201251535 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適合使用於可撓式電路基板的金屬 被覆積層板，特別是，關於一種絕緣層由聚醯亞胺樹脂所 構成之具有可撓性的可撓式金屬被覆積層板。 【先前技術】 近年來’隨著行動電話或數位相機、數位攝影機、PDA、 汽車導航、硬碟其他各種電子機器的高功能化、小型化及 輕量化’作為此等之電性配線用基板材料，採用與以往可 使用之硬式基板不同之配線自由度變高、容易薄型化之可 撓式印刷基板的例子正在增加。然後，關於更高度化此等 機器中所使用之可撓式印刷基板，復提高小型高密度化、 多層化、微細化、高耐熱化等要求。 為了對應此種要求，於專利文獻1等揭示一種方法， 係藉由於導體上直接塗佈形成聚醯亞胺樹脂層，並使熱膨 脹係數相異的複數聚醯亞胺樹脂層多層化而形成，可提供 對於溫度變化的尺寸安定性、接著力、再者蚀刻後的平面 性等信賴性佳的可撓式印刷基板。 關於此種可撓式印刷基板中所使用之不具有接著劑層 之銅被覆積層板，例如專利文獻2、專利文獻3、專利文獻 4等’可使用為了提高與樹脂層之接著力而使銅落表面經 粗化處理之銅箔。 此外，近年來，需要對應隨著無鉛化之焊劑接合溫度 的上升，如同專利文獻5般由於與_鄰接之聚酿 324051 4 201251535 脂層的高耐熱化，在熱壓附時銅箔與聚酿亞胺層之間容易 生成微孔，因在電路加工時的酸洗淨液滲入而產生配線剝 - 落等接著信賴性降低的問題。對於此等問題，如同專利文 獻6，雖然有抑制粗化處理高度而控制銅箔粗化處理面的 鍍覆層的方法，但藉由此種方法會有初期剝離強度降低的 疑慮，因而留下課題。 [先前技術文獻] [專利文獻] > [專利文獻1]日本特公平6-93537號公報 [專利文獻2]日本特開平2-292894號公報 [專利文獻3]日本特開平6-169168號公報 [專利文獻4]曰本特開平8-335775號公報 [專利文獻 5]W02002/085616 [專利文獻 6]W02010/010892 【發明内容】 (發明欲解決之課題） 本發明的目的係提供一種金屬被覆積層板，其不僅是 與經粗化處理之金屬箔鄰接的聚醯亞胺層具有高耐熱性， 抑制金屬箔與聚醢亞胺（polyimide)層間產生的微孔，並且 提升金屬箔與聚醯亞胺層的接著信賴性，因而可抑制因酸 洗淨液的滲入所引起的電路剝落。 (解決課題之手段） 本發明者等為了解決上述課題反覆精心研究的結果發 現’使用金職表面特有的粗化特性者，與此金屬箱鄰接 324051 5 201251535 的聚醯亞胺樹脂使用有特定特性的樹脂，藉此可解決上述 課題，遂完成本發明。 亦即，本發明係一種於聚醯亞胺層的單面或雙面具有 金屬箔之金屬被覆積層板，與金屬箔鄰接之聚醯亞胺層（i) 的玻璃轉移溫度為30(TC以上，前述金屬箔之與聚醯亞胺 層鄰接之粗化處理面係滿足下述（a)至（c)的條件， (a) 粗化處理面的表面粗度（Rz)為0.5至4/zm的範圍； (b) 粗化處理面的表層部成為由多數個粗化粒子所形成之 微細突起形狀，在前述微細突起形狀的一突起物中，以相 對於其根本部分的寬度L之突起向度Η的比所表示之寬高 比（H/L)為1.5至5的範圍’突起高度為1至3/zra的範圍 之突起形狀的比例相對於全部突起的數量為50%以下； (c) 鄰接之突起物之間的深度為〇.5//m以上，鄰接突起物 之間距離為〇. 〇 〇 1至1 // m範圍之間隙的存在比例為全部突 起形狀數量的50%以下。 (發明之效果） 本發明之金屬被覆積層板係構成絕緣層之聚醯亞胺具 有高耐熱性，不僅顯示優良的尺寸安定性，可抑制金屬箔 和與其鄰接之聚醯亞胺層之間的微孔產生，可撓式配線板 的電路加工時等之耐藥品性亦優良，因此，適合使用於高 精細的加工所要求之電路基板，其有用性非常高者。、呵 【實施方式】 n 以下，詳細說明本發明。 本發明之金>1被覆積層板係於聚酿亞胺層的單面或雙 324051 6 .201251535 % 金屬箱。若與罐鄰接之聚酿亞胺層的玻璃轉移 ::為：〇C以上，聚醯亞胺層可為單層或由複數層所構 、”、、而&佳為由玻璃轉移溫度為30(TC以上之聚酿 亞胺層（1)與其他的聚酿亞胺層所構成，其他的聚醯亞胺詹 係由具有玻璃轉移溫度比聚酿亞胺層⑴之玻璃轉移溫度 高出50。0：以上之聚酿亞胺層⑴）所構成者。作為金屬落， 只要顯示後述表面粗化形狀者並無特別限制其種類，然 而’以銅箔或合金銅箔為佳。 使用銅fg、合金鋼㈣為金屬箱時，此等之厚度以5 至50//m之範圍為佳，考慮到對於可撓式配線基板的適用 性時’以9至30以m之範圍為更佳。 本發明中使用的金屬羯之與聚醯亞胺層鄰接之粗化處 理面必須滿足下述（a)至（c)的條件， (a) 粗化處理面的表面粗度（Rz)為〇 5至4//111的範圍； (b) 粗化處理面的表層部成為由多數個粗化粒子所形成之 微細突起形狀’在前述微細突起形狀的一突起物中，以相 對於其根本部分的寬度L之突起高度η的比所表示之寬高 比（H/L)為1. 5至5的範圍，突起高度為1至3em的範圍 之突起形狀的比例相對於全部突起的數量為50%以下； (c)鄰接之突起物之間的深度為0.5em以上，鄰接突起物 之間距離為0. 001至範圍之間隙的存在比例為全部突 起形狀數量的50%以下。 首先，粗化處理面的表面粗度（Rz)必須在0. 5至4/z m 之範圍。Rz值未滿0· 5#m時，金屬箔與聚醯亞胺層之接 324051 7 201251535 著力低下，超過4/zm時，電路進行微細圖案加工時之蝕刻 殘渣會增加，其結果使得電性信賴性降低。在此，粗化疼 理面的表面粗度（Rz)係指JISB 〇6〇卜1994「表面粗度的定 義與表示」之「5.1+點平均粗度」之定義所規定之Rz。 接著，粗化處理面之表層部成為由多數個粗化粒子所 形成之微細突起形狀，在前述微細突起形狀之一突起物 中’以，對於其根本部分的£度[之妓高^之比所表 示之寬高比（H/L)為1.5至5的範圍，突起高度為j至3// m的範圍之突起形狀的比例，相對於全部突起形狀的數量 必須為50%以下。當上述寬高比與突起高度之條件超過5〇% 時，表面粗化形狀會變粗，因而在加熱壓附耐熱性（玻璃轉 移溫度）高的聚醯亞胺層時，流動性不足，變得容易產生微 孔。 再者，在金屬羯表面的粗化處理面，鄰接之突起物之 間的深度為0.5/zm以上，鄰接突起物之間距離為〇 〇〇1至 1 β m的範圍之間隙的存在比例必須為全部突起狀數量的 50%以下。當此比例超過5〇%時，樹脂對間隙的填充無法充 分進行’容易產生微孔。 在此，使用第1圖說明關於本發明中使用的金屬箔之 粗化處理面。帛1圖係模式性表示金職剖面的表面部分 放大者。在本發明中，粗化處理面的微細突起形狀之寬高 比，例如第1圖所示，微細突起形狀之一突起物的高度H 除以突起物根本部分的寬度L之值。突起高度係表示由鄰 接之谷的底部連接之中心開始最長的長度之值。 324051 8 201251535 此外，若談到關於本發明上述（c)條件之條件，鄰接突 起物之間有深度為〇. 5 " m以上之間隙，判斷此間隙，之鄰 接突起物間的距離為（^謝至⑹之間隙存在者的存在比 =°於第1圖中，突起物p與突起物q為鄰接之突起物， 突起物p與q之間具有〇.5_以上深度的然後，此 鄰接間距離為G.GGl至之範圍。本發明以此種間隙越 少越好，換言之，（c)的條件係具有突起物間的深度為〇 5 /zm以上深度的間隙，至此深度之鄰接間距離為〇〇〇丨至t 的範圍者相對於全部突起形狀數量為5〇%以下的數量。 於本發明使用之金屬羯表面所形成之粗化形狀，朝向 頂點方向之寬度大於根本部分之寬L而存在的突起形狀的 比例，相對於全部突起形狀的數量較佳為2〇%以下，更佳 為10%以下。當此比例㈣識時，在突起形狀的根本部分 有容易產生微孔的傾向。 在本發明的金屬羯之粗化面，經粗化處理之突起物的 形狀為細長者時，容易產生微孔的傾向，因此，高产1 以上的突起形狀的平均寬度為以上者在全部突起形 狀占有的比例較佳為1(^以上，更佳為3〇%以上。在此，突 起形狀的平均寬可將突起形狀之1/2高度之寬度作為平二 寬。並且，有市售此種經粗化處理之銅箔，只要滿足本發 明之粗化處理面的條件者，可由市售品取得。 金屬箔的粗化處理面較佳為粗化處理面以Ni、如、^ 鍍覆處理，Ni含量為〇· lmg/dm2以上，且以亮度計測量之γ 值（壳度）為25以上者。此亮度係試樣表面的光，以光的反 324051 9 201251535 射量作為亮度，因此，成為觀測表面粗度的指標。亮度低 係指反射率低，亦表示鄰接之突起物間的間隙多為窄深 者，容易在熱壓附時產生微孔。Ni含量未達0. lmg/dm2時， 由於耐腐蝕性不足，不僅因聚醯亞胺的填充性，也會因酸 而腐银。 接著，說明本發明之金屬被覆積層板中作為絕緣層的 聚醯亞胺層。 如上述說明，在本發明中，聚醯亞胺層必須為聚醯亞 胺層（i)作為與金屬箔鄰接之層，較佳為由複數層聚醯亞胺 層所構成。作為較佳具體的聚醯亞胺層的構成例，可列舉 下述構成例。並且，在下述構成例中，Μ為金屬箔的簡稱， ΡΙ為聚醯亞胺的簡稱，再者，ΡΙ層（i)為玻璃轉移溫度為 300°C以上的聚醢亞胺層，PI層（ii)為玻璃轉移溫度比聚 醯亞胺層（i)者高出50°C以上的層。 (1) M/ΡΙ 層（i)/PI 層（ii)/PI 層（i)201251535 VI. Description of the Invention: [Technical Field] The present invention relates to a metal-clad laminate suitable for use in a flexible circuit substrate, and more particularly to an insulating layer composed of a polyimide resin. Flexible flexible metal coated laminate. [Prior Art] In recent years, 'the high-functionality, miniaturization, and weight reduction of mobile phones, digital cameras, digital cameras, PDAs, car navigation, and other electronic devices, as the substrate materials for electrical wiring. An example of a flexible printed circuit board having a higher degree of freedom in wiring and being easier to be thinner than a rigid substrate that can be used in the past is increasing. Then, in order to increase the height of the flexible printed circuit board used in these devices, it is required to increase the compactness, density, multilayering, miniaturization, and high heat resistance. In order to cope with such a request, Patent Document 1 and the like disclose a method in which a