平均粒度之二硫化鉬粉末於5〇 ml之含有0.1 g之溶解之矽烷偶合劑（其為咪唑與r-縮水 甘油氧丙基二甲氧基矽烷之等莫耳反應產物）之2_丙醇溶 液中於室溫下攪拌10分鐘〇在將溶劑（2_丙醇）蒸餾除去 後’將一硫化齒粉末於105 C下乾燥達6〇分鐘。在將二硫 化钥粉末於50 ml之Pd活化之溶液（CG — 535a)中於室溫下授 拌達20分鐘後’將活化溶液濾除，及進一步使用約5〇 ml 之去離子水洗條’及其後於1〇5 °c下乾燥6〇分鐘，以在粉 末之表面上使用貴金屬進行活化處理。藉由使用無電鍍鋼 溶液（KC-500)使二硫化鉬粉末於72°c下進行鍍層。能夠在 粉末之表面上形成以二硫化鉬粉末之重量為準之僅1重量 %之無電銅鑛層之均勻鋼鍍膜，及能夠完全覆蓋基材表面 (二硫化鉬）。 [比較例8 ] 將具有50微米之平均粒度之二硫化鉬粉末於5〇 mi之 Pd活化之溶液（CG-535A)中於室溫下攪拌達20分鐘，將活 化溶液濾除，及進一步使用5 〇 in 1之去離子水洗滌，及其 後於105 eC下乾燥60分鐘，以在粉末之表面上使用貴金屬 進行活化處理。藉由使用無電鍍銅溶液（KC_50 0 )使二硫化 组粉末於72 °C下進行鍍層，但藉由此無電鍍銅，形成稀少 之銅鍍膜。 [實例6] 將50克具有100微米之平均粒度之氧化鎂粉末於1〇〇ΙΗϋη HR C: \ ProgramFiles \ Patent \ 3I0707.ptd No. 15 Buy 4389 0 5 V. Description of the Invention (12) [Example 5] 25 grams of molybdenum disulfide powder with an average particle size of 50 microns was contained in 50 ml of 0.1 g of a dissolved silane coupling agent (which is a mole reaction product of imidazole and r-glycidyloxypropyldimethoxysilane) in a 2-propanol solution and stirred at room temperature for 10 minutes. 2-propanol) After distillation, the monosulfide tooth powder was dried at 105 C for 60 minutes. After stirring the disulfide powder in 50 ml of Pd-activated solution (CG-535a) at room temperature for 20 minutes, 'the activated solution is filtered off, and the strip is further washed with about 50 ml of deionized water' It was then dried at 105 ° C for 60 minutes to activate the surface of the powder with precious metals. The molybdenum disulfide powder was plated at 72 ° C by using an electroless steel solution (KC-500). It can form a uniform steel coating on the surface of the powder with only 1% by weight of molybdenum disulfide powder, and can completely cover the surface of the substrate (molybdenum disulfide). [Comparative Example 8] Molybdenum disulfide powder having an average particle size of 50 microns was stirred in a Pd-activated solution (CG-535A) at 50 mi for 20 minutes at room temperature, the activated solution was filtered off, and further used Wash with 50in 1 of deionized water and then dry at 105 eC for 60 minutes to activate the surface of the powder with precious metals. The electroless copper solution (KC_50 0) was used to coat the disulfide powder at 72 ° C. However, the electroless copper was used to form a rare copper plating film. [Example 6] 50 g of magnesium oxide powder having an average particle size of 100 μm was added to 100
C:\Prograra Files\Patent\310707.ptd 第 16 頁 43890 5__ 五、發明說明¢13) ml之含有0.2 g之溶解之矽烷偶合劑（其為咪唑與r-縮水 甘油氧丙基三乙氧基矽烷之等莫耳反應產物）之2-丙醇溶 液中於室溫下攪拌10分鐘。在將溶劑（2-丙醇）蒸餾除去 後，於105 °C下乾燥達30分鐘。在將氧化鎂粉末於1〇〇 ml 之Pd活化之溶液（CG-535A)中於室溫下攪拌達20分鐘後， 將活化溶液濾除，及使用100 ml之去離子水洗滌，及其後 於105 °C下乾燥30分鐘’以在粉末之表面上使用貴金屬進 行活化處理。藉由使用無電鍍銅溶液（KC-50 0 )使氧化鎂粉 末於72 °C下進行鍍層。能夠在粉末之表面上形成以氧化鎂 粉末之重量為準之僅1重量％之無電銅鍍層之均勻銅鍍 膜，及能夠完全覆蓋基材表面（氧化鎮）。 [實例7 ] 將25克具有100微米之平均粒度之天然石墨粉末於50 ml之含有0.1 g之溶解之矽烷偶合劑（其為2-乙基-4 -甲基 咪唑與7 -縮水甘油氧丙基三甲氡基矽烷之等莫耳反應產 物）之乙醇溶液中於室溫下攪拌10分鐘。在將溶劑（2-丙 醇）蒸餾除去後，將石墨粉末於105 °C下乾燥達30分鐘。在 將石墨粉末於100 ml之Pd活化之溶液（CG-535A)中於室溫 下攪拌達20分鐘後，將活化溶液濾除，及使用約50 ml之 去離子水洗蘇，及其後於105 °C下乾燥30分鐘，以在粉末 之表面上使用貴金屬進行活化處理。藉由使用無電鍍銅溶 液（KC-500)使石墨粉末於72°C下進行鍍層。能夠在粉末之 表面上形成以石墨粉末之重量為準之6重量％之無電銅鍍 層之均勻銅鍍膜。