201131021 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種可防止導線架、印刷配線板等電子 材料等中所使用之銅合金（含純銅）變色且可提高樹脂（有 機物）密合性之表面處理劑及其處理方法。 【先前技術】 一般而言’導線架、弓丨板、印刷配料電子零件多使 用銅或銅合金，對該銅或鋼合金材料實施銀等之部分電 鑛2進行樹脂密封。於該等步驟中，進行於酸或鹼液中 之/文 >貝、保管、力σ埶、接人. 接D(bondlng)以及樹脂密封。因此， ==引板⑽）、印刷配線等要求接著性、耐熱性、 耐化予。。性。進而要求於搬運或保管時或加熱時亦不變色。 根據上述要求，尤复# m & … 尤其針對導線架提出有各種防變色方 '。例如，下述所示之專利文ϋ 1 cb j. ^ 文獻1中，提出有含有5-甲基 本开二唑之防銅變色劑。 二’專利文獻2中提出有含有炫氧基 機》谷劑之導線架之表面處理劑。 I、有 乏耐前者雖於常溫下之防變色效果方面優異，但缺 ’，加熱時氧化皮膜容易剥落，因此广/ ώ 、 接著性下降之問題。又 + 、樹脂之 但並盔常$ 者係雖與樹脂之接著性提高， ‘…下之防變色效果，且亦缺之耐熱性。 由此’提出有於含有作為銅 環化合物η * 巧幻之抑制劑而發揮作用之雜 (參照專利文獻3)。缺而，“：“其鹽之防變色液 …、 已知其於低溫下與樹脂之接著 201131021 力變低。 〜叫q1雨合劑及比鋼 之金屬或其鹽作為主成分’進而含有水或有機溶劑作為— 劑之防變色液（參照專利文獻4)。該等雖有&，但必需^ 擇添加比銅貴之金屬或其鹽，有製造步驟變得繁雜之缺點| 又，如上所述，因為電子材料等中所使用之鋼合金j含 純銅）與㈣劑或膜等之樹脂（有機物）接著之情形較多3, 故有為了提高樹脂密合性而進行矽烷偶合劑處理之^形 (參照專利文獻1及專利文獻2 ) 0 月/ 但通常矽 、耐腐蝕 管時或製 下降或樹 該矽烷偶合劑處理對提高樹脂密合性有效， 烷偶合劑無銅合金之防銹性能（耐濕性、耐熱性 性等）或防銹性能低，因此於製品及在製品之保 扣之使用時銅合金氧化或腐蝕，成為導致電特性 脂密合性下降之原因。 為解決以上各種問題，提出有將矽烷偶合劑與防銹劑 併用（參照專利文獻7)。該專利文獻7中，係於銅箱之兩 面塗佈由3-胺基-1，2,4-三唑、矽烷偶合劑 '羧酸或其衍生物 所構成之有機防銹劑。於此情形時’羧酸或其衍生物成 必要條件。 右添加羧酸，則溶液具有腐蝕性，導致銅之變色或銅 配線之斷線，因此即便視情況添加羧酸，但於經常使用 存在問題。 ' 專利文獻1 :日本特開平4_ 1 6〇丨73號公報 專利文獻2 :日本特開平6_35〇〇〇〇號公報 4 201131021 專利文獻3·曰本特開平9_287〇82號公報 專利文獻4 ·曰本專利第337 1〇72號公報 專利文獻5.日本特開平8·3〇6?38號公報 專利文獻6:日本特開平8 295736號公報 專利文獻7:日本特開平7-258870號公報 【發明内容】 胃根據以上所述，為解決上述問題，本發明之課題在於 提供-種可防止導線架、印刷配線板等電子材料等中所使 2之銅合金（含純銅）變色’且可提高樹脂（有機物）密 &性之表面處理劑及其處理方法。又，本發明之課題在於 提供—種可簡便地製造該表面處理劑，獲得可極力降低製 造成本之表面處理劑。 本發明人等以防止導線架、印刷配線板等電子材料等 之銅合金（含純銅）變色，且提高樹脂（有機物） 性為目的而進行銳意研究，結果獲得如下見解：藉由 於銅或銅合金中組合特定之處理劑，可解決上述之問題。 根據該見解’本發明提供： 1 ).-種銅或銅合金之表面處理劑，其特徵在於含有以 八者刀子中含2個以上氮原子之矽烷偶合劑、及分子 3 3個以上氮原子之雜環化合物； )如上述1)之銅或銅合金之矣而考丨田杰丨 偶合劑為！八；由目士 金之表面處理劑，其中矽烷 刀 八有唑基及烷氧基矽烷基（alkoxysilyl)之 石夕貌化合物，.該雜環化合物為苯并三嗤 雙四唑或其衍生物； 飞者 201131021 3) 如上述2)之銅或鋼合金之表面處理劑，其令唑矽 烧化合物為㈣找、三切u四切m環化合物 為I，2,3·苯并三。坐、敌基笨并三„坐、甲基苯并三哇、5,5，聯 -1H-四唑或5,5，-聯-1H-四唑·二銨鹽； 4) 如上述1) i 3)中任一項之銅或銅合金之表面處 理劑，其中含有石夕烧偶合劑lmg/L〜· g/L，且含有雜環 化合物1 mg/L〜200 g/L ; 5) -種銅或銅合金之表面處理方法，其特徵在於：藉 由使用上述1 )至4 )中任一項之表面處理劑，於5〜9代 下對銅或銅合金處理（M〜3⑻秒’而提高與樹脂之密合性 及防銹性。 本發明提供一種銅或鋼合令夕主工疮^ + 又％。金之表面處理劑，其特徵在 於含有以下兩者：分子中含2個！^ μ ^ 7 刀卞T 3 2個以上氣原子之石夕烧偶合劑、 及分子中I 3個以上氮原子之雜環化合物；且具有可提高 與樹脂之密合性及防銹性之優異效果。 【實施方式】 (浴組成） 如上所述，本發明之銅或銅合金 Λ j D鱼之表面處理劑係以含 有下列兩者為基本：分子中含2個 如Λ x 1U以上氮原子之矽烷偶合 劑ϋ子中含3個以上氮原子之雜環化合物。 其係成為本案發明之基礎之重要條件。上述石夕烧偶人 :可選擇1分子中具有唾基及院氧基錢基之”烧化： 物。又，上述雜環化合物可選擇 = 雔 ...^ —。坐或其衍生物或者 又四唑或其衍生物。該等之選擇為任意。 201131021 上述°坐矽烷化合物’有咪唑矽烷、三唑矽烷或四唆石夕 烧。又’上述雜環化合物，有丨，2,3-苯并三唑、羧基笨并二 口坐、甲基苯并三唑、5,5，_聯_1H_四唑或5,5，_聯_1H, _ 敍鹽。本案發明可自該等中任意選擇，但不必限定於該等， 可選擇其他唑矽烷化合物或雜環化合物。 上述矽烷偶合劑通常含有1 mg/L〜500 g/L。較佳為含 有10 mg/L〜200 g/L。未達1 mg/L時，提高密合性之欵果 變弱’又，即便含有超過500 g/L，亦效果飽和，故而較理 想為設為上述範圍。該等可根據銅或銅合金之表面處理條 件而選擇。 ' 雜環化合物通常含有i mg/L〜200 g/L。較佳為含有ι〇 mg/L〜50 g/L。未達1 mg/L時，防變色效果變弱，又即 便含有超過200 g/L ’亦效果飽和，故而較理想為設為上述 魟圍。該等可根據銅或銅合金之表面處理條件而選擇。 (溶劑） 於成分難溶於水之情形時，視需要可添加醇、酮等有 機溶劑。於必需使用該有機溶劑之情形時，較理想為添加 〇·1〜200 g/L、較佳為1〜5〇 g/L之溶劑量。 其原因在於：未達〇 · 1 g/L時溶解性低 肝r低而即便超過200 g ，效果亦飽和。又，於忌水系處理之,γ + , 地之11形時，僅以該有 機/谷劑為溶劑即可。若為當業者則 谷易理解：該溶劑之 "J、、加為任意’並非必要條件。 (PH值緩衝劑） 於欲提高溶液之pH值緩衝性之情 月^時’視需要可添加 201131021 磷酸系、硼酸系、有機酸系pH值緩衝劑〇」〜“〇 g/L、較 佳為hSOg/L。其原因在於：未達〇 4化時阳值緩衝性 低，而即便超過200 g/L，效果亦飽和。若為當業者則可容 易理解：該pH值緩衝劑之添加為任意，並非必要條件。 (錯合劑） 於溶液中有金屬溶出之情形時，視需要可添加胺系、 胺基羧酸、羧酸系錯合劑〇」〜_ g/L、較佳為U — 作為金屬隱蔽劑（metal masking reagents卜其原因在於：當 該錯合劑為（Mg/L以下時金屬之錯合力低，而即便超過雇 g/L，效果亦飽和。若為者f本 右m者則可容易理解：該錯合劑之 添加為任意，並非必要條件。 (pH值、處理溫度、處理時間） 表面處理劑之pH值通常於ι〜14 14之乾圍内進行調整。 較佳為3〜1 1之範圍内。 又’使用上述表面處理劑，通堂 w 通书於5〜90。(：下，對錮痠 鋼合金處理〇. 1〜3〇〇秒。哕况泞 ' 、+, '•亥度及處理時間為任意，但上 述溫度及處理時間為較佳之處理條件。 一 以上之組成及處理條件〇並 ^ , 要疋為了於銅或銅合金之表 形成上述矽烷偶合劑與雜環化日 即可。II ^ n 物之〜合層而適當調整 P T 藉此’本發明之表面處理劍且古π切> 合性月狀妫μ值 W具有可提尚與樹脂之密 。〖生及防銹性之優異特徵。 實施例 繼而，基於實施例對本案發明加以說[Technical Field] The present invention relates to a copper alloy (including pure copper) used for preventing electronic materials such as lead frames and printed wiring boards from being discolored and improving resin (organic matter) density. Synthetic surface treatment agent and its treatment method. [Prior Art] In general, a lead frame, a bow plate, and a printing dosing electronic component are often made of copper or a copper alloy, and a part of the ore 2 of silver or the like is subjected to resin sealing of the copper or steel alloy material. In these steps, it is carried out in an acid or an alkali solution, and the storage, force σ埶, access, D (bondlng), and resin sealing. Therefore, == lead plate (10)), printed wiring, etc. require adhesiveness, heat resistance, and chemical resistance. . Sex. Further, it is required not to change color during transportation or storage or during heating. According to the above requirements, Yu Fu # m & ... especially for the lead frame proposed a variety of anti-tarnishing side '. For example, the patent document 1 cb j. ^ shown in the following document 1 proposes a copper-resistant color-changing agent containing 5-methyl-opened diazole. In the 'Patent Document 2, a surface treatment agent for a lead frame containing a silicate catalyst is proposed. I. Although the former is excellent in anti-tarnishing effect at normal temperature, it lacks, and the oxide film is easily peeled off during heating, so the problem of wide/ώ and subsequent decline is caused. Also +, resin, but the helmet is often $, although the adhesion with the resin is improved, ‘...the anti-tarnish effect, and lack of heat resistance. Thus, it has been proposed to contain impurities which act as an inhibitor of the copper ring compound η* (see Patent Document 3). Missing, ": "The anti-tarnishing solution of its salt ..., it is known that it will be lower at the low temperature and the resin 201131021. The anti-tarnishing liquid (refer to Patent Document 4) is called a q1 rain-mixing agent and a metal or a salt thereof as a main component and further contains water or an organic solvent as a solvent. Although there is a &, it is necessary to add a metal or a salt thereof which is more expensive than copper, and there is a disadvantage that the manufacturing steps become complicated. Further, as described above, since the steel alloy j used in an electronic material or the like contains pure copper) (4) Resin (organic matter) such as a film or a film is often used in the case of a decane coupling agent in order to improve the resin adhesion (see Patent Document 1 and Patent Document 2). When the corrosion resistant tube is used, the system is lowered or the decane coupling agent is treated to improve the resin adhesion, and the alkane coupling agent has no rust resistance (moisture resistance, heat resistance, etc.) or rust resistance. Oxidation or corrosion of the copper alloy during use of the product and the insured product is a cause of a decrease in the adhesion of the electrical property. In order to solve the above problems, it has been proposed to use a decane coupling agent in combination with a rust inhibitor (see Patent Document 7). In Patent Document 7, an organic rust inhibitor composed of a 3-amino-1,2,4-triazole or a decane coupling agent 'carboxylic acid or a derivative thereof is applied to both surfaces of a copper box. In this case, the carboxylic acid or its derivative is a necessary condition. When a carboxylic acid is added to the right, the solution is corrosive, causing discoloration of copper or disconnection of copper wiring. Therefore, even if a carboxylic acid is added as the case may be, it is problematic to use it frequently. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In order to solve the above problems, the present invention has been made in view of the above-mentioned problems, and it is possible to prevent discoloration of a copper alloy (including pure copper) which is caused by an electronic material such as a lead frame or a printed wiring board, and to improve the resin. (organic) dense & ampistic surface treatment agent and its treatment method. Further, an object of the present invention is to provide a surface treatment agent which can be easily produced, and to obtain a surface treatment agent which can minimize the production cost. The present inventors have conducted intensive studies for the purpose of preventing discoloration of a copper alloy (including pure copper) such as a lead frame or a printed wiring board, and improving the resin (organic matter), and as a result, the following findings have been obtained: by copper or copper alloy The combination of specific treatment agents can solve the above problems. According to the present invention, the present invention provides: 1) a surface treatment agent for copper or copper alloy, which comprises a decane coupling agent containing two or more nitrogen atoms in an eight-knife knife, and three or more nitrogen atoms in a molecule. Heterocyclic compound;) as in the above 1) copper or copper alloy 矣 丨 丨 丨 丨 丨 丨 ! ! !! VIII; a surface treatment agent from jinshijin, wherein the decane knife has an oxazolyl group and an alkoxysilyl group, the heterocyclic compound is benzotriazole bistetrazole or a derivative thereof. Flyer 201131021 3) The surface treatment agent of copper or steel alloy as in the above 2), which makes the oxazolidine compound (4) find, tri-cut u-cut m-ring compound I, 2, 3 · benzotriene. Sitting, enemy base and three „sitting, methyl benzotrim, 5,5, hydrazine-1H-tetrazole