polyimine resin layer is directly coated on a conductor, and a plurality of polyimine resin layers having different thermal expansion coefficients are formed. It is possible to provide a flexible printed circuit board having excellent reliability such as dimensional stability, adhesion, and planarity after etching. For a copper-clad laminate which does not have an adhesive layer used in such a flexible printed circuit board, for example, Patent Document 2, Patent Document 3, and Patent Document 4 can be used to increase the adhesion to the resin layer. A copper foil having a roughened surface. In addition, in recent years, it is necessary to cope with the increase in the solder bonding temperature with lead-free, and as in Patent Document 5, due to the high heat resistance of the adhesive layer of 324051 4 201251535 adjacent to the _, the copper foil and the poly-broth during the hot press-fitting Micropores are likely to be formed between the imine layers, and the acid cleaning liquid infiltrates during circuit processing to cause problems such as wiring peeling and the like, and reliability is lowered. With regard to such a problem, as in Patent Document 6, although there is a method of controlling the plating layer of the roughened surface of the copper foil by suppressing the height of the roughening treatment, there is a concern that the initial peel strength is lowered by such a method, and thus Question. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] JP-A-H08-335775 [Patent Document 5] WO2002/085616 [Patent Document 6] WO2010/010892 [Disclosure] The object of the present invention is to provide a metal coating. A laminate which not only has a high heat resistance adjacent to the roughened metal foil, but also suppresses micropores generated between the metal foil and the polyimide layer, and lifts the metal foil and the polyimide The subsequent imidence of the imine layer can suppress circuit peeling due to penetration of the acid cleaning solution. (Means for Solving the Problem) In order to solve the above problems, the inventors of the present invention have found that the use of the poly-imine resin adjacent to the metal box 324051 5 201251535 has specific characteristics. The resin can solve the above problems and the present invention has been completed. That is, the present invention is a metal-clad laminate having a metal foil on one or both sides of the polyimide layer, and the glass transition temperature of the polyimide layer (i) adjacent to the metal foil is 30 (TC or more) The roughened surface of the metal foil adjacent to the polyimide layer satisfies the following conditions (a) to (c), and (a) the surface roughness (Rz) of the roughened surface is 0.5 to 4/ (b) The surface layer portion of the roughened surface is a fine protrusion shape formed by a plurality of roughened particles, and a protrusion having a width L with respect to a fundamental portion thereof in a protrusion of the fine protrusion shape The ratio of the aspect ratio (H/L) indicated by the ratio 向 to the range of 1.5 to 5, and the ratio of the protrusion shape in the range of the protrusion height of 1 to 3/zra is 50% or less with respect to the total number of protrusions; c) The depth between adjacent protrusions is 〇.5//m or more, and the distance between adjacent protrusions is 〇. The ratio of the gaps in the range of 〇〇1 to 1 // m is 50% of the total number of protrusion shapes. (Effect of the invention) The metal-coated laminated board of the present invention is a polyimide which has an insulating layer and has high heat resistance. The property not only exhibits excellent dimensional stability, but also suppresses the generation of micropores between the metal foil and the polyimide layer adjacent thereto, and the chemical resistance of the flexible wiring board during circuit processing is also excellent, and therefore, it is suitable. The circuit board required for high-precision processing is extremely useful. [Embodiment] n Hereinafter, the present invention will be described in detail. The gold > 1 coated laminate of the present invention is attached to a polyimide layer. Single-sided or double 324051 6 .201251535 % metal box. If the glass transition of the polyimine layer adjacent to the tank:: 〇C or more, the polyimide layer can be a single layer or composed of a plurality of layers, ",, and & preferably consists of a glass transition temperature of 30 (TC or more of the poly-imine layer (1) and other poly-imine layers, other polyimines have a glass transition temperature The glass transition temperature of the chitosan layer (1) is higher than the glass transition temperature of 50:0 or more. The metal halide layer is not particularly limited as long as it exhibits a surface roughening shape to be described later. 