TW202302917A - Surface-treated copper foil, copper-clad laminate board, and printed wiring board - Google Patents
Surface-treated copper foil, copper-clad laminate board, and printed wiring board Download PDFInfo
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/16—Electroplating with layers of varying thickness
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- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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- H05K1/00—Printed circuits
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- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/002—Etching of the substrate by chemical or physical means by liquid chemical etching
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- H—ELECTRICITY
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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Abstract
Description
本發明係關於一種表面處理銅箔、覆銅積層板及印刷配線板。The invention relates to a surface-treated copper foil, a copper-clad laminate and a printed wiring board.
覆銅積層板於撓性印刷配線板等各種用途被廣泛使用。此撓性印刷配線板,係對覆銅積層板之銅箔進行蝕刻而形成導體圖案(亦稱為「配線圖案」),然後利用焊料將電子零件連接並構裝於導體圖案上,藉此而製造。Copper-clad laminates are widely used in various applications such as flexible printed wiring boards. In this flexible printed wiring board, the copper foil of the copper-clad laminate is etched to form a conductive pattern (also called "wiring pattern"), and then the electronic parts are connected and assembled on the conductive pattern with solder, thereby achieving manufacture.
近年來,於個人電腦、行動終端等電子機器中,隨著通訊高速化及大容量化,電訊號越來越高頻化,需要能夠因應其之撓性印刷配線板。特別是電訊號之頻率越為高頻,訊號功率之損耗(衰減)越大,越容易讀不出資料,因此需要減少訊號功率之損耗。In recent years, in electronic devices such as personal computers and mobile terminals, with the increase in communication speed and capacity, electrical signals have become more and more high-frequency, and flexible printed wiring boards that can respond to them are required. In particular, the higher the frequency of the electrical signal, the greater the loss (attenuation) of the signal power, and the easier it is to fail to read the data, so it is necessary to reduce the loss of the signal power.
電子電路中之訊號功率損耗(傳輸損耗)產生的原因大體可分為兩種。其一係導體損耗,即由銅箔所引起之損耗,其二係介電損耗,即由樹脂基材所引起之損耗。 導體損耗具有如下特性,即於高頻帶存在集膚效應,電流於導體表面流動,因此若銅箔表面粗糙,則電流會沿複雜之路徑流動。因此,為了減少高頻訊號之導體損耗,較理想的是減小銅箔之表面粗糙度。以下,本說明書中,於簡單地記為「傳輸損耗」及「導體損耗」之情形時,主要係指「高頻訊號之傳輸損耗」及「高頻訊號之導體損耗」。 The causes of signal power loss (transmission loss) in electronic circuits can be roughly divided into two types. One is the conductor loss, that is, the loss caused by the copper foil, and the other is the dielectric loss, that is, the loss caused by the resin substrate. Conductor loss has the following characteristics, that is, there is a skin effect in the high frequency band, and the current flows on the surface of the conductor. Therefore, if the surface of the copper foil is rough, the current will flow along a complicated path. Therefore, in order to reduce the conductor loss of high-frequency signals, it is ideal to reduce the surface roughness of copper foil. Hereinafter, in this specification, when simply referred to as "transmission loss" and "conductor loss", it mainly refers to "transmission loss of high-frequency signal" and "conductor loss of high-frequency signal".
另一方面,介電損耗取決於樹脂基材之種類,因此於高頻訊號流動之電路基板中,較理想的是使用由低介電材料(例如液晶聚合物、低介電聚醯亞胺)形成之樹脂基材。又,介電損耗亦會因接著銅箔與樹脂基材之間的接著劑而受到影響,因此較理想的是銅箔與樹脂基材之間在不使用接著劑下接著。 由此,為了不使用接著劑而將銅箔與樹脂基材之間接著,提出過於銅箔之至少一面形成表面處理層。例如於專利文獻1提出了如下方法:於銅箔上設置由粗化粒子形成之粗化處理層,並且於最表層形成矽烷偶合處理層。 [先前技術文獻] [專利文獻] On the other hand, dielectric loss depends on the type of resin substrate, so it is ideal to use low-dielectric materials (such as liquid crystal polymers, low-dielectric polyimide) in circuit substrates where high-frequency signals flow. Formed resin substrate. In addition, the dielectric loss will also be affected by the adhesive between the copper foil and the resin substrate, so it is ideal to bond the copper foil and the resin substrate without using an adhesive. Therefore, in order to bond copper foil and a resin base material without using an adhesive, it has been proposed to form a surface treatment layer on at least one surface of the copper foil. For example, Patent Document 1 proposes a method in which a roughening treatment layer formed of roughening particles is provided on a copper foil, and a silane coupling treatment layer is formed on the outermost layer. [Prior Art Literature] [Patent Document]
[專利文獻1]日本特開2012-112009號公報[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-112009
於供形成表面處理層之銅箔的表面,一般存在微小之凹凸部。例如於壓延銅箔之情形時,壓延時因壓延油而形成之油坑會以微小凹凸部的形態形成於表面。又,於電解銅箔之情形時,研磨時形成之旋轉滾筒之研磨條紋,會引起析出形成於旋轉滾筒上之電解銅箔之旋轉滾筒側表面的微小凹凸部。 若於銅箔表面存在微小之凹凸部,則例如於形成粗化處理層時,在銅箔表面之凸部處電流集中而使得粗化粒子過度生長,另一方面,在銅箔表面之凹部及其周邊未充分供給電流而難以生長粗化粒子。其結果成為如下狀態,即,於銅箔表面之凸部形成粗大之粗化粒子,另一方面,銅箔表面之凹部及其周邊的粗化粒子過小,特別是油坑之端部附近之粗化粒子的附著不充分,即銅箔表面之粗化粒子未均勻地形成。粗大之粗化粒子多的表面處理銅箔,有時會在與樹脂基材接合後,若賦予使表面處理銅箔剝離之力,則應力集中於粗大之粗化粒子而容易折斷,結果,對樹脂基材之接著力降低。又,粗化粒子之大小不充分的表面處理銅箔,有時由粗化粒子所致之定錨效應降低,無法充分獲得銅箔與樹脂基材之接著性。 特別是由液晶聚合物、低介電聚醯亞胺等低介電材料形成之樹脂基材,較以往之樹脂基材難以與銅箔接著,因此期望開發出提高銅箔與樹脂基材之間之接著性的方法。 又,矽烷偶合處理層雖具有提高銅箔與樹脂基材之間之接著性的效果,但根據其種類,接著性之提高效果有時亦不足。 On the surface of the copper foil on which the surface treatment layer is formed, there are generally minute unevenness. For example, in the case of rolling copper foil, oil pits formed by rolling oil during rolling are formed on the surface in the form of minute unevenness. Also, in the case of the electrolytic copper foil, the grinding stripes of the rotating drum formed during the grinding will cause the precipitation of minute irregularities formed on the rotating drum side surface of the electrolytic copper foil on the rotating drum. If there are tiny concave-convex portions on the surface of the copper foil, for example, when forming a roughening treatment layer, the current concentration at the convex portion of the copper foil surface causes excessive growth of roughened particles. On the other hand, the concave and convex portions of the copper foil surface It is difficult to grow roughened particles because the current is not sufficiently supplied to the periphery. As a result, coarse roughened particles are formed on the convex portion of the surface of the copper foil. On the other hand, the roughened particles on the concave portion and the periphery of the copper foil surface are too small, especially the roughened particles near the end of the oil pit. Insufficient adhesion of the roughened particles means that the roughened particles on the surface of the copper foil are not uniformly formed. Surface-treated copper foil with many coarse roughened particles may be bonded to a resin base material, and if a force is applied to peel the surface-treated copper foil, the stress will concentrate on the coarse roughened particles and it will be easily broken. The adhesion of the resin substrate is reduced. Moreover, the surface-treated copper foil whose size of the roughened particle is insufficient may reduce the anchoring effect by the roughened particle, and may fail to obtain sufficient adhesiveness between the copper foil and the resin base material. In particular, resin substrates made of low-dielectric materials such as liquid crystal polymers and low-dielectric polyimides are more difficult to bond to copper foil than conventional resin substrates. The follow-up method. Also, although the silane coupling treatment layer has the effect of improving the adhesiveness between the copper foil and the resin base material, depending on the type, the effect of improving the adhesiveness may be insufficient.
本發明之實施形態係為解決如上述之問題而完成者,於一態樣中,旨在提供一種能夠提高與樹脂基材特別是適合高頻用途之樹脂基材之接著性的表面處理銅箔。 又,本發明之實施形態於另一態樣中,旨在提供一種樹脂基材特別是適合高頻用途之樹脂基材與表面處理銅箔之間之接著性優異的覆銅積層板。 並且,本發明之實施形態於另一態樣中,旨在提供一種樹脂基材特別是適合高頻用途之樹脂基材與電路圖案之間之接著性優異的印刷配線板。 Embodiments of the present invention are completed to solve the above-mentioned problems. In one aspect, it is intended to provide a surface-treated copper foil capable of improving adhesion to resin substrates, especially resin substrates suitable for high-frequency applications. . Moreover, the embodiment of this invention aims at providing the copper clad laminate excellent in the adhesiveness between the resin base material especially suitable for a high-frequency application, and surface-treated copper foil in another aspect. Moreover, the embodiment of this invention aims at providing the printed wiring board which is excellent in the adhesiveness between resin base material especially suitable for high frequency use, and a circuit pattern in another aspect.
本發明人等為解決上述問題,經對表面處理銅箔進行潛心研究後,結果獲得如下見解:藉由在用於形成粗化處理層之鍍覆液添加微量之鎢化合物,以抑制形成於銅箔表面凸部之粗化粒子的過度生長,並且容易於銅箔表面之凹部周邊形成粗化粒子。而且,本發明人等對如此獲得之表面處理銅箔之表面形狀進行分析後,發現表面處理層之Sk的變化量與其表面形狀密切相關,從而完成本發明之實施形態。In order to solve the above-mentioned problems, the inventors of the present invention obtained the following insights after intensive research on surface-treated copper foil: by adding a small amount of tungsten compound to the plating solution used to form the roughening treatment layer, the formation of tungsten on copper foil can be suppressed. Excessive growth of roughened particles on the convex part of the foil surface, and easy to form roughened particles around the concave part of the copper foil surface. Furthermore, the inventors of the present invention analyzed the surface shape of the surface-treated copper foil thus obtained, and found that the amount of change in Sk of the surface-treated layer is closely related to the surface shape, thereby completing the embodiment of the present invention.