or 5,5,-linked-1H-tetrazole·diammonium salt; 4) as above 1) i 3) The surface treatment agent for copper or copper alloy according to any one of the above, which contains a sulphur coupling agent of 1 mg/L to g/L, and contains a heterocyclic compound of 1 mg/L to 200 g/L; 5) - a surface treatment method of copper or copper alloy, characterized in that copper or copper alloy is treated under 5 to 9 generations by using the surface treatment agent of any one of the above 1) to 4) (M to 3 (8) seconds 'Improving adhesion to resin and rust prevention. The present invention provides a surface treatment agent for copper or steel, which is characterized by containing two of the following: 2 in the molecule ^ μ ^ 7 卞 卞 T 3 2 or more gas atoms of the sulphur coupling agent, and a heterocyclic compound of 3 or more nitrogen atoms in the molecule; and has improved adhesion to the resin and rust resistance [Embodiment] (Bath Composition) As described above, the surface treatment agent for copper or copper alloy 本 j D of the present invention is basically as follows: two molecules such as Λ x 1U are contained in the molecule. A heterocyclic compound containing three or more nitrogen atoms in a decane coupling agent of a nitrogen atom, which is an important condition for the basis of the invention of the present invention. The above-mentioned Shi Xi burned person: one can have a salivary group and a thyloxy group in one molecule. "Kiji" "burning: the substance. In addition, the above heterocyclic compound can be selected = 雔 ... ^ -. Sitting or its derivatives or tetrazolium or its derivatives. The choice of these is arbitrary. 201131021 above ° ° decane The compound 'has an imidazolium, a triazolium or a tetraterpene. The above heterocyclic compound has an anthracene, a 2,3-benzotriazole, a carboxyl group, a dibenzophenone, a methylbenzotriazole, and 5 , 5, ___1H_tetrazole or 5,5, ___1H, _ salt. The invention of the present invention can be arbitrarily selected from the above, but is not necessarily limited thereto, and other oxazolidine compounds or heterocyclic rings may be selected. The above-mentioned decane coupling agent usually contains 1 mg/L to 500 g/L, preferably 10 mg/L to 200 g/L. When the amount is less than 1 mg/L, the effect of improving the adhesion becomes weaker. Further, even if it contains more than 500 g/L, the effect is saturated, so it is preferable to set it as the above range. These may be based on the surface of copper or copper alloy. The treatment conditions are selected. 'The heterocyclic compound usually contains i mg/L to 200 g/L. It preferably contains ι〇mg/L~50 g/L. When it is less than 1 mg/L, the anti-tarnishing effect becomes weak. Further, even if it contains more than 200 g/L', the effect is saturated, so it is preferable to set it as the above-mentioned circumference. These may be selected according to the surface treatment conditions of copper or copper alloy. (Solvent) When the composition is hardly soluble in water An organic solvent such as an alcohol or a ketone may be added as needed. When it is necessary to use the organic solvent, it is preferred to add a solvent amount of 〇1 to 200 g/L, preferably 1 to 5 〇g/L. The reason is that if the concentration is less than 1 g/L, the solubility is low, and the liver is low, and even if it exceeds 200 g, the effect is saturated. Further, in the case of the γ + and the ground 11 in the case of the water treatment, only the organic/age agent may be used as the solvent. If it is a practitioner, Gu Yi understands that the solvent's "J, plus any is not a requirement. (pH buffer) When you want to increase the pH of the solution, you can add 201131021 phosphate, boric acid, organic acid pH buffer 视 to 〇g/L, preferably. It is hSOg/L. The reason is that the yang value is not low when it is not reached, and even if it exceeds 200 g/L, the effect is saturated. If it is for the practitioner, it can be easily understood that the pH buffer is added as Arbitrary, not necessary. (Miscellaneous agent) When metal is dissolved in the solution, an amine-based, aminocarboxylic acid, or carboxylic acid-based complexing agent 〇"~_g/L, preferably U- As a metal masking reagent, the reason is that when the wrong agent is (Mg/L or less, the metal has a low mismatching force, and even if it exceeds the g/L, the effect is saturated. If it is the one that is the right It can be easily understood that the addition of the wrong agent is arbitrary and is not a requirement. (pH value, treatment temperature, treatment time) The pH of the surface treatment agent is usually adjusted within a dry circumference of ι to 14 14. Preferably, 3 Within the range of ~1 1. Also 'using the above surface treatment agent 5~90. (: Next, the treatment of bismuth acid steel alloy 〇. 1~3 〇〇 seconds. 