'It is better to use copper foil or alloy copper foil. Use copper fg, When the alloy steel (4) is a metal case, the thickness is preferably in the range of 5 to 50/m, and it is more preferably in the range of 9 to 30 in terms of the applicability to the flexible wiring board. The roughened surface adjacent to the polyimide layer used in the invention must satisfy the following conditions (a) to (c), and (a) the surface roughness (Rz) of the roughened surface is 〇5. (b) the surface layer portion of the roughened surface is a fine protrusion shape formed by a plurality of roughened particles, in a protrusion of the fine protrusion shape, with respect to the fundamental portion thereof The aspect ratio (H/L) of the ratio of the protrusion height η of the width L is 1.5 to 5, and the ratio of the protrusion shape in the range of the protrusion height of 1 to 3 cm is 50% with respect to the total number of protrusions. (c) The depth between the adjacent protrusions is 0.5 em or more, and the distance between the adjacent protrusions is 0.00. The ratio of the gap to the range is 50% or less of the total number of protrusion shapes. The surface roughness (Rz) of the roughened surface must be in the range of 0.5 to 4/z m. When the Rz value is less than 0·5#m, the connection between the metal foil and the polyimide layer is 324051 7 201251535. When the voltage exceeds 4/zm, the etching residue in the micro pattern processing of the circuit increases, and the result is electrical. Reduced reliability. Here, the surface roughness (Rz) of the roughened pain surface refers to Rz defined by the definition of "5.1+ point average roughness" of JISB 〇6〇b 1994 "Definition and Expression of Surface Thickness". Then, the surface layer portion of the roughened surface is a fine protrusion shape formed by a plurality of roughened particles, and the ratio of the base portion of the protrusion of the fine protrusion shape to the fundamental portion is higher than The aspect ratio (H/L) indicated is in the range of 1.5 to 5, and the ratio of the protrusion shape in the range of the protrusion height in the range of j to 3//m must be 50% or less with respect to the total number of protrusion shapes. When the condition of the aspect ratio and the height of the protrusion exceeds 5〇%, the surface roughening shape becomes coarse, and when the polyimine layer having a high heat resistance (glass transition temperature) is heated, the fluidity is insufficient. It is easy to produce micropores. Further, in the roughened surface of the surface of the metal crucible, the depth between the adjacent protrusions is 0.5/zm or more, and the ratio of the gap between the adjacent protrusions in the range of 〇〇〇1 to 1β m must be It is 50% or less of the total number of protrusions. When the ratio exceeds 5%, the filling of the gap by the resin cannot be sufficiently performed. Here, the roughened surface of the metal foil used in the present invention will be described using Fig. 1 . The 帛1 pattern is a schematic representation of the surface portion of the gold section. In the present invention, the aspect ratio of the fine protrusion shape of the roughened surface is, for example, the value of the height H of one of the protrusions in the fine protrusion shape divided by the width L of the root portion of the protrusion as shown in Fig. 1 . The height of the protrusions represents the value of the longest length from the center of the bottom connection of the adjacent valleys. 324051 8 201251535 In addition, when referring to the condition of the above condition (c) of the present invention, the depth between adjacent protrusions is 〇. 5 " m or more, and the gap between the adjacent protrusions is judged as ( ^The ratio of the existence of the gap to the (6) is =° in the first figure, the protrusion p and the protrusion q are adjacent protrusions, and the protrusions p and q have a depth of 〇.5_ or more, and then The distance between the adjacent ones is in the range of G.GG1. In the present invention, the smaller the gap, the better, in other words, the condition of (c) is a gap having a depth between the protrusions of 〇5 /zm or more, and the depth is adjacent thereto. The distance between the range of 〇〇〇丨 and t is 5% or less with respect to the total number of protrusion shapes. The roughened shape formed by the surface of the metal ruthenium used in the present invention has a width toward the apex direction larger than the fundamental portion. The ratio of the shape of the protrusions which is present in the width L is preferably 2% or less, more preferably 10% or less, based on the total number of the protrusion shapes. When the ratio (4) is known, micropores are easily generated in the fundamental portion of the protrusion shape. Tendency. In the present invention In the roughened surface of the metal crucible, when the shape of the roughened protrusion is elongated, the micropore tends to be generated. Therefore, the average width of the protrusion shape having a high yield of 1 or more is higher than the ratio of all the protrusion shapes. Preferably, it