1238027 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（f ) [發明之詳細說明] [發明所屬之技術領域] 本發明係有關於一種能有效率地形成印刷電路基板的 層間連接孔、在雷射鑽孔性優異的銅箔。 又本發明之銅箔，非僅限於銅箔本身，銅面積層板或 於積層板上直接形成銅層者（含電鍍形成者）均包括在內 〇 近來，在以銅箔作爲導電體來使用的電子元件及配線 基板之製造上，隨著配線的高密度化，相較於傳統的機械 式鑽孔，能進行更微細的加工之使用雷射之鑽孔的方法日 益廣被使用。 然而，欲照射通用性高的二氧化碳雷射光對銅箔表面 行鑽孔加工的場合，由於銅在二氧化碳雷射之波長l〇#m 附近的反射率接近100 %，雷射加工效率極差是一個問題 點。 爲彌補這加工率低的問題，必須使用高輸出的二氧化 碳雷射，然而使用高輸出之雷射，以高能量進行加工的場 合，與銅箔同時被鑽孔的樹脂基板因加工過度而受到損害 ，因此有不易依照希望的形狀來鑽孔的問題存在。 又，隨著加工生成的飛散物變多，會有對裝置及加工 物的非加工部份造成污染的問題。 爲了避免上述問題，有將銅箔部分預先以化學鈾刻法 開孔，之後將樹脂部份使用雷射進行鑽孔的做法。但是’ 此做法相較於將銅箔和樹脂部份一次鑽孔的情形’在製程 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------1T--------- (請先閱讀背面之注意事項再填寫本頁) 1238027 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（>) 數增加，成本也較高，是其缺點。 另一方面，一般對於在雷射光波長下之反射率高的金 屬行雷射加工的方法爲，於金屬表面覆以吸收率高的物質 ’使其吸收雷射光，藉以生熱來進行加工，或者，對欲加 工的表面使其凹凸不平，同樣可以提高加工效率，此爲眾 所周知的。 此外，爲提高銅箔鑽孔加工之際的吸收率，已提出對 銅表面施以氧化處理（黑化處理）等。 然則，上述各種提案都使得操作與處理趨於複雜，而 所提升之雷射加工的效率則不成比例，而且設置上述表面 處理層者，因處理層脆弱，易造成剝離等，成爲製程中的 污染源。 又，也提出將銅箔本身薄化則即使以低能量的雷射也 可行鑽孔加工。然而，實際使用的銅箔爲厚度介於9〜36 的各種膜厚者，薄化銅箔的方法，只能適合於一部份 的材料而已。又欲使用該低能量條件進行鑽孔時，銅箔厚 度須爲3〜5//m的極端薄的才可，此場合，會有處理上的 問題。 如上所述，向來爲改良銅箔的數多提案，雷射所進行 之鑽孔不夠充分，現狀上尙無法獲得適於雷射加工的銅箔 材料。 [發明所欲解決之課題] 本發明係鑑於上述問題點之解決所提出者，目的爲提 供一種銅箔，於製造印刷電路基板之際，藉著改善銅箔之 4 t--------IT--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1238027 A7 B7 五、發明說明（々） 表面，使霄射所進行之鑽孔變得極爲容易，適合形成小孔 徑的層間連接孔。 [用以解決課題之手段] 基於上述者，本發明爲提供： 1·-種雷射鑽孔用銅箔，係使用雷射作鑽孔加工；其 特徵在於，對於該銅箔之至少雷射入射面施以含有銅之至 少1種之金屬之電鍍，於該面形成0.01〜3/zm的粒子層。 2·上述1項所述之雷射鑽孔用銅箔，於上述以金屬電 鍍形成有粒子層的面，在不改變其表面形狀下，進一步形 成被覆皮膜。 [發明之實施形態] 本發明著眼於經由表面電鍍處理所形成的表面形態， 進行檢討之結果，發現經由表面電鍍形成0.01〜3//m粒子 層之場合可得到良好的鑽孔性。 該由微細之（λ〇1〜3/zm的粒子層所形成的銅箔之粗化 處理面會使雷射光不規則反射，提高如同光吸收同樣的效 果，即使以二氧化碳雷射所提供之低能量仍可確保充份的 鑽孔性。 此時，與銅並用的電鍍層金屬須能吸收雷射光並對雷 射鑽孔有效果，經確認者有Ni、Co、Sn、Zn、In及此等金 屬的合金都可使用。然而，並非僅侷限於上述這些金屬， 其他的金屬也可使用。 藉由本發明的做法，在銅箔的雷射光入射面施以含有 銅的金屬電鍍’形成0.01〜3//m的粒子層，可獲得更局之 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) I 裝--------訂·-------- 經濟部智慧財產局員工消費合作社印製 1238027 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（γ) 雷射加工性。 又，也考慮使用不含銅的上述Ni、Co、Sn、Zn、In及 此等金屬的合金，形成〇·〇1〜3//m的粒子層，來提高雷射 鑽孔性。的確藉著此等電鍍所形成的粒子層可提高雷射鑽 孔性。然而，發現此等電鍍處理層會發生剝離與脫落的情 形，有時甚至僅是摩擦等即會輕易發生剝離現象。 例如，於銅箔上施以鈷單體的凹凸電鍍，經確認具有 充份的鑽孔性，但此電鍍處理層很脆，只經摩擦即會發生 粒子的脫離。 爲改善此脫落與剝離的現象之問題，而將電鍍的附著 量減低、降低凹凸程度，卻使得鑽孔性變得不充份。因此 ，僅是形成上述之金屬層，即使也能提高雷射鑽孔性，但 實際上稱不上是適當的處理層。 基於上述情形，進一步就銅箔上電鑛的金屬層做過種 種的檢討之結果，知道在形成上述粒子層的電鍍組成物含 有銅之時，其電鍍層的附著力會增加，可有效地防止處理 層的剝離與脫落。 而且，爲防止上述的剝離與脫落的問題，於粗化處理 面上施以至少1種的金屬之覆鍍是更有效的。 此覆鍍以通常使用的電鍍條件（正常電鍍)即可，在無 損於以前述粗化面處理所形成的0.01〜3//m的粒子層的前 提下進行電鍍。亦即，爲不使雷射光鑽孔性降低，粒子層 實質存在於0·01〜3/zm之範圍是必要的。 此用以形成被覆皮膜的電鍍，可以是用以形成上述粒 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ---- (請先閱讀背面之注意事項再填寫本頁) 訂 · 1238027 A7 B7 五、發明說明（f) 子層的粗化電鍍’也可以是另外的電鍍。 較佳者爲與上述形成粒子層的粗化電鍍同樣地使用N1 、Co、Sn、Zn、In及此等金屬的合金’可更加改善雷射鑽 孔性。如此，經由在粗化處理後進一步施以覆鍍，就不會 發生剝離與剝落，並可確保充份的雷射鑽孔性。 本發明所使用的銅箔可爲電解銅箔或壓延鋦(|*自， 都適用。又，爲了用於高密度配線上，銅箔的厚度以18// m以下爲佳。然而，本發明之提高雷射鑽孔性的銅[筢並不 侷限於此厚度，較此更厚者也是當然適用者。 此等經由電鍍等所形成的粒子層（粗化處理），可對 銅箔的雷射光照射面作部份或銅箔全面地處理。此等電鍍 處理必須符合無損於其適合作爲電路基板的特性之要求是 不言而喻的，本發明的處理能完全滿足此等條件。 經上述電鍍處理後，可進一步施以含有鉻或鋅的防銹 處理。此等防銹處理的方法或處理液並沒有特別的限制。 此防銹處理可施於前述電鍍處理面上，亦即可對銅箔的雷 射光照射面的部份或銅箔全面上施以處理。 同上述，此防銹處理須不損及適用於電路基板的銅箔 所須有的特性是理所當然的，本發明的防銹處理能充份滿 足此等條件。又，此防銹處理對雷射鑽孔性殆無影響。 欲形成作爲本發明的金屬電鍍層之例如Cu、Ni、Co、 Sn、Zn、In及此等金屬的合金之電鍍層，可採用後述的電 鍍處理法。以下爲其代表例。可藉由於此範圍內設定適宜 的條件，進行粗化處理與覆鍍。 