哕 泞 ', +, '• Haidu and processing time is arbitrary, but the above temperature and processing time is better treatment Conditions: One or more compositions and treatment conditions are to be formed in order to form the above-mentioned decane coupling agent and the heterocyclic ring date on the surface of copper or copper alloy. 'The surface treatment of the present invention and the ancient π cut> The composite monthly 妫μ value W has an excellent characteristic that can be improved with the resin. The characteristics of the raw and rust-proof properties. Embodiments Next, the invention according to the embodiment Say
所示之實施例等係表示本案UT 孕乂佳一例，而並非由其 8 201131021 限制本案發明。亦即，本案發明在整篇 術思想下包括所有實施例以外之變形或態樣。領之技 (實施例1 ) ,使用咪唑矽烷：5 g/L作為矽烷偶合劑，使用1 “ 并三唑：0.2 g/L作為雜環化合物。咪嗤石夕 ，2,3·笨 氧基丙基三甲氧基錢與㈣之反應產物Γ 水甘油 添加2-丙醇：5 g/L作為溶劑’且設pH值：$ 〇、 溫度：25t、處理時間：1〇秒（s)。 處理 將上述實施例i之條件及評價結果示於表卜鋼入 金之表面處理劑之評價係根據外觀、耐濕性、耐熱性、: 脂密合性1、樹脂密合性2、焊料潤濕性進 樹 .. 〇Ί丨貝。έ亥評僧 方法於以下實施例及比較例中亦同樣適用。 、 外觀.以目視觀察處理不均等外觀不良，其怎 右無外觀不 良則記為〇，若有外觀不良則記為χ。 而才濕性：以目視觀察於4(TC、90%x96 hr加濕後之銅箱 表面有無變色，若無變色則記為〇，若有變色則記為X。冷 耐熱性：以目視觀察於烘箱中加熱16〇txl hr後之銅 箔表面有無變色’若無變色則記為〇，若有變色則記為X。 樹脂密合性1 :若與環氧模製樹脂之密合性（剪切強度） 超過40kgf/cm2則記為〇，若為25〜40kgf/cm2則記為△， 若未達25 kgf/cm2則記為χ。 樹脂密合性2 :若與聚醯亞胺覆蓋膜之密合性（9〇度 剝離強度）超過1 kgf/cm2則記為〇，若為〇 6〜丨〇 kgf/cm2 則記為△，若未達〇·6 kgf/cm2則記為χ。 201131021 焊料潤濕性：以40 C、90%χ96 hr加濕後，後助熔劑（post flux) ( R型）處理經175°C x6 hr加熱之印刷配線板（銅電 路寬度0.8 mm)，於銅電路部搭載0.6 mm0之錫鉛共晶焊 球’回流焊後’右焊料濁濕長度為3 mm以上則記為〇，若 為2 mm以上、未達3 mm則記為△，若未達2 mm則記為χ。 201131021 〔II 實施例 咪唑矽烷 5g/L 5,5'-聯-1H-四唑-二銨鹽：0.2g/L u-> Sr (N 1 1 〇 ι〇 <N 〇 〇 〇 〇 〇 〇 < Η為〇，若有外觀不良則為X。 m 四σ坐矽炫 ! 5g/L 羧基苯并三唑 0.2 g/L 乙醇：5 g/L W 1 〇 »/> rN Ο 〇 〇 〇 〇 〇 〇 (N 三唑矽烷 5g/L 甲基笨并三唑 0.2 g/L 乙醇：5 g/L 焦磷酸：1 g/L 乙二胺四乙酸四鈉：1 g/L 〇 in (Ν ο 〇 〇 〇 〇 〇 〇 咪唑矽烷 5g/L 1，2,3-苯并三唑 0.2 g/L in 屯: (N 1 1 〇 in fN ο 〇 〇 〇 〇 〇 〇 矽烷偶合劑 雜環化合物 溶劑 W X Q. 錯合劑 X 處理溫度（°c) 處理時間（s) 外觀 ! 耐濕性 对熱性 樹脂密合性1 樹脂密合性2 焊料潤濕性 ίΓ £ Β) 端 主成分 副成分 處理條件 評價結果 ^^硪^®-^硪《甾-ε:奴钤硪粜 ^^f^i T-<*lve^-e-(^o<*l®)-3-z :域备硪^^f^ffi-w^®^®i^>^$f-e:^^-f^fi 荟剜鹌^ν^0^^^^«?®-^·^νΕ:^^^ψ^塄，e:鉍^寺0- ^$ψ 。x^«lmu(N?F<^- ν碳 ί-ΜΤΧΤ i 3 嫦垛 * 〇_i-MTr<i £嫦^啲瘦羯实玫垛-^玫痗0*铦玟吨沭璜|^^ $1116 90铒绝命誼1.琛矣*(日£80^1誼1.塚)璀婼108苺5-^^^49><3。^1趔劫螬(到^)蘅玆备^-_^矣4 96父％06,30对3:£1-瘐转案玫 。X : 3UIU/J^9O?F^* V : 13/J^o· 一〜9.0.〇：^UIU/J^O.ItF欺(奶缌錐f-f^f06)±i-<(n银粜？？嫿鉍铼：3±1-^锲铛荜 。X : ^mo/J^sCNfF^- V : iu/JboJl 0寸〜〇：3UKVJ^0t7^^(靶想拉铱)3!1-^俤》柴率鉍«^蛘铼：11!1-^银餿荜 。Χ^ί-Μβ^杷砌-〇^isc<aD鉍璀砌- β&(#.杷妷塚w^.qx3o9I 癍与夺婼¾食腺癍.^gx-f :±1癍蒈 。Χ^ί-Μβ粼杷砌-〇嫦菡«3鉍谏垛*«]刹瑞杷《<髁塚wa<搜-¾上96xys6 ,_〇。0寸矣被癍軺囬^:±1-瘦盲 201131021 比較例 (N 胺基^夕炫 5S/L 1,2,3-苯并三唑 0.2 g/L 2-丙醇：5 g/L 1 1 〇 <> (N 〇 〇 〇 X X 〇 < 0 X 竺 me 1 f 環氧基矽烷 5g/L 1，2,3-苯并三唑 0.2 g/L 2-丙醇：5g/L 1 t 〇 (N 〇 〇 〇 X X X < 實施例 二胺基矽烷 5g/L 1，2,3-苯并三唑 0.2 g/L 乙醇：5g/L 1 乙二胺四乙酸四鈉：1 g/L 〇 ν〇 ίΝ Ο ir^ 〇 〇 〇 0 0 < in 咪唑矽炫 5r/L 羧基苯并三唑 0.2 g/L 乙醇：5g/L 硼酸：1 g/L 1 〇 νο VO Ο »-H 〇 〇 〇 〇 〇 〇 tv 〇 ππζ κ- w 女 ίφ 踅 κ· PN.l 矽烷偶合劑 雜環化合物 溶劑 pH值緩衝劑 錯合劑 pH值 處理溫度（°C) 處理時間（S) 外觀 耐濕性 耐熱性 樹脂密合性1 樹脂密合性2 焊料潤濕性 主成分 副成分 處理條件 評價結果 ^^^wffi-M^ve雄-ε: ^^^^®-ΜΫ€集-ε-(_ο 硇粜)-ζ-Ν :鉍给硇粜4 鉍备Ϋ^Β-Μ^«^^-ffii-B-^猓-ε:鉍^Ϋ^Ιί - ^s»0^^sd^-ϊψ^... ^·$ψ 。x%-sifs^<^< ν^ί-ϊτνί |2礎垛 * 〇_f-MTr<-r ^^-瘦羥 #玫砌-^玫痗0* 馇玫吨沭球瓌 w 免震90蘇竣命-¾¾瑕食A圍80^¾¾¾¾)^愈超f-晻VS-W戚-^q 9XPS卜一邀W喊(到β)蘅效苗游*^搜-&4396x0/006,3。0寸^:寒瘦摂实欢 。>< :3un/JooJ{9o?F<- V : JUIU/J^O·一〜90-〇：3^/;^2^墩(甸想織1:^06)3!1.^街》琏碱：1绪*1饍鉍€:2±1-冷掷餿荜 。X : 3111355^幻物<< V : ruKVJ^o 寸〜ln(N< 〇：iuIU/5^0 寸瓚欺(甸娥这铱)±1-^梯》餿率鉍鹚^龄硪：1±!-<!0锑餿荜 。xitf-MW^枇垛 < 〇^ί-ϊβ1!<#.垛 <<63琢难杷妷塚^趣一一 IXP091 癍-&斗猓玫矣餘癍.^03¾ :±1'戚苫 枇垛-O^f-Me^#.讲 <<03谢#-枇喵嵴 li 塚W^wi-S-C96xrc06 , P0 寸矣铋^^απχ-f :封-瘦苫 201131021 如表1所示’實施例1之銅或銅合金之表面處理劑的 外觀、耐濕性、耐熱性、樹脂密合性丨、樹脂密合性2、焊 料潤濕性中任一者均為良好。 由以上可知，實施例1可提高與樹脂之密合性及防錄 性’且於製造使用銅或銅合金之材料之導線架、印刷配線 板等電子材料時，該表面處理劑之應用為有用。 (實施例2) 使用一 °坐石夕烧.5 g/L作為石夕烧偶合劑，使用甲基苯并 三唑：〇.2 g/L作為雜環化合物。上述三唑矽烷為％縮水甘 油氧基丙基三甲氧基矽烷與三唑之反應產物。 =口乙醇：5g/L作為溶劑，焦填酸：⑽作為阳值 ^材’乙二胺四乙酸四鈉：WL作為錯合劑，spH值. .〇、處理溫度：25。(：、處理時間1G秒⑴為處理條件。 、上述實施例2之條件及評價結果示於表丨。盥 同，銅或銅合金之矣面卢神w /、上返相 而… 表面處理劑之評價係根據外觀、耐渴性、 耐熱性、樹脂密合性1、樹脂密合性2、焊心、 價。 f 2焊枓潤濕性進行評 所示，貫施例2之銅或銅合 外觀、耐濕性、耐熱性、樹脂密合性卜^：=處理劑的 料潤濕性中任—者均為良好。 “曰役合性2、焊 由以上可知，實施例2 性’且於製造使用銅或鋼合之密合性及防錄 板等電子材料時，該廄導線架、印刷配線 (實施例3) 劑之應用為有用。 13 201131021 使用四唾矽烷：5 g/L作為矽烷偶合劑，使用羧基苯并 二唾·’ 0.2 g/L作為雜環化合物。上述四唑矽烷為3_縮水甘 油氧基丙基三甲氧基矽烷與四唑之反應產物。 添加乙醇：5 g/L作為溶劑，使用硼酸：1 g/£作為pH 值緩衝材。設pH值·· 5.0、處理溫度：25t:、處理時間1〇 秒（s )為處理條件。 將上述實施例3之條件及評價結果示於表1。與上述相 同，銅或銅合金之表面處理劑之評價係根據外觀、耐濕性' 耐熱性、樹脂密合性卜樹脂密合性2、悍料潤濕性 價。 如表1所示，實施例3之銅或銅合金之表面處理劑的 外觀、耐濕性、耐熱性、樹脂密合性i、樹脂密合性2，焊 料潤濕性中任一者均為良好。 由以上可知，實施例3可提高與樹脂之密合性及防錄 且於製造使用銅或銅合金之好粗+描& 4 拓㈣“ 材枓之導線架、印刷配線 板專電子材料時，該表面處理劑之應用為有用。 (實施例4) WW5g/L作為錢偶合劑，使用W，善见 坐·一釦鹽.0.2 g/L·作為雜環化人 甘油ϋ Iα物。咪唑矽烷為3-縮水 丙基三甲氧基石夕燒與味。坐之反應產物。 添加2-丙醇：5g/L作為溶劑。設阳值 度：25C、處理時間1〇秒⑴為處理條件。. 將上述實施例4之條件及評價結 同，銅或銅合金之表面處理不；與上述相 之…貝係根據外觀、耐濕性、 14 201131021 :熱性、樹脂密合性】、樹脂密合性2、焊料潤濕性進行評 $如表1所示，實施例4之銅或銅合金之表面處理劑的 外觀、耐濕性、耐熱性、樹脂密合性1、樹脂密合性2中任 者均為良好。僅焊料潤濕性稍許下降。但在使用上並未 成為問題。 由以上可知，實施例4可提高與樹脂之密合性及防銹 ^ *且於製造使用銅或銅合金之材料之導線架、印刷配線 反等電子材料時，該表面處理劑之應用為有用。 、 (實施例5 ) _，使㈣切貌：5 g/L作為⑪㈣合劑，使諸基苯并 坐.0.2 g/L作為雜環化合物。咪唑矽烷為縮水甘油氧 土丙基三甲氧基矽烷與咪唑之反應產物。 添加乙# ·· 5 g/L作為溶劑，使用硼酸：i —作為阳 值緩衝材。設pH值：6.0、處理、、田 处段/皿度.25 C、處理時間i〇 秒（s )為處理條件。 门將上述實施例5之條件及評價結果示於表卜與上述相 2銅或銅合金之表面處理狀評價係根據外觀、耐濕性、 J熱性、樹脂密合性丨、樹脂密合性2、焊料潤濕性進行評 外 斤丁實施例5之銅或銅合金之表面處理劑的 外觀、耐濕性、耐熱性、樹 MB密σ性1、樹脂密合性2、焊 枓潤濕性中任一者均為良好。 由以上可知’實施例古 J权阿與樹脂之密合性及防銹 15 201131021 印刷配線 性，且於製造使用銅或銅合金之材料之導線架、 板等電子材料時，該表面處理劑之應用為有用。 (實施例6) 使用二胺基矽烷：5 S/L作為矽烷偶合劑，使用丨23 笨并三g/L作為雜環化合物。上述二胺基錢為 N-2-(胺基乙基）_3_胺丙基三甲氧基矽烷。 四鈉：1 處理時 添加乙醇：5g/L作為溶劑，使用乙二胺四乙酸 g/L作為錯合劑。設pH值：6.〇、處理溫度：25它、 間1 〇秒（S )為處理條件。 將上述實施例6之條件及評價結果示於表卜與上述相 同’銅或銅合金之表面處理劑之評價係根據外觀、耐渴性、 樹脂密合性2'焊料潤濕性進行評 如表1所示’實施例6之銅或銅合金之表面處理劑的 外觀、耐濕性 '财熱性中任—者均為良好。但，樹脂密合 性1、樹脂密合性2、焊料潤濕性呈現稍差之結果，但並非 特別成為問題之級別。 •由以上可知，實施例6可提高與樹脂之密合性及防銹 '且於製造使用銅或銅合金之材料之導線架、印刷配線 板等電子材料時，該表面處理劑之應用為有用。 (比較例1 ) “、使用環氧基矽烷：5 g/L作為矽烷偶合劑，使用m j并—坐.〇 2 g/L作為雜環化合物。上述環氧基矽烷為％ 縮水甘油氧基丙基三曱氧基矽烷。 201131021 添加2·丙醇：5g/L作為溶劑。設阳值：6〇 度：25°c、處理時間10秒（Ο為處理條件。 狐 2述比較例！之條件及評價結果示於表（。與上述相 …3或銅合金之表面處理劑之評價係根據外觀、耐濕 ::熱性、樹脂密合性丨、樹脂密合性2、焊料潤濕性進行評 ❹如表、1所示，比較例1之銅或銅合金之表面處理劑的 •、耐濕性良好，但耐熱性、樹脂密合性1、樹脂密合性 2差，焊料潤濕性呈現梢差 ° 夕 之、，'。果已知s亥比較例之問題較 二於製造使用銅或銅合金之材料之導線架、印刷配線板 寻電子材料時，該表面處理劑之應用不適合。 (比較例2 ) 使用胺基石夕院：5 g/L作為石夕烧偶合劑，使帛i 2 3笨 :三唾：0.2 g/L作為雜環化合物。上述胺基 ，3:: 基三甲氧基矽烷。 妝内 = 2-:醇：5g/L作為溶劑。設阳值：6〇、處理溫 度· 25C、處理時間10秒（s)為處理條件。 將上述比較例2之條件及評價結果示於表〖。與上述相 同’銅或銅合金之表面處理劑之評價係根據外觀、耐濕性、 :熱性、樹脂密合性1、樹脂密合性2、焊料潤濕性進行評 4貝0 如表1所示’比較例2之銅或銅合金之表面處理劑的 二觀、耐濕性、樹脂密合性2為良好，但耐熱性、樹脂密 。性1差，且焊料潤濕性呈現猶差之結果。已知該比較例 17 201131021 之問題較多’於製造使用銅或銅合金 <材料之導線架、印 刷配線板等電子材料時，該表面處理劑 ' 應用不適合。 根據以上之實施例及比較例，含.八7 ,.« , 有刀子中包含2個以 上氮原子之矽烷偶合劑及分子中包含 1固以上氣原子之雜 環化合物兩者的銅或銅合金之表面處 王削，其外觀、耐濕 性、对熱性'樹脂密合性卜樹脂密合性2、辉料潤濕性中 任一者均為良好。 又’即便為上述實施例以外之條件，只要係本案發明 所指定之條件之範圍，均可獲得良好之結果。 [產業上之可利用性] 本發明提供一種銅或铜A公夕主工士 纠及钔β金之表面處理劑，其特徵在 於含有以下兩者：分子中会2個卜备 刀丁1r 3 2個以上氮原子之矽烷偶合劑' 及刀子中έ 3個以上氮原子之雜環化合物，且具有可提高 與樹脂之密合性及防銹性之優異特徵。藉此，彳用於製： 使用銅或銅合金之材料之導線架、印刷配線板等電子材料。 【圖式簡單說明】 無 【主要元件符號說明】 無 18The illustrated embodiment and the like represent an example of the UT pregnancy in this case, and the invention is not limited by its 8 201131021. That is, the invention of the present invention includes variations or aspects other than the embodiments throughout the entire teachings. Technique (Example 1), using imidazolium: 5 g/L as a decane coupling agent, using 1 "triazole: 0.2 g/L as a heterocyclic compound. Midazopurine, 2,3. The reaction product of propyltrimethoxyl and (iv) Γglycidol added 2-propanol: 5 g/L as solvent' and pH value: $ 〇, temperature: 25 t, treatment time: 1 sec (s). The conditions and evaluation results of the above Example i are shown in the table. The evaluation of the surface treatment agent for steel deposits is based on appearance, moisture resistance, heat resistance, grease adhesion, resin adhesion, and solder wettability. Into the tree.. 〇Ί丨贝. The method of έ海僧 is also applicable in the following examples and comparative examples. 、 Appearance. Visually observing the uneven appearance of the treatment, If there is a poor appearance, it is marked as χ. And wetness: visually observe 4 (TC, 90% x 96 hr, the surface of the copper box after humidification is discolored, if there is no discoloration, it is marked as 〇, if there is discoloration, it is recorded as X Cold heat resistance: visually observe whether there is discoloration on the surface of the copper foil after heating for 16 〇txl hr in an oven. In the case of discoloration, it is referred to as X. Resin adhesiveness 1: When the adhesion (shear strength) to the epoxy molding resin exceeds 40 kgf/cm2, it is marked as 〇, and if it is 25 to 40 kgf/cm2, it is recorded as △. If it is less than 25 kgf/cm2, it is marked as χ. Resin Adhesion 2: If the adhesion to the polyimide film (9〇 peel strength) exceeds 1 kgf/cm2, it is marked as 〇, if 〇6~丨〇kgf/cm2 is recorded as △, if it is less than 6 kgf/cm2, it is marked as χ. 201131021 Solder wettability: after 40 C, 90% χ 96 hr humidification, post flux (post Flux) (R type) processed printed wiring board heated at 175 °C x6 hr (copper circuit width 0.8 mm), with 0.6 mm0 tin-lead eutectic solder ball in the copper circuit section 'reflow soldering' right solder wet length If it is 3 mm or more, it is marked as 〇. If it is 2 mm or more and less than 3 mm, it is