TWI613940B - Copper foil with printed carrier, printed wiring board, laminated body, electronic device, and printed wiring board manufacturing method - Google Patents
Copper foil with printed carrier, printed wiring board, laminated body, electronic device, and printed wiring board manufacturing method Download PDFInfo
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本發明涉及一種附載體的銅箔、印刷配線板、積層體、電子機器及印刷配線板的製造方法。 The present invention relates to a copper foil with a carrier, a printed wiring board, a laminate, an electronic device, and a method of manufacturing a printed wiring board.
印刷配線板通常經過如下步驟而製造：將絕緣基板黏合到銅箔而製成覆銅積層板後，藉由蝕刻在銅箔面形成導體圖案。隨著近年來電子機器的小型化、高性能化需求的增長，搭載零件的高密度安裝化或信號的高頻化不斷發展，對印刷配線板要求導體圖案的微細化(微間距化)或應對高頻等。 The printed wiring board is usually manufactured by bonding an insulating substrate to a copper foil to form a copper clad laminate, and then forming a conductor pattern on the copper foil surface by etching. In recent years, the demand for miniaturization and high performance of electronic devices has increased, and high-density mounting of components and high-frequency signals have been progressing, and it is required to reduce the size (fine pitch) of conductor patterns on printed wiring boards. High frequency and so on.
對應於微間距化，最近要求厚度9μm以下、進而厚度5μm以下的銅箔，但這種極薄銅箔的機械強度低，容易在製造印刷配線板時破裂或產生皺褶，所以出現了如下附載體的銅箔：將具有厚度的金屬箔用作載體，並將極薄銅層隔著剝離層電沉積在金屬箔。在將極薄銅層的表面貼合到絕緣基板並進行熱壓接後，經由剝離層將載體剝離去除。藉由利用抗蝕劑在露出的極薄銅層上形成電路圖案後，利用硫酸-過氧化氫系的蝕刻劑將極薄銅層蝕刻去除的方法(MSAP：Modified-Semi-Additive-Process) 而形成微細電路。 Corresponding to the fine pitch, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less has recently been required. However, such an ultra-thin copper foil has low mechanical strength and is liable to be broken or wrinkled when the printed wiring board is manufactured. Carrier copper foil: A metal foil having a thickness is used as a carrier, and an extremely thin copper layer is electrodeposited on the metal foil via a release layer. After bonding the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, the carrier is peeled off by the peeling layer. A method of etching an extremely thin copper layer by a sulfuric acid-hydrogen peroxide-based etchant by using a resist to form a circuit pattern on the exposed ultra-thin copper layer (MSAP: Modified-Semi-Additive-Process) And a fine circuit is formed.
此處，對於成為和樹脂的黏合面的附載體的銅箔的極薄銅層的表面，主要要求極薄銅層和樹脂基材的剝離強度充分，以及在高溫加熱、濕式處理、焊接、化學品處理等的後亦得以充分保持其剝離強度。作為提高極薄銅層和樹脂基材之間的剝離強度的方法，通常代表性的方法是在增大了表面的輪廓(凹凸、粗糙度)的極薄銅層上附著大量粗化粒子 Here, the surface of the ultra-thin copper layer of the copper foil which is the carrier of the adhesive surface of the resin is required to have sufficient peeling strength of the ultra-thin copper layer and the resin substrate, and high-temperature heating, wet processing, soldering, After the chemical treatment, etc., the peel strength is also sufficiently maintained. As a method of increasing the peel strength between the ultra-thin copper layer and the resin substrate, a generally representative method is to attach a large amount of roughened particles to the extremely thin copper layer which increases the contour (concavity, roughness) of the surface.
然而，若對印刷配線板中尤其是必須形成微細電路圖案的半導體封裝基板使用這種輪廓(凹凸、粗糙度)大的極薄銅層，則在電路蝕刻時會殘留不需要的銅粒子，產生電路圖案間的絕緣不良等問題。 However, when an extremely thin copper layer having a large profile (concavity, roughness, and roughness) is used for a semiconductor package substrate in which a fine circuit pattern must be formed in a printed wiring board, unnecessary copper particles remain during circuit etching, resulting in generation of unnecessary copper particles. Problems such as poor insulation between circuit patterns.
因此，在WO2004/005588號(專利文獻1)中，作為以半導體封裝基板為代表的微細電路用途之附載體的銅箔，嘗試使用沒有對極薄銅層的表面實施粗化處理之附載體的銅箔。這種沒有實施粗化處理的極薄銅層和樹脂的密合性(剝離強度)由於極薄銅層的低輪廓(凹凸、粗度、粗糙度)的影響，而有低於通常的印刷配線板用銅箔的傾向。因此，對附載體的銅箔要求進一步的改善。 In the case of the copper foil with a carrier for the fine circuit use typified by the semiconductor package substrate, it is attempted to use a carrier which does not have a roughened surface on the surface of the ultra-thin copper layer, in the WO2004/005588 (patent document 1). Copper foil. The adhesion (peel strength) of the ultra-thin copper layer and the resin which are not subjected to the roughening treatment is lower than the usual printed wiring due to the influence of the low profile (concavity, roughness, roughness) of the ultra-thin copper layer. The tendency of the board to use copper foil. Therefore, further improvement is required for the copper foil with the carrier.
因而，在日本專利特開2007-007937號公報(專利文獻2)及日本專利特開2010-006071號公報(專利文獻3)中，記載了在附載體的極薄銅箔之與聚醯亞胺系樹脂基板接觸(黏合)的面設置Ni層或/及Ni合金層、設置鉻酸鹽層、設置Cr層或/及Cr合金層、設置Ni層和鉻酸鹽層、設置Ni層和Cr層。藉由設置這些表面處理層，可以不進行粗化處理或者降低粗化處理的程度(微細化)而使聚醯亞胺系樹脂基板和附載體的極薄銅箔的密合強度獲得所需的黏合強度。並且，還記載了利用矽烷偶合劑 進行表面處理，或實施防銹處理。 In the ultrathin copper foil with a carrier, it is described in JP-A-2007-007937 (Patent Document 2) and JP-A-2010-006071 (Patent Document 3). The surface of the resin substrate is contacted (bonded) with a Ni layer or/and a Ni alloy layer, a chromate layer, a Cr layer or/and a Cr alloy layer, a Ni layer and a chromate layer, and a Ni layer and a Cr layer. . By providing these surface treatment layers, it is possible to obtain the desired adhesion strength of the polyimide-based resin substrate and the ultra-thin copper foil with a carrier without performing the roughening treatment or reducing the degree of the roughening treatment (reduction). Bond strength. Also, the use of a decane coupling agent is described. Surface treatment or anti-rust treatment.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]WO2004/005588號 [Patent Document 1] WO2004/005588
[專利文獻2]日本特開2007-007937號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-007937
[專利文獻3]日本特開2010-006071號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-006071
在附載體的銅箔的開發中，至今將重點放在確保極薄銅層和樹脂基材的剝離強度。因此，關於極薄銅層的電路形成性，還沒有進行充分的研究，仍留有改善的餘地。 In the development of copper foil with a carrier, attention has been focused so far on ensuring the peel strength of an extremely thin copper layer and a resin substrate. Therefore, regarding the circuit formability of the ultra-thin copper layer, sufficient research has not been conducted, and there is still room for improvement.
在將附載體的銅箔從極薄銅層側貼合到樹脂時會進行熱壓，但此時有由於在載體/極薄銅層間產生的水蒸氣等氣體而產生氣泡(鼓出(swelling))的情況。若產生這種鼓出，則會產生用於形成電路的極薄銅層凹陷，對電路形成性產生不良影響的問題。本發明提供一種附載體的銅箔，藉由抑制對附載體的銅箔在特定條件下進行加熱處理時產生的鼓出的個數，而具有良好蝕刻性。或者，本發明提供一種附載體的銅箔，藉由抑制對附載體的銅箔在特定條件下進行加熱處理時產生的水份量，而抑制由產生於載體/極薄銅層間的水蒸氣等氣體所導致的鼓出的產生，而具有良好蝕刻性。 When the copper foil with a carrier is bonded to the resin from the side of the ultra-thin copper layer, hot pressing is performed, but at this time, bubbles are generated due to gas such as water vapor generated between the carrier/very thin copper layer (swelling). )Case. If such bulging occurs, there is a problem that an extremely thin copper layer recess for forming a circuit adversely affects circuit formability. The present invention provides a copper foil with a carrier which has good etching property by suppressing the number of bulging which is generated when a copper foil with a carrier is subjected to heat treatment under specific conditions. Alternatively, the present invention provides a copper foil with a carrier which suppresses gas such as water vapor generated between a carrier/very thin copper layer by suppressing the amount of water generated when the copper foil with a carrier is subjected to heat treatment under specific conditions. The resulting bulging is produced with good etchability.
基於以上見解完成的本發明在一方面中是一種附載體的銅 箔，依序具備載體、中間層及極薄銅層，將該附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量為160ppm/g以下。 The invention based on the above findings is in one aspect a copper with a carrier The foil is provided with a carrier, an intermediate layer, and an extremely thin copper layer in this order, and the amount of water generated when the copper foil of the carrier is heated to 500 ° C at 30 ° C / min is 160 ppm / g or less.
本發明的附載體的銅箔在一實施方式中，將該附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量為0~130ppm/g。 In the embodiment, the copper foil with a carrier of the present invention has a water content of 0 to 130 ppm/g when the copper foil of the carrier is heated to 500 ° C at 30 ° C / min.
本發明的附載體的銅箔在另一實施方式中，將該附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量為0~110ppm/g。 In another embodiment of the copper foil with a carrier of the present invention, the amount of water generated when the copper foil of the carrier is heated to 500 ° C at 30 ° C / min is 0 to 110 ppm / g.