進一步，當使類似的經過貴金屬活化之C: \ Prograra Files \ Patent \ 310707.ptd Page 16 43890 5__ 5. Description of the invention ¢ 13) ml of 0.2 g of dissolved silane coupling agent (which is imidazole and r-glycidyloxypropyltriethoxy In a 2-propanol solution of a mol reaction product such as silane, the mixture was stirred at room temperature for 10 minutes. After the solvent (2-propanol) was distilled off, it was dried at 105 ° C for 30 minutes. After the magnesium oxide powder was stirred in 100 ml of a Pd-activated solution (CG-535A) at room temperature for 20 minutes, the activation solution was filtered off, washed with 100 ml of deionized water, and thereafter Dry at 105 ° C for 30 minutes' to activate the powder with precious metals on the surface. The magnesium oxide powder was plated at 72 ° C by using an electroless copper solution (KC-50 0). It can form a uniform copper coating on the surface of the powder with only 1% by weight of the electroless copper coating based on the weight of the magnesium oxide powder, and can completely cover the surface of the substrate (oxidized ball). [Example 7] 25 g of natural graphite powder having an average particle size of 100 μm was dissolved in 50 ml of 0.1 g of a dissolved silane coupling agent (which is 2-ethyl-4-methylimidazole and 7-glycidyloxypropyl). A solution of Moire reaction product such as trimethylsulfanylsilane in ethanol solution was stirred at room temperature for 10 minutes. After the solvent (2-propanol) was distilled off, the graphite powder was dried at 105 ° C for 30 minutes. After stirring the graphite powder in 100 ml of a Pd-activated solution (CG-535A) at room temperature for 20 minutes, the activated solution was filtered off, washed with about 50 ml of deionized water, and then 105 Dry at 30 ° C for 30 minutes to activate the powder with precious metals on the surface. The graphite powder was plated at 72 ° C by using an electroless copper solution (KC-500). It is possible to form a uniform copper plating film on the surface of the powder with an electroless copper plating layer of 6% by weight based on the weight of the graphite powder. Further, when similarly activated by precious metals,
C:\ProgramFiles\Patent\310707.ptd 第 17 頁 438905 五、發明說明（14) 石墨粉末浸潰於80 eC下之無電鍍鎳溶液（ΝΙΚΟΜϋ 7N)中達4 分鐘時’在表面上實質上均勻沉積無電錄鍵嫉，粉末顏色 自黑色改變成灰色，及基材表面能夠完全被鎳覆蓋。 [實例8] 將8克具有70微米之平均粒度之SiC粉末於100 ml之含 有0.2 g之溶解之矽烷偶合劑（其為咪唑與γ -縮水甘油氡 丙基三甲氧基矽烷之等莫耳反應產物）之甲醇溶液中於室 溫下攪拌10分鐘。在將溶劑（甲醇）蒸餾除去後，於105 °C 下乾燥達30分鐘。在將SiC粉末於100 ml之Pd活化之溶液 (CG-53 5A)中於室溫下攪拌達20分鐘後，將活化溶液濾 除，及使用100 ml之去離子水洗滌粉末，及其後於105 °C 下乾燥30分鐘，以在粉末之表面上使用貴金屬進行活化處 理。藉由使用無電鍍銅溶液（KC- 500)使SiC粉末於72 °C下 進行鍍層。能夠在粉末之表面上形成以SiC粉末之重量為 準之僅1重量％之無電銅鍍層之均勻銅鍍膜，粉末完全改 變成銅顏色，及綠色SiC粉末能夠完全被覆蓋。 [比較例9 ] 將50克具有70微米之平均粒度之SiC粉末於100 ml之 Pd活化之溶液（CG-535A)中於室溫下攪拌達20分鐘，將活 化溶液濾除，及使用100 ml之去離子水洗滌，及其後於 105 °C下乾燥30分鐘，以在粉末之表面上使用貴金屬進行 活化處理。藉由使用無電鍍銅溶液（KC-500 )使SiC粉末於 72 °C下進行鍍層。能夠在粉末之表面上形成無電銅鍍膜， 但大於20%之SiC粉末無法被覆蓋。C: \ ProgramFiles \ Patent \ 310707.ptd Page 17 438905 V. Description of the invention (14) Graphite powder is immersed in an electroless nickel solution (NΙΚΟΜϋ 7N) at 80 eC for 4 minutes' and is substantially uniform on the surface The deposit has no recording keys, the powder color changes from black to gray, and the surface of the substrate can be completely covered with nickel. [Example 8] 8 g of SiC powder with an average particle size of 70 microns was dissolved in 100 ml of 0.2 g of a dissolved silane coupling agent (which is an equal molar reaction between imidazole