marked as △. If it is less than 2 mm, it is marked as χ. 201131021 [II Example Imidazoxane 5g/L 5,5'-linked -1H-tetrazole-diammonium salt: 0.2 g/L u-> Sr (N 1 1 〇ι〇<N 〇〇〇〇〇〇< Η is 〇, if there is a poor appearance, it is X. m Four σ sitting 矽 Hyun! 5g / L carboxy benzotriazole 0.2 g / L ethanol :5 g/LW 1 〇»/> rN Ο 〇〇〇〇〇〇(N triazolidine 5g/L methyl benzotriazole 0.2 g/L ethanol: 5 g/L pyrophosphoric acid: 1 g/L Tetrasodium edetate: 1 g/L 〇in (Ν ο 〇〇〇〇〇〇 矽 矽 5 5g/L 1,2,3-benzotriazole 0.2 g/L in 屯: (N 1 1 〇 In fN ο decane coupling agent heterocyclic compound solvent WX Q. Wound agent X treatment temperature (°c) treatment time (s) appearance! moisture resistance to thermal resin adhesion 1 resin adhesion 2 Solder wettability Γ Β 主 主 主 ® ® ® ε ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^o<*l®)-3-z : Domain 硪^^f^ffi-w^®^®i^>^$fe:^^-f^fi 剜鹌^^^^^^^ ^«?®-^·^νΕ:^^^ψ^塄,e:铋^ Temple 0- ^$ψ . X^«lmu(N?F<^- ν carbon ί-ΜΤΧΤ i 3 嫦垛* 〇_i-MTr<i £嫦^啲瘦羯实垛垛-^玫痗0*铦玟吨沭璜|^ ^ $1116 90铒绝命谊1.琛矣*(日£80^1谊1.冢)璀婼108莓5-^^^49><3.^1趔趔趔(到^)蘅备^-_^矣4 96 Parent%06,30 Pairs 3: £1-瘐转案玫.X : 3UIU/J^9O?F^* V : 13/J^o· One ~9.0.〇:^UIU /J^O.ItF bullying (milk cone ff^f06)±i-<(n silver 粜??婳铋铼:3±1-^锲铛荜.X: ^mo/J^sCNfF^- V : iu/JboJl 0 inch ~ 〇: 3UKVJ^0t7^^(Target wants to pull) 3! 1-^俤"Chai rate 铋«^蛘铼:11!1-^银馊荜.Χ^ί-Μβ^杷 〇 - 〇 ^isc<aD铋璀 - - β &(#.杷妷冢w^.qx3o9I 癍 and 婼 婼 3⁄4食腺癍.^gx-f : ±1癍蒈.Χ^ί-Μβ粼杷砌-〇嫦菡«3铋谏垛*«] 杷瑞杷 "<髁冢wa< search -3⁄4 on 96xys6, _〇. 0 inch 矣 was smashed back ^: ±1 - thin blind 201131021 Comparative example ( N-amino group Xi Xi Xuan 5S/L 1,2,3-benzotriazole 0.2 g/L 2-propanol: 5 g/L 1 1 〇<> (N 〇〇〇XX 〇< 0 X竺me 1 f Epoxy decane 5g/L 1,2,3-benzotriazole 0.2 g/L 2-propanol: 5g/L 1 t 〇(N 〇〇 XXX < Example Diamine decane 5g / L 1,2,3-benzotriazole 0.2 g / L Ethanol: 5g / L 1 Ethylenediaminetetraacetic acid tetrasodium: 1 g / L 〇ν〇ίΝ Ο ir ^ 〇〇〇0 0 < in imidazolium 5r/L carboxybenzotriazole 0.2 g/L Ethanol: 5g/L Boric acid: 1 g/L 1 〇νο VO Ο »-H 〇〇〇〇〇〇tv 〇ππζ κ- w Female ίφ 踅κ· PN.l decane coupling agent heterocyclic compound solvent pH buffering agent pH treatment temperature (°C) treatment time (S) appearance moisture resistance heat resistance resin adhesion 1 Resin Adhesion 2 Solder Wettability Principal Component Subcomponent Composition Condition Evaluation Results ^^^wffi-M^ve雄-ε: ^^^^®-ΜΫ€集-ε-(_ο 硇粜)-ζ-Ν :铋给硇粜4 铋备Ϋ^Β-Μ^«^^-ffii-B-^猓-ε:铋^Ϋ^Ιί - ^s»0^^sd^-ϊψ^... ^·$ Oh. X%-sifs^<^< ν^ί-ϊτνί |2基垛* 〇_f-MTr<-r ^^-瘦 hydroxy#玫砌-^玫痗0* 馇玫吨沭球瓌w震90苏竣命命-3⁄43⁄4瑕食A circumference 80^3⁄43⁄43⁄43⁄4)^More super f-dark VS-W戚-^q 9XPS Bu invited to shout (to β) 蘅效苗游*^搜-&4396x0/ 006, 3. 0 inch ^: Cold and thin. ><:3un/JooJ{9o?F<- V : JUIU/J^O·一～90-〇:3^/;^2^Dian (Dianxiang Weaving 1:^06)3!1.^ Street" 琏 alkali: 1 * * 1 meal 铋 €: 2 ± 1 - cold roll 馊荜. X : 3111355^幻物<<V : ruKVJ^o inch~ln(N< 〇:iuIU/5^0 inch 瓒 ((娥甸娥)±1-^梯》馊 rate铋鹚^硪:1±!-<!0锑馊荜.xitf-MW^枇垛<〇^ί-ϊβ1!<#.垛<<63琢难杷妷冢^趣一一 IXP091 癍-&斗033玫矣余癍.^033⁄4 :±1'戚苫枇垛-O^f-Me^#.讲<<03谢#-枇喵嵴li 冢W^wi-S-C96xrc06 , P0矣铋 矣铋 ^^απχ-f : sealing-skinny 201131021 As shown in Table 1, 'the appearance of the surface treatment agent of copper or copper alloy of Example 1, moisture resistance, heat resistance, resin adhesion 丨, resin density Both of the properties 2 and the solder wettability are good. From the above, it can be understood that the first embodiment can improve the adhesion to the resin and the anti-recording property, and the lead frame for manufacturing a material using copper or a copper alloy, When an electronic material such as a wiring board is printed, the application of the surface treatment agent is useful. (Example 2) Using a 1 ° sitting stone shovel. 5 g/L as a Shi Xi siu coupling agent, using methyl benzotriazole: 〇 .2 g / L as a heterocyclic compound. The above triazolium is the inverse of % glycidoxypropyl trimethoxy decane and triazole Product: = mouth ethanol: 5g / L as a solvent, coke filling acid: (10) as a positive value ^ material 'ethylene diamine tetraacetic acid tetrasodium: WL as a wrong agent, spH value. 〇, processing temperature: 25. (:, The processing time is 1 Gsec (1), which is the processing condition. The conditions and evaluation results of the above Example 2 are shown in Table 丨. Same as the copper or copper alloy, the surface of the god Lu W /, the upper phase reciprocal... The evaluation of the surface treatment agent According to appearance, thirst resistance, heat resistance, resin adhesion, resin adhesion, solder core, and price. f 2 Weldability of soldering, the copper or copper appearance of Example 2, Moisture resistance, heat resistance, and resin adhesion are all good in the wettability of the treatment agent. "The compatibility of the treatment 2, the welding is known from the above, the performance of the second embodiment" and the manufacture The application of the tantalum lead frame and the printed wiring (Example 3) is useful when using copper or steel adhesion and an electronic material such as an anti-recording plate. 