即,本發明之實施形態於一態樣中,係關於一種表面處理銅箔,該表面處理銅箔具有銅箔及形成於上述銅箔之至少一面的表面處理層, 上述表面處理層以下述式(1)表示之Sk之變化量為0.180~0.600 μm。 Sk之變化量=P2-P1 ・・・(1) 式中,P1係應用截止值λs為2 μm之λs濾波器而算出之Sk,P2係不應用上述λs濾波器而算出之Sk。 That is, in one aspect, the embodiment of the present invention relates to a surface-treated copper foil having a copper foil and a surface-treated layer formed on at least one surface of the copper foil, The change amount of Sk represented by the following formula (1) of the said surface treatment layer is 0.180-0.600 micrometers. Change of Sk = P2 - P1 ・・・(1) In the formula, P1 is Sk calculated by applying a λs filter with a cut-off value λs of 2 μm, and P2 is Sk calculated without applying the above-mentioned λs filter.
又,本發明之實施形態於另一態樣中,係關於一種覆銅積層板,該覆銅積層板具備上述表面處理銅箔,及接著於上述表面處理銅箔之上述表面處理層的樹脂基材。 並且,本發明之實施形態於另一態樣中,係關於一種印刷配線板,該印刷配線板具備對上述覆銅積層板之上述表面處理銅箔進行蝕刻而形成的電路圖案。 In another aspect, an embodiment of the present invention relates to a copper-clad laminate including the above-mentioned surface-treated copper foil, and a resin-based resin substrate for the above-mentioned surface-treated layer next to the above-mentioned surface-treated copper foil. material. Moreover, embodiment of this invention relates to the printed wiring board provided with the circuit pattern formed by etching the said surface-treated copper foil of the said copper-clad laminate board in another aspect.
若根據本發明之實施形態,於一態樣中,可提供一種能夠提高與樹脂基材特別是適合高頻用途之樹脂基材之接著性的表面處理銅箔。 又,若根據本發明之實施形態,於另一態樣中,可提供一種樹脂基材特別是適合高頻用途之樹脂基材與表面處理銅箔之間之接著性優異的覆銅積層板。 進而,若根據本發明之實施形態,於另一態樣中,可提供一種樹脂基材特別是適合高頻用途之樹脂基材與電路圖案之間之接著性優異的印刷配線板。 According to an embodiment of the present invention, in one aspect, it is possible to provide a surface-treated copper foil capable of improving the adhesiveness with a resin base material, especially a resin base material suitable for high-frequency use. Moreover, according to the embodiment of the present invention, in another aspect, a copper-clad laminate excellent in adhesion between a resin base material, especially a resin base material suitable for high-frequency applications, and a surface-treated copper foil can be provided. Furthermore, according to the embodiment of this invention, in another aspect, the printed wiring board which is excellent in the adhesiveness between resin base materials suitable for high frequency use, and a circuit pattern can be provided.
以下,對本發明之較佳實施形態具體地進行說明,但本發明不應限定於此等來進行解釋,可於不脫離本發明主旨之範圍內,基於該行業者之知識來進行各種變更、改良等。以下之實施形態所揭示之多個構成要素,可藉由適當組合而形成各種發明。例如,可自以下實施形態所示之所有構成要素中刪除若干構成要素,亦可將不同實施形態之構成要素加以適當組合。Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention should not be interpreted as being limited thereto, and various changes and improvements can be made based on the knowledge of those in the industry without departing from the gist of the present invention. wait. A plurality of constituent elements disclosed in the following embodiments can be appropriately combined to form various inventions. For example, some constituent elements may be deleted from all the constituent elements shown in the following embodiments, and constituent elements of different embodiments may be appropriately combined.
本發明之實施形態的表面處理銅箔具有銅箔及形成於銅箔之至少一面的表面處理層。 表面處理層可僅形成於銅箔之一面,亦可形成於銅箔之兩面。當在銅箔之兩面形成表面處理層的情形時,表面處理層之種類可相同,亦可不同。 The surface-treated copper foil according to the embodiment of the present invention has a copper foil and a surface-treated layer formed on at least one surface of the copper foil. The surface treatment layer may be formed on only one side of the copper foil, or may be formed on both sides of the copper foil. When forming surface treatment layers on both surfaces of copper foil, the types of surface treatment layers may be the same or different.
表面處理層之表面形狀,可使用表面性狀參數來進行特定,該表面性狀參數可依據ISO 25178-2:2012來測定表面性狀,並對自測定資料算出之負載曲線進行解析,藉此而得。 說明負載曲線時,首先對負載面積率進行說明。 所謂負載面積率,係指將相當於立體之測定對象物以某高度面切斷時之測定對象物之剖面的區域除以測定視域之面積而求得之比率。再者,本發明中,設定銅箔或表面處理銅箔之表面處理層等作為測定對象物。負載曲線係表示各高度處之負載面積率的曲線。負載面積率0%附近表示測定對象物最高之部分的高度,負載面積率100%附近之高度則表示測定對象物最低之部分的高度。 The surface shape of the surface treatment layer can be specified using surface shape parameters, which can be obtained by measuring the surface shape according to ISO 25178-2:2012 and analyzing the load curve calculated from the measurement data. When explaining the load curve, first, the load area ratio will be explained. The so-called load area ratio refers to the ratio obtained by dividing the area corresponding to the cross-section of the measurement object when the three-dimensional measurement object is cut at a certain height plane by the area of the measurement field of view. In addition, in this invention, the surface treatment layer of copper foil or surface-treated copper foil, etc. are set as a measurement object. The load curve is a curve showing the load area ratio at each height. The height near 0% of the load area ratio indicates the height of the highest portion of the object to be measured, and the height near 100% of the load area ratio represents the height of the lowest portion of the object to be measured.
接下來,圖1表示表面處理層之典型的負載曲線。可活用負載曲線及自負載曲線導出之等效直線,來表現表面處理層之突出谷部、核心部及突出山部的大小。 等效直線係依據JIS B0681-2:2018之5.2項而求得。即,首先,使自負載面積率0%沿負載曲線以負載面積率之差為40%所畫之負載曲線的割線自負載面積率0%向100%移動,將割線之傾斜最平緩之位置設為負載曲線之中央部分。接下來,將相對於該中央部分而縱軸方向之偏差之平方和最小的直線稱為等效直線。使用如此求出之等效直線及負載曲線來區分測定對象物之核心部、突出山部及突出谷部。即,測定對象物中,處於等效直線上之負載面積率0%至100%之高度範圍的部分為核心部,自核心部向上突出之部分為突出山部,自核心部向下凹陷之部分為突出谷部。 圖1中,Sk係指核心部之級差(核心部之上限級與下限級之差),Spk係指突出山部高度(處於核心部之上之突出山部的平均高度),Svk係指突出谷部深度(處於核心部之下之突出谷部的平均深度),Smr1係指將突出山部與核心部分離之負載面積率,Smr2係指將突出谷部與核心部分離之負載面積率。 再者,突出山部係指測定對象物中特別高之區域。突出谷部係指測定對象物中特別低之區域。核心部係指測定對象物中突出山部與突出谷部以外之區域,即接近於平均之高度之區域。 Next, FIG. 1 shows a typical load curve of the surface treatment layer. The load curve and the equivalent straight line derived from the load curve can be used to express the size of the protruding valleys, cores and protruding mountains of the surface treatment layer. The equivalent straight line is obtained according to item 5.2 of JIS B0681-2:2018. That is, first, move the secant line of the load curve drawn from the load area ratio of 0% along the load curve with the difference of the load area ratio being 40% from the load area ratio of 0% to 100%, and set the position where the slope of the secant line is the gentlest It is the central part of the load curve. Next, a straight line whose sum of squares of deviations in the vertical axis direction is the smallest with respect to the central portion is called an equivalent straight line. Using the equivalent straight line and load curve obtained in this way, the core portion, the protruding mountain portion, and the protruding valley portion of the object to be measured are distinguished. That is, in the measurement object, the part in the height range of the load area ratio of 0% to 100% on the equivalent straight line is the core part, the part protruding upward from the core part is the protruding mountain part, and the part concave downward from the core part To highlight the valley. In Figure 1, Sk refers to the level difference of the core part (the difference between the upper limit level and the lower limit level of the core part), Spk refers to the height of the protruding mountain part (the average height of the protruding mountain part above the core part), and Svk refers to Protruding valley depth (the average depth of the protruding valley below the core), Smr1 refers to the load area ratio separating the protruding mountain from the core, Smr2 refers to the load area ratio separating the protruding valley from the core . In addition, the protruding mountain portion refers to a particularly high region in the object to be measured. The protruding valley refers to the particularly low area of the object to be measured. The core part refers to the area other than the protruding mountains and valleys of the measurement object, that is, the area close to the average height.
突出山部高度Spk係突出山部,即測定對象物之高度高之區域之高度的平均值,係指表面處理層中高度特別高之區域之高度的平均值。此處,表面處理層中高度特別高之區域,可解釋為由粒子(特別是粗化粒子)中過度生長之粒子引起的區域。 關於核心部,測定對象物之高度為平均之區域高度,可說為表面處理層之平均高度之區域,因此核心部之級差Sk,於一態樣中,可說是構成表面處理層之平均大小之粒子(特別是粗化粒子)中的最大高度之粒子(特別是粗化粒子)與最小高度之粒子(特別是粗化粒子)之差。又,若關注於核心部為表面處理層之平均之區域高度此一態樣,則核心部之級差Sk可解釋為與平均大小之粒子(特別是粗化粒子)之附著量相關之值。 總之,本發明人等以上述方式進行分析之結果,獲得如下見解:於本發明之實施形態的表面處理銅箔中,Sk與構成表面處理層之平均大小之粒子的附著量相關,Spk與過度生長之粒子的高度相關。再者,以下,以設粗化粒子為粒子之情形為例來進行說明,但應注意粒子並不限定於粗化粒子。 The height of the protruding mountain portion Spk is the average value of the height of the protruding mountain portion, that is, the area where the height of the object to be measured is high, and refers to the average value of the height of the area with a particularly high height in the surface treatment layer. Here, regions of particularly high height in the surface treatment layer can be interpreted as regions caused by overgrown particles in particles (in particular, roughened particles). Regarding the core part, the height of the object to be measured is the average height of the region, which can be said to be the region of the average height of the surface treatment layer. Therefore, the level difference Sk of the core part can be said to be the average height of the surface treatment layer in one aspect. The difference between the largest height particle (especially coarse particle) and the smallest height particle (especially coarse particle) among the particle size (especially coarse particle). Also, if attention is paid to the fact that the core portion is the average area height of the surface treatment layer, the level difference Sk of the core portion can be interpreted as a value related to the adhesion amount of particles of average size (especially roughened particles). In short, as a result of the analysis conducted by the present inventors in the above-mentioned manner, it was found that in the surface-treated copper foil according to the embodiment of the present invention, Sk is related to the adhesion amount of particles of an average size constituting the surface-treated layer, and Spk is related to excessive The height correlation of the growing particles. In addition, in the following, the case where the coarsening particle is used as an example is demonstrated, but it should be noted that the particle is not limited to the roughening particle.