is 1 or more, more preferably 3 % by weight or more. Here, the average width of the protrusion shape may have a width of 1/2 of the height of the protrusion as the width of the second. Further, there is a commercially available such roughening treatment. The copper foil may be obtained from a commercially available product as long as it satisfies the conditions of the roughened surface of the present invention. The roughened surface of the metal foil is preferably a roughened surface treated with Ni, for example, and has a Ni content of 〇·lmg/dm2 or more, and the gamma value (shell ratio) measured by the luminance meter is 25 or more. This brightness is the light on the surface of the sample, and the light is reflected by the light of the 324051 9 201251535, so that it becomes the observation surface. The low-intensity index means that the reflectance is low, and the gap between the adjacent protrusions is mostly narrow, and it is easy to generate micropores during hot pressing. The Ni content is less than 0.1 mg/dm2, because Insufficient corrosion resistance, not only due to the filling properties of polyimine Next, silver is also rotted by acid. Next, a polyimine layer as an insulating layer in the metal-clad laminate of the present invention will be described. As described above, in the present invention, the polyimide layer must be a polyimide. The layer (i) is a layer adjacent to the metal foil, and is preferably composed of a plurality of layers of polyimine layers. Examples of preferred specific examples of the polyimide layer include the following structural examples. In the above-mentioned configuration example, Μ is an abbreviation for metal foil, ΡΙ is an abbreviation for poly liminimide, and further, ruthenium layer (i) is a polyimide layer having a glass transition temperature of 300 ° C or higher, and PI layer (ii) A layer having a glass transition temperature higher than 50 ° C above the polyimine layer (i). (1) M/ΡΙ layer (i) / PI layer (ii) / PI layer (i)
(2) M/ΡΙ 層（i)/PI 層（ii)/PI 層（i)/M(2) M/ΡΙ layer (i)/PI layer (ii)/PI layer (i)/M
(3) M/ΡΙ 層（ii)/PI 層（i)/M 構成聚醯亞胺層的聚醯亞胺通常如下述式（1)所示，可 實質上等莫耳使用二胺成分與酸二酐成分，藉由已知的方 法在有機極性溶劑中聚合而製造。 324051 10 201251535(3) M/ΡΙ layer (ii)/PI layer (i)/M The polyimine which constitutes the polyimine layer is generally represented by the following formula (1), and substantially can be used in combination with the diamine component. The acid dianhydride component is produced by polymerization in an organic polar solvent by a known method. 324051 10 201251535
一-N Ο Ο人Λ γΑΓΐΝ^Ν-ΑΓ2- Ο Ο -Π 式（1) 在此，An為具有1個以上芳香環的4價有機基，Ar2 為具有1個以上芳香環的2價有機基，η表示重複數。亦 即，Ar 1為酸二酐的殘基，Ar2為二胺的殘基。 聚醯亞胺的聚合中所使用的溶劑，例如可列舉二曱基 乙酿胺、η-曱基0比σ各咬酮、2-丁酮、二甘二曱醚（diglyme)、 二曱苯。此等可使用1種或將2種以上併用。此外，關於 聚合可得之聚醯胺酸（聚醯亞胺前驅物）的樹脂黏度，較佳 為作成500cps至35000cps之範圍。 作為原料使用之二胺成分及酸二酐成分，考慮構成絕 緣層的聚醯亞胺層（i)、聚醯亞胺層（ii)所要求的各種特 性，可由下述所例示的各原料成分中選擇最適當者。 作為酸二酐，較佳為例如0(C0)2-An-(C0)20所示之芳 香族四羧酸二酐，以下述式（2)所示芳香族酸酐殘基作為 Αιί而得者為例。 324051 11 201251535 式（2)1-N Ο Ο人Λ γΑΓΐΝ^Ν-ΑΓ2- Ο Ο -Π Formula (1) Here, An is a tetravalent organic group having one or more aromatic rings, and Ar2 is a divalent organic compound having one or more aromatic rings. Base, η represents the number of repetitions. That is, Ar 1 is a residue of an acid dianhydride, and Ar 2 is a residue of a diamine. Examples of the solvent used in the polymerization of the polyimine include dimercaptoacetamide, η-fluorenyl 0 to σ each, ketone, 2-butanone, diglyme, and diphenylbenzene. . These may be used alone or in combination of two or more. Further, the resin viscosity of the polylysine (polyimine precursor) which is polymerizable is preferably in the range of 500 cps to 35,000 cps. The diamine component and the acid dianhydride component used as a raw material may be various raw material components exemplified below, in consideration of various properties required for the polyimide phase (i) and the polyimide phase (ii) constituting the insulating layer. Choose the most appropriate one. The acid dianhydride is preferably an aromatic tetracarboxylic dianhydride represented by, for example, 0(C0)2-An-(C0)20, which is obtained by using an aromatic acid anhydride residue represented by the following formula (2) as Αιί. For example. 324051 11 201251535 style (2)
此外，作為二胺，較佳為例如Η2Ν-ΑΓ2-ΝΗ2所示之芳香 族二胺，以下述式（3)所示之芳香族二胺殘基作為Ar2而得 者為例。 式（3) 324051 12 201251535In addition, as the diamine, for example, an aromatic diamine represented by Η2Ν-ΑΓ2-ΝΗ2 is preferable, and an aromatic diamine residue represented by the following formula (3) is used as Ar2. Formula (3) 324051 12 201251535