13 201131021 Using tetradecane: 5 g/L as a decane couple As a mixture, a carboxybenzobisin-0.2 g/L is used as a heterocyclic compound. The above tetrazoxane is a 3-glycidoxypropyl group. The reaction product of methoxy decane and tetrazole. Add ethanol: 5 g / L as solvent, boric acid: 1 g / £ as pH buffer material. Set pH · · 5.0, processing temperature: 25t:, processing time 1 The leap seconds (s) are the processing conditions. The conditions and evaluation results of the above Example 3 are shown in Table 1. As in the above, the evaluation of the surface treatment agent of copper or copper alloy was based on the appearance, moisture resistance, heat resistance, and resin. Adhesiveness, resin adhesion, and wettability. As shown in Table 1, the appearance, moisture resistance, heat resistance, resin adhesion i, resin adhesion 2, and solder wettability of the surface treatment agent of copper or copper alloy of Example 3 were all good. From the above, it can be seen that the third embodiment can improve the adhesion with the resin and prevent the recording, and in the manufacture of copper or copper alloys, the use of copper or copper alloys, the use of copper or copper alloys, the use of copper and copper alloys, the conductors of printed materials, printed circuit boards, and electronic materials. The application of the surface treatment agent is useful. (Example 4) WW5g/L is used as a money coupling agent, and W is used, and it is good to sit and take a salt. 0.2 g/L· as a heterocyclic human glycerol guanidine Iα. The decane is a 3-condensed propyl trimethoxy sulphur and a taste reaction product. The 2-propanol: 5 g/L is added as a solvent. The positive value is 25 C, and the treatment time is 1 sec (1). The conditions and evaluation of the above-mentioned Example 4 are the same, and the surface treatment of copper or copper alloy is not performed; the above-mentioned phase is based on the appearance, moisture resistance, 14 201131021: heat, resin adhesion, and resin adhesion. 2. Solder Wettability Evaluation As shown in Table 1, the surface treatment agent of copper or copper alloy of Example 4 has the appearance, moisture resistance, heat resistance, resin adhesion, and resin adhesion. Both are good. Only the solder wettability is slightly decreased, but it is not a problem in use. In the fourth embodiment, the adhesion to the resin and the rust prevention can be improved, and the application of the surface treatment agent is useful when manufacturing a lead frame or a printed wiring reverse electronic material using a material of copper or a copper alloy. Example 5) _, (4) cut: 5 g / L as 11 (four) mixture, the base benzo sit. 0.2 g / L as a heterocyclic compound. Imidazoxane is glycidoxypropyl trimethoxy decane and imidazole Adding B# ·· 5 g/L as solvent, using boric acid: i — as a positive buffer material. Set pH: 6.0, treatment, field section / dish degree. 25 C, treatment time i〇 The second (s) is the processing condition. The conditions and evaluation results of the above-mentioned Example 5 are shown in the table and the evaluation of the surface treatment of the phase 2 copper or copper alloy is based on the appearance, moisture resistance, J heat, and resin adhesion. The appearance, moisture resistance, heat resistance, tree MB density, and resin adhesion of the surface treatment agent of the copper or copper alloy of Example 5 were evaluated for the properties of the resin, the resin adhesion, and the solder wettability. Both of the properties 2 and the wettability of the soldering iron are good. From the above, it can be seen that the 'example is J. Resin Adhesiveness and Rust Prevention 15 201131021 Printing and wiring properties, and the use of this surface treatment agent is useful when manufacturing electronic materials such as lead frames and plates using copper or copper alloy materials. (Example 6) Amino decane: 5 S/L as a decane coupling agent, using 丨23 stupid and three g/L as a heterocyclic compound. The above diamine hydroxy is N-2-(aminoethyl)_3-aminopropyltrimethoxy Base sulphate. Tetrasodium: 1 Add ethanol at the time of treatment: 5 g/L as solvent, and use ethylenediaminetetraacetic acid g/L as a wrong agent. Set pH: 6. 