對於用以測定本發明之實施形態的表面處理銅箔之表面性狀之測定資料,例如可使用共焦雷射顯微鏡等雷射顯微鏡來獲取。此處,對該測定資料實施傅立葉變換,藉此可將測定資料分離為具有各種週期及振幅之波形。本發明人等認為在對分離後之各波形應用使特定範圍之頻率之波形的振幅衰減的濾波器後,再次將所有波形進行合成,並對合成所得之資料進行解析,由此可自測定資料算出應關注之表面性狀參數。Measurement data for measuring the surface properties of the surface-treated copper foil according to the embodiment of the present invention can be acquired using, for example, laser microscopes such as a confocal laser microscope. Here, by performing Fourier transform on the measurement data, the measurement data can be separated into waveforms having various cycles and amplitudes. The inventors of the present invention think that after applying a filter that attenuates the amplitude of a waveform with a frequency in a specific range to each of the separated waveforms, and then synthesizing all the waveforms again, and analyzing the synthesized data, the measured data can be obtained. Calculate the surface properties parameters that should be paid attention to.
於表面粗糙度之測定資料的解析中,本發明人等獲得如下見解:將應用截止值λs為2 μm之λs濾波器而算出之表面性狀參數及不應用該λs濾波器而算出之表面性狀參數進行組合使用,藉此可獲得本發明之實施形態的表面處理層之特徵性表面形狀(特別是構成表面處理層之粗化粒子的附著狀態)的詳細資訊。 此處,λs濾波器係使較截止值λs小之波長之波形的振幅大幅衰減的輪廓曲線濾波器。λs濾波器相當於ISO 25178-2:2012中之S濾波器。λs濾波器使振幅衰減之大小,根據波形之波長而有所不同。於截止值λs之波長中,使振幅衰減至原來值之50%,於波長較此小之波形中,可使振幅更大地衰減。 2 μm之截止值λs,係位於構成表面處理層之粗化粒子之尺寸與油坑之尺寸之間的大小。藉由將截止值λs設定為2 μm而得之測定資料,係源自較截止值λs更短週期之波形的資料,因此可理解為將源自粗化粒子之資料去除而得之資料。若基於此,則可說不應用截止值λs為2 μm之λs濾波器而算出之表面性狀參數,與應用該λs濾波器而算出之表面性狀參數的差量,係將油坑之資訊去除後之表面處理層的資訊,即構成表面處理層之粗化粒子的資訊。 In the analysis of the measurement data of surface roughness, the inventors of the present invention obtained the following insights: the surface texture parameters calculated by applying the λs filter with a cut-off value λs of 2 μm and the surface texture parameters calculated without applying the λs filter By using them in combination, it is possible to obtain detailed information on the characteristic surface shape of the surface treatment layer according to the embodiment of the present invention (particularly, the adhesion state of the roughened particles constituting the surface treatment layer). Here, the λs filter is a profile filter that greatly attenuates the amplitude of a waveform of a wavelength smaller than the cutoff value λs. The λs filter is equivalent to the S filter in ISO 25178-2:2012. The magnitude of amplitude attenuation by the λs filter varies according to the wavelength of the waveform. In the wavelength of the cutoff value λs, the amplitude is attenuated to 50% of the original value, and in the waveform with a wavelength smaller than this, the amplitude can be attenuated more. The cut-off value λs of 2 μm is a size between the size of the roughened particles constituting the surface treatment layer and the size of the oil pit. The measurement data obtained by setting the cut-off value λs to 2 μm are data derived from a waveform with a shorter period than the cut-off value λs, so it can be understood as data obtained by removing the data originating from the coarsening particles. Based on this, it can be said that the difference between the surface property parameters calculated without applying the λs filter whose cut-off value λs is 2 μm, and the surface property parameters calculated by applying the λs filter is after removing the information of the oil pit The information of the surface treatment layer is the information of the roughened particles constituting the surface treatment layer.
本發明人等基於上述見解,對自負載曲線獲得之各種表面性狀參數進行解析後,發現表面處理層以下述式(1)表示之Sk的變化量與構成表面處理層之平均之粗化粒子的附著量密切相關。 Sk之變化量=P2-P1 ・・・(1) 式中,P1係應用截止值λs為2 μm之λs濾波器而算出之Sk,P2係不應用上述λs濾波器而算出之Sk。 Based on the above findings, the present inventors analyzed various surface property parameters obtained from the load curve, and found that the amount of change in Sk of the surface treatment layer represented by the following formula (1) is related to the average roughening particle constituting the surface treatment layer. Attachment is closely related. Change of Sk = P2 - P1 ・・・(1) In the formula, P1 is Sk calculated by applying a λs filter with a cut-off value λs of 2 μm, and P2 is Sk calculated without applying the above-mentioned λs filter.
此處,圖2表示用以說明構成表面處理層之粗化粒子及Sk的示意性概略圖。如圖2所示,表面處理層包含平均大小之粗化粒子A、過度生長之粗化粒子B。如上所說明,可認為Sk與形成在銅箔表面之相對較平滑部分之平均大小之粗化粒子A的附著量相關。Sk不少受到油坑等宏觀形狀之影響,為了更精確地讀出表面處理層之資訊,需要將宏觀形狀之影響去除。P1可解釋為將源自粗化粒子之資訊去除後之Sk值,換言之,係將源自油坑等之資訊保留之Sk值。取P2與P1之差,係指將Sk所含之源自油坑等宏觀形狀之資訊去除。其結果,可高精度地抽取與平均大小之粗化粒子相關之資訊。 認為形成於銅箔表面之相對較平滑部分之平均大小的粗化粒子A,密切地關係到樹脂基材與表面處理層之接著力。認為過度生長(粗大)之粗化粒子B會引起粗化折斷,而過小之粗化粒子根本就嵌不進樹脂基材。因此,藉由形成為將與平均大小之粗化粒子A之附著量相關的Sk變化量控制在適當範圍的表面處理銅箔,而能夠提高與樹脂基材之接著性。 自上述觀點,Sk之變化量為0.180~0.600 μm之本發明之實施形態的表面處理銅箔,表現出對樹脂基材之充分接著力。自穩定獲得該效果之觀點,Sk變化量較佳為0.180~0.500 μm,更佳為0.210~0.410 μm。 Here, FIG. 2 shows a schematic schematic diagram for explaining the roughening particles and Sk constituting the surface treatment layer. As shown in FIG. 2 , the surface treatment layer includes roughened particles A with an average size and roughened particles B with excessive growth. As explained above, it can be considered that Sk is related to the adhesion amount of the average-sized roughening particles A formed on the relatively smooth portion of the surface of the copper foil. Sk is largely affected by macroscopic shapes such as oil pits. In order to read the information of the surface treatment layer more accurately, it is necessary to remove the influence of macroscopic shapes. P1 can be interpreted as the Sk value after removing the information from the coarsening particles, in other words, it is the Sk value that retains the information from the oil pits and the like. Taking the difference between P2 and P1 refers to removing the information contained in Sk derived from macroscopic shapes such as oil pits. As a result, information on roughened particles of average size can be extracted with high precision. It is considered that the average size of the roughened particles A formed on the relatively smooth portion of the copper foil surface is closely related to the adhesive force between the resin substrate and the surface treatment layer. It is considered that overgrown (coarse) coarsening particles B cause roughening and breaking, while coarsening particles B that are too small cannot be embedded into the resin substrate at all. Therefore, the adhesiveness with a resin base material can be improved by making it the surface-treated copper foil which controls the amount of change of Sk concerning the adhesion amount of the roughening particle A of an average size in an appropriate range. From the above viewpoint, the surface-treated copper foil according to the embodiment of the present invention in which the amount of change in Sk is 0.180 to 0.600 μm exhibits sufficient adhesion to the resin base material. From the viewpoint of obtaining this effect stably, the amount of change in Sk is preferably 0.180 to 0.500 μm, more preferably 0.210 to 0.410 μm.
表面處理層不應用上述λs濾波器而算出之Sku(峰度)較佳為2.50~4.50。 Sku係以平均高度為基準來製作高度之直方圖的情形時,表示該直方圖之尖銳程度(尖度)的參數。例如,於Sku=3.00之情形時,意味著高度分佈為常態分佈。又,於Sku>3.00之情形時,數值越大,意味著高度分佈越集中。反之,於Sku<3.00之情形時,數值越小,意味著高度分佈越分散。 The Sku (kurtosis) calculated without applying the above-mentioned λs filter to the surface treatment layer is preferably 2.50 to 4.50. Sku is a parameter indicating the sharpness (sharpness) of the histogram when the height histogram is created based on the average height. For example, in the case of Sku=3.00, it means that the height distribution is a normal distribution. Also, in the case of Sku>3.00, the larger the numerical value, the more concentrated the height distribution is. Conversely, in the case of Sku<3.00, the smaller the value, the more dispersed the height distribution.