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂·-------- (請先閱讀背面之注意事項再填寫本頁) [238027 A7 B7 五、發明說明（ 又，此等電鍍處理例，均僅用以表示適用的例子 發明並不受此等例子所侷限。 (銅電鍍處理） Cl!濃度 ：1〜30g/L 電解液溫度：20〜60°C 電流密度 5〜60A/dm2 本 pH : 1.0〜4.0 電鍍時間：0.5〜4秒 (鎳電鍍處理） Ni 濃度 ·· 1 〜30g/L 電解液溫度：25〜60°C 電流密度 0.5〜5A/dm2 pH : 1.0〜4.0 電鑛時間：0.5〜4秒 (請先閱讀背面之注意事項再填寫本頁) (鈷電鍍處理） Co濃度： 1〜30g/L 電解液溫度：20〜60°C 電流密度 0.5〜5A/dm2 pH : 1.0〜4.0 電鍍時間：0.5〜4秒 -裝·-------tr---------' 經濟部智慧財產局員工消費合作社印製 (錫電鍍處理） Sn 濃度 ：5〜100g/L 電解液溫度：25〜40°C 電流密度 1.0〜5A/dm2 硫酸：40〜150g/L pH : 1.0〜4.0 電鍍時間：0.5〜4秒1238027 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of Invention (f) [Detailed Description of Invention] [Technical Field to Which the Invention belongs] The present invention relates to an interlayer connection capable of efficiently forming a printed circuit board Copper foil with holes and laser drillability. The copper foil of the present invention is not limited to the copper foil itself, and includes copper area laminates or those that directly form a copper layer on a laminate (including those formed by electroplating). Recently, copper foils have been used as electrical conductors. In the manufacture of electronic components and wiring substrates, with the increase in the density of wiring, laser drilling is used more widely than conventional mechanical drilling. However, when the carbon dioxide laser light with high versatility is to be drilled on the surface of copper foil, the reflectivity of copper near the wavelength of carbon dioxide laser 10 # m is close to 100%, and the laser processing efficiency is extremely poor. Problems. In order to make up for the low processing rate, a high output carbon dioxide laser must be used. However, when a high output laser is used to process at high energy, the resin substrate drilled at the same time as the copper foil is damaged due to excessive processing. Therefore, there is a problem that it is difficult to drill a hole in a desired shape. In addition, as the number of scattered materials generated by processing increases, there is a problem that the non-processed parts of the device and the processed materials are contaminated. In order to avoid the above-mentioned problems, the copper foil portion is opened by chemical uranium engraving method in advance, and then the resin portion is drilled by laser. However, 'this method is compared to the case where the copper foil and the resin part are drilled at a time'. In the process 3, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -1T --------- (Please read the notes on the back before filling this page) 1238027 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. The number of inventions (>) increases and costs also increase Higher is its disadvantage. On the other hand, in general, a laser processing method for a metal having a high reflectance at the wavelength of the laser light is to coat the metal surface with a substance having a high absorptivity so as to absorb the laser light and process it by generating heat, or It is well known that the unevenness of the surface to be processed can also improve the processing efficiency. In addition, in order to increase the absorptivity during copper foil drilling, it has been proposed to apply an oxidation treatment (blackening treatment) to the copper surface. However, the above-mentioned