and γ-glycidylpropyltrimethoxysilane). Product) in a methanol solution at room temperature for 10 minutes. After the solvent (methanol) was distilled off, it was dried at 105 ° C for 30 minutes. After stirring the SiC powder in 100 ml of a Pd-activated solution (CG-53 5A) at room temperature for 20 minutes, the activation solution was filtered off, and the powder was washed with 100 ml of deionized water, and thereafter Dry at 105 ° C for 30 minutes to activate precious metals on the surface of the powder. The SiC powder was plated at 72 ° C by using an electroless copper solution (KC-500). A uniform copper plating film of only 1% by weight of electroless copper plating based on the weight of the SiC powder can be formed on the surface of the powder, the powder completely changes to a copper color, and the green SiC powder can be completely covered. [Comparative Example 9] 50 grams of SiC powder having an average particle size of 70 microns was stirred in 100 ml of a Pd-activated solution (CG-535A) at room temperature for 20 minutes, the activation solution was filtered off, and 100 ml was used It was washed with deionized water, and then dried at 105 ° C for 30 minutes to activate the surface of the powder with a precious metal. The SiC powder was plated at 72 ° C by using an electroless copper solution (KC-500). It can form an electroless copper coating on the surface of the powder, but more than 20% of the SiC powder cannot be covered.
C:\Program Files\Patent\310707,ptd 第 18 頁 438905 五、發明說明（15) [實例9] 將50克具有30微米之平均粒度之氧化锆粉末於l〇G ml 之含有0.2 g之溶解之矽烷偶合劑（其為2-甲基咪唑與γ-縮水甘油氧丙基三曱氧基矽烷之等莫耳反應產物）之甲醇 溶液中於室溫下攪拌10分鐘。在將溶劑（甲醇）蒸餾除去 後’於105 °C下乾燥達30分鐘。在將氧化锆粉末於mi 之Pd活化之溶液（CG-535A)中於室溫下攪拌達20分鐘後， 將活化溶液濾除，及使用100 ml之去離子水洗滌，及其後 於105 °C下乾燥30分鐘，以在粉末之表面上使用貴金屬進 行活化處理。當使氧化锆粉末浸潰於8〇 °c下之無電鍍鎳溶 液（NIK OMU 7N)_達4分鐘時，在氧化锆表面上實質上均勻 沉積無電錄鑛膜’及基材表面能夠完全被覆蓋。 [實例1 0 ] 將約1克具有0.3 mm之直徑之特夫綸絲於250 ml之含 有0.02 g之溶解之石夕烧偶合劑（其為咪吨與縮水甘油氧 丙基三甲氧基矽烧之等莫耳反應產物）之乙醇溶液中於室 溫下攪拌10分鐘。在將溶劑（乙醇）蒸餾除去後，於1〇 5 下乾燥達3G分鐘。在將絲浸漬於5〇 之pd活化之溶液 (CG-535A)中於室溫下攪拌達2〇分鐘後，將活化溶液濾 除，及使用50 mi之去離子水洗滌，及其後於1〇5^下乾燥 30分鐘，以在絲之表面上使用責金屬進行活化處理。當使 特夫綸絲浸潰於80 °C下之無電鍍鎳溶液（NIK〇MU 7N)中達4 分鐘時，在絲之表面上實質上均勻沉積無電鎳鍍膜，及基 材表面能夠完全被覆蓋，及絲轉變成灰色。C: \ Program Files \ Patent \ 310707, ptd Page 18 438905 V. Description of the invention (15) [Example 9] 50 g of zirconia powder having an average particle size of 30 microns was dissolved in 10 G ml containing 0.2 g The silane coupling agent (which is a mole reaction product of 2-methylimidazole and γ-glycidoxypropyltrimethoxysilane) in a methanol solution was stirred at room temperature for 10 minutes. After the solvent (methanol) was distilled off, it was' dried at 105 ° C for 30 minutes. After stirring the zirconia powder in mi-Pd-activated solution (CG-535A) at room temperature for 20 minutes, the activation solution was filtered off, washed with 100 ml of deionized water, and then at 105 ° Dry for 30 minutes at C to activate the powder with a precious metal on the surface. When the zirconia powder is immersed in an electroless nickel solution (NIK OMU 7N) at 80 ° C for 4 minutes, the electroless recording film is substantially uniformly deposited on the zirconia surface and the surface of the substrate can be completely cover. [Example 10] Approximately 1 g of Teflon yarn having a diameter of 0.3 mm was