本發明之實施形態的表面處理銅箔於表面具有凹凸,該凹凸有助於提高銅箔與樹脂基材之接著性。表面處理層之Sku成為評估該凹凸之高度分佈之指標。 表面處理層之Sku為2.50~4.50,意味著高度分佈為常態分佈或接近於此的分佈狀態。另一方面,表面處理層之Sku未達2.50,則意味著表面處理層之高度(距銅箔表面之高度)低的部分與高的部分各種交織,結果為高度分佈不偏倚之分佈狀態。表面處理層之Sku大於4.50,意味著為高度分佈偏倚之分佈狀態,即,表面處理層之表面係某高度之部分突出地佔據多處的狀態。 表面處理層之高度分佈為常態分佈或接近於此之分佈狀態,意味著例如當在銅箔表面形成粗化處理層之情形時,在銅箔表面之凸部過度生長之粒子,即粗大之粒子,或在銅箔表面之凹部周邊(凸部之端部)中未形成粒子之部位少。因此,表面處理層之Sku為2.50~4.50,意味著形成於銅箔表面之凸部之粒子的過度生長受到抑制,且亦於銅箔表面之凹部周邊形成有粗化粒子的狀態。 The surface-treated copper foil according to the embodiment of the present invention has unevenness on the surface, and the unevenness contributes to the improvement of the adhesiveness between the copper foil and the resin base material. The Sku of the surface treatment layer becomes an index for evaluating the height distribution of the unevenness. The Sku of the surface treatment layer is 2.50 to 4.50, which means that the height distribution is a normal distribution or a distribution state close to this. On the other hand, if the Sku of the surface treatment layer is less than 2.50, it means that the height of the surface treatment layer (height from the surface of the copper foil) is intertwined with the lower part and the higher part, resulting in an unbiased distribution state of the height distribution. When the Sku of the surface treatment layer is greater than 4.50, it means that the distribution state of the height distribution is biased, that is, the surface of the surface treatment layer is a state where a certain height part protrudes and occupies many places. The height distribution of the surface treatment layer is a normal distribution or a distribution state close to it, which means that, for example, when a roughening treatment layer is formed on the surface of the copper foil, the particles that grow excessively on the convex portion of the copper foil surface, that is, coarse particles , or there are few parts where no particles are formed in the periphery of the concave part (the end of the convex part) on the surface of the copper foil. Therefore, the Sku of the surface treatment layer is 2.50 to 4.50, which means that the excessive growth of particles formed on the convex portion of the copper foil surface is suppressed, and roughened particles are also formed around the concave portion of the copper foil surface.
粗大之粒子多的表面處理銅箔,及存在未形成粒子之部位的表面處理銅箔,自與樹脂基材之接著性的觀點,均欠佳。例如,於粗大之粒子多的表面處理銅箔,認為在與樹脂基材接合後,若賦予使表面處理銅箔剝離之力,則應力集中於粗大之粒子而容易折斷,結果,對樹脂基材之接著力反而降低。又,於存在未形成粒子之部位的表面處理銅箔,認為會有如下情況:無法充分確保由粒子所致之定錨效應,表面處理銅箔與樹脂基材之接著力降低。 因此,自穩定地獲得對樹脂基材之接著力的觀點,表面處理層之Sku的下限值較佳為2.90,上限值較佳為4.10。 再者,表面處理層之Sku,可依據ISO 25178-2:2012來測定表面粗糙度,並對自測定資料算出之輪廓曲線進行解析,藉此而特定。 Surface-treated copper foil with many coarse particles and surface-treated copper foil with areas where no particles are formed are unfavorable from the viewpoint of adhesion to the resin substrate. For example, if a surface-treated copper foil with many coarse particles is bonded to a resin substrate, if a force is applied to peel the surface-treated copper foil, the stress will concentrate on the coarse particles and it will be easily broken. The sticking force is reduced instead. In addition, in surface-treated copper foil where no particles are present, the anchoring effect due to particles cannot be sufficiently ensured, and the adhesive force between the surface-treated copper foil and the resin base material may decrease. Therefore, from the viewpoint of stably obtaining adhesion to the resin substrate, the lower limit of Sku of the surface treatment layer is preferably 2.90, and the upper limit is preferably 4.10. Furthermore, the Sku of the surface treatment layer can be specified by measuring the surface roughness according to ISO 25178-2:2012, and analyzing the contour curve calculated from the measurement data.
表面處理層不應用上述λs濾波器而算出之Sq(均方根高度)較佳為0.20~0.60 μm。Sq係由ISO 25178-2:2012規定之高度方向的參數,表示表面處理層表面上之凸部高度的偏差。 表面處理層之Sq大,係指表面處理層表面上之凸部高度的偏差大。若Sq過大(凸部高度之偏差過大),則自作為工業製品之品質管理的觀點,有時會成為問題。因此,藉由使表面處理層之Sq為上述範圍,既可略微容許凸部高度之偏差而確保生產性,又可進行適當之品質管理。自穩定獲得此種效果之觀點,表面處理層之Sq的下限值較佳為0.26 μm,更佳為0.30 μm,再更佳為0.34 μm,上限值較佳為0.53 μm,更佳為0.48 μm,再更佳為0.43 μm。 再者,表面處理層之Sq,可依據ISO 25178-2:2012來測定表面粗糙度,並對自測定資料算出之輪廓曲線進行解析,藉此而特定。 The Sq (root mean square height) calculated without applying the above-mentioned λs filter to the surface treatment layer is preferably 0.20 to 0.60 μm. Sq is a parameter in the height direction specified by ISO 25178-2:2012, and represents the variation in the height of the convex portion on the surface of the surface treatment layer. The large Sq of the surface treatment layer means that the variation in the height of the protrusions on the surface of the surface treatment layer is large. If Sq is too large (the variation in the height of the convex portion is too large), it may become a problem from the viewpoint of quality control of industrial products. Therefore, by making Sq of the surface treatment layer into the above-mentioned range, it is possible to slightly allow variation in the height of the convex portion to secure productivity, and to perform appropriate quality control. From the viewpoint of stably obtaining this effect, the lower limit of Sq of the surface treatment layer is preferably 0.26 μm, more preferably 0.30 μm, and still more preferably 0.34 μm, and the upper limit is preferably 0.53 μm, more preferably 0.48 μm, more preferably 0.43 μm. Furthermore, the Sq of the surface treatment layer can be specified by measuring the surface roughness according to ISO 25178-2:2012, and analyzing the contour curve calculated from the measurement data.
表面處理層不應用上述λs濾波器而算出之Sa(算術平均高度)較佳為0.20~0.40 μm。Sa係由ISO 25178-2:2012規定之高度方向的參數,表示距平均面之高低差的平均。 若表面處理層之Sa大,則表面處理層之表面變得粗糙,因此在將表面處理銅箔接著於樹脂基材之情形時,容易發揮定錨效應。另一方面,若表面處理層之Sa過大,則對將表面處理銅箔與樹脂基材接著而成之覆銅積層板進行加工來製作電路基板的情形時,因表面處理銅箔之集膚效應而導致傳輸損耗變大。因此,藉由使表面處理層之Sa為上述範圍,可確保表面處理銅箔對樹脂基材之接著力之確保與傳輸損耗之抑制的均衡。自穩定獲得此種效果之觀點,表面處理層之Sa的下限值較佳為0.23 μm,更佳為0.24 μm,上限值較佳為0.35 μm。 又,於重視由集膚效應所致之傳輸損耗之抑制及作為工業製品之品質管理之容易性的情形時,表面處理層較佳為Sa為0.20~0.32 μm,且Sq為0.26~0.40 μm。 再者,表面處理層之Sa,可依據ISO 25178-2:2012來測定表面粗糙度,並對自測定資料算出之輪廓曲線進行解析,藉此而特定。 The Sa (arithmetic mean height) calculated without applying the above-mentioned λs filter to the surface treatment layer is preferably 0.20 to 0.40 μm. Sa is a parameter in the height direction specified by ISO 25178-2:2012, which represents the average of the height difference from the mean plane. When Sa of the surface treatment layer is large, the surface of the surface treatment layer becomes rough, and therefore, when the surface treatment copper foil is adhered to the resin base material, the anchoring effect is easily exhibited. On the other hand, if the Sa of the surface-treated layer is too large, when the surface-treated copper foil is bonded to the resin base material to process a copper-clad laminate to produce a circuit board, the skin effect of the surface-treated copper foil will This results in larger transmission loss. Therefore, by making Sa of a surface treatment layer into the said range, the balance of the securing of the adhesive force of a surface-treated copper foil to a resin base material, and suppression of a transmission loss can be ensured. From the viewpoint of obtaining such an effect stably, the lower limit of Sa in the surface treatment layer is preferably 0.23 μm, more preferably 0.24 μm, and the upper limit is preferably 0.35 μm. Also, when emphasizing the suppression of transmission loss due to the skin effect and the ease of quality control as an industrial product, the surface treatment layer preferably has a Sa of 0.20 to 0.32 μm and a Sq of 0.26 to 0.40 μm. Furthermore, Sa of the surface treatment layer can be specified by measuring the surface roughness according to ISO 25178-2:2012, and analyzing the contour curve calculated from the measurement data.
表面處理層不應用上述λs濾波器而算出之Ssk(歪度)較佳為-1.10~0.60。 Ssk係以平均高度為基準製作高度之直方圖的情形時表現該直方圖之偏斜程度(歪度)的參數。例如於Ssk=0.00之情形時,意味著高度分佈相對於平均線對稱。又,於Ssk>0.00之情形時,數值越大,意味著高度分佈相對於平均線越向下側偏斜。反之,於Ssk<0.00之情形時,數值越小,則意味著高度分佈相對於平均線越向上側偏斜。因此,表面處理層之Ssk與Sku相同,係評估表面處理層之凹凸之高度分佈的指標。 例如當在銅箔表面形成粗化處理層之情形時,Ssk為-1.10~0.60意味著在銅箔表面之凸部處過度生長之粗化粒子即粗大之粗化粒子,或在銅箔表面之凹部周邊(凸部之端部)未形成粗化粒子之部位少。另一方面,若未達-1.10,則為在銅箔表面之凹部周邊未形成粗化粒子之部位多的狀態。又,若Ssk超過0.60,則為在銅箔表面之凸部過度生長之粗化粒子多的狀態。 自穩定獲得對樹脂基材之接著力的觀點,表面處理層之Ssk的上限值較佳為0.40,下限值較佳為-0.80。 再者,表面處理層之Ssk,可依據ISO 25178-2:2012來測定表面粗糙度,並對自測定資料算出之輪廓曲線進行解析,藉此而特定。 The Ssk (skew) calculated without applying the above-mentioned λs filter to the surface treatment layer is preferably -1.10 to 0.60. Ssk is a parameter that expresses the degree of skewness (skew) of the histogram when the histogram of the height is created based on the average height. For example, in the case of Ssk=0.00, it means that the height distribution is symmetrical with respect to the mean line. Also, in the case of Ssk>0.00, a larger numerical value means that the height distribution is more skewed downward with respect to the average line. Conversely, in the case of Ssk<0.00, the smaller the numerical value, the more skewed the height distribution is to the upper side with respect to the average line. Therefore, Ssk of the surface treatment layer is the same as Sku, and is an index for evaluating the height distribution of unevenness of the surface treatment layer. For example, when a roughened layer is formed on the surface of copper foil, Ssk being -1.10 to 0.60 means that roughened particles that are excessively grown on the convex part of the surface of copper foil, that is, coarse roughened particles, or roughened particles on the surface of copper foil. There are few parts where roughened particles are not formed in the periphery of the concave portion (the end portion of the convex portion). On the other hand, if it is less than -1.10, it will be a state where there are many places where the roughening particle is not formed in the periphery of the recessed part on the copper foil surface. Moreover, when Ssk exceeds 0.60, it will be in the state with many roughening particles which grow excessively on the convex part of a copper foil surface. From the standpoint of obtaining stable adhesion to the resin substrate, the upper limit of Ssk of the surface treatment layer is preferably 0.40, and the lower limit is preferably -0.80. Furthermore, the Ssk of the surface treatment layer can be specified by measuring the surface roughness according to ISO 25178-2:2012, and analyzing the contour curve calculated from the measurement data.