various proposals make the operation and processing more complicated, and the efficiency of the laser processing improved is disproportionate. Moreover, those who provide the above-mentioned surface treatment layer are vulnerable to peeling due to the fragile treatment layer, which has become a source of pollution in the manufacturing process. . Furthermore, it has been proposed that thinning the copper foil itself allows drilling to be performed even with a low-energy laser. However, the actual copper foil used is a thickness between 9 and 36, and the method of thinning the copper foil is only suitable for some materials. When using this low-energy condition for drilling, the thickness of the copper foil must be extremely thin at 3 to 5 // m. In this case, there are problems in handling. As described above, there have been many proposals for improving copper foil, and laser drilling has not been sufficient, and it is currently impossible to obtain a copper foil material suitable for laser processing. [Problems to be Solved by the Invention] The present invention is made by the present invention in view of solving the above-mentioned problems. The purpose is to provide a copper foil, which is used to improve the 4 t of copper foil when manufacturing printed circuit boards. --IT --------- (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1238027 A7 B7 V. Invention Explanation (々) The surface makes the drilling of Xia She extremely easy, suitable for forming interlayer connection holes with small apertures. [Means for solving the problem] Based on the above, the present invention provides: 1 · -a copper foil for laser drilling, which uses laser for drilling processing; characterized in that at least the laser of the copper foil The incident surface is electroplated with at least one metal containing copper, and a particle layer of 0.01 to 3 / zm is formed on the surface. 2. The copper foil for laser drilling according to the above item 1, further forming a coating film on the surface on which the particle layer is formed by metal plating without changing its surface shape. [Embodiments of the Invention] The present invention focuses on the surface morphology formed by the surface plating treatment, and as a result of review, it was found that when 0.01 to 3 // m particle layer is formed by the surface plating, good drillability can be obtained. The roughened surface of the copper foil formed by the fine particle layer (λ〇1 ~ 3 / zm) will cause irregular reflection of laser light, improving the same effect as light absorption, even if the carbon dioxide laser provides low Energy can still ensure sufficient drilling. At this time, the metal of the plating layer used with copper must be able to absorb laser light and have an effect on laser drilling. The confirmed ones include Ni, Co, Sn, Zn, In, and so on. Alloys such as metals can be used. However, it is not limited to these metals, and other metals can also be used. By the method of the present invention, a copper-containing metal plating is applied to the laser light incident surface of a copper foil to form 0.01 ~ 3 // m particle layer, you can get 5 more rounds. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page). I Pack- ------ Order · -------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238027 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (γ) Laser processability It is also considered to use the above-mentioned Ni, Co, Sn, and Zn which do not contain copper. , In and alloys of these metals form a particle layer of 0.001 to 3 // m to improve the laser drillability. Indeed, the particle layer formed by such plating can improve the laser drillability. However, it has been found that peeling and peeling of these plating treatment layers may occur, and sometimes peeling easily occurs even just by rubbing. For example, it is confirmed that the copper foil has a sufficient bump plating on the copper foil to have sufficient However, this electroplated layer is very brittle, and particle separation will occur only after rubbing. In order to improve this problem of peeling and peeling, reducing the amount of plating and reducing the degree of unevenness makes drilling Therefore, the formation of the above-mentioned metal layer can improve the laser drillability, but it is not actually a suitable treatment layer. Based on the above situation, the copper ore on the copper foil is further refined. As a result of various reviews of the metal layer, it is known that when the plating composition forming the particle layer contains copper, the adhesion of the plating layer will increase, which can effectively prevent the treatment layer from peeling and falling off. The above-mentioned problems of peeling and peeling are more effective by applying at least one kind of metal to the roughened surface. This plating can be performed under the usual plating conditions (normal plating), without prejudice to the foregoing Electroplating is performed on the premise of a particle layer of 0.01 to 3 // m formed by roughening the surface. That is, in order not to reduce the laser drillability, the particle layer substantially exists in the range of 0.01 to 3 / zm. Necessary. The electroplating used to form the coating film can be used to form the above-mentioned particles. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) ---- (Please read the note on the back first Please fill in this page for further details) Order · 1238027 A7 B7 V. Description of the invention (f) Rough plating of the sub-layers may also be another plating. It is preferable to use N1, Co, Sn, Zn, In, and alloys of these metals in the same manner as in the rough plating for forming the particle layer, to further improve laser drilling properties. In this way, by further performing plating after the roughening treatment, peeling and peeling do not occur, and sufficient laser drillability can be ensured. The copper foil used in the present invention may be an electrolytic copper foil or a calendered copper foil. It is also preferable that the thickness of the copper foil is 18 // m or less for high-density wiring. However, the present invention Copper [筢] is not limited to this thickness, but thicker than this is of course applicable. The particle layer (roughening treatment) formed by electroplating or the like can be used for copper foils. The light irradiated surface is partially or completely treated with copper foil. It is self-evident that these plating treatments must meet the requirements that do