本發明在另一方面中是一種附載體的銅箔，其依序具備載體、中間層及極薄銅層，將該附載體的銅箔以220℃加熱4小時時所產生的鼓出為20個/dm2以下。 In another aspect, the invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer and an ultra-thin copper layer in this order, and the bulging produced by heating the copper foil of the carrier at 220 ° C for 4 hours is 20 Below /dm 2 .
本發明的附載體的銅箔在進而另一實施方式中，將該附載體的銅箔以220℃加熱4小時時所產生的鼓出為0~15個/dm2以下。 In still another embodiment of the copper foil with a carrier of the present invention, the bulging generated when the copper foil with a carrier is heated at 220 ° C for 4 hours is 0 to 15 / dm 2 or less.
本發明的附載體的銅箔在進而另一實施方式中，將該附載體的銅箔以400℃加熱10分鐘時所產生的鼓出為0~60個/dm2以下。 In still another embodiment of the copper foil with a carrier of the present invention, when the copper foil with a carrier is heated at 400 ° C for 10 minutes, the bulging is 0 to 60 / dm 2 or less.
本發明的附載體的銅箔在進而另一實施方式中，該中間層含有選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn、該等之合金、該等之水合物、該等之氧化物、有機物組成之群中的一種或兩種以上。 In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an alloy selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, and the like. One or more of a group of hydrates, such oxides and organic compounds.
本發明的附載體的銅箔在進而另一實施方式中，該中間層在含有Cr的情況下，含有5μg/dm2以上100μg/dm2以下的Cr，在含有Mo的情況下，含有50μg/dm2以上1000μg/dm2以下的Mo，在含有Ni的情況下，含有100μg/dm2以上40000μg/dm2以下的Ni，在含有Co的情況下，含有100μg/dm2以上40000μg/dm2以下的Co，在含有Zn的情況下，含有1μg/dm2以上120μg/dm2以下的Zn。 In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains Cr of 5 μg/dm 2 or more and 100 μg/dm 2 or less in the case of containing Cr, and 50 μg/ in the case of containing Mo. Ni dm 2 or more 1000μg / dm 2 or less Mo, in case of containing Ni containing 100μg / dm 2 or more 40000μg / dm 2 or less, in the case of containing Co, and containing 100μg / dm 2 or more 40000μg / dm 2 or less In the case where Zn is contained, Co contains 1 μg/dm 2 or more and 120 μg/dm 2 or less of Zn.
本發明的附載體的銅箔在進而另一實施方式中，該中間層以25nm以上80nm以下的厚度含有有機物。 In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an organic substance in a thickness of 25 nm or more and 80 nm or less.
本發明的附載體的銅箔在進而另一實施方式中，該有機物是由選自含氮有機化合物、含硫有機化合物及羧酸中的一種或兩種以上構成的有機物。 In still another embodiment of the copper foil with a carrier of the present invention, the organic substance is an organic material composed of one or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.
本發明的附載體的銅箔在進而另一實施方式中，在該極薄銅層表面或該載體的表面的任一面或兩面具有粗化處理層。 In still another embodiment of the copper foil with a carrier of the present invention, a roughened layer is provided on either or both surfaces of the surface of the ultra-thin copper layer or the surface of the carrier.
本發明的附載體的銅箔在進而另一實施方式中，在該粗化處理層的表面具有選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層組成之群中的一種以上的層。 In still another embodiment of the copper foil with a carrier of the present invention, the surface of the roughened layer has one selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer, and a decane coupling treatment layer. Above layer.
本發明的附載體的銅箔在進而另一實施方式中，該防銹層及該耐熱層的至少一層含有選自鎳、鈷、銅、鋅中的一種以上的元素。 In still another embodiment of the copper foil with a carrier of the present invention, at least one of the rustproof layer and the heat-resistant layer contains one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc.
本發明的附載體的銅箔在進而另一實施方式中，該防銹層及該耐熱層的至少一層由選自鎳、鈷、銅、鋅中的一種以上的元素構成。 In still another embodiment of the copper foil with a carrier of the present invention, at least one of the rustproof layer and the heat-resistant layer is composed of one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc.
本發明的附載體的銅箔在進而另一實施方式中，在該粗化處理層上具有該耐熱層。 In still another embodiment of the copper foil with a carrier of the present invention, the heat-resistant layer is provided on the roughened layer.
本發明的附載體的銅箔在進而另一實施方式中，在該粗化處理層或該耐熱層上具有該防銹層。 In still another embodiment of the copper foil with a carrier of the present invention, the rustproof layer is provided on the roughened layer or the heat-resistant layer.
本發明的附載體的銅箔在進而另一實施方式中，在該防銹層上具有該鉻酸鹽處理層。 In still another embodiment of the copper foil with a carrier of the present invention, the chromate treatment layer is provided on the rustproof layer.
本發明的附載體的銅箔在進而另一實施方式中，在該鉻酸鹽處理層上具有該矽烷偶合處理層。 In still another embodiment of the copper foil with a carrier of the present invention, the decane coupling treatment layer is provided on the chromate treatment layer.
本發明的附載體的銅箔在進而另一實施方式中，在該極薄銅層的表面具有選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層組成之群中的一種以上的層。 In still another embodiment of the copper foil with a carrier of the present invention, the surface of the ultra-thin copper layer has one selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer. Above layer.
本發明的附載體的銅箔在進而另一實施方式中，在該極薄銅層上具備樹脂層。 In still another embodiment of the copper foil with a carrier of the present invention, a resin layer is provided on the ultra-thin copper layer.
本發明的附載體的銅箔在進而另一實施方式中，在該粗化處理層上具備樹脂層。 In still another embodiment of the copper foil with a carrier of the present invention, a resin layer is provided on the roughened layer.
本發明的附載體的銅箔在進而另一實施方式中，在選自由該耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層組成之群中的一種以上的層上具備樹脂層。 In still another embodiment of the copper foil with a carrier of the present invention, a resin layer is provided on one or more layers selected from the group consisting of the heat resistant layer, the rustproof layer, the chromate treatment layer, and the decane coupling treatment layer. .
本發明的附載體的銅箔在進而另一實施方式中，該樹脂層含有介電質。 In still another embodiment of the copper foil with a carrier of the present invention, the resin layer contains a dielectric.
本發明在進而另一方面中是一種印刷配線板，使用本發明的附載體的銅箔所製造。 The present invention, in still another aspect, is a printed wiring board manufactured using the copper foil with a carrier of the present invention.
本發明在進而另一方面中是一種電子機器，使用本發明的印刷配線板所製造。 The present invention, in still another aspect, is an electronic device manufactured using the printed wiring board of the present invention.
本發明在進而另一方面中是一種積層體，使用本發明的附載體的銅箔所製造。 The present invention, in still another aspect, is a laminate which is produced using the copper foil with a carrier of the present invention.
本發明在進而另一方面中是一種積層體，含有本發明的附載體的銅箔和樹脂，該附載體的銅箔的端面的一部分或全部被該樹脂覆蓋。 The present invention, in still another aspect, is a laminate comprising the copper foil with a carrier of the present invention and a resin, and a part or all of the end faces of the copper foil of the carrier is covered with the resin.
本發明在進而另一方面中是一種積層體，將一片本發明的附載體的銅箔從該載體側或該極薄銅層側積層在另一片本發明的附載體的銅 箔的該載體側或該極薄銅層側而成。 In still another aspect, the present invention is a laminate in which a piece of copper foil with a carrier of the present invention is laminated from the side of the carrier or the side of the ultra-thin copper layer to another copper of the carrier of the present invention. The carrier side of the foil or the side of the very thin copper layer is formed.
本發明的積層體在一實施方式中，是將該一片附載體的銅箔的該載體側表面或該極薄銅層側表面和該另一片附載體的銅箔的該載體側表面或該極薄銅層側表面根據需要經由黏合劑直接積層而構成。 In one embodiment, the laminate of the present invention is the carrier side surface of the copper foil with the carrier or the side surface of the ultra-thin copper layer and the carrier side surface or the pole of the copper foil of the other carrier The side surface of the thin copper layer is formed by directly laminating via a binder as needed.
本發明的積層體在另一實施方式中，該一片附載體的銅箔的該載體側表面或該極薄銅層側表面和該另一片附載體的銅箔的該載體或該極薄銅層連接。 In another embodiment, the carrier side surface of the copper foil with a carrier or the side surface of the ultra-thin copper layer and the carrier of the copper foil of the other carrier or the ultra-thin copper layer connection.
本發明在進而另一方面中是一種印刷配線板的製造方法，使用本發明的積層體。 The present invention is, in still another aspect, a method of producing a printed wiring board using the laminated body of the present invention.
本發明在進而另一方面中是一種積層體，其端面的一部分或全部被樹脂覆蓋。 The present invention, in still another aspect, is a laminate in which part or all of the end faces are covered with a resin.
本發明在進而另一方面中是一種印刷配線板的製造方法，包括如下步驟：在本發明的積層體至少設置1次樹脂層和電路之兩層；及至少形成1次該樹脂層及電路之兩層後，從該積層體的附載體的銅箔剝離該極薄銅層。 In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: providing at least one layer of a resin layer and a circuit in the laminated body of the present invention; and forming the resin layer and the circuit at least once. After the two layers, the ultra-thin copper layer was peeled off from the copper foil with the carrier of the laminate.
本發明在進而另一方面中是一種印刷配線板的製造方法，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；及將該附載體的銅箔和絕緣基板進行積層後，經過剝離該附載體的銅箔的銅箔載體的步驟而形成覆銅積層板，然後藉由半加成法、減成法、部分加成法或改良半加成法中的任一種方法形成電路。 The present invention, in still another aspect, is a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil and the insulating substrate with the carrier; After laminating the copper foil with the carrier and the insulating substrate, the copper clad laminate is formed by peeling off the copper foil carrier of the copper foil with the carrier, and then by semi-additive method, subtractive method, partial addition method or Any of the modified semi-additive methods forms a circuit.