表面處理層之種類並未特別限定,可使用該技術領域中周知之各種表面處理層。 作為表面處理層之例,可列舉粗化處理層、耐熱處理層、防銹處理層、鉻酸鹽處理層、矽烷偶合處理層等。該些層可單獨或組合2種以上使用。其中,表面處理層自與樹脂基材之接著性的觀點,較佳含有粗化處理層。 又,於表面處理層含有選自由耐熱處理層、防銹處理層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中1種以上之層的情形時,該些層較佳設置於粗化處理層上。 The type of the surface treatment layer is not particularly limited, and various surface treatment layers known in the technical field can be used. Examples of the surface treatment layer include a roughening treatment layer, a heat-resistant treatment layer, an antirust treatment layer, a chromate treatment layer, a silane coupling treatment layer, and the like. These layers can be used individually or in combination of 2 or more types. Among them, the surface treatment layer preferably includes a roughening treatment layer from the viewpoint of adhesion with the resin base material. Also, when the surface treatment layer contains one or more layers selected from the group consisting of a heat-resistant treatment layer, an antirust treatment layer, a chromate treatment layer, and a silane coupling treatment layer, these layers are preferably provided on the rough surface. on the processing layer.
此處,圖3表示作為一例之於銅箔之一面具有粗化處理層的表面處理銅箔的示意性放大剖面圖。
如圖3所示,形成於銅箔10之一面的粗化處理層,包含粗化粒子20及被覆粗化粒子20之至少一部分的被覆鍍層30。粗化粒子20不僅形成於銅箔10表面之凸部11的中央附近,亦形成於凹部12周邊(凸部11之端部)。又,形成於銅箔10表面之凸部11的粗化粒子20,因在鍍覆液添加微量之鎢化合物,過度生長受到抑制。因此,該粗化粒子20不會過度生長成粒徑大之粒子,而具有向各方向生長之複雜形狀。認為藉由將表面處理層之Sk的變化量控制為上述範圍,而可獲得此種構造。
Here, FIG. 3 shows a schematic enlarged cross-sectional view of a surface-treated copper foil having a roughening treatment layer on one surface of the copper foil as an example.
As shown in FIG. 3 , the roughening treatment layer formed on one surface of the
作為粗化粒子20並未特別限定,可由選自由銅、鎳、鈷、磷、鎢、砷、鉬、鉻及鋅所組成之群中的單一元素,或含有該些元素之2種以上的合金形成。其中,粗化粒子20較佳由銅或銅合金,特別是由銅形成。
作為被覆鍍層30並未特別限定,可由銅、銀、金、鎳、鈷、鋅等形成。
The
粗化處理層可藉由電鍍形成。特別是粗化粒子20可藉由使用添加有微量鎢化合物之鍍覆液的電鍍而形成。
作為鎢化合物並未特別限定,例如可使用鎢酸鈉(Na
2WO
4)等。
鍍覆液中之鎢化合物的含量,較佳為1 ppm以上。若為此種含量,則可抑制形成於凸部11之粗化粒子20的過度生長,並且容易於凹部12周邊形成粗化粒子20。再者,鎢化合物之含量的上限值並未特別限定,自抑制電阻增大之觀點,較佳為20 ppm。
The roughening layer can be formed by electroplating. In particular, the roughened
形成粗化處理層時之電鍍條件,根據所使用之電鍍裝置等來進行調整即可,並未特別限定,典型之條件如下。再者,各電鍍可進行1次,亦可進行複數次。 (粗化粒子20之形成條件) 鍍覆液組成:5~15 g/L之Cu,40~100 g/L之硫酸,1~6 ppm之鎢酸鈉 鍍覆液溫度:20~50℃ 電鍍條件:電流密度30~90 A/dm 2,時間0.1~8秒 The plating conditions for forming the roughened layer may be adjusted according to the plating apparatus to be used, and are not particularly limited, but typical conditions are as follows. In addition, each electroplating may be performed once, and may be performed plural times. (Conditions for the formation of coarse particles 20) Plating solution composition: 5-15 g/L of Cu, 40-100 g/L of sulfuric acid, 1-6 ppm of sodium tungstate Plating solution temperature: 20-50°C Electroplating Conditions: current density 30-90 A/dm 2 , time 0.1-8 seconds
(被覆鍍層30之形成條件) 鍍覆液組成:10~30 g/L之Cu,70~130 g/L之硫酸 鍍覆液溫度:30~60℃ 電鍍條件:電流密度4.8~15 A/dm 2,時間0.1~8秒 (Conditions for the formation of coating layer 30) Plating solution composition: 10-30 g/L Cu, 70-130 g/L sulfuric acid Plating solution temperature: 30-60°C Electroplating conditions: current density 4.8-15 A/dm 2 , time 0.1 ~ 8 seconds
作為耐熱處理層及防銹處理層,並未特別限定,可由該技術領域中周知之材料形成。再者,耐熱處理層有時亦作為防銹處理層發揮功能,因此亦可形成具有耐熱處理層及防銹處理層這兩者之功能的1層來作為耐熱處理層及防銹處理層。 作為耐熱處理層及/或防銹處理層,可形成為包含選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭之群中1種以上之元素(亦可為金屬、合金、氧化物、氮化物、硫化物等之任一形態)之層。其中,耐熱處理層及/或防銹處理層較佳為Ni-Zn層。 The heat-resistant treated layer and the rust-resistant treated layer are not particularly limited, and may be formed of materials known in the technical field. In addition, since the heat-resistant treatment layer may also function as a rust-proof treatment layer, one layer having both the functions of the heat-resistant treatment layer and the rust-proof treatment layer may be formed as the heat-resistant treatment layer and the rust-proof treatment layer. As a heat-resistant treatment layer and/or an anti-rust treatment layer, it can be formed to contain nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group A layer of one or more elements in the group of elements, iron, and tantalum (it can also be in any form of metal, alloy, oxide, nitride, sulfide, etc.). Among them, the heat-resistant treatment layer and/or the anti-rust treatment layer is preferably a Ni-Zn layer.
耐熱處理層及防銹處理層可藉由電鍍形成。其條件根據所使用之電鍍裝置來調整即可,並未特別限定,使用一般之電鍍裝置形成耐熱處理層(Ni-Zn層)時之條件如下。再者,電鍍可進行1次,亦可進行複數次。 鍍覆液組成:1~30 g/L之Ni,1~30 g/L之Zn 鍍覆液pH值:2~5 鍍覆液溫度:30~50℃ 電鍍條件:電流密度0.1~10 A/dm 2,時間0.1~5秒 The heat-resistant treatment layer and the anti-rust treatment layer can be formed by electroplating. The conditions may be adjusted according to the plating apparatus used, and are not particularly limited. The conditions for forming the heat-resistant treatment layer (Ni—Zn layer) using a general plating apparatus are as follows. In addition, electroplating may be performed once or multiple times. Plating solution composition: 1-30 g/L Ni, 1-30 g/L Zn pH value of plating solution: 2-5 Plating solution temperature: 30-50°C Electroplating conditions: current density 0.1-10 A/ dm 2 , time 0.1~5 seconds
作為鉻酸鹽處理層並未特別限定,可由該技術領域中周知之材料形成。 此處,本說明書中「鉻酸鹽處理層」,係指由包含鉻酸酐、鉻酸、二鉻酸、鉻酸鹽或二鉻酸鹽之液體形成之層。鉻酸鹽處理層可為包含鈷、鐵、鎳、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷、鈦等元素(亦可為金屬、合金、氧化物、氮化物、硫化物等之任一形態)之層。作為鉻酸鹽處理層之例,可列舉經鉻酸酐或二鉻酸鉀水溶液處理之鉻酸鹽處理層、經包含鉻酸酐或二鉻酸鉀及鋅之處理液處理的鉻酸鹽處理層等。 The chromate treatment layer is not particularly limited, and can be formed of a material known in the technical field. Here, the "chromate treatment layer" in this specification refers to a layer formed from a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer can contain elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium (also can be metal, alloy, oxide, nitride, sulfide any form of things, etc.). Examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate treatment layer treated with a treatment solution containing chromic anhydride or potassium dichromate, and zinc, etc. .
鉻酸鹽處理層可藉由浸漬鉻酸鹽處理、電解鉻酸鹽處理等周知之方法形成。其等之條件並未特別限定,例如形成一般之鉻酸鹽處理層時的條件如下。再者,鉻酸鹽處理可進行1次,亦可進行複數次。 鉻酸鹽液組成:1~10 g/L之K 2Cr 2O 7,0.01~10 g/L之Zn 鉻酸鹽液pH值:2~5 鉻酸鹽液溫度:30~55℃ 電解條件:電流密度0.1~10 A/dm 2,時間0.1~5秒(電解鉻酸鹽處理之情形) The chromate treatment layer can be formed by known methods such as dip chromate treatment and electrolytic chromate treatment. These conditions are not particularly limited, for example, the conditions for forming a general chromate treatment layer are as follows. In addition, chromate treatment may be performed once, and may be performed plural times. Chromate solution composition: 1-10 g/L of K 2 Cr 2 O 7 , 0.01-10 g/L of Zn Chromate solution pH value: 2-5 Chromate solution temperature: 30-55°C Electrolysis conditions : Current density 0.1~10 A/dm 2 , time 0.1~5 seconds (in the case of electrolytic chromate treatment)
作為矽烷偶合處理層並未特別限定,可由該技術領域中周知之材料形成。 此處,本說明書中「矽烷偶合處理層」,係指由矽烷偶合劑形成之層。 作為矽烷偶合劑並未特別限定,可使用該技術領域中周知者。作為矽烷偶合劑之例,可列舉胺基系矽烷偶合劑、環氧系矽烷偶合劑、巰基系矽烷偶合劑、甲基丙烯醯氧基系矽烷偶合劑、乙烯基矽烷偶合劑、咪唑系矽烷偶合劑、三系矽烷偶合劑等。該等中,較佳為胺基系矽烷偶合劑、環氧系矽烷偶合劑。上述矽烷偶合劑可單獨或組合2種以上使用。 作為代表性之矽烷偶合處理層之形成方法,可舉藉由塗佈上述矽烷偶合劑之1~3體積%水溶液並進行乾燥而形成矽烷偶合處理層之方法。 The silane coupling treatment layer is not particularly limited, and may be formed of materials known in the technical field. Here, the "silane coupling treatment layer" in this specification refers to a layer formed of a silane coupling agent. It does not specifically limit as a silane coupling agent, Those well-known in this technical field can be used. Examples of silane coupling agents include amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, methacryloxy silane coupling agents, vinyl silane coupling agents, and imidazole silane coupling agents. mixture, three Department of silane coupling agent, etc. Among them, amino-based silane coupling agents and epoxy-based silane coupling agents are preferred. The said silane coupling agent can be used individually or in combination of 2 or more types. A representative method for forming a silane coupling treatment layer is a method of forming a silane coupling treatment layer by applying a 1 to 3 volume % aqueous solution of the above-mentioned silane coupling agent and drying it.