not detract from the characteristics suitable as circuit boards, and the treatment of the present invention can fully meet these conditions. After the plating treatment, a rust-preventive treatment containing chromium or zinc may be further applied. There is no particular limitation on the rust-preventive treatment method or treatment liquid. The rust-preventive treatment can be applied to the aforementioned electroplated treatment surface, that is, the Part of the laser light irradiated surface of the copper foil or the copper foil is completely treated. As mentioned above, it is a matter of course that this rust prevention treatment does not impair the characteristics required for the copper foil suitable for the circuit board. Rust treatment can fully meet this The conditions. In addition, this rust prevention treatment has no effect on the laser drillability. To form the electroplated layer of the metal plating layer of the present invention such as Cu, Ni, Co, Sn, Zn, In and alloys of these metals, The plating method described below can be used. The following is a representative example. Roughening and plating can be performed by setting appropriate conditions within this range. 7 This paper size applies Chinese National Standard (CNS) A4 (210 X 297) (Mm) -------- Order · -------- (Please read the notes on the back before filling out this page) [238027 A7 B7 V. Description of the invention (also, these examples of plating treatment , Are only used to indicate that the applicable invention is not limited by these examples. (Copper plating treatment) Cl! Concentration: 1 ~ 30g / L electrolyte temperature: 20 ~ 60 ° C current density 5 ~ 60A / dm2 this pH: 1.0 ~ 4.0 Plating time: 0.5 ~ 4 seconds (nickel plating treatment) Ni concentration ·· 1 ~ 30g / L Electrolyte temperature: 25 ~ 60 ° C Current density 0.5 ~ 5A / dm2 pH: 1.0 ~ 4.0 Electric ore time : 0.5 ~ 4 seconds (Please read the precautions on the back before filling this page) (Cobalt plating treatment) Co concentration: 1 ~ 30g / L Electrolysis Temperature: 20 ~ 60 ° C Current density 0.5 ~ 5A / dm2 pH: 1.0 ~ 4.0 Plating time: 0.5 ~ 4 seconds Printed by the Consumer Cooperative of the Property Bureau (tin plating treatment) Sn concentration: 5 ~ 100g / L Electrolyte temperature: 25 ~ 40 ° C Current density 1.0 ~ 5A / dm2 Sulfuric acid: 40 ~ 150g / L pH: 1.0 ~ 4.0 : 0.5 ~ 4 seconds
(銦電鍍處理） In 濃度：10〜50g/L(Indium plating treatment) In concentration: 10 ~ 50g / L
硫酸：10〜50g/L 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1238027 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7 ) 電解液溫度：20〜40°C pH : 1.0〜4.0 電流密度 1.0〜20A/dm2 電鍍時間：0.5〜4秒 (鋅一鈷電鍍處理）Sulfuric acid: 10 ~ 50g / L This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1238027 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) Electrolyte temperature: 20 ~ 40 ° C pH: 1.0 ~ 4.0 Current density 1.0 ~ 20A / dm2 Plating time: 0.5 ~ 4 seconds (zinc-cobalt plating treatment)
Zn濃度 :1〜20g/L Co濃度：1〜 30g/L 電解液溫度: :25 〜50°C pH : 1.5〜4.0 電流密度 0.5 〜5A/dm2 電鍍時間： 〜3秒 (銅-鎳電鍍處理）Zn concentration: 1 to 20g / L Co concentration: 1 to 30g / L Electrolyte temperature: 25 to 50 ° C pH: 1.5 to 4.0 Current density 0.5 to 5A / dm2 Plating time: to 3 seconds (copper-nickel plating treatment )