〇, treatment temperature: 25 it, 1 〇 second ( S) is the processing condition. The conditions and evaluation results of the above-mentioned Example 6 are shown in the table. The evaluation of the surface treatment agent of the same copper or copper alloy is based on the appearance, the thirst resistance, and the resin adhesion 2' solder wettability. (1) The appearance and moisture resistance of the surface treatment agent of the copper or copper alloy of Example 6 are all good. However, resin adhesion, resin adhesion, and solder wettability are slightly inferior, but they are not particularly problematic. From the above, it can be seen that the application of the surface treatment agent is useful in the case of improving the adhesion to the resin and the rust prevention in the case of manufacturing an electronic material such as a lead frame or a printed wiring board using a material of copper or a copper alloy. . (Comparative Example 1) ", using epoxy decane: 5 g / L as a decane coupling agent, using mj and - 〇 2 g / L as a heterocyclic compound. The above epoxy decane is % glycidoxy propyl Base tridecyloxydecane 201131021 Add 2·propanol: 5g/L as a solvent. Set positive value: 6〇 degree: 25°c, treatment time 10 seconds (Ο is the processing condition. Fox 2 describes the comparison example! The evaluation results are shown in the table. The evaluation of the surface treatment agent with respect to the above phase 3 or copper alloy is based on the appearance, moisture resistance: heat, resin adhesion, resin adhesion, and solder wettability. As shown in Table 1, the surface treatment agent of copper or copper alloy of Comparative Example 1 has good moisture resistance, but heat resistance, resin adhesion, and resin adhesion are poor, and solder wettability is exhibited. The difference between the tip and the temperature is that the problem of the surface treatment is not suitable when the lead frame of the material using copper or copper alloy or the electronic component of the printed wiring board is used. Comparative Example 2) Using an amine stone garden: 5 g/L as a stone smelting coupling agent, making 帛i 2 3 stupid: three saliva: 0 .2 g / L as a heterocyclic compound. The above amine group, 3:: base trimethoxy decane. Inside the makeup = 2-: alcohol: 5g / L as a solvent. Set the positive value: 6 〇, treatment temperature · 25C, treatment The time of 10 seconds (s) is the processing condition. The conditions and evaluation results of the above Comparative Example 2 are shown in the table. The same as the above, the evaluation of the surface treatment agent of copper or copper alloy is based on appearance, moisture resistance, heat, Resin Adhesiveness 1, Resin Adhesiveness 2, Solder Wettability Evaluation 4B. As shown in Table 1, the surface treatment agent of copper or copper alloy of Comparative Example 2 has two properties, moisture resistance, and resin adhesion. The property 2 is good, but heat resistance and resin density are poor, and the solder wettability is not bad. It is known that the problem of the comparative example 17 201131021 is more than 'the use of copper or copper alloy < material In the case of electronic materials such as lead frames and printed wiring boards, the surface treatment agent is not suitable for application. According to the above examples and comparative examples, a decane coupling agent containing two or more nitrogen atoms in a knife and a copper or copper alloy containing both a heterocyclic compound having 1 or more gas atoms in the molecule In the case of the king, the appearance, the moisture resistance, the thermal 'resin adhesion, the resin adhesion, and the wettability are good. Even the conditions other than the above examples are as long as Good results can be obtained by the scope of the conditions specified in the invention of the present invention. [Industrial Applicability] The present invention provides a surface treatment agent for copper or copper A, and a surface treatment agent for 钔β gold, which is characterized by It consists of two kinds of compounds: a sulfonium coupling agent of two or more argon sulphonates in the molecule, and a heterocyclic compound of three or more nitrogen atoms in the knives, and has an adhesion to the resin. Excellent characteristics of sex and rust resistance. In this way, 彳 is used for: electronic materials such as lead frames and printed wiring boards using materials of copper or copper alloy. [Simple diagram description] None [Main component symbol description] None 18