本發明在進而另一方面中是一種印刷配線板的製造方法，包括如下步驟：在本發明的附載體的銅箔的該極薄銅層側或該載體側表面形 成電路；以埋沒該電路的方式在該附載體的銅箔的該極薄銅層側或該載體側表面形成樹脂層；在該樹脂層上形成電路；在該樹脂層上形成電路後，剝離該載體或該極薄銅層；及剝離該載體或該極薄銅層後，藉由去除該極薄銅層或該載體而使形成在該極薄銅層側表面或該載體側表面的埋沒在該樹脂層中的電路露出。 The present invention, in still another aspect, is a method of producing a printed wiring board comprising the steps of: forming the ultra-thin copper layer side or the carrier side surface of the copper foil with a carrier of the present invention Forming a circuit; forming a resin layer on the ultra-thin copper layer side of the copper foil of the carrier or the carrier side surface by burying the circuit; forming a circuit on the resin layer; forming a circuit on the resin layer, peeling off The carrier or the ultra-thin copper layer; and after the carrier or the ultra-thin copper layer is peeled off, the surface of the ultra-thin copper layer or the side surface of the carrier is buried by removing the ultra-thin copper layer or the carrier The circuit in the resin layer is exposed.
本發明的印刷配線板的製造方法在一實施方式中，該在樹脂層上形成電路的步驟是將另外的附載體的銅箔從極薄銅層側或載體側貼合在該樹脂層上，使用貼合在該樹脂層上的附載體的銅箔而形成該電路的步驟。 In a preferred embodiment of the method for producing a printed wiring board of the present invention, the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the ultra-thin copper layer side or the carrier side. The step of forming the circuit is performed using a copper foil with a carrier attached to the resin layer.
本發明的印刷配線板的製造方法在另一實施方式中，該貼合在樹脂層上的另外的附載體的銅箔是本發明的附載體的銅箔。 In another embodiment of the method for producing a printed wiring board of the present invention, the additional copper foil with a carrier attached to the resin layer is a copper foil with a carrier of the present invention.
本發明的印刷配線板的製造方法在進而另一實施方式中，該在樹脂層上形成電路的步驟是藉由半加成法、減成法、部分加成法或改良半加成法中的任一種方法進行。 In still another embodiment of the method for producing a printed wiring board of the present invention, the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method is carried out.
本發明的印刷配線板的製造方法在進而另一實施方式中，該要在表面形成電路的附載體的銅箔在該附載體的銅箔的載體側的表面或極薄銅層側的表面具有基板。 In still another embodiment of the present invention, the copper foil with a carrier on which the circuit is formed on the surface has a surface on the carrier side of the copper foil of the carrier or a surface on the side of the ultra-thin copper layer. Substrate.
本發明在進而另一方面中是一種印刷配線板的製造方法，包括如下步驟：將本發明的附載體的銅箔的該極薄銅層側表面或該載體側表面和樹脂基板進行積層；在該附載體的銅箔的和與樹脂基板積層的一側為相反側的極薄銅層側表面或該載體側表面至少設置1次樹脂層和電路之兩層；及在至少形成1次該樹脂層及電路之兩層後，從該附載體的銅箔剝離 該載體或該極薄銅層。 The present invention, in still another aspect, is a method of manufacturing a printed wiring board, comprising the steps of: laminating the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate; The copper foil with the carrier and the ultra-thin copper layer side surface on the opposite side to the side on which the resin substrate is laminated or the carrier side surface are provided with at least one resin layer and two layers of the circuit; and the resin is formed at least once. After the two layers of the layer and the circuit are stripped from the copper foil of the carrier The carrier or the very thin copper layer.
本發明在進而另一方面中是一種印刷配線板的製造方法，包括如下步驟：將本發明的附載體的銅箔的該載體側表面和樹脂基板進行積層；在該附載體的銅箔的和與樹脂基板積層的一側為相反側的極薄銅層側表面至少設置1次樹脂層和電路之兩層；及至少形成1次該樹脂層及電路之兩層後，從該附載體的銅箔剝離該載體。 The present invention, in still another aspect, is a method of producing a printed wiring board comprising the steps of: laminating the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate; and the sum of the copper foil of the carrier The surface of the ultra-thin copper layer on the opposite side to the side on which the resin substrate is laminated is provided with at least one layer of the resin layer and the circuit; and after at least two layers of the resin layer and the circuit are formed, the copper from the carrier is provided The foil peels off the carrier.
根據本發明，可以提供一種電路形成性良好的附載體的銅箔。 According to the present invention, it is possible to provide a copper foil with a carrier having good circuit formation properties.
圖1A~C是使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例之到鍍敷電路、去除抗鍍敷劑為止的步驟中配線板剖面的示意圖。 1A to 1C are schematic views showing a cross section of a wiring board in a step of a plating circuit and a step of removing a plating resist, which are specific examples of a method for producing a printed wiring board of a copper foil with a carrier according to the present invention.
[圖1]A~C是使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例之到鍍敷電路、去除抗鍍敷劑為止的步驟中配線板剖面的示意圖。 [Fig. 1] A to C are schematic views of a cross section of a wiring board in a step of a plating circuit and a step of removing a plating resist, which are specific examples of a method for producing a printed wiring board of a copper foil with a carrier according to the present invention.
[圖2]D~F是使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例之從積層樹脂及第2層附載體的銅箔到雷射開孔為止的步驟中配線板剖面的示意圖。 [Fig. 2] D to F are wirings in the step from the laminated resin and the copper foil of the second layer carrier to the laser opening in the specific example of the method for producing the printed wiring board of the copper foil with a carrier of the present invention. Schematic diagram of the plate section.
[圖3]G~I是使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例之從形成通孔填充物(via-fill)到剝離第1層載體為止的步驟中配線板剖面的示意圖。 [Fig. 3] G to I is a wiring in a step from the formation of a via-fill to the peeling of the first layer carrier, which is a specific example of a method of manufacturing a printed wiring board using a copper foil with a carrier of the present invention. Schematic diagram of the plate section.
[圖4]J~K是使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例之從快速蝕刻到形成凸塊‧銅柱為止的步驟中配線板剖面的示意圖。 [Fig. 4] J to K are schematic views of a cross section of a wiring board in a step from rapid etching to formation of a bump and a copper pillar, in a specific example of a method of manufacturing a printed wiring board using a copper foil with a carrier of the present invention.
圖5是實施例中的電路圖案的寬度方向的橫截面的示意圖及使用該示意圖的蝕刻係數(EF)的計算方法的概略。 5 is a schematic view showing a cross section in the width direction of the circuit pattern in the embodiment and an outline of a calculation method of the etching coefficient (EF) using the schematic diagram.
本發明的附載體的銅箔依序具備載體、中間層及極薄銅層。附載體的銅箔本身的使用方法係業者眾所周知，例如可以將極薄銅層的表面貼合在紙基材酚樹脂、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/玻璃無紡布複合基材環氧樹脂及玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺膜、液晶聚合物膜、氟樹脂膜等絕緣基板並進行熱壓接後剝離載體，將黏合在絕緣基板的極薄銅層蝕刻成目標的導體圖案，最終製造印刷配線板。 The copper foil with a carrier of the present invention is provided with a carrier, an intermediate layer and an extremely thin copper layer in this order. The method of using the copper foil with the carrier itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth / Paper composite substrate epoxy resin, glass cloth/glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film, etc. After the substrate is thermocompression bonded, the carrier is peeled off, and an extremely thin copper layer adhered to the insulating substrate is etched into a target conductor pattern to finally produce a printed wiring board.
可以用於本發明的載體典型而言為金屬箔或樹脂膜，例如以銅箔、銅合金箔、鎳箔、鎳合金箔、鐵箔、鐵合金箔、不銹鋼箔、鋁箔、鋁合金箔、絕緣樹脂膜、聚醯亞胺膜、LCD膜的形態提供。 The carrier which can be used in the present invention is typically a metal foil or a resin film such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin. The form of the film, the polyimide film, and the LCD film are provided.
可以用於本發明的載體典型而言以壓延銅箔或電解銅箔的形態提供。通常，電解銅箔是使銅從硫酸銅鍍浴電解析出到鈦或不銹鋼的轉筒上而製造，壓延銅箔是反覆進行利用壓延輥的塑性加工和熱處理而製造。作為銅箔的材料，除了精銅(JIS H3100合金編號C1100)或無氧銅(JIS H3100合金編號C1020或JIS H3510合金編號C1011)等高純度銅以外，例如亦可以 使用摻Sn銅、摻Ag銅、添加了Cr、Zr或Mg等的銅合金、添加了Ni及Si等的卡遜系銅合金之類的銅合金。 The carrier which can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeatedly performing plastic working and heat treatment by a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy No. C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, A copper alloy doped with Sn copper, Ag-doped copper, Cr, Zr or Mg, or a copper alloy such as a Cason-based copper alloy such as Ni or Si is used.
另外，作為電解銅箔，可以利用以下電解液組成及製造條件製作。 Further, the electrolytic copper foil can be produced by the following electrolyte composition and production conditions.
在以下條件製造電解銅箔的情況，可以獲得銅箔表面的TD(銅箔的製造設備中和銅箔的行進方向呈直角的方向(寬度方向))之Rz小、TD的60度光澤度高的電解銅箔。 When the electrolytic copper foil is produced under the following conditions, it is possible to obtain TD (the direction in which the copper foil is produced in a direction perpendicular to the traveling direction of the copper foil (width direction)) of the copper foil is small, and the TD has a high gloss of 60 degrees. Electrolytic copper foil.