Cu濃度 ：5〜20g/L Ni濃度： 5〜20g/L 電解液溫度：25〜50°C pH ： 1.0- '4.0 電流密度 10〜45A/dm2 電鍍時間 :1〜3秒 (銅一鈷電鍍處理） Cu 濃度 ·· 5 〜20g/L Co濃度： 5〜20g/L 電解液溫度：25〜50°C pH : 1.5 〜4.0 電流密度 10〜45A/dm2 電鍍時間 :1〜3秒 (鋅一鎳電鍍處理） Zn濃度 ：1〜10g/L Ni濃度： 10〜30g/L 電解液溫度：40〜50°C pH ： 3.0~ 4.0 電流密度 0.5〜5 A/dm2 電鍍時間 :1〜3秒 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------IT--------- (請先閱讀背面之注意事項再填寫本頁) 1238027 Α7 Β7 五、發明說明（ (銘-鎮電鑛處理） Co濃度 ：5〜20g/L 電解液溫度 ：25〜50°C 電流密度 0.5〜10A/dm:Cu concentration: 5 ~ 20g / L Ni concentration: 5 ~ 20g / L Electrolyte temperature: 25 ~ 50 ° C pH: 1.0- '4.0 Current density 10 ~ 45A / dm2 Plating time: 1 ~ 3 seconds (copper-cobalt plating Treatment) Cu concentration: 5 to 20g / L Co concentration: 5 to 20g / L Electrolyte temperature: 25 to 50 ° C pH: 1.5 to 4.0 Current density 10 to 45A / dm2 Plating time: 1 to 3 seconds (Zinc one Nickel plating treatment) Zn concentration: 1 ~ 10g / L Ni concentration: 10 ~ 30g / L Electrolyte temperature: 40 ~ 50 ° C pH: 3.0 ~ 4.0 Current density 0.5 ~ 5 A / dm2 Plating time: 1 ~ 3 seconds Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------- IT --------- (Please read the precautions on the back before filling this page) 1238027 Α7 Β7 V. Description of the invention ((Ming-Zhendian Mine Treatment) Co concentration: 5 ~ 20g / L Electrolyte temperature: 25 ~ 50 ° C Current density 0.5 ~ 10A / dm:
Ni濃度：5〜20g/L pH : 1.0〜4.0 電鍍時間：1〜180秒 經濟部智慧財產局員工消費合作杜印製 (銅一姑一錬電鑛處理） Co濃度 :1〜15g/L Cu 濃度 ·· 5〜25g/L 電解液溫度：20〜50°C 電流密度 1.0〜30A/dm2 [實施例] 後述係基於實施例來加以說明。又本實施例僅用以表 示適用的例子，因此本發明並不侷限於此等實施例。因之 ，凡屬本發明之技術思想所涵蓋的變形、其他實施例或者 樣態，均完全屬於本發明之範疇。 又，爲與本發明相對照，於後面部份將揭載比較例。 (實施例1 ) 於厚度12//m的電解銅箔的光澤面（S面）上，依上 述條件行銅一鈷一鎳合金之電鍍，形成約0.1〜0.8//m的 粒子層者。圖1爲形成此粒子層的粗化面的顯微鏡相&。 (實施例2 ) 於厚度12//m的電解銅范的光澤面（s面）上，丨衣上 述條件行銅一鈷一鎳合金之電鍍，形成約0.丨〜〇 8//m的 粒子層，再於其上依上述電鍍條件行鈷一鎳合金之覆鑛（Ni concentration: 5 ~ 20g / L pH: 1.0 ~ 4.0 Plating time: 1 ~ 180 seconds Made by consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs (copper-copper ore processing) Co concentration: 1 ~ 15g / L Cu Concentration: 5 to 25 g / L Electrolyte temperature: 20 to 50 ° C Current density 1.0 to 30 A / dm2 [Example] The following description is based on the example. In addition, this embodiment is only used to indicate an applicable example, so the present invention is not limited to these embodiments. Therefore, all the variants, other embodiments, or aspects covered by the technical idea of the present invention are completely included in the scope of the present invention. For comparison with the present invention, a comparative example will be described later. (Example 1) A copper-cobalt-nickel alloy plating was performed on the glossy surface (S surface) of an electrolytic copper foil having a thickness of 12 // m under the above conditions to form a particle layer of about 0.1 to 0.8 // m. Fig. 1 is a microscope phase & of the roughened surface forming this particle layer. (Example 2) On the glossy surface (s-side) of an electrolytic copper fan having a thickness of 12 // m, the copper-cobalt-nickel alloy plating was performed under the above conditions to form about 0.18 ~ / 8 // m of The particle layer is then coated with cobalt-nickel alloy over the above plating conditions (