本發明中之聚醯亞胺層（i)為與金屬箔鄰接之玻璃轉 移溫度300°C以上的聚醯亞胺層。從與金屬箔之接著性的 觀點來看，聚醯亞胺層（i)必須顯示與金屬箔加熱壓附時的 熱塑性，然而，當玻璃轉移溫度低時耐熱性隨著降低。由 此觀點來看，聚醯亞胺層（i)之較佳玻璃轉移溫度宜未達 350Ϊ 者。 構成此種聚醯亞胺層（i)之酸二酐成分，可列舉如上述 324051 13 201251535 式⑵所示者’以笨均四酸二酐⑽a)作為必 等作為主成分，特佳為使用8〇莫耳％以上、= 酿亞胺層⑴的二胺成分，可列舉如上述式⑶所示^成^ 別疋以2,2-雙[4-(4、胺基苯氧基）苯基]顿 = 須成分’以此等作為主成分，特佳為使用8 =必 在此，可個2種以上其他的酸二酐及二胺 匕以上的層。由與金屬箔的接著性之 點來看’ W亞胺層㈤未與金射接接觸，以隔著 醯亞胺層⑴與金料成為—體化為佳。 Λ 構成此種聚酿亞胺層⑼的酸二針成分，較佳為使用 選自苯均四酸二酐⑽……，，“、聯苯基四羧酸二酐 (ΒΡΜ) 3, 3，4, 4 -二笨甲酮四羧酸二酐（bTDA)、 3, 3’，4, 4’ -二苯基砜四羧酸二酐（DSDA)及4, 4, _氧基二酞 酸二肝（GDPA)者’此等可單獨使用或混合2種以上使用。 此外，構成聚醯亞胺層（Π)的二胺成分，作為適當者 可列示如二胺基二苯基醚（DAPE)、2，_甲氧二 苯甲醯胺苯（MAM)、2,2，-二甲基-4,4，_二；胺基聯^ (m-TB)、對-苯二胺（p-pda)、l，3-雙（4-胺基苯氧基）苯 (TPE-R)、1，3-雙（3-胺基笨氧基）苯（APB)、丨，4_雙（4_胺基 笨氧基）苯（TPE-Q)及2, 2-雙[4-(4-胺基苯氧基）苯基]丙烷 (BAPP)，此等可單獨使用或混合2種以上使用。 本發明中之聚醯亞胺層的厚度較佳為8至40/zm，更 佳為9至30#m。此外，聚醯亞胺層（i)作用為保持與金屬 324051 14 201251535 層的接著性、維持因控制絕緣層全體的線膨脹係數所致的 平衡’其厚度以1至3" m的範圍為佳。聚醯亞胺層⑴可 設置於聚醯亞胺層（ii)的一側或兩側。 如上所述’本發明中絕緣層由單層或複數層的聚醯亞 胺層所構成’因此，本發明較佳為絕緣層全體（輯亞胺層 全體）線膨服係數（CTE)成為⑺沿^至幻的範圍 為佳。聚醯亞胺層為複數層時，上述聚醯亞胺層（ii)的線 膨脹係數（CTE)較佳為3〇xi〇-6以下，特佳為1χ10-6至20xl0-6 [1/K]的範圍。此外，在此情形，聚醯亞胺層（丨）以在2〇x 1(Γ6 至 60χ10—6[1/κ]的範圍為佳，以 3〇χ1〇-6 至 50x10-6[1/k] 的範圍為特佳。 以下，在本發明之金屬被覆積層板的製造方法中，以 積層體的上述構成例（2)者[μ/pi層（i)/PI層（ii)/PI層 (i)/M]為基礎說明。並且，在下述例中，μ為使用銅箔者。 在本例中，首先，在經粗化處理的銅箔之表面直接塗 佈作為用以成為聚醯亞胺層（i)之聚醯亞胺前驅物的聚醯 胺酸溶液，將樹脂溶液中所含的溶劑以150°C以下的溫度 去除至某種程度。 接著’直接塗佈用以成為聚醯亞胺層（ii)之聚醯亞胺 前驅物之聚醯胺酸溶液，將樹脂溶液中所含的溶劑以15〇 C以下的溫度去除至某種程度。 然後，復直接塗佈用以成為聚醯亞胺層（i)之聚醯亞胺 前驅物的聚醯胺酸溶液，將樹脂溶液中所含的溶劑以150 °C以下的溫度去除至某種程度。如此，而於銅箔上形成複 324051 15 201251535 數層之溶液去除至某種程度的聚醯亞胺前驅物層，進—步 在100至450 c，較佳為300至45(TC的溫度範圍’進行熱 處理5至4G分鐘左右’復進行溶劑的去除及酿亞胺化。 在此狀態，銅笛上形成由3層聚醯亞胺層所構成的單 面銅被覆積層板，於此單面銅被覆積層板的聚酿亞胺層⑴ 面側加熱壓附經粗化處理之㈣。加熱屋附係以猶微高於 聚醯亞胺層⑴的玻璃轉移溫度的溫度將其加熱壓附，本發 明使用上述特定的粗化處理面的㈣因此可抑制微孔的產 生。本例係於聚醯亞胺層的兩側使用經粗化處理的銅落， 然而，本發明另—方面亦可僅在適當的加熱壓附側的銅箱 使用上述規定之特定銅落。 藉此，本發明即使在要求对熱性之與金屬箱鄰接的層 使用高玻_移溫度之韻亞胺狀情形，由於使用星有 特定表面性狀之經粗化處理的㈣，可_尺寸安定性、 接著㈣其他金騎覆㈣㈣各雜，㈣可抑制微孔 的產生。 實施例 以下’以實施例為基礎更詳細說明本發明。並且，在 以下的實施例中’若無特別備註則各種評估係如下述者。 [玻璃轉移溫度的測定] 將基材銅羯敍刻成為薄膜狀態之聚醢亞胺，使用SII nanotechnology公司製的動態黏彈性測定裝置 ⑽-丨⑴，將於拉伸模式丨烏之溫度分散測定的加占 的峰頂當作玻璃轉移溫度。 324051 16 201251535 [粗化處理面的評估] 粗化處理面的形狀評估係將以剖面試料裝置（Cn3SS section polisher，日本電子公司製SM-09010)製作的銅 箔剖面藉由FE-SEM(日立High-tech公司製S-47〇〇型）觀 察，評估在寬度25ym的範圍内粗化部分的形狀。 此外，粗化處理面的Ni量係藉由僅於聚醯亞胺鄰接的 面以1N硝酸定溶之iCP-AES(Perkinelmer公司製〇ptima 4300)而測定。再者，使用Sugatest公司製SM-4測定亮度 Y ° [耐酸性的測定] 耐酸性的測定係於可撓式單面銅被覆積層板進行線寬 lmm之電路加工，在鹽酸l8wt%的水溶液中於5〇。(：浸潰6〇 分鐘後，由絕緣層（聚醯亞胺層）侧將電路端部使用2〇〇倍 的光學顯微鏡測定因鹽酸滲入所致之變色寬度。在此，鹽 酸滲入寬度為200 /zm以下者評估為優良。 [接著力（剝離強度）的測定] 銅箔與聚醯亞胺樹脂層之間的接著力係對於銅羯上形 成由聚醯亞胺樹脂所構成之絕緣層而得之可撓式單面鋼被 覆積層板進行線寬lmm之電路加工’使用東洋精機股份有 限公司製拉伸測試機（STR0GRAPH-M1)，將銅箔以180。方向 撕下’測定初期剝離強度’此外測定在前述耐酸性測定後 的剝離強度，耐酸後剝離強度/初期剝離強度xlQ〇%當作保 持率。 合成例1 324051 17 201251535 於具備熱電偶及攪拌機且可導入氮氣的反應容器中倒 入N’N-二甲基乙醢胺。於此反應容器中一邊將2,2_雙 [4-(4-胺基苯氧基）苯基]丙烷（BApp)於容器中攪拌一邊使 其溶解。接著，加入苯均四酸二酐（PMDA)，使單體的投入 總量成為12wt%。之後’持賴拌3小時，得到聚酿胺酸 的樹脂溶液b。聚醢胺酸的樹脂溶液b的溶 3,000cps。由此聚醢胺酸所得之聚醯亞胺顯示超過3〇χΐρ (1/κ)的線膨脹係數，具有315t的玻璃轉移溫度。 合成例2 於具備熱電偶及機且可導入氮氣的反應容器中倒 入N，N-二曱基乙醯胺。於此反應容器中一邊將2,2，一二 基-“’-胺基聯笨^⑻於容器帽拌—邊使其溶解 著’加入3,3’’4,4’-聯笨基四舰二_雇）及苯均 二酐⑽A)。使單體的投人總量為，各酸 比例⑽以MDA)成為20:8〇的方式投入。之後，持續= 拌3小時’得到聚醯胺酸的樹脂溶液a。聚醯胺酸的樹， 溶液&的溶_度為2Q’_PS。由此聚醯胺酸所得^ 酿亞胺顯示2〇χ1(Τ(1/Κ)以下的低線膨脹係數， ^ 塑性之性質。 3邱熱 實施例1 準備將作為表面處理層的以具有胺基之石夕烧偶 烧搞合處理之具有表1所示粗化處理面之電解綱作= 羯。此㈣厚度為1 一，表面粗度為⑽$ 銅伯上’依序塗佈合成例2調製之聚醢胺酸的樹脂溶夜匕 324051 18 201251535 合成例1調整之聚醯胺酸的樹脂溶液a及合成例2調製之 聚醯胺酸的樹脂溶液b，在乾燥後，進行最終3〇(rc以上約 ίο分鐘之熱處理，得到聚醯亞胺層的厚度為25#m之可撓 式單面銅被覆積層板。並且，聚醯亞胺層係具有由聚醯胺 酸的樹脂溶液a而得之21 _的層與於其兩側由聚酿胺酸 的樹脂溶液b而得之各2am的層者。 、對於藉此所得之可撓式單面銅被覆積層板，於其聚酿 亞月女層面進步將與上述同樣的銅箔在加熱/加壓下使其 通過金屬輥之間藉此加熱壓附。剝離強度及耐酸性的特性 評估係：可撓式雙面銅箔被覆積層板之加熱壓 附面側進 ^銅、，自與聚醯亞胺層間之1mm剝離的初期接著力為 1.95kN/m。此外，其電路的耐酸性試驗之渗入寬度為 m，剝離強度保持率為_。結果表示於表2。 實施例2、3、比較例1、2 示了使用表面金屬量相異之表^所示的電解銅箔之 外 >、實施例1進行同樣操作，評估剝離強度、鹽酸滲入 性、剝離保持率。結果表示於表2。 雖然表1中並未顯示，然而，實施例、比較例所使用 之王°卩的銅箔的粗化處理面經Ni、Zn及Cr鍍覆處理。 表1中， 的寬高比數量/全部突起數量係表示相對於所測定之 王〇卩犬起數量，寬高比（H/L)為1.5至5的範圍，突起高度 為1至3/zm的範圍者之數量的比例。 (c)突起間的狹間隙/全部突起數量係表示相對於所測定之 324051 19 201251535 全部突起數量，具有鄰接之突起物間之深度為0.5//m以 上，鄰接突起物間距離為0. 001至1 /zm的範圍之間隙者的 數量之比例。 此外，（d)膨脹突起數量/全部突起數量係表示相對於 所測定之全部突起數量，具有寬度寬於根底的寬度L之突 起形狀的數量之比例。 再者，（e)突起平均寬度l//m以上/全部突起數量係表 示相對於所測定之全部突起數量，突起的平均寬度為lym 以上者的數量之比例。 並且，實施例1中使用的銅箔剖面的照片表示於第2圖， 比較例2中使用的銅箔剖面的照片表示於第3圖。在此， 實施例2及3中使用的銅箔係Rz相異者的表面的微細粗化 形狀與第2圖類似，比較例1中使用的銅箔係Rz相異者的 表面的微細粗化形狀與第3圖類似。 324051 20 201251535 [表1] (a) Rz []x m] (b) 高的寬高比 數量/全部 突起數量 (C) 突起間的 狭間隙數 量/全部突 起數量 (d) 膨脹突起 數量/全部 突起數量 (e) 平均宽度 1卩m以上 的突起數量 /全部突起 數量 Ni含量 [mg/dm2] 亮度 [AV] 實施例1 1.20 5% 21% 5% 37% 0.23 25.8 實施例2 3. 15 15¾ 42% 19¾ 31¾ 0.23 25. 5 實施例3 2. 90 20% 40¾ 16% 52¾ 0. 14 26.3 比較例1 3. 00 46% 68% 43% 7% 0. 12 21. 9 比較例2 1. 10 54¾ 54¾ 35% 23¾ 0. 12 21.4 [表2] 初期剝離強度 [kN/m] 鹽酸滲入寬度 [β m] 剝離強度保持率 m 實施例1 1. 95 69 89 實施例2 1. 97 138 82 實施例3 1. 96 189 74 比較例1 1. 95 396 30 比較例2 1. 90 499 33 確認實施例1、2、3所得之銅被覆積層板在鹽酸處理 後之電路端部的變色在200/zm以下，剝離強度保持率在 70%以上。另一方面，確認比較例1、2中之電路端部全部 因電路剝落而變色，剝離強度保持率為未達70%。 此種本發明所得之可撓式銅被覆積層板抑制鹽酸處理 324051 21 201251535 後的渗入，不會發生電路剝落，因此確認為信賴性高的材 料。 【圖式簡單說明】 第1圖係用以說明在銅箔的銅箔剖面之粗化形狀之模 式圖。 第2圖係實施例1所使用之銅箔的銅箔剖面照片。 第3圖係比較例2所使用之銅箔的銅箔剖面照片。 