<電解液組成> <electrolyte composition>
銅：90~110g/L Copper: 90~110g/L
硫酸：90~110g/L Sulfuric acid: 90~110g/L
氯：50~100ppm Chlorine: 50~100ppm
調平劑1(雙(3-磺丙基)二硫化物)：10~30ppm Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm
調平劑2(胺化合物)：10~30ppm Leveling agent 2 (amine compound): 10~30ppm
該胺化合物可以使用以下化學式的胺化合物。 As the amine compound, an amine compound of the following chemical formula can be used.
另外，用於本發明的電解、表面處理或鍍敷等所使用的處理液的剩餘部分只要沒有特別明示，則為水。 Further, the remainder of the treatment liquid used for electrolysis, surface treatment, plating, etc. of the present invention is water unless otherwise specified.
(該化學式中，R1及R2選自由羥基烷基、醚基、芳基、芳香族取代烷基、不飽和烴基、烷基組成之群) (In the formula, R 1 and R 2 are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)
<製造條件> <Manufacturing conditions>
電流密度：70~100A/dm2 Current density: 70~100A/dm 2
電解液溫度：50~60℃ Electrolyte temperature: 50~60°C
電解液線速度：3~5m/sec Electrolyte line speed: 3~5m/sec
電解時間：0.5~10分鐘 Electrolysis time: 0.5~10 minutes
另外，本說明書中將用語“銅箔”單獨使用時，亦包括銅合金箔在內。 In addition, when the term "copper foil" is used alone in this specification, it also includes a copper alloy foil.
關於可以用於本發明的載體的厚度亦沒有特別限制，只要適當調整成在發揮作為載體的作用的方面所合適的厚度便可，例如可以設為5μm以上。但若過厚，則生產成本提高，所以通常較佳設為35μm以下。因此，載體的厚度典型而言為8~70μm，更典型而言為12~70μm，更典型而言為18~35μm。另外，從降低原料成本的觀點來說，較佳載體的厚度小。因此，載體的厚度典型而言為5μm以上35μm以下，較佳為5μm以上18μm以下，較佳為5μm以上12μm以下，較佳為5μm以上11μm以下，較佳為5μm以上10μm以下。另外，在載體厚度小的情況下，在載體通箔時容易產生皺褶。為了防止產生皺褶，有效的是例如使附載體的銅箔製造裝置的運送輥平滑，或縮短運送輥和下一運送輥的距離。另外，在作為印刷配線板的製造方法的一的埋入法(Enbedded Process)使用附載體的銅箔的情況下，載體的剛性必須為高。因此，在用於埋入法的情況下，載體的厚度較佳為18μm以上300μm以下，較佳為25μm以上150μm 以下，較佳為35μm以上100μm以下，進一步更較佳為35μm以上70μm以下。 The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a thickness suitable for the function as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost is increased, so it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically from 8 to 70 μm, more typically from 12 to 70 μm, and more typically from 18 to 35 μm. Further, from the viewpoint of reducing the raw material cost, the thickness of the preferred carrier is small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, and preferably 5 μm or more and 10 μm or less. Further, in the case where the thickness of the carrier is small, wrinkles are likely to occur when the carrier is passed through the foil. In order to prevent wrinkles from occurring, it is effective to smooth the conveying roller of the copper foil manufacturing apparatus with a carrier, for example, or to shorten the distance between the conveying roller and the next conveying roller. Further, in the case of using a copper foil with a carrier as an encapsuladed process for manufacturing a printed wiring board, the rigidity of the carrier must be high. Therefore, in the case of the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm. Hereinafter, it is preferably 35 μm or more and 100 μm or less, and more preferably 35 μm or more and 70 μm or less.
另外，亦可以在載體之與設置極薄銅層一側的表面為相反側的表面設置粗化處理層。可以使用公知的方法設置該粗化處理層，亦可以利用下述粗化處理設置。在載體之與設置極薄銅層一側的表面為相反側的表面設置粗化處理層具有如下優點：將載體從該具有粗化處理層的表面側積層到樹脂基板等支撐體時，載體和樹脂基板不易剝離。 Further, a roughened layer may be provided on the surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided. The roughening treatment layer may be provided by a known method, or may be set by the following roughening treatment. Providing a roughened layer on the surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided has an advantage that when the carrier is laminated from the surface side having the roughened layer to the support such as a resin substrate, the carrier and The resin substrate is not easily peeled off.
<中間層> <intermediate layer>
在載體的單面或雙面上設置中間層。在載體和中間層之間亦可以設置其它層。本發明所使用的中間層以如下方式構成：在附載體的銅箔積層到絕緣基板的步驟前，使極薄銅層不易從載體剝離，另一方面，在積層到絕緣基板的步驟後，使極薄銅層可從載體剝離。例如，本發明的附載體的銅箔的中間層可以含有選自由Ni以及Cr、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn、該等之合金、該等之水合物、該等之氧化物、有機物組成之群中的一種或兩種以上。另外，中間層可為多層。 An intermediate layer is provided on one or both sides of the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is configured such that the extremely thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with the carrier to the insulating substrate, and on the other hand, after the step of laminating to the insulating substrate, The very thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may contain a compound selected from the group consisting of Ni and Cr, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or more of the group of oxides and organic compounds. In addition, the intermediate layer may be a plurality of layers.
另外，中間層較佳在載體上依序積層鎳或含鎳合金的任一種的層及含鉻、鉻合金、鉻的氧化物中一種以上的層而構成。而且，鎳或含鎳合金的任一種的層及/或含鉻、鉻合金、鉻的氧化物中的一種以上的層中較佳含有鋅。此處，含鎳合金是指由鎳和選自由鈷、鐵、鉻、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素構成的合金。含鎳合金亦可為由3種以上的元素構成的合金。另外，鉻合金是指由 鉻和選自由鈷、鐵、鎳、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素構成的合金。鉻合金亦可為由3種以上的元素構成的合金。另外，含鉻、鉻合金、鉻的氧化物中的一種以上的層亦可以是鉻酸鹽處理層。此處，鉻酸鹽處理層是指經過含有鉻酸鹽或重鉻酸鹽的液體處理的層。鉻酸鹽處理層亦可以含有鈷、鐵、鎳、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦等金屬。在本發明中，將經過鉻酸酐或重鉻酸鉀水溶液處理的鉻酸鹽處理層稱為純鉻酸鹽處理層。另外，在本發明中，將經含有酸酐或重鉻酸鉀及鋅的處理液處理過的鉻酸鹽處理層稱為鋅鉻酸鹽處理層。 Further, the intermediate layer is preferably formed by sequentially laminating a layer of any one of nickel or a nickel-containing alloy and one or more layers containing an oxide of chromium, a chromium alloy or chromium. Further, it is preferable that at least one of a layer of nickel or a nickel-containing alloy and/or one or more layers containing an oxide of chromium, a chromium alloy or chromium is contained. Here, the nickel-containing alloy means an alloy composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. . The nickel-containing alloy may be an alloy composed of three or more elements. In addition, chrome alloy refers to An alloy of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The chromium alloy may be an alloy composed of three or more elements. Further, one or more layers of the chromium-containing, chromium alloy, and chromium oxide may be a chromate-treated layer. Here, the chromate treatment layer means a layer treated with a liquid containing chromate or dichromate. The chromate treatment layer may also contain metals such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. In the present invention, a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, a chromate treatment layer treated with a treatment liquid containing an acid anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.
另外，中間層較佳在載體上依序積層鎳、鎳-鋅合金、鎳-磷合金、鎳-鈷合金中的任一種層及鋅鉻酸鹽處理層、純鉻酸鹽處理層、鉻鍍層中的任一種層而構成，中間層進一步較佳在載體上依序積層鎳層或鎳-鋅合金層及鋅鉻酸鹽處理層而構成，或依序積層鎳-鋅合金層及純鉻酸鹽處理層或鋅鉻酸鹽處理層而構成。因為鎳和銅的黏合力高於鉻和銅的黏合力，所以剝離極薄銅層時，成為在極薄銅層和鉻酸鹽處理層的介面上剝離。另外，期待中間層的鎳之防止銅成分從載體擴散到極薄銅層的阻隔效果。另外，較佳在中間層形成鉻酸鹽處理層而非鉻鍍層。鉻鍍層因為在表面形成緻密的鉻氧化物層，所以在利用電鍍形成極薄銅箔時電阻上升而容易產生針孔。形成了鉻酸鹽處理層的表面因為形成不如鉻鍍層緻密的鉻氧化物層，所以不易成為利用電鍍形成極薄銅箔時的電阻，可以減少針孔。此處，藉由形成鋅鉻酸鹽處理層作為鉻酸鹽處理層，利用電鍍形成極薄銅箔時的電阻變得低於通常的鉻酸鹽處理層，可以進一步抑制針孔的產生。 In addition, the intermediate layer preferably sequentially stacks any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy and zinc chromate treatment layer, pure chromate treatment layer, chrome plating layer on the carrier. The intermediate layer is further preferably formed by sequentially laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer on the carrier, or sequentially laminating a nickel-zinc alloy layer and pure chromic acid. It is composed of a salt treatment layer or a zinc chromate treatment layer. Since the adhesion of nickel and copper is higher than the adhesion of chromium and copper, when the ultra-thin copper layer is peeled off, it peels off on the interface between the ultra-thin copper layer and the chromate-treated layer. Further, it is expected that the nickel of the intermediate layer prevents the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer. Further, it is preferred to form a chromate treatment layer instead of a chrome plating layer in the intermediate layer. Since the chrome plating layer forms a dense chromium oxide layer on the surface, when the ultra-thin copper foil is formed by electroplating, the electric resistance rises and pinholes are likely to occur. Since the surface on which the chromate-treated layer is formed is formed as a chromium oxide layer which is less dense than the chrome plating layer, it is less likely to be an electric resistance when forming an extremely thin copper foil by electroplating, and pinholes can be reduced. Here, by forming the zinc chromate-treated layer as the chromate-treated layer, the electric resistance when the ultra-thin copper foil is formed by electroplating becomes lower than that of the normal chromate-treated layer, and the occurrence of pinholes can be further suppressed.