placed in 250 ml of a dissolved ishibuya coupling agent containing 0.02 g (which is mitoxane and glycidyloxypropyltrimethoxysilane). Ethanol reaction product) in ethanol solution was stirred at room temperature for 10 minutes. After the solvent (ethanol) was distilled off, it was dried at 105 for 3 G minutes. After the silk was immersed in a 50% pd-activated solution (CG-535A) and stirred at room temperature for 20 minutes, the activation solution was filtered off, washed with 50 mi of deionized water, and thereafter at 1 Dry at 30 ° C for 30 minutes to perform activation treatment on the surface of the silk with a metal. When the Teflon wire was immersed in an electroless nickel plating solution (NIKOM 7N) at 80 ° C for 4 minutes, the electroless nickel plating film was substantially uniformly deposited on the surface of the wire, and the surface of the substrate could be completely covered. Cover, and silk turns gray.
438905 五、發明說明（16) [工業應用性] 如上述所解釋者，藉由使用如本發明之新穎金屬鍍層 前處理劑之無電鍍層方法，能夠進行較佳之無電鍍層，即 使在習用方法不易應用之鏡面材料或粉末上亦然，及要被 鍍層之材料不因其性質與形狀而受限。438905 V. Description of the invention (16) [Industrial applicability] As explained above, by using the electroless plating method of the novel metal plating pretreatment agent according to the present invention, a better electroless plating layer can be performed, even in the conventional method The same applies to mirror materials or powders that are not easy to apply, and the materials to be coated are not limited by their nature and shape.
C:\ProgramFiles\Patent\310707_ptd 第 20 頁C: \ ProgramFiles \ Patent \ 310707_ptd page 20
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19160198 | 1998-07-07 | ||
| PCT/JP1999/002180 WO2000001862A1 (en) | 1998-07-07 | 1999-04-23 | Pretreating agent for metal plating, and method for metal plating using the same |
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| Publication Number | Publication Date |
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| TW438905B true TW438905B (en) | 2001-06-07 |
Family
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| TW088111492A TW438905B (en) | 1998-07-07 | 1999-07-07 | Metal plating pertreatment agent and metal plating method using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3277463B2 (en) |
| KR (1) | KR100367164B1 (en) |
| CN (1) | CN1195099C (en) |
| HK (1) | HK1028907A1 (en) |
| TW (1) | TW438905B (en) |
| WO (1) | WO2000001862A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI427026B (en) * | 2008-06-10 | 2014-02-21 | Hon Hai Prec Ind Co Ltd | Method for metal plating carbon nanotubes |
| TWI790360B (en) * | 2018-03-09 | 2023-01-21 | 日商有澤製作所股份有限公司 | Laminate and method of manufacturing the same |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4836312B2 (en) * | 2000-08-01 | 2011-12-14 | Ｊｘ日鉱日石金属株式会社 | Silver plating pretreatment agent and silver plating method |
| JP4270768B2 (en) | 2000-11-08 | 2009-06-03 | Ｊｆｅスチール株式会社 | Tin-plated steel sheet and chemical treatment liquid |
| EP1538237B1 (en) | 2002-09-10 | 2009-09-30 | Nippon Mining & Metals Co., Ltd. | Method for metal plating and pre-treating agent |
| JP4270517B2 (en) * | 2003-06-09 | 2009-06-03 | 日鉱金属株式会社 | Electroless plating method and plated metal |