作為銅箔10並未特別限定,可為電解銅箔或壓延銅箔之任一者。
電解銅箔一般藉由自硫酸銅鍍覆浴將銅電解析出於鈦或不鏽鋼之滾筒上而製造,具有形成於旋轉滾筒側之平坦的S面(磨光面)與形成於S面之相反側的M面(消光面)。電解銅箔之M面一般具有微小之凹凸部。又,電解銅箔之S面由於轉印有研磨時形成之旋轉滾筒的研磨條紋,故具有微小之凹凸部。
又,壓延銅箔由於在壓延時會因壓延油而形成油坑,因此於表面具有微小之凹凸部。
It does not specifically limit as the
作為銅箔10之材料並未特別限定,於銅箔10為壓延銅箔之情形時,可使用通常作為印刷配線板之電路圖案來使用的精銅(JIS H3100 合金編號C1100)、無氧銅(JIS H3100 合金編號C1020或JIS H3510 合金編號C1011)等高純度銅。又,例如,亦可使用摻Sn之銅、摻Ag之銅、添加有Cr、Zr或Mg等之銅合金、添加有Ni及Si等之卡遜系銅合金之類的銅合金。再者,本說明書中,「銅箔10」係亦包含銅合金箔之概念。The material of the
銅箔10之厚度並未特別限定,例如可設為1~1000 μm,或1~500 μm,或1~300 μm,或3~100 μm,或5~70 μm,或6~35 μm,或9~18 μm。The thickness of the
具有如上述之構成的表面處理銅箔,可依照該技術領域中周知之方法來進行製造。此處,表面處理層之Sk的變化量等參數,可藉由調整表面處理層之形成條件,特別是上述粗化處理層之形成條件等而進行控制。The surface-treated copper foil having the above-mentioned structure can be manufactured according to a method well known in the technical field. Here, parameters such as the amount of change in Sk of the surface treatment layer can be controlled by adjusting the formation conditions of the surface treatment layer, especially the formation conditions of the above-mentioned roughening treatment layer.
本發明之實施形態的表面處理銅箔,由於將表面處理層之Sk的變化量控制為0.180~0.600 μm,因此可提高與樹脂基材特別是適合高頻用途之樹脂基材的接著性。In the surface-treated copper foil according to the embodiment of the present invention, since the variation of Sk of the surface-treated layer is controlled to 0.180-0.600 μm, the adhesion to resin substrates, especially resin substrates suitable for high-frequency applications can be improved.
本發明之實施形態的覆銅積層板,具備上述表面處理銅箔及接著於該表面處理銅箔之表面處理層的樹脂基材。 該覆銅積層板可藉由將樹脂基材接著於上述表面處理銅箔之表面處理層而製造。 作為樹脂基材並未特別限定,可使用該技術領域中周知者。作為樹脂基材之例,可列舉紙基材酚樹脂、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃布-紙複合基材環氧樹脂、玻璃布-玻璃不織布複合基材環氧樹脂、玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺樹脂、液晶聚合物、氟樹脂等。該等中,樹脂基材較佳為聚醯亞胺樹脂。 A copper-clad laminate according to an embodiment of the present invention includes the above-mentioned surface-treated copper foil and a resin base material for a surface-treated layer next to the surface-treated copper foil. This copper-clad laminate can be manufactured by adhering a resin substrate to the surface-treated layer of the above-mentioned surface-treated copper foil. It does not specifically limit as a resin base material, Those well-known in this technical field can be used. Examples of resin substrates include paper-based phenolic resins, paper-based epoxy resins, synthetic fiber cloth-based epoxy resins, glass cloth-paper composite substrates, and glass cloth-glass nonwoven composite substrates. Epoxy resin, glass cloth base epoxy resin, polyester film, polyimide resin, liquid crystal polymer, fluororesin, etc. Among these, the resin substrate is preferably polyimide resin.
作為表面處理銅箔與樹脂基材之接著方法,並未特別限定,可依照該技術領域中周知之方法來進行。例如,可將表面處理銅箔與樹脂基材積層並進行熱壓接合。 以上述方式製造之覆銅積層板,可用於印刷配線板之製造。 The bonding method between the surface-treated copper foil and the resin substrate is not particularly limited, and it can be performed according to a method known in the technical field. For example, a surface-treated copper foil and a resin base material can be laminated and bonded by thermocompression. The copper clad laminate manufactured in the above manner can be used in the manufacture of printed wiring boards.
本發明之實施形態的覆銅積層板,由於使用上述表面處理銅箔,因此可提高與樹脂基材特別是適合高頻用途之樹脂基材的接著性。Since the copper-clad laminate according to the embodiment of the present invention uses the above-mentioned surface-treated copper foil, the adhesion to resin substrates, especially resin substrates suitable for high-frequency applications can be improved.
本發明之實施形態的印刷配線板,具備對上述覆銅積層板之表面處理銅箔進行蝕刻而形成的電路圖案。 該印刷配線板,可藉由對上述覆銅積層板之表面處理銅箔進行蝕刻而形成電路圖案來製造。作為電路圖案之形成方法,並未特別限定,可使用減成法、半加成法等周知方法。其中,電路圖案之形成方法較佳為減成法。 A printed wiring board according to an embodiment of the present invention includes a circuit pattern formed by etching the surface-treated copper foil of the above-mentioned copper-clad laminate. This printed wiring board can be manufactured by etching the surface-treated copper foil of the said copper-clad laminate board, and forming a circuit pattern. It does not specifically limit as a formation method of a circuit pattern, Well-known methods, such as a subtractive method and a semi-additive method, can be used. Among them, the method for forming the circuit pattern is preferably a subtractive method.
於藉由減成法來製造印刷配線板之情形時,較佳以如下方式進行。首先,於覆銅積層板之表面處理銅箔的表面塗佈抗蝕劑,並進行曝光及顯影,藉此形成特定抗蝕劑圖案。接下來,將未形成抗蝕劑圖案之部分(多餘部)之表面處理銅箔藉由蝕刻去除而形成電路圖案。最後,將表面處理銅箔上之抗蝕劑圖案去除。 再者,該減成法中之各種條件並未特別限定,可依照該技術領域中周知之條件來進行。 When manufacturing a printed wiring board by the subtractive method, it is preferable to carry out as follows. First, a resist is coated on the surface of the surface-treated copper foil of the copper-clad laminate, and then exposed and developed to form a specific resist pattern. Next, a circuit pattern was formed by etching away the surface-treated copper foil of the part (excess part) in which the resist pattern was not formed. Finally, the resist pattern on the surface-treated copper foil is removed. In addition, various conditions in this subtraction method are not specifically limited, It can carry out according to the well-known conditions in this technical field.
本發明之實施形態的印刷配線板,由於使用上述覆銅積層板,因此樹脂基材特別是適合高頻用途之樹脂基材與電路圖案之間的接著性優異。 [實施例] Since the printed wiring board according to the embodiment of the present invention uses the above-mentioned copper-clad laminate, it is excellent in the adhesion between the resin base material, especially the resin base material suitable for high-frequency applications, and the circuit pattern. [Example]
以下,對本發明之實施形態藉由實施例更具體地進行說明,但本發明不受該些實施例任何限定。Hereinafter, although the embodiment of this invention is demonstrated more concretely using an Example, this invention is not limited at all by these Examples.
(實施例1) 準備厚度12 μm之壓延銅箔(JX金屬股份公司製造之HA-V2箔),對一面進行脫脂及酸洗後,依次形成粗化處理層、耐熱處理層(Ni-Zn層)、鉻酸鹽處理層及矽烷偶合處理層來作為表面處理層,藉此獲得表面處理銅箔。各處理層之形成條件如下。 (1)粗化處理層 <粗化粒子之形成條件> 鍍覆液組成:11 g/L之Cu,50 g/L之硫酸,5.3 ppm之鎢(源自鎢酸鈉二水合物) 鍍覆液溫度:27℃ 電鍍條件:電流密度46.8 A/dm 2,時間1.01秒 電鍍處理次數:2次 (Example 1) A rolled copper foil (HA-V2 foil manufactured by JX Metal Co., Ltd.) with a thickness of 12 μm was prepared. After degreasing and pickling one side, a roughening treatment layer and a heat-resistant treatment layer (Ni-Zn layer ), a chromate treatment layer and a silane coupling treatment layer as the surface treatment layer, thereby obtaining a surface-treated copper foil. The formation conditions of each treatment layer are as follows. (1) Roughening treatment layer <Formation conditions of roughened particles> Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid, 5.3 ppm tungsten (derived from sodium tungstate dihydrate) Plating Liquid temperature: 27℃ Electroplating conditions: current density 46.8 A/dm 2 , time 1.01 seconds Electroplating treatment times: 2 times
<被覆鍍層之形成條件> 鍍覆液組成:20 g/L之Cu,100 g/L之硫酸 鍍覆液溫度:50℃ 電鍍條件:電流密度9.6 A/dm 2,時間1.44秒 電鍍處理次數:2次 <Conditions for the formation of coating layer> Plating solution composition: 20 g/L Cu, 100 g/L sulfuric acid Plating solution temperature: 50°C Electroplating conditions: current density 9.6 A/dm 2 , time 1.44 seconds Electroplating treatment times: 2 times
(2)耐熱處理層 <Ni-Zn層之形成條件> 鍍覆液組成:23.5 g/L之Ni,4.5 g/L之Zn 鍍覆液pH值:3.6 鍍覆液溫度:40℃ 電鍍條件:電流密度0.88 A/dm 2,時間0.73秒 電鍍處理次數:1次 (2) Heat-resistant treatment layer <Ni-Zn layer formation conditions> Plating solution composition: 23.5 g/L Ni, 4.5 g/L Zn Plating solution pH value: 3.6 Plating solution temperature: 40°C Electroplating conditions: Current density 0.88 A/dm 2 , time 0.73 seconds Electroplating treatment times: 1 time
(3)鉻酸鹽處理層 <電解鉻酸鹽處理層之形成條件> 鉻酸鹽液組成:3 g/L之K 2Cr 2O 7,0.33 g/L之Zn 鉻酸鹽液pH值:3.7 鉻酸鹽液溫度:55℃ 電解條件:電流密度1.42 A/dm 2,時間0.73秒 鉻酸鹽處理次數:2次 (3) Chromate treatment layer <Formation conditions of electrolytic chromate treatment layer> Chromate solution composition: 3 g/L K 2 Cr 2 O 7 , 0.33 g/L Zn Chromate solution pH value: 3.7 Chromate solution temperature: 55°C Electrolysis conditions: current density 1.42 A/dm 2 , time 0.73 seconds Chromate treatment times: 2 times
(4)矽烷偶合處理層 塗佈N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷之1.2體積%水溶液,並進行乾燥,藉此形成矽烷偶合處理層。 (4) Silane coupling treatment layer A 1.2 volume % aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane was applied and dried to form a silane coupling treatment layer.