【主要元件符號說明】 L 微細突起形狀的根本部分的寬度 Η 微細突起形狀的高度 ρ 鄰接於q之1突起物 q 鄰接於ρ之1突起物 324051 22The polyimine layer (i) in the present invention is a polyimine layer having a glass transition temperature of 300 ° C or higher adjacent to the metal foil. From the viewpoint of adhesion to the metal foil, the polyimide layer (i) must exhibit thermoplasticity upon heat-bonding with the metal foil, however, heat resistance decreases as the glass transition temperature is low. From this point of view, the preferred glass transition temperature of the polyimine layer (i) is preferably less than 350 Å. The acid dianhydride component constituting the polyimine layer (i) may be, for example, the above-mentioned 324051 13 201251535 (2), which is a main component, and particularly preferably used. 8〇摩尔% or more, = diamine component of the imine layer (1), which can be exemplified by the above formula (3), 2,2-bis[4-(4,aminophenoxy)benzene Base] Dun = whisker component 'This is the main component, and it is particularly preferable to use 8 = must be here, and two or more layers of other acid dianhydride and diamine oxime may be used. From the point of view of the adhesion to the metal foil, the W-imine layer (5) is not in contact with the gold, and it is preferred to form the metal with the yttrium imide layer (1). Λ The acid two-needle component constituting the polyimine layer (9) is preferably selected from the group consisting of pyromellitic dianhydride (10), ", biphenyltetracarboxylic dianhydride (ΒΡΜ) 3, 3, 4, 4 - dimercapto ketone tetracarboxylic dianhydride (bTDA), 3, 3', 4, 4'-diphenyl sulfone tetracarboxylic dianhydride (DSDA) and 4, 4, oxy phthalic acid The second liver (GDPA) can be used alone or in combination of two or more. Further, the diamine component constituting the polyimine layer (Π) can be listed as diaminodiphenyl ether as appropriate. DAPE), 2, methoxybenzobenzamide (MAM), 2,2,-dimethyl-4,4,_di; amine linkage (m-TB), p-phenylenediamine ( P-pda), l,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenyloxy)benzene (APB), hydrazine, 4_double (4_Amino-p-oxy)benzene (TPE-Q) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), these may be used alone or in combination The thickness of the polyimine layer in the present invention is preferably from 8 to 40/zm, more preferably from 9 to 30 #m. Further, the polyimine layer (i) acts to maintain the metal with 324051 14 201251535 Layer adhesion, The balance due to controlling the coefficient of linear expansion of the entire insulating layer is preferably in the range of 1 to 3 " m. The polyimine layer (1) may be disposed on one side or both of the polyimide layer (ii). As described above, the insulating layer of the present invention is composed of a single layer or a plurality of layers of polyimine layers. Therefore, the present invention preferably has a line expansion coefficient (CTE) of the entire insulating layer (the entire imine layer). It is preferable that (7) is in the range of ^ to illusion. When the polyimine layer is a plurality of layers, the linear expansion coefficient (CTE) of the polyimine layer (ii) is preferably 3 〇 xi -6 or less. It is in the range of 1χ10-6 to 20x10-6 [1/K]. Further, in this case, the polyimine layer (丨) is in the range of 2〇x 1 (Γ6 to 60χ10-6 [1/κ] Preferably, the range of 3〇χ1〇-6 to 50x10-6[1/k] is particularly preferable. In the method for producing a metal-clad laminate according to the present invention, the above-described configuration example (2) of the laminate is used. [μ/pi layer (i) / PI layer (ii) / PI layer (i) / M] is based on the description. In the following examples, μ is a copper foil. In this example, first, in the The surface of the roughened copper foil is directly coated The cloth is used as a polyaminic acid solution for forming a polyimine imine precursor of the polyimine layer (i), and the solvent contained in the resin solution is removed to a certain temperature at a temperature of 150 ° C or lower. The polyamic acid solution for forming the polyimide precursor of the polyimine layer (ii) is directly applied, and the solvent contained in the resin solution is removed to a certain temperature at a temperature of 15 ° C or lower. Then, the polyamic acid solution for forming the polyimine precursor of the polyimine layer (i) is directly coated, and the solvent contained in the resin solution is removed to a temperature of 150 ° C or lower. degree. Thus, a solution of a plurality of layers of 324051 15 201251535 formed on the copper foil is removed to a certain degree of the polyimide precursor layer, and the temperature is in the range of 100 to 450 c, preferably 300 to 45 (TC). 'The heat treatment is carried out for about 5 to 4 minutes, and the solvent is removed and the imidization is carried out. In this state, a single-sided copper-coated laminate composed of three layers of polyimide layers is formed on the copper flute. The poly-imide layer (1) of the copper-clad laminate is heated and pressed on the surface side by heat treatment (4). The heated house is heated and pressed at a temperature higher than the glass transition temperature of the polyimide layer (1). The present invention uses the above-mentioned specific roughening treatment surface (4), thereby suppressing the generation of micropores. In this example, the roughened copper is used on both sides of the polyimide layer, however, the present invention may also The specific copper drop specified above is used only on the copper case on