在使用電解銅箔作為載體的情況下，從減少針孔的觀點來說，較佳在亮面設置中間層。 In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on a bright surface from the viewpoint of reducing pinholes.
中間層中的鉻酸鹽處理層薄薄地存在於極薄銅層的介面從可以獲得如下特性方面來說為較佳：在積層到絕緣基板的步驟前極薄銅層不會從載體剝離，另一方面，在積層到絕緣基板的步驟後可以從載體剝離極薄銅層。在不設置鎳層或含鎳的合金層(例如鎳-鋅合金層)而使鉻酸鹽處理層存在於載體和極薄銅層的邊界的情況下，剝離性幾乎不會提高，在沒有鉻酸鹽處理層而將鎳層或含鎳的合金層(例如鎳-鋅合金層)和極薄銅層直接積層的情況下，根據鎳層或含鎳的合金層(例如鎳-鋅合金層)中的鎳量，剝離強度過強或過弱，無法獲得適當的剝離強度。 The interface in which the chromate-treated layer in the intermediate layer is thinly present on the ultra-thin copper layer is preferable in that the ultra-thin copper layer is not peeled off from the carrier before the step of laminating to the insulating substrate, and On the one hand, the ultra-thin copper layer can be peeled off from the carrier after the step of laminating to the insulating substrate. In the case where a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is not provided and the chromate-treated layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property hardly increases, and no chromium is present. In the case where the acid layer is treated to directly deposit a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) and an extremely thin copper layer, according to a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) The amount of nickel in the peeling strength is too strong or too weak to obtain an appropriate peel strength.
另外，若鉻酸鹽處理層存在於載體和鎳層或含鎳的合金層(例如鎳-鋅合金層)的邊界，則在剝離極薄銅層時中間層亦會隨之剝離，也就是說在載體和中間層之間會產生剝離，因而欠佳。這種狀況不僅當在與載體的介面設置鉻酸鹽處理層的情況下會產生，即使與極薄銅層的介面設置鉻酸鹽處理層，若鉻量過多，則亦可能產生。認為其原因在於：由於銅和鎳容易固溶，故若該等接觸，則會因為相互擴散而使黏合力提高，不易剝離，另一方面，由於鉻和銅不易固溶，不易產生相互擴散，所以在鉻和銅的介面，黏合力弱，容易剝離。另外，在中間層的鎳量不足的情況下，因為在載體和極薄銅層之間只存在微量的鉻，所以兩者密合而不易剝離。 In addition, if the chromate treatment layer is present at the boundary between the support and the nickel layer or the nickel-containing alloy layer (for example, the nickel-zinc alloy layer), the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, Peeling occurs between the carrier and the intermediate layer, which is not preferable. This condition occurs not only when a chromate treatment layer is provided on the interface with the carrier, but even if a chromate treatment layer is provided on the interface of the ultra-thin copper layer, if the amount of chromium is too large, it may occur. The reason is considered to be that copper and nickel are easily dissolved in solid solution. Therefore, if these contacts are in contact with each other, the adhesion is increased due to mutual diffusion, and the adhesion is not easily caused. On the other hand, since chromium and copper are not easily dissolved, mutual diffusion is less likely to occur. In the interface between chrome and copper, the adhesion is weak and easy to peel off. Further, in the case where the amount of nickel in the intermediate layer is insufficient, since only a trace amount of chromium exists between the carrier and the ultra-thin copper layer, the two are tightly bonded and are not easily peeled off.
中間層的鎳層或含鎳的合金層(例如鎳-鋅合金層)例如可以利用電鍍、無電鍍敷及浸漬鍍敷之類的濕式鍍敷，或者濺鍍、CVD及PDV之類的乾式鍍敷形成。從成本的觀點來說較佳為電鍍。另外，在載體為樹 脂膜的情況下，可以利用CVD及PDV之類的乾式鍍敷或者無電鍍敷及浸漬鍍敷之類的濕式鍍敷形成中間層。 The nickel layer of the intermediate layer or the alloy layer containing nickel (for example, a nickel-zinc alloy layer) may be, for example, wet plating such as electroplating, electroless plating, or immersion plating, or dry plating such as sputtering, CVD, and PDV. Plating is formed. From the viewpoint of cost, electroplating is preferred. In addition, the carrier is a tree In the case of a lipid film, an intermediate layer can be formed by dry plating such as CVD or PDV or wet plating such as electroless plating or immersion plating.
另外，鉻酸鹽處理層例如可以利用電解鉻酸鹽或浸漬鉻酸鹽等形成，但利用電解鉻酸鹽形成由於可提高鉻濃度，使極薄銅層從載體的剝離強度變良好，所以較佳。 Further, the chromate treatment layer can be formed, for example, by electrolytic chromate or impregnated chromate. However, since the electrolytic chromate is formed, the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier can be improved. good.
另外，較佳中間層中鎳的附著量為100~40000μg/dm2，鉻的附著量為5~100μg/dm2，鋅的附著量為1~70μg/dm2。藉由如此控制鎳、鉻、鋅的附著量，本發明的附載體的銅箔可以控制從附載體的銅箔剝離極薄銅層後之極薄銅層的表面的Ni量。為了如此控制剝離後的極薄銅層表面的Ni量，較佳減少中間層的Ni附著量，並且使中間層含有抑制Ni向極薄銅層側擴散的金屬種類(Cr、Zn)。從此種觀點而言，中間層的Ni含量較佳為100~40000μg/dm2，進一步較佳為200μg/dm2以上20000μg/dm2以下，進一步較佳為500μg/dm2以上10000μg/dm2以下，進一步較佳為700μg/dm2以上5000μg/dm2以下。另外，Cr較佳含有5~100μg/dm2，進一步較佳為8μg/dm2以上50μg/dm2以下，進一步較佳為10μg/dm2以上40μg/dm2以下，進一步較佳為12μg/dm2以上30μg/dm2以下。Zn較佳含有1~70μg/dm2，進一步較佳為3μg/dm2以上30μg/dm2以下，進一步較佳為5μg/dm2以上20μg/dm2以下。若控制從附載體的銅箔剝離極薄銅層後的極薄銅層表面的Ni量(例如Ni量為5~300μg/dm2)，則有極薄銅層的蝕刻性(易溶解性或電路形狀等)提高等效果。另外，亦可以使用鈷代替該的鎳。此時鈷的附著量可以和鎳的附著量設為相同。 Further, it is preferable that the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm 2 , the adhesion amount of chromium is 5 to 100 μg/dm 2 , and the adhesion amount of zinc is 1 to 70 μg/dm 2 . By controlling the adhesion amount of nickel, chromium, and zinc in this manner, the copper foil with a carrier of the present invention can control the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil with the carrier. In order to control the amount of Ni on the surface of the ultra-thin copper layer after peeling, the amount of Ni deposited on the intermediate layer is preferably reduced, and the intermediate layer contains a metal species (Cr, Zn) that suppresses diffusion of Ni toward the ultra-thin copper layer side. From this viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm 2, more preferably 2 or less 200μg / dm 2 or more 20000μg / dm, more preferably 500μg / dm 2 or more 10000μg / dm 2 or less Further, it is more preferably 700 μg/dm 2 or more and 5000 μg/dm 2 or less. Further, Cr preferably contains 5 to 100 μg/dm 2 , more preferably 8 μg/dm 2 or more and 50 μg/dm 2 or less, further preferably 10 μg/dm 2 or more and 40 μg/dm 2 or less, and further preferably 12 μg/dm. 2 or more and 30 μg/dm 2 or less. Zn preferably contains 1 to 70 μg/dm 2 , more preferably 3 μg/dm 2 or more and 30 μg/dm 2 or less, and still more preferably 5 μg/dm 2 or more and 20 μg/dm 2 or less. If the amount of Ni on the surface of the ultra-thin copper layer after peeling off the ultra-thin copper layer from the copper foil with the carrier (for example, the amount of Ni is 5 to 300 μg/dm 2 ), the etching property of the extremely thin copper layer (solubility or Circuit shape, etc.) improve the effect. Alternatively, cobalt may be used instead of the nickel. At this time, the amount of adhesion of cobalt can be made the same as the amount of adhesion of nickel.