(實施例2) 除變更以下之條件以外,以與實施例1相同之條件獲得表面處理銅箔。 <粗化粒子之形成條件> 鍍覆液組成:11 g/L之Cu,50 g/L之硫酸,5 ppm之鎢(源自鎢酸鈉二水合物) 鍍覆液溫度:27℃ 電鍍條件:電流密度74.8 A/dm 2,時間0.61秒 <被覆鍍層之形成條件> 電鍍條件:電流密度8.2 A/dm 2,時間1.15秒 <Ni-Zn層之形成條件> 電鍍條件:電流密度0.63 A/dm 2,時間0.59秒 <電解鉻酸鹽處理層之形成條件> 電解條件:電流密度1.81 A/dm 2,時間0.59秒 (Example 2) Except having changed the following conditions, the surface-treated copper foil was obtained on the same conditions as Example 1. <Conditions for the formation of roughened particles> Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate) Plating solution temperature: 27°C Electroplating conditions : current density 74.8 A/dm 2 , time 0.61 seconds <formation condition of coating layer> electroplating condition: current density 8.2 A/dm 2 , time 1.15 seconds <formation condition of Ni-Zn layer> electroplating condition: current density 0.63 A/ dm 2 , time 0.59 seconds <Conditions for forming electrolytic chromate treatment layer> Electrolysis conditions: current density 1.81 A/dm 2 , time 0.59 seconds
(實施例3) 除變更以下之條件以外,以與實施例1相同之條件獲得表面處理銅箔。 <粗化粒子之形成條件> 鍍覆液組成:11 g/L之Cu,50 g/L之硫酸,3 ppm之鎢(源自鎢酸鈉二水合物) 電鍍條件:電流密度38.8 A/dm 2,時間1.27秒 <被覆鍍層之形成條件> 電鍍條件:電流密度8.2 A/dm 2,時間1.44秒 <Ni-Zn層之形成條件> 電鍍條件:電流密度0.59 A/dm 2,時間0.73秒 (Example 3) Except having changed the following conditions, the surface-treated copper foil was obtained on the same conditions as Example 1. <Conditions for the formation of roughened particles> Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid, 3 ppm tungsten (derived from sodium tungstate dihydrate) Electroplating conditions: current density 38.8 A/dm 2. Time 1.27 seconds <Formation condition of coating layer> Electroplating condition: current density 8.2 A/dm 2 , time 1.44 seconds <Ni-Zn layer formation condition> Electroplating condition: Current density 0.59 A/dm 2 , time 0.73 second
(實施例4) 除變更以下之條件以外,以與實施例1相同之條件獲得表面處理銅箔。 <粗化粒子之形成條件> 鍍覆液組成:11 g/L之Cu,50 g/L之硫酸,5 ppm之鎢(源自鎢酸鈉二水合物) 鍍覆液溫度:27℃ 電鍍條件:電流密度46.8 A/dm 2,時間1.01秒 電鍍處理次數:2次 (Example 4) Except having changed the following conditions, the surface-treated copper foil was obtained on the same conditions as Example 1. <Conditions for forming coarse particles> Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate) Plating solution temperature: 27°C Electroplating conditions : Current density 46.8 A/dm 2 , time 1.01 seconds Electroplating treatment times: 2 times
(實施例5) 準備厚度12 μm之壓延銅箔(JX金屬股份公司製造之HG箔),對一面進行脫脂及酸洗後,依次形成粗化處理層、耐熱處理層(Ni-Zn層)、鉻酸鹽處理層及矽烷偶合處理層來作為表面處理層,藉此獲得表面處理銅箔。各處理層之形成條件如下。 (1)粗化處理層 <粗化粒子之形成條件> 鍍覆液組成:12 g/L之Cu,50 g/L之硫酸,5 ppm之鎢(源自鎢酸鈉二水合物) 鍍覆液溫度:27℃ 電鍍條件:電流密度48.3 A/dm 2,時間0.81秒 電鍍處理次數:2次 (Example 5) A rolled copper foil (HG foil manufactured by JX Metal Co., Ltd.) with a thickness of 12 μm was prepared. After degreasing and pickling one side, a roughening treatment layer, a heat-resistant treatment layer (Ni-Zn layer), and The chromate treatment layer and the silane coupling treatment layer are used as the surface treatment layer to obtain surface-treated copper foil. The formation conditions of each treatment layer are as follows. (1) Coarsening treatment layer <Formation conditions of coarsening particles> Plating solution composition: 12 g/L Cu, 50 g/L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate) Plating Liquid temperature: 27℃ Electroplating conditions: current density 48.3 A/dm 2 , time 0.81 seconds Electroplating treatment times: 2 times
<被覆鍍層之形成條件> 鍍覆液組成:20 g/L之Cu,100 g/L之硫酸 鍍覆液溫度:50℃ 電鍍條件:電流密度11.9 A/dm 2,時間1.15秒 電鍍處理次數:2次 <Conditions for the formation of coating layer> Plating solution composition: 20 g/L Cu, 100 g/L sulfuric acid Plating solution temperature: 50°C Electroplating conditions: current density 11.9 A/dm 2 , time 1.15 seconds Electroplating treatment times: 2 times
(2)耐熱處理層 <Ni-Zn層之形成條件> 鍍覆液組成:23.5 g/L之Ni,4.5 g/L之Zn 鍍覆液pH值:3.6 鍍覆液溫度:40℃ 電鍍條件:電流密度1.07 A/dm 2,時間0.59秒 電鍍處理次數:1次 (2) Heat-resistant treatment layer <Ni-Zn layer formation conditions> Plating solution composition: 23.5 g/L Ni, 4.5 g/L Zn Plating solution pH value: 3.6 Plating solution temperature: 40°C Electroplating conditions: Current density 1.07 A/dm 2 , time 0.59 seconds Electroplating treatment times: 1 time
(3)鉻酸鹽處理層 <電解鉻酸鹽處理層之形成條件> 鉻酸鹽液組成:3 g/L之K 2Cr 2O 7,0.33 g/L之Zn 鉻酸鹽液pH值:3.65 鉻酸鹽液溫度:55℃ 電解條件:電流密度1.91 A/dm 2,時間0.59秒 鉻酸鹽處理次數:2次 (3) Chromate treatment layer <Formation conditions of electrolytic chromate treatment layer> Chromate solution composition: 3 g/L K 2 Cr 2 O 7 , 0.33 g/L Zn Chromate solution pH value: 3.65 Chromate solution temperature: 55°C Electrolysis conditions: current density 1.91 A/dm 2 , time 0.59 seconds Chromate treatment times: 2 times
(4)矽烷偶合處理層 塗佈N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷之1.2體積%水溶液,並進行乾燥,藉此形成矽烷偶合處理層。 (4) Silane coupling treatment layer A 1.2 volume % aqueous solution of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane was applied and dried to form a silane coupling treatment layer.
(比較例1) 將實施例1中所使用之壓延銅箔(未進行表面處理之銅箔)用作比較。 (comparative example 1) The rolled copper foil (copper foil without surface treatment) used in Example 1 was used for comparison.