Ni濃度：1〜15g/L pH : 1.0〜4.0 電鍍時間：1〜180秒 (請先閱讀背面之注意事項再填寫本頁) 訂--------- Ρ 1238027 A7 B7 五、發明說明) 形成被覆層）者。 (比較例1) 使用未經處理的厚度12/zm的電解銅箔。圖2爲電解 銅箔表面的顯微鏡相片。 (比較例2 ) 於厚度12/zm的電解銅箔的光澤面（s面）上，依上 述條件行鈷之電鍍，形成約0.3〜1 /zm的粒子層。圖3爲 形成此粒子層的粗化面的顯微鏡相片。 將上面實施例1、2及比較例1、2之試料以預浸材 (FR- 4)作成單面基板，各對1〇〇個處所，以下述條件作二 氧化碳零射光照射，比較其開口率。結果如表1所示。 (雷射照射條件） 使用裝置··二氧化碳雷射加工裝置 孔徑（Spot Size) : 144/zm0 脈衝寬度·· 32/z秒 頻率：4〇〇Hz 照射(Shot)次數：1次（Shot) -----------t--------IT--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 雷射開口率 (條件1 ) 雷射開口率 (條件2 ) 施以摩擦之 掉粉狀況 實施例1 100 % 100 % 〇 實施例2 100 % 100 % ◎ 比較例1 0 % Γ 9 % ◎ 比較例2 100 % r 100 % X X掉粉 ◦極微量掉粉◎全無掉粉 於實施例1中，條件1和條件2兩者的開口率都爲 100 %，顯示出極爲優異的開口率。此例中施以摩擦雖有微 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1238027 A7 B7 五、發明說明（f0 ) 量的掉粉（電鍍層的剝離、脫落）情形，並非達到足以成 爲問題的程度。 此爲形成本發明之粒子層之電鍍之中，其電鍍層中含 有銅者，對防止電鍍層的剝離與脫落有效的實證。 實施例2中，與上述實施例1同樣地，條件1和條件 2兩者的開口率也都爲100%，顯示極爲優異的開口率。此 例中施以摩擦也沒有掉粉（電鍍層的剝離、脫落）的情形 〇 此爲本發明之形成粒子層之後進一步施以鈷-鎳覆鍍 的例子，此覆鍍對於防止剝離、脫落爲有效的方法在此得 以確認。 比較例1爲未經處理的銅箔的情形，雖沒有因摩擦導 致掉粉的現象，但以條件1的雷射開口率爲〇，亦即事實 上無法開口。又條件2的鑽孔率僅爲9 %，是相當不良的 結果。 比較例2中，條件1和條件2均爲100 %的鑽孔率， 顯示有極優異的開口率。 經濟部智慧財產局員工消費合作社印製 k衣---- (請先閱讀背面之注意事項再填寫本頁) 然而有施以摩擦導致掉粉情形（電鍍層的剝離、脫落 )，並非能夠實際使用者。 由上述可知，未經處理的銅箔要以二氧化碳雷射作鑽 孔事實上是不可能的。本發明經由形成0.01〜3#m的粒子 層，如同上述實施例所示，能夠提高二氧化碳雷射鑽孔的 效率。 又，有關掉粉的現象’經由形成粒子層之際’使電鑛 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1238027 A7 B7 五、發明說明（ίI) 組成裡含有銅的方法，可以有效地防止。又，藉著施以覆 鍍，可更進一步加以強固的防止，有必要時，可採行此等 方法。 [發明之效果] 使用本發明之處理方法，於製造印刷電路基板之際， 能用二氧化碳等低能量雷射行銅箔直接鑽孔及簡便地形成 層間連接孔’又對於因摩擦等導致的電鍍層剝離與脫落之 防止有顯著的效果。 [圖式之簡單說明] 圖1係實施例1之形成粒子層的粗化面的顯微鏡相片 0 圖2係比較例1之電解銅箔表面的顯微鏡相片。 圖3係比較例2之形成粒子層的粗化面的顯微鏡相片 --------IT--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Ni concentration: 1 ~ 15g / L pH: 1.0 ~ 4.0 Plating time: 1 ~ 180 seconds (Please read the precautions on the back before filling this page) Order --------- Ρ 1238027 A7 B7 V. Invention Explanation) Forming a coating layer). (Comparative Example 1) An untreated electrolytic copper foil having a thickness of 12 / zm was used. Figure 2 is a photomicrograph of the surface of an electrolytic copper foil. (Comparative Example 2) Cobalt plating was performed on the glossy surface (s-surface) of an electrolytic copper foil having a thickness of 12 / zm under the above conditions to form a particle layer of about 0.3 to 1 / zm. Fig. 3 is a photomicrograph of a roughened surface forming the particle layer. The samples of Examples 1 and 2 and Comparative Examples 1 and 2 above were made of single-sided substrates using prepreg (FR-4), each pair of 100 places, and the carbon dioxide zero light irradiation was performed under the following conditions to compare the aperture ratios. . The results are shown in Table 1. (Laser Irradiation Conditions) Using Equipment ·· CO2 Laser Processing Equipment Aperture (Spot Size): 144 / zm0 Pulse Width ·· 32 / z Second Frequency: 400Hz Shots: 1 Shot- ---------- t -------- IT --------- (Please read the precautions on the back before filling out this page) Employee Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed laser aperture ratio (Condition 1) Laser aperture ratio (Condition 2) Status of powder loss caused by friction Example 1 100% 100% 〇 Example 2 100% 100% ◎ Comparative Example 10% Γ 9% ◎ Comparative Example 2 100% r 100% XX powder-removing ◦ Very small powder-removing ◎ No powder-removing In Example 1, the opening ratios of both Condition 1 and Condition 2 were 100%, showing extremely excellent opening ratios. Although friction is applied in this example, the paper size is in compliance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1238027 A7 B7. 