本發明的附載體的銅箔的中間層可在載體上依序積層鎳層及含有含氮有機化合物、含硫有機化合物及羧酸中任一種的有機物層而構成，中間層中鎳的附著量為100~40000μg/dm2。另外，本發明的附載體的銅箔的中間層亦可在載體上依序積層含有含氮有機化合物、含硫有機化合物及羧酸中任一種的有機物層及鎳層而構成，中間層中鎳的附著量為100~40000μg/dm2。如上所述，本發明的附載體的銅箔中，從附載體的銅箔剝離極薄銅層後極薄銅層表面的Ni量得到控制，為了如此控制剝離後的極薄銅層表面的Ni量，較佳減少中間層的Ni附著量，並且使中間層含有抑制Ni向極薄銅層側擴散的含有含氮有機化合物、含硫有機化合物及羧酸中任一種的有機物層。從此種觀點而言，中間層的Ni含量較佳為100~40000μg/dm2，進一步較佳為200μg/dm2以上20000μg/dm2以下，進一步較佳為300μg/dm2以上10000μg/dm2以下，進一步較佳為500μg/dm2以上5000μg/dm2以下。另外，亦可以使用鈷代替該鎳。此時鈷的附著量可以設為和鎳的附著量相同。另外，作為該含有含氮有機化合物、含硫有機化合物及羧酸中任一種的有機物，可以列舉BTA(苯併***)、MBT(巰基苯併噻唑)等。 The intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating a nickel layer and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid on the carrier, and the amount of nickel attached to the intermediate layer. It is 100~40000μg/dm 2 . Further, the intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating an organic layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on the carrier, and nickel in the intermediate layer. The adhesion amount is 100 to 40000 μg/dm 2 . As described above, in the copper foil with a carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer after peeling off the ultra-thin copper layer from the copper foil with the carrier is controlled, in order to control the Ni of the surface of the ultra-thin copper layer after peeling The amount of Ni is preferably reduced by the amount of Ni deposited in the intermediate layer, and the intermediate layer contains an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, which suppresses diffusion of Ni to the ultra-thin copper layer side. From this viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm 2, more preferably 2 or less 200μg / dm 2 or more 20000μg / dm, more preferably 300μg / dm 2 or more 10000μg / dm 2 or less , more preferably 500μg / dm 2 or more 5000μg / dm 2 or less. Alternatively, cobalt may be used instead of the nickel. At this time, the amount of cobalt attached can be set to be the same as the amount of adhesion of nickel. In addition, examples of the organic substance containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid include BTA (benzotriazole), MBT (mercaptobenzothiazole), and the like.
另外，作為中間層所含有的有機物，較佳使用由選自含氮有機化合物、含硫有機化合物及羧酸中的一種或兩種以上構成的有機物。含氮有機化合物、含硫有機化合物及羧酸中，含氮有機化合物包括具有取代基的含氮有機化合物。作為具體的含氮有機化合物，較佳使用作為具有取代基的***化合物的1,2,3-苯併***、羧基苯併***、N’,N’-雙(苯併***基甲基)脲、1H-1,2,4-***及3-氨基-1H-1,2,4-***等。 Moreover, as the organic substance contained in the intermediate layer, an organic material composed of one or two or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid is preferably used. In the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. As a specific nitrogen-containing organic compound, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzotriazolyl) which is a triazole compound having a substituent is preferably used. Methyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.
含硫有機化合物較佳使用巰基苯併噻唑、2-巰基苯併噻唑鈉、三聚硫氰酸及2-苯併咪唑硫醇等。 As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiol or the like is preferably used.
作為羧酸，特別較佳使用單羧酸，其中較佳使用油酸、亞麻油酸及次亞麻油酸等。 As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid, and the like are preferably used.
該有機物較佳以厚度計含有25nm以上80nm以下，更佳含有30nm以上70nm以下。中間層亦可以含有多種(一種以上)該有機物。 The organic substance preferably contains 25 nm or more and 80 nm or less in thickness, more preferably 30 nm or more and 70 nm or less. The intermediate layer may also contain a plurality (more than one) of the organic matter.
另外，有機物的厚度可以利用以下方式測量。 In addition, the thickness of the organic matter can be measured in the following manner.
<中間層的有機物厚度> <intermediate layer organic thickness>
將附載體的銅箔的極薄銅層從載體剝離後，對露出的極薄銅層之中間層側的表面和露出的載體之中間層側的表面進行XPS測量，製作縱深分析。並且，可以將從極薄銅層的中間層側的表面起碳濃度最先成為3at%以下的深度設為A(nm)，將從載體的中間層側的表面起碳濃度最先成為3at%以下的深度設為B(nm)，將A和B的總合設為中間層的有機物的厚度(nm)。 After the ultra-thin copper layer of the copper foil with a carrier was peeled from the carrier, the surface of the intermediate layer side of the exposed ultra-thin copper layer and the surface of the intermediate layer side of the exposed carrier were subjected to XPS measurement to prepare a depth analysis. In addition, the depth at which the carbon concentration is 3 at% or less from the surface on the intermediate layer side of the ultra-thin copper layer can be A (nm), and the carbon concentration from the surface on the intermediate layer side of the carrier is 3 at% first. The following depth is set to B (nm), and the total of A and B is set to the thickness (nm) of the organic substance of the intermediate layer.
XPS的運轉條件如下所示。 The operating conditions of the XPS are as follows.
‧裝置：XPS測量裝置(ULVAC-PHI公司，型號5600MC) ‧Device: XPS measuring device (ULVAC-PHI, model 5600MC)
‧極限真空度：3.8×10-7Pa ‧ ultimate vacuum: 3.8 × 10 -7 Pa
‧X射線：單色為AlK α或非單色為MgK α，X射線輸出為300W，檢測面積為800μm
‧離子束：離子種類為Ar+，加速電壓為3kV，掃描面積為3mm×3mm，濺鍍速率為2.8nm/min(以SiO2換算) ‧Ion beam: The ion type is Ar + , the accelerating voltage is 3kV, the scanning area is 3mm×3mm, and the sputtering rate is 2.8nm/min (calculated as SiO 2 )
關於中間層所含有的有機物的使用方法，以下，一面亦對在 載體箔上形成中間層的方法進行敘述一面進行說明。可以將該有機物溶解於溶劑中並於該溶劑中浸漬載體，或者對將要形成中間層的面使用噴淋、噴霧法、滴下法及電沉積法等而將中間層形成於載體上，並沒有特別採用限定的方法的必要性。此時溶劑中有機系劑的濃度在該有機物全部中較佳為濃度為0.01g/L~30g/L、液溫為20~60℃的範圍。有機物的濃度並沒有特別限定，濃度高或低本來並沒有問題。另外，有機物的濃度越高、此外載體和溶解該有機物的溶劑的接觸時間越長，則有中間層的有機物厚度越增大的傾向。並且，在中間層的有機物厚度厚的情況下，有抑制Ni向極薄銅層側擴散的有機物之效果增大的傾向。 Regarding the use method of the organic matter contained in the intermediate layer, the following is also true A method of forming an intermediate layer on a carrier foil will be described while describing. The organic substance may be dissolved in a solvent and the carrier may be impregnated in the solvent, or the intermediate layer may be formed on the carrier by spraying, spraying, dropping, electrodeposition or the like on the surface on which the intermediate layer is to be formed, and there is no particular The need to adopt a defined method. The concentration of the organic agent in the solvent at this time is preferably in the range of 0.01 g/L to 30 g/L and the liquid temperature in the range of 20 to 60 ° C in the entire organic matter. The concentration of the organic substance is not particularly limited, and the high or low concentration is not problematic. Further, the higher the concentration of the organic substance and the longer the contact time between the carrier and the solvent in which the organic substance is dissolved, the greater the thickness of the organic substance in the intermediate layer tends to increase. Further, when the thickness of the organic material in the intermediate layer is thick, the effect of suppressing the organic matter in which Ni diffuses toward the ultra-thin copper layer side tends to increase.
另外，中間層較佳在載體上依序積層鎳和鉬或鈷或鉬-鈷合金而構成。由於鎳和銅的黏合力高於鉬或鈷和銅的黏合力，所以在剝離極薄銅層時，可以在極薄銅層和鉬或鈷或鉬-鈷合金的介面剝離。另外，期待中間層的鎳的防止銅成分從載體向極薄銅層擴散的阻隔效果。 Further, the intermediate layer is preferably formed by sequentially laminating nickel and molybdenum or cobalt or a molybdenum-cobalt alloy on the carrier. Since the adhesion of nickel and copper is higher than that of molybdenum or cobalt and copper, when the ultra-thin copper layer is peeled off, the interface between the extremely thin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy can be peeled off. Further, it is expected that the nickel of the intermediate layer has a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer.
另外，該鎳亦可以是含鎳的合金。此處，含鎳的合金是指由鎳和選自由鈷、鐵、鉻、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素構成的合金。另外，該鉬亦可以是含鉬的合金。此處，含鉬的合金是指由鉬和選自由鈷、鐵、鉻、鎳、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素所構成的合金。另外，該鈷亦可以是含鈷的合金。此處，含鈷的合金是指由鈷和選自由鉬、鐵、鉻、鎳、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素所構成的合金。 Alternatively, the nickel may be an alloy containing nickel. Here, the nickel-containing alloy is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. alloy. Alternatively, the molybdenum may be an alloy containing molybdenum. Here, the molybdenum-containing alloy is composed of molybdenum and one or more elements selected from the group consisting of cobalt, iron, chromium, nickel, zinc, lanthanum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Alloy. Alternatively, the cobalt may be an alloy containing cobalt. Here, the cobalt-containing alloy is composed of cobalt and one or more elements selected from the group consisting of molybdenum, iron, chromium, nickel, zinc, lanthanum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Alloy.
鉬-鈷合金亦可以含有鉬、鈷以外的元素(例如選自由鈷、 鐵、鉻、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦組成之群中的一種以上的元素)。 The molybdenum-cobalt alloy may also contain elements other than molybdenum or cobalt (for example, selected from cobalt, One or more elements of the group consisting of iron, chromium, molybdenum, zinc, antimony, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium).
在使用電解銅箔作為載體的情況下，從減少針孔的觀點而言，較佳在亮面設置中間層。 In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on a bright surface from the viewpoint of reducing pinholes.