| US20070269680A1 (en) * | 2004-09-10 | 2007-11-22 | Toshifumi Kawamura | Electroless Plating Pretreatment Agent and Copper-Clad Laminate for Flexible Substrate |
| WO2006135113A1 (en) * | 2005-06-17 | 2006-12-21 | Sumitomo Metal Mining Co., Ltd. | Coating liquid for nickel film formation, nickel film and method for producing same |
| WO2007102253A1 (en) * | 2006-03-07 | 2007-09-13 | Nara Institute Of Science And Technology | Metal-coated lipid bimolecular membrane endoplasmic reticulum and process for producing the same |
| JP5604787B2 (en) * | 2009-01-21 | 2014-10-15 | 富士通株式会社 | Method for producing electroless plating |
| US9499912B2 (en) | 2014-05-26 | 2016-11-22 | Rohm And Haas Electronic Materials Llc | Copolymers of diglycidyl ether terminated polysiloxane compounds and non-aromatic polyamines |
| EP3296428B1 (en) * | 2016-09-16 | 2019-05-15 | ATOTECH Deutschland GmbH | Method for depositing a metal or metal alloy on a surface |
| JP6620277B1 (en) * | 2018-08-07 | 2019-12-18 | 株式会社豊光社 | Method for producing plated glass substrate |
| CN111826643B (en) * | 2020-07-14 | 2023-05-12 | 华东理工大学 | Method for improving binding force of plating layer by activating copper plating on surface of modified metal |
| CN111910231B (en) * | 2020-07-22 | 2022-09-27 | 东莞市百镀通五金电镀实业有限公司 | Roughening liquid for roughening glass fiber reinforced plastic and roughening method |
| CN113445031B (en) * | 2021-06-24 | 2022-07-08 | 广东硕成科技股份有限公司 | Metal active agent and preparation method thereof |
| CN117385346B (en) * | 2023-12-12 | 2024-02-23 | 江苏中科智芯集成科技有限公司 | Method for copper-based chemical nickel-plating palladium-gold in wafer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2780373B2 (en) * | 1989-09-07 | 1998-07-30 | 三菱瓦斯化学株式会社 | Method for producing α-hydroxycarboxylic acid amide |
| JPH05239657A (en) * | 1992-02-27 | 1993-09-17 | Mitsubishi Gas Chem Co Inc | Production of moisture resistant copper clad substrate |
| JPH06256358A (en) * | 1993-03-01 | 1994-09-13 | Japan Energy Corp | New imidazolesilane compound and its production, and metal surface treating agent using the same |
| JPH07102380A (en) * | 1993-09-30 | 1995-04-18 | Nisshinbo Ind Inc | Pretreatment for plating of glass fiber |
| JPH0839728A (en) * | 1994-07-27 | 1996-02-13 | Sumitomo Metal Mining Co Ltd | Production of metal-clad laminate substrate |
-
1999
- 1999-04-23 CN CNB998000094A patent/CN1195099C/en not_active Expired - Lifetime
- 1999-04-23 JP JP54029899A patent/JP3277463B2/en not_active Expired - Lifetime
- 1999-04-23 KR KR10-1999-7008155A patent/KR100367164B1/en not_active IP Right Cessation
- 1999-04-23 WO PCT/JP1999/002180 patent/WO2000001862A1/en active IP Right Grant
- 1999-07-07 TW TW088111492A patent/TW438905B/en not_active IP Right Cessation
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI427026B (en) * | 2008-06-10 | 2014-02-21 | Hon Hai Prec Ind Co Ltd | Method for metal plating carbon nanotubes |
| TWI790360B (en) * | 2018-03-09 | 2023-01-21 | 日商有澤製作所股份有限公司 | Laminate and method of manufacturing the same |
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| JP3277463B2 (en) | 2002-04-22 |
| KR100367164B1 (en) | 2003-01-06 |
| WO2000001862A1 (en) | 2000-01-13 |
| HK1028907A1 (en) | 2001-03-09 |
| CN1262711A (en) | 2000-08-09 |
| CN1195099C (en) | 2005-03-30 |
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