5. Description of the invention (f0) The amount of powder loss (the peeling and peeling of the plating layer) ) The situation is not to a degree sufficient to be a problem. This is an example of the electroplating for forming the particle layer of the present invention, in which the electroplated layer contains copper, is effective in preventing peeling and peeling of the electroplated layer. In Example 2, similarly to the above-mentioned Example 1, the aperture ratios of both of the conditions 1 and 2 were 100%, which showed extremely excellent aperture ratios. In this case, there is no powder loss when the friction is applied (the peeling and peeling of the electroplated layer). This is an example of further applying cobalt-nickel plating after forming the particle layer of the present invention. Effective methods are confirmed here. Comparative Example 1 is a case of untreated copper foil. Although there is no phenomenon of powder loss due to friction, the laser aperture ratio of condition 1 is 0, which means that it cannot be opened in fact. In addition, the drilling rate of Condition 2 is only 9%, which is quite a bad result. In Comparative Example 2, both of the conditions 1 and 2 had a drilling rate of 100%, and showed extremely excellent aperture ratios. K-shirts printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ---- (Please read the precautions on the back before filling out this page) However, there are cases where the powder is dropped due to friction (the peeling and peeling of the plating layer), which is not practical. user. From the above, it is known that it is practically impossible to drill a carbon dioxide laser for untreated copper foil. The present invention can improve the efficiency of carbon dioxide laser drilling by forming a particle layer of 0.01 to 3 # m as shown in the above embodiment. In addition, the phenomenon related to powder loss, through the occasion of the formation of a particle layer, makes the power ore 12 paper sizes applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238027 A7 B7 V. Description of the invention (ίI) Methods containing copper can be effectively prevented. In addition, it can be further strengthened by plating, and if necessary, these methods can be adopted. [Effects of the Invention] Using the processing method of the present invention, when manufacturing printed circuit boards, low-energy lasers such as carbon dioxide can be used to directly drill copper foil and easily form interlayer connection holes. The prevention of layer peeling and peeling has a significant effect. [Brief description of the drawings] FIG. 1 is a microscope photograph of a roughened surface forming a particle layer in Example 1. FIG. 2 is a microscope photograph of a surface of an electrolytic copper foil of Comparative Example 1. FIG. Figure 3 is a microscope photograph of the roughened surface forming the particle layer of Comparative Example -------- IT --------- (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau's Employee Cooperatives 13 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)