中間層中的鉬或鈷或鉬-鈷合金層薄薄地存在於極薄銅層的介面從獲得如下特性方面而言為較佳：在積層到絕緣基板的步驟前，極薄銅層不會從載體剝離，另一方面，在積層到絕緣基板的步驟後可以從載體剝離極薄銅層。在不設置鎳層而使鉬或鈷或鉬-鈷合金層存在於載體和極薄銅層的邊界的情況下，有剝離性幾乎不會提高的情況，在沒有鉬或鈷或鉬-鈷合金層而將鎳層和極薄銅層直接積層的情況下，有根據鎳層中的鎳量，剝離強度過強或過弱而無法獲得適當的剝離強度的情況。 The interface in which the molybdenum or cobalt or molybdenum-cobalt alloy layer in the intermediate layer is thinly present on the ultra-thin copper layer is preferable in terms of obtaining characteristics that the ultra-thin copper layer does not pass from the step of laminating to the insulating substrate. The carrier is peeled off, and on the other hand, the ultra-thin copper layer can be peeled off from the carrier after the step of laminating to the insulating substrate. In the case where a nickel layer is not provided and a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer, there is a case where the peeling property hardly increases, and there is no molybdenum or cobalt or molybdenum-cobalt alloy. In the case where the nickel layer and the ultra-thin copper layer are directly laminated, there is a case where the peel strength is too strong or too weak depending on the amount of nickel in the nickel layer, and an appropriate peel strength cannot be obtained.
另外，若鉬或鈷或鉬-鈷合金層存在於載體和鎳層的邊界，則有剝離極薄銅層時中間層亦隨之剝離的情況，也就是說有載體和中間層之間會產生剝離因而欠佳的情況。此種狀況不僅當在和載體的介面設置鉬或鈷或鉬-鈷合金層的情況下會產生，即使和極薄銅層的介面設置鉬或鈷或鉬-鈷合金層，若鉬量或鈷量過多，則亦可能產生。認為其原因在於：由於銅和鎳容易固溶，所以若該等接觸，則會因為相互擴散而使黏合力提高，不易剝離，另一方面，由於鉬或鈷和銅不易固溶，不易產生相互擴散，所以在鉬或鈷或鉬-鈷合金層和銅的介面上，黏合力弱，容易剝離。另外，在中間層的鎳量不足的情況下，有因為在載體和極薄銅層之間只存在微量的鉬或鈷，所以兩者密合而不易剝離的情況。 In addition, if a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the support and the nickel layer, the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, between the carrier and the intermediate layer. Peeling is therefore not good. This condition is produced not only when a layer of molybdenum or cobalt or a molybdenum-cobalt alloy layer is provided with the interface of the carrier, even if a layer of molybdenum or cobalt or a molybdenum-cobalt alloy is provided with the interface of the very thin copper layer, if the amount of molybdenum or cobalt If the amount is too much, it may also occur. The reason is considered to be that copper and nickel are easily dissolved in solid solution. Therefore, if these contacts are in contact with each other, the adhesion is increased due to mutual diffusion, and peeling is not easy. On the other hand, molybdenum or cobalt and copper are not easily dissolved, and mutual diffusion is less likely to occur. Therefore, the adhesion between the molybdenum or cobalt or molybdenum-cobalt alloy layer and the copper interface is weak and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, there is a case where only a trace amount of molybdenum or cobalt is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and are not easily peeled off.
中間層的鎳及鈷或鉬-鈷合金例如可以利用電鍍、無電鍍敷 及浸漬鍍敷之類的濕式鍍敷，或者濺鍍、CVD及PDV之類的乾式鍍敷形成。另外，鉬可以只利用CVD及PDV之類的乾式鍍敷形成。從成本的觀點而言較佳電鍍。 The intermediate layer of nickel and cobalt or molybdenum-cobalt alloy can be used, for example, by electroplating or electroless plating. And wet plating such as immersion plating, or dry plating such as sputtering, CVD, and PDV. Further, molybdenum can be formed only by dry plating such as CVD or PDV. Electroplating is preferred from the viewpoint of cost.
中間層中，較佳鎳的附著量為100~40000μg/dm2，鉬的附著量為10~1000μg/dm2，鈷的附著量為10~1000μg/dm2。如上所述，本發明的附載體的銅箔控制從附載體的銅箔剝離極薄銅層後極薄銅層的表面的Ni量，為了如此控制剝離後的極薄銅層表面的Ni量，較佳減少中間層的Ni附著量，並且使中間層含有抑制Ni向極薄銅層側擴散的金屬種類(Co、Mo)。從此種觀點而言，鎳附著量較佳設為100~40000μg/dm2，較佳設為200~20000μg/dm2，更佳設為300~15000μg/dm2，更佳設為300~10000μg/dm2。在中間層含有鉬的情況下，鉬附著量較佳設為10~1000μg/dm2，鉬附著量較佳設為20~600μg/dm2，更佳設為30~400μg/dm2。在中間層含有鈷的情況下，鈷附著量較佳設為10~1000μg/dm2，鈷附著量較佳設為20~600μg/dm2，更佳設為30~400μg/dm2。 In the intermediate layer, the adhesion amount of nickel is preferably 100 to 40000 μg/dm 2 , the adhesion amount of molybdenum is 10 to 1000 μg/dm 2 , and the adhesion amount of cobalt is 10 to 1000 μg/dm 2 . As described above, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil of the carrier, in order to control the amount of Ni on the surface of the ultra-thin copper layer after peeling, It is preferable to reduce the Ni adhesion amount of the intermediate layer, and to provide the metal layer (Co, Mo) which suppresses the diffusion of Ni to the ultra-thin copper layer side. From such a viewpoint, the nickel adhesion amount is preferably from 100 to 40,000 μg/dm 2 , preferably from 200 to 20,000 μg/dm 2 , more preferably from 300 to 15,000 μg/dm 2 , still more preferably from 300 to 10,000 μg/ Dm 2 . When the intermediate layer contains molybdenum, the molybdenum adhesion amount is preferably 10 to 1000 μg/dm 2 , and the molybdenum adhesion amount is preferably 20 to 600 μg/dm 2 , more preferably 30 to 400 μg/dm 2 . When the intermediate layer contains cobalt, the cobalt adhesion amount is preferably 10 to 1000 μg/dm 2 , and the cobalt adhesion amount is preferably 20 to 600 μg/dm 2 , more preferably 30 to 400 μg/dm 2 .
再者，如上所述，中間層在載體上依序積層鎳和鉬或鈷或鉬-鈷合金的情況下，若降低用來設置鉬或鈷或鉬-鈷合金層的鍍敷處理中的電流密度，減緩載體的運送速度，則有鉬或鈷或鉬-鈷合金層的密度提高的傾向。若含有鉬及/或鈷的層的密度提高，則鎳層的鎳不易擴散，可以控制剝離後的極薄銅層表面的Ni量。 Further, as described above, in the case where the intermediate layer is sequentially laminated with nickel and molybdenum or cobalt or a molybdenum-cobalt alloy on the carrier, if the current in the plating treatment for setting the molybdenum or cobalt or molybdenum-cobalt alloy layer is lowered The density, which slows down the transport speed of the carrier, tends to increase the density of the molybdenum or cobalt or molybdenum-cobalt alloy layer. When the density of the layer containing molybdenum and/or cobalt is increased, the nickel of the nickel layer is less likely to diffuse, and the amount of Ni on the surface of the ultra-thin copper layer after peeling can be controlled.
在只在單面設置中間層的情況下，較佳在載體的相反面設置Ni鍍層等防銹層。另外，在利用鉻酸鹽處理或鋅鉻酸鹽處理或鍍敷處理設置中間層的情況下，認為有鉻或鋅等附著的金屬的一部分變成水合物或氧 化物的情況。 In the case where the intermediate layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the opposite side of the carrier. Further, in the case where the intermediate layer is provided by chromate treatment or zinc chromate treatment or plating treatment, it is considered that a part of the metal to which the chromium or zinc is attached becomes a hydrate or oxygen. The case of the compound.
本發明的附載體的銅箔在一方面中被控制為以30℃/分鐘加熱到500℃時所產生的水份量成為160ppm/g以下。若加熱附載體的銅箔，則會有因為在載體/極薄銅層間產生的水蒸氣等氣體而產生氣泡(鼓出)的情況。若產生此種鼓出，則會產生用於形成電路的極薄銅層凹陷，對電路形成性造成不良影響的問題。與此相對，藉由採用如上所述抑制了特定熱處理後水份的產生的附載體的銅箔，可以良好地抑制鼓出的產生，極薄銅層的電路形成性變得良好。將附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量若超過160ppm/g，則載體/極薄銅層間鼓出的個數成為30個/dm2以上，難以蝕刻極薄銅層而形成比L/S=30μm/30μm更微細的配線、例如L/S=25μm/25μm的微細配線、例如L/S=20μm/20μm的微細配線、例如L/S=15μm/15μm的微細配線。 The copper foil with a carrier of the present invention is controlled in one aspect to have a water content of 160 ppm/g or less when heated at 30 ° C / min to 500 ° C. When the copper foil with a carrier is heated, there is a case where a bubble (bulging) is generated by a gas such as water vapor generated between the carrier/very thin copper layer. If such bulging occurs, there is a problem that an extremely thin copper layer recess for forming a circuit adversely affects circuit formability. On the other hand, by using the copper foil with a carrier which suppresses the generation of the moisture after the specific heat treatment as described above, the occurrence of bulging can be favorably suppressed, and the circuit formation property of the ultra-thin copper layer becomes favorable. When the amount of water generated when the copper foil with a carrier is heated to 500 ° C at 30 ° C / min exceeds 160 ppm / g, the number of bulging between the carrier / ultra-thin copper layer becomes 30 / dm 2 or more, and it is difficult to etch the pole. A thin copper layer is formed to have a finer wiring than L/S=30 μm/30 μm, for example, a fine wiring of L/S=25 μm/25 μm, for example, a fine wiring of L/S=20 μm/20 μm, for example, L/S=15 μm/15 μm. Fine wiring.
本發明的附載體的銅箔較佳控制為以30℃/分鐘加熱到500℃時所產生的水份量成為0~130ppm/g，更佳控制為0~110ppm/g，進一步更佳控制為0~90ppm/g，進一步更佳控制為0~70ppm/g。 The copper foil with carrier of the present invention is preferably controlled to have a water content of 0 to 130 ppm/g when heated at 30 ° C/min to 500 ° C, more preferably 0 to 110 ppm/g, and further preferably controlled to 0. ~90ppm/g, further better controlled to 0~70ppm/g.