the appropriate heated press-side side. Thus, the present invention uses a high glass-shift temperature of the imine-like state even in the case of a layer adjacent to the metal case for heat. Using the roughened (4) of the star with a specific surface trait, The size stability may be followed by (4) other gold riding (4) (4), and (4) suppressing the generation of micropores. EXAMPLES Hereinafter, the present invention will be described in more detail based on the examples, and in the following examples, Special notes are as follows. [Measurement of glass transition temperature] The substrate bismuth is etched into a film-state polyimine, using a dynamic viscoelasticity measuring device (10)-丨(1) manufactured by SII Nanotechnology Co., Ltd. The peak of the addition of the temperature dispersion measurement in the tensile mode is taken as the glass transition temperature. 324051 16 201251535 [Evaluation of the roughened surface] The shape evaluation of the roughened surface is to be a section sampler (Cn3SS section polisher The copper foil cross section produced by SM-09010, manufactured by JEOL Ltd., was observed by FE-SEM (S-47 type manufactured by Hitachi High-tech Co., Ltd.), and the shape of the roughened portion in the range of 25 μm in width was evaluated. The amount of Ni in the roughened surface was measured by iCP-AES (〇 ptima 4300, manufactured by Perkinelmer Co., Ltd.) which was dissolved in 1 N nitric acid only on the surface adjacent to the polyimide. The measurement was carried out using SM-4 manufactured by Sugatest Co., Ltd. bright Degree Y ° [Determination of acid resistance] The acid resistance was measured by a circuit with a line width of 1 mm on a flexible single-sided copper-clad laminate, and it was 5 Torr in an aqueous solution of 18 wt% hydrochloric acid. (: 6 min. Then, the width of the discoloration due to the infiltration of hydrochloric acid was measured by an optical microscope of 2 times the end of the circuit from the side of the insulating layer (polyimine layer). Here, the penetration width of the hydrochloric acid was 200 / zm or less. [Measurement of Adhesion (Peel Strength)] The adhesive force between the copper foil and the polyimide resin layer is a flexible one-sided surface formed by forming an insulating layer composed of a polyimide resin on the copper beryllium. The steel-clad laminate was subjected to a circuit processing with a line width of 1 mm. Using a tensile tester (STR0GRAPH-M1) manufactured by Toyo Seiki Co., Ltd., the copper foil was 180. Direction tearing "Measurement initial peel strength" In addition, the peel strength after the acid resistance measurement was measured, and the peeling strength after acid resistance/initial peel strength xlQ〇% was regarded as the retention ratio. Synthesis Example 1 324051 17 201251535 N'N-dimethylacetamide was poured into a reaction vessel equipped with a thermocouple and a stirrer and introduced with nitrogen. In the reaction vessel, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BApp) was dissolved in a vessel while stirring. Next, pyromellitic dianhydride (PMDA) was added to make the total amount of the monomer input 12 wt%. Thereafter, the mixture was stirred for 3 hours to obtain a resin solution b of polyacrylic acid. The resin solution b of polylysine was dissolved in 3,000 cps. The polyimine obtained from the polyamic acid thus showed a linear expansion coefficient exceeding 3 〇χΐρ (1/κ) and a glass transition temperature of 315 t. Synthesis Example 2 N,N-dimercaptoacetamide was poured into a reaction vessel equipped with a thermocouple and a machine and nitrogen gas was introduced. In the reaction vessel, 2,2,2-diyl-"'-amino group is combined with (8) in a container cap to dissolve it, and '3,3''4,4'-linked stupid base is added. Ship II _employed) and benzene phthalic anhydride (10) A). The total amount of monomer input is, the ratio of each acid (10) is 20:8 以 in MDA). After that, continue = mix for 3 hours to get 醯Amine acid resin solution a. Polyammonic acid tree, solution & the solubility _ degree is 2Q'_PS. The polyimine acid obtained from the imine yields 2〇χ1 (Τ(1/Κ) or less Low coefficient of linear expansion, ^ Properties of plasticity. 