(比較例2) 除變更以下之條件以外,以與實施例1相同之條件獲得表面處理銅箔。 <粗化粒子之形成條件> 鍍覆液組成:11 g/L之Cu,50 g/L之硫酸 電鍍條件:電流密度38.8 A/dm 2,時間1.27秒 <被覆鍍層之形成條件> 電鍍條件:電流密度8.2 A/dm 2,時間1.44秒 <Ni-Zn層之形成條件> 電鍍條件:電流密度0.59 A/dm 2,時間0.73秒 (Comparative example 2) Except having changed the following conditions, the surface-treated copper foil was obtained on the conditions similar to Example 1. <Conditions for the formation of coarse particles> Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid Electroplating conditions: current density 38.8 A/dm 2 , time 1.27 seconds <Conditions for the formation of coating layers> Electroplating conditions: Current density 8.2 A/dm 2 , time 1.44 seconds <Ni-Zn layer formation conditions> Electroplating conditions: current density 0.59 A/dm 2 , time 0.73 seconds
對上述實施例及比較例中獲得之表面處理銅箔或銅箔進行下述特性評估。 <Sk、Sku、Sq、Sa及Ssk> 依據ISO 25178-2:2012,使用奧林巴斯股份公司製造之雷射顯微鏡(LEXT OLS4000)來進行測定(圖像拍攝)。拍攝之圖像的解析係使用奧林巴斯股份公司製造之雷射顯微鏡(LEXT OLS4100)之解析軟體來進行。結果,使用在任意5處測定及解析之值的平均值。再者,測定時之溫度設為23~25℃。又,雷射顯微鏡及解析軟體之主要設定條件如下。 物鏡:MPLAPON50XLEXT(倍率:50倍,數值孔徑:0.95,液浸類型:空氣,機械鏡筒長度:∞,蓋玻璃厚度:0,視域數:FN18) 光學變焦倍率:1倍 掃描模式:XYZ高精度(高度解析度:60 nm,取入資料之像素數:1024×1024) 取入圖像尺寸[像素數]:橫257 μm×縱258 μm[1024×1024] (由於在橫向上測定,因此評估長度相當於257 μm) DIC:關閉 Multilayer:關閉 雷射強度:100 補償:0 共焦級:0 光束直徑光闌:關閉 取圖像平均值:1次 雜訊降低:打開 亮度不均修正:打開 光學雜訊濾波器:打開 截止:測定P1(Sk)時,應用λc=200 μm及λs=2 μm,不應用λf。測定P2(Sk)、Sku、Sq、Sa及Ssk時,應用λc=200 μm,不應用λs及λf。 濾波器:高斯濾波器 雜訊去除:測定前處理 表面(斜率)修正:實施 明亮度:調整為30~50之範圍 明亮度係應根據測定對象之色調來適當設定之值。上述設定係當測定L*為-69~-10,a*為2~32,b*為221之表面處理銅箔的表面時適合之值。 又,對於Sk,依照上述式(1)來算出Sk之變化量。 再者,λc濾波器相當於ISO 25178-2:2012中之L濾波器。 The following characteristic evaluations were performed on the surface-treated copper foils or copper foils obtained in the above Examples and Comparative Examples. <Sk, Sku, Sq, Sa and Ssk> According to ISO 25178-2:2012, a laser microscope (LEXT OLS4000) manufactured by Olympus Co., Ltd. was used for measurement (image capture). Analysis of the captured image was performed using analysis software of a laser microscope (LEXT OLS4100) manufactured by Olympus Corporation. As a result, the average value of the values measured and analyzed at arbitrary 5 places was used. In addition, the temperature at the time of measurement was made into 23-25 degreeC. In addition, the main setting conditions of the laser microscope and analysis software are as follows. Objective lens: MPLAPON50XLEXT (magnification: 50 times, numerical aperture: 0.95, liquid immersion type: air, mechanical tube length: ∞, cover glass thickness: 0, field number: FN18) Optical zoom ratio: 1 times Scanning mode: XYZ high precision (height resolution: 60 nm, number of pixels to capture data: 1024×1024) Imported image size [number of pixels]: horizontal 257 μm x vertical 258 μm [1024 x 1024] (Evaluation length corresponds to 257 μm due to measurement in transverse direction) DIC: off Multilayer: off Laser Strength: 100 Compensation: 0 Confocal level: 0 Beam Diameter Diaphragm: Closed Take image average: 1 time Noise Reduction: On Uneven Brightness Correction: On Optical Noise Filter: On Cut-off: When measuring P1(Sk), apply λc=200 μm and λs=2 μm, and do not apply λf. When measuring P2(Sk), Sku, Sq, Sa and Ssk, apply λc=200 μm, and do not apply λs and λf. Filter: Gaussian filter Noise removal: pre-measurement processing Surface (slope) correction: implemented Brightness: adjust to the range of 30-50 Brightness is a value that should be appropriately set according to the hue of the measurement object. The above setting is a suitable value when measuring the surface of the surface-treated copper foil whose L* is -69~-10, a* is 2~32, and b* is 221. Also, regarding Sk, the amount of change in Sk is calculated according to the above formula (1). Furthermore, the λc filter is equivalent to the L filter in ISO 25178-2:2012.
<測定對象之色調的測定> 使用HunterLab公司製造之MiniScan(註冊商標)EZ Model 4000L作為測定器,依據JIS Z8730:2009來進行CIE L*a*b*表色系統之L*、a*及b*的測定。具體而言,將上述實施例及比較例中所獲得之表面處理銅箔或銅箔的測定對象面壓抵於測定器之感光部,在光不自外部進入之情況下進行測定。又,L*、a*及b*之測定,係基於JIS Z8722:2009之幾何條件C來進行。再者,測定器之主要條件如下。 光學系統:d/8°,積分球尺寸:63.5 mm,觀察光源:D65 測定方式:反射 照明直徑:25.4 mm 測定直徑:20.0 mm 測定波長、間隔:400~700 nm、10 nm 光源:脈衝氙氣燈、1發光/測定 追溯性標準:基於CIE 44及ASTM E259之美國標準技術研究所(NIST)準據校正 標準觀察者:10° 又,成為測定基準之白色瓷磚使用下述物體顏色者。 以D65/10°測定時,於CIE XYZ表色系統之值係X:81.90、Y:87.02、Z:93.76 <Measurement of color tone of measurement object> Using MiniScan (registered trademark) EZ Model 4000L manufactured by HunterLab as a measuring device, L*, a* and b* of the CIE L*a*b* colorimetric system were measured in accordance with JIS Z8730:2009. Specifically, the measurement target surface of the surface-treated copper foil or copper foil obtained in the above-mentioned Examples and Comparative Examples was pressed against the photosensitive part of the measuring device, and the measurement was performed without light entering from the outside. In addition, the measurement of L*, a*, and b* was performed based on the geometric condition C of JIS Z8722:2009. In addition, the main conditions of the measuring device are as follows. Optical system: d/8°, integrating sphere size: 63.5 mm, observation light source: D65 Measuring method: reflection Lighting diameter: 25.4 mm Measuring diameter: 20.0 mm Measurement wavelength, interval: 400~700 nm, 10 nm Light source: pulsed xenon lamp, 1 light emission/measurement Traceable standards: Calibration based on CIE 44 and ASTM E259 of the National Institute of Standards and Technology (NIST) Standard Observer: 10° In addition, the following object colors were used for the white tile used as a measurement standard. When measured by D65/10°, the values in the CIE XYZ color system are X: 81.90, Y: 87.02, Z: 93.76
<剝離強度> 將表面處理銅箔與聚醯亞胺樹脂基材貼合後,沿MD方向(壓延銅箔之長邊方向)形成寬度3 mm之電路。電路之形成係按照通常方法來實施。接下來,依據JIS C6471:1995來測定將電路(表面處理銅箔)相對於樹脂基材之表面以50 mm/分鐘之速度向90°方向,即相對於樹脂基材之表面向鉛直上方剝離時的強度(MD90°剝離強度)。測定進行3次,將其平均值作為剝離強度之結果。若剝離強度為0.50 kgf/cm以上,則可說電路(表面處理銅箔)與樹脂基材之接著性良好。 再者,比較例1之銅箔由於無法與聚醯亞胺樹脂基材貼合,因此不進行上述評估。 <Peel Strength> After laminating the surface-treated copper foil and the polyimide resin substrate, a circuit with a width of 3 mm was formed along the MD direction (the long side direction of the rolled copper foil). Formation of the circuit is carried out according to a usual method. Next, according to JIS C6471: 1995, when the circuit (surface-treated copper foil) is peeled off at a speed of 50 mm/minute to the 90° direction relative to the surface of the resin substrate, that is, when it is peeled vertically upward relative to the surface of the resin substrate The strength (MD90 ° peel strength). The measurement was performed 3 times, and the average value was taken as the result of the peel strength. When the peel strength is 0.50 kgf/cm or more, it can be said that the adhesion between the circuit (surface-treated copper foil) and the resin base material is good. Furthermore, since the copper foil of Comparative Example 1 could not be bonded to the polyimide resin substrate, the above-mentioned evaluation was not carried out.
將上述特性評估之結果示於表1。Table 1 shows the results of the above characteristic evaluation.
[表1]
如表1所示,表面處理層之Sk的變化量為0.180~0.600 μm之範圍內的實施例1~5其表面處理銅箔之剝離強度高。 另一方面,表面處理層之Sk的變化量為特定範圍外之比較例2其表面處理銅箔之剝離強度低。 As shown in Table 1, in Examples 1 to 5 in which the amount of change in Sk of the surface treatment layer was in the range of 0.180 to 0.600 μm, the peel strength of the surface treatment copper foil was high. On the other hand, the amount of change in Sk of the surface treatment layer was out of the specified range in Comparative Example 2, and the peel strength of the surface treatment copper foil was low.
若參照以上結果及至此為止所述之本發明之實施形態的考察,則若根據本發明之實施形態,可提供能夠提高與樹脂基材特別是適合高頻用途之樹脂基材之接著性的表面處理銅箔。又,若根據本發明之實施形態,可提供樹脂基材特別是適合高頻用途之樹脂基材與表面處理銅箔之間之接著性優異的覆銅積層板。進而,若根據本發明之實施形態,可提供樹脂基材特別是適合高頻用途之樹脂基材與電路圖案之間之接著性優異的印刷配線板。With reference to the above results and the examination of the embodiments of the present invention described so far, according to the embodiments of the present invention, it is possible to provide a surface capable of improving adhesion to resin substrates, especially resin substrates suitable for high-frequency applications. Handle copper foil. Furthermore, according to the embodiment of the present invention, it is possible to provide a copper-clad laminate having excellent adhesion between a resin base material, especially a resin base material suitable for high-frequency applications, and a surface-treated copper foil. Furthermore, according to the embodiment of this invention, the printed wiring board which is excellent in the adhesiveness between the resin base material suitable for high-frequency use, and a circuit pattern especially can be provided.
10:銅箔 11:凸部 12:凹部 20:粗化粒子 30:被覆鍍層 Sk:核心部之級差(核心部之上限級與下限級之差) Spk:突出山部高度(處於核心部之上之突出山部之平均高度) Svk:突出谷部深度(處於核心部之下之突出谷部之平均深度) Smr1:將突出山部與核心部分離之負載面積率 Smr2:將突出谷部與核心部分離之負載面積率 10: copper foil 11: convex part 12: Concave 20: coarse particles 30: coated coating Sk: The difference between the core part (the difference between the upper limit level and the lower limit level of the core part) Spk: Protruding mountain height (the average height of the protruding mountain above the core) Svk: Protruding valley depth (average depth of protruding valleys below the core) Smr1: load area ratio separating the protruding mountain portion from the core portion Smr2: load area ratio separating the protruding valley from the core
[圖1]係表面處理層之典型的負載曲線。 [圖2]係用以說明構成表面處理層之粗化粒子及Sk的示意性概略圖。 [圖3]係於銅箔之一面具有粗化處理層之表面處理銅箔的示意性放大剖面圖。 [Fig. 1] is a typical load curve of the surface treatment layer. [ Fig. 2 ] is a schematic diagram for explaining roughening particles and Sk constituting the surface treatment layer. [ Fig. 3 ] A schematic enlarged cross-sectional view of a surface-treated copper foil having a roughened layer on one side of the copper foil.
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