3. Qiu Thermal Example 1 Preparation of a surface treatment layer with an amine-based stone-fired kiwi-fired alloy having the roughened surface shown in Table 1 = 羯. This (4) has a thickness of 1 and a surface roughness of (10)$ on the copper plate. The resin is dissolved in the composite of the compound of the second example. The resin is dissolved in the night 匕 324051 18 201251535 Synthetic Example 1 Adjusted polylysine The resin solution a of the resin solution a and the polyaminic acid prepared in Synthesis Example 2 are dried, and then subjected to a heat treatment of rc or more for about 0.25 hours to obtain a thickness of the polyimide layer of 25 μm. The flexible single-sided copper coated laminate is provided, and the polyimide layer has a layer of 21 _ obtained from the resin solution a of poly-proline and a resin solution b of poly-branolic acid on both sides thereof. The layers of each of 2am are obtained. For the flexible single-sided copper-coated laminate obtained by this, the same copper foil as above is passed through the metal under heating/pressurization. The rolls were heated and pressed by each other. The evaluation of the peel strength and the acid resistance was carried out by adding the copper side of the heated pressure-bonding surface of the flexible double-sided copper foil-clad laminate, and peeling off from the layer of 1 mm from the polyimide layer. The initial adhesion force was 1.95 kN/m. Further, the penetration resistance width of the circuit of the circuit was m, and the peel strength retention rate was _. The results are shown in Table 2. Examples 2, 3 and Comparative Examples 1 and 2 show The same procedure as in Example 1 was carried out except that the surface metal amount was different from that of the electrodeposited copper foil shown in Table 1. The peel strength, the hydrochloric acid penetration property, and the peel retention ratio were evaluated. The results are shown in Table 2. Not shown, however, the roughening of the copper foil used in the examples and comparative examples The surface is treated by Ni, Zn and Cr plating. In Table 1, the aspect ratio/the total number of protrusions indicates the number of the king's dogs measured, and the aspect ratio (H/L) is 1.5 to The range of 5, the ratio of the number of protrusions in the range of 1 to 3 / zm. (c) The gap between the protrusions / the total number of protrusions indicates the number of protrusions relative to the measured 324051 19 201251535, with adjacent protrusions The depth between the objects is 0.5//m or more, and the distance between the adjacent protrusions is the ratio of the number of gaps in the range of 0.001 to 1 /zm. Further, (d) the number of expansion protrusions/the total number of protrusions is expressed relative to The total number of protrusions measured has a ratio of the number of protrusion shapes having a width L wider than the root width. Further, (e) the average width of the protrusions l//m or more / the total number of protrusions represents the ratio of the number of all the protrusions measured, and the average width of the protrusions is lym or more. Further, a photograph of a cross section of the copper foil used in Example 1 is shown in Fig. 2, and a photograph of a cross section of the copper foil used in Comparative Example 2 is shown in Fig. 3. Here, the finely roughened surface of the surface of the copper foil-based Rz phase used in Examples 2 and 3 is similar to that of FIG. 2, and the surface of the copper foil Rz used in Comparative Example 1 is finely roughened. The shape is similar to Figure 3. 324051 20 201251535 [Table 1] (a) Rz []xm] (b) High aspect ratio number / total number of protrusions (C) Number of gaps between protrusions / Number of all protrusions (d) Number of expansion protrusions / All protrusions Quantity (e) Number of protrusions with an average width of 1 卩m or more / Total number of protrusions Ni content [mg/dm2] Brightness [AV] Example 1 1.20 5% 21% 5% 37% 0.23 25.8 Example 2 3. 15 153⁄4 42 % 193⁄4 313⁄4 0.23 25. 5 Example 3 2. 90 20% 403⁄4 16% 523⁄4 0. 14 26.3 Comparative Example 1 3. 00 46% 68% 43% 7% 0. 12 21. 9 Comparative Example 2 1. 10 543⁄4 543⁄4 35% 233⁄4 0. 12 21.4 [Table 2] Initial peel strength [kN/m] Hydrochloric acid penetration width [β m] Peel strength retention rate m Example 1 1. 95 69 89 Example 2 1. 97 138 82 Example 3 1. 96 189 74 Comparative Example 1 1. 95 396 30 Comparative Example 2 1. 90 499 33 It was confirmed that the discoloration of the copper-clad laminate obtained in Examples 1, 2, and 3 after the hydrochloric acid treatment was 200/zm. Hereinafter, the peel strength retention rate is 70% or more. On the other hand, it was confirmed that all of the circuit end portions in Comparative Examples 1 and 2 were discolored due to peeling of the circuit, and the peel strength retention ratio was less than 70%. The flexible copper-clad laminate obtained by the present invention inhibits the infiltration of the hydrochloric acid treatment 324051 21 201251535, and the circuit does not peel off, so that it is confirmed to be a highly reliable material. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view for explaining the roughened shape of a copper foil cross section of a copper foil. Fig. 2 is a photograph showing a cross section of a copper foil of the copper foil used in Example 1. Fig. 3 is a photograph of a cross section of a copper foil of a copper foil used in Comparative Example 2. [Description of main component symbols] L Width of the fundamental portion of the microprotrusion shape Η Height of the microprotrusion shape ρ Adjacent to the protrusion of q q Adjacent to the protrusion of ρ 1 324051 22