本發明的附載體的銅箔在另一方面中，將附載體的銅箔控制為以220℃加熱4小時時所產生的鼓出成為20個/dm2以下。若加熱附載體的銅箔，則會有因為載體/極薄銅層間所產生的水蒸氣等氣體而產生氣泡(鼓出)的情況。若產生此種鼓出，則會產生用於形成電路的極薄銅層凹陷，對電路形成性造成不良影響的問題。與此相對，本發明的附載體的銅箔良好地抑制鼓出的產生，極薄銅層的電路形成性變良好。若將附載體的銅箔以220℃加熱4小時時所產生的鼓出超過20個/dm2，則難以蝕刻極薄 銅層而形成比L/S=30μm/30μm更微細的配線、例如L/S=25μm/25μm的微細配線、例如L/S=20μm/20μm的微細配線、例如L/S=15μm/15μm的微細配線。另外，該“以220℃加熱4小時”表示將附載體的銅箔貼合在絕緣基板並進行熱壓接的情況下的典型的加熱條件。 On the other hand, the copper foil with a carrier of the present invention controls the copper foil with a carrier to have a bulging of 20 / dm 2 or less when heated at 220 ° C for 4 hours. When the copper foil with a carrier is heated, a bubble (bulging) may be generated by a gas such as water vapor generated between the carrier/very thin copper layer. If such bulging occurs, there is a problem that an extremely thin copper layer recess for forming a circuit adversely affects circuit formability. On the other hand, the copper foil with a carrier of the present invention satisfactorily suppresses the occurrence of bulging, and the circuit formation property of the ultra-thin copper layer is improved. When the copper foil with a carrier is heated at 220 ° C for 4 hours, the bulging is more than 20 / dm 2 , it is difficult to etch an extremely thin copper layer to form a wiring finer than L / S = 30 μm / 30 μm, for example, L /S = 25 μm / 25 μm fine wiring, for example, fine wiring of L / S = 20 μm / 20 μm, for example, fine wiring of L / S = 15 μm / 15 μm. In addition, the "heating at 220 ° C for 4 hours" means a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonding is performed.
本發明的附載體的銅箔較佳控制為以220℃加熱4小時時所產生的鼓出成為0~15個/dm2以下，更佳控制為0~12個/dm2，進一步更佳控制為0~9個/dm2，進一步更佳控制為0~5個/dm2。 The copper foil with a carrier of the present invention is preferably controlled so that the bulging generated when heated at 220 ° C for 4 hours becomes 0 to 15 / dm 2 or less, more preferably 0 to 12 / dm 2 , and further better control It is 0~9/dm 2 , and further better control is 0~5/dm 2 .
另外，本發明的附載體的銅箔進一步更佳控制為在作為進一步嚴苛的加熱條件的以400℃加熱10分鐘時所產生的鼓出成為0~60個/dm2以下，更佳控制為0~50個/dm2，進一步更佳控制為0~40個/dm2，進一步更佳控制為0~30個/dm2。 Further, the copper foil with a carrier of the present invention is further preferably controlled to have a bulging of 0 to 60 pieces/dm 2 or less when heated at 400 ° C for 10 minutes as a further severe heating condition, and more preferably controlled to be 0~50/dm 2 , further better control is 0~40/dm 2 , and further better control is 0~30/dm 2 .
為了製作如上所述的加熱時的水份產生量得到控制或鼓出的個數得到控制的附載體的銅箔，重要的是如下所示的製造時的控制。 In order to produce the copper foil with a carrier whose control of the amount of moisture generation and the number of bulging is controlled as described above, it is important to control at the time of manufacture as shown below.
[用來形成中間層的鍍敷條件] [Plating conditions for forming the intermediate layer]
藉由基於以下鍍敷條件形成中間層，可以製作如上所述的加熱時的水份產生量得到控制或鼓出之個數得到控制的附載體的銅箔。 By forming the intermediate layer based on the following plating conditions, it is possible to produce a copper foil with a carrier whose amount of moisture generation during heating is controlled or the number of bulging is controlled.
(1)前處理 (1) pre-treatment
藉由進行脫脂及酸洗作為前處理，可以有效地進行後續的鍍敷處理。 By performing degreasing and pickling as a pretreatment, the subsequent plating treatment can be effectively performed.
(脫脂) (degreased)
藉由脫脂，被鍍敷面被清潔，表面潤濕性提升，所以可以有效地進行後續的酸洗。 By degreasing, the plated surface is cleaned and the surface wettability is improved, so that subsequent pickling can be performed efficiently.
‧基本處理：將載體浸漬於氫氧化鈉水溶液(1~100g/L)。 ‧Basic treatment: The carrier is immersed in an aqueous solution of sodium hydroxide (1 to 100 g/L).
‧表面活性劑：若在氫氧化鈉水溶液中添加適量表面活性劑，則表面張力降低，更有效而較佳。 ‧Surfactant: If an appropriate amount of surfactant is added to the aqueous sodium hydroxide solution, the surface tension is lowered, which is more effective and preferable.
‧電解脫脂：若並用以下任一電解，則可以更有效地進行脫脂。 ‧ Electrolytic degreasing: If any of the following electrolysis is used in combination, degreasing can be performed more efficiently.
(a)只有陰極脫脂(10A/dm2左右) (a) Only the cathode is degreased (about 10A/dm 2 )
(b)只有陽極脫脂(5A/dm2左右) (b) degreasing only the anode (5A / dm 2 about)
(c)陰極脫脂→陽極脫脂 (c) Cathodic degreasing → Anode degreasing
(d)陰極脫脂→陽極脫脂→陰極脫脂 (d) Cathode degreasing→Anode degreasing→Cathode degreasing
(酸洗) (pickling)
在該脫脂後藉由進行酸洗，在載體為銅箔的情況下，可以去除表面的氧化銅等，可以使活性的銅表面露出。因此，可以有效地進行後續的鍍鎳。 After the degreasing, pickling is carried out, and when the carrier is a copper foil, copper oxide or the like on the surface can be removed, and the active copper surface can be exposed. Therefore, subsequent nickel plating can be performed efficiently.
‧氧化劑：較佳使硫酸中含有過硫酸鹽、過氧化氫等氧化劑。藉由含有氧化劑，可以略微削減載體表面而露出活性的表面。 ‧Oxidant: It is preferred to contain oxidizing agent such as persulfate or hydrogen peroxide in sulfuric acid. By containing an oxidizing agent, the surface of the carrier can be slightly reduced to expose the active surface.
(2)鍍鎳或鍍鈷 (2) Nickel plating or cobalt plating
在前處理後，接著進行鍍鎳或鍍鈷。此時，重要的是精加工成緻密、均勻且沒有缺陷的鍍層。作為鍍鎳或鍍鈷，在以下條件進行。 After the pretreatment, nickel plating or cobalt plating is then carried out. At this point, it is important to finish into a dense, uniform and defect free coating. As nickel plating or cobalt plating, it is carried out under the following conditions.
‧鍍液 ‧ plating solution
鎳或鈷：20~200g/L Nickel or cobalt: 20~200g/L
硼酸：5~60g/L Boric acid: 5~60g/L
液溫：40~65℃ Liquid temperature: 40~65°C
pH：1.5~5.0，較佳2.0~3.0。藉由將pH設置得略低階段性地進行鍍敷處理，而產生氫氣，使陰極表面成為還原環境。因此，可以抑制氧化物、氫氧化物、水合物等產生水份的原因要素的產生。 pH: 1.5 to 5.0, preferably 2.0 to 3.0. By performing a plating treatment by setting the pH slightly lower, hydrogen gas is generated to make the surface of the cathode a reducing environment. Therefore, it is possible to suppress the generation of factors causing moisture such as oxides, hydroxides, and hydrates.
電流密度：0.5~20A/dm2，較佳2~8A/dm2。在低電流密度下進行處理由於不易導致鍍敷粗脆，成為缺陷少而緻密的鍍層，所以較佳。 Current density: 0.5~20A/dm 2 , preferably 2~8A/dm 2 . It is preferred to carry out the treatment at a low current density because it is less likely to cause plate plating to be brittle and to form a dense coating with few defects.
‧攪拌(液迴圈量) ‧ stirring (liquid circulation)
100~1000L/分鐘。液迴圈量多會使產生的氫氣的氣體釋放變良好，針孔等缺陷變少。另外，有減小擴散層厚度的效果，可以抑制氫氧化物等產生水份的原因要素的產生。 100~1000L/min. The amount of liquid circulation is large, and the gas release of hydrogen gas is made good, and defects such as pinholes are reduced. Further, there is an effect of reducing the thickness of the diffusion layer, and it is possible to suppress the generation of a factor causing moisture such as a hydroxide.
‧運送速度 ‧Transport speed
2~30m/分鐘，較佳5~10m/分鐘。運送速度慢會形成平滑且緻密的Ni層。 2~30m/min, preferably 5~10m/min. Slow transport results in a smooth and dense Ni layer.
‧添加劑 ‧additive
添加劑較佳使用以下一次光澤劑及二次光澤劑。藉此，晶體變得平滑且緻密。因此，鍍敷所產生的缺陷減少，水份的吸收減少。 The additive is preferably the following primary glossing agent and secondary glossing agent. Thereby, the crystal becomes smooth and dense. Therefore, the defects generated by the plating are reduced, and the absorption of moisture is reduced.
(一次光澤劑) (primary gloss agent)
其為1,5-萘二磺酸鈉：2~10g/L、1,3,6-萘三磺酸鈉：10~30g/L、對甲苯磺醯胺：0.5~4g/L、糖精鈉：0.5~5g/L中的任一種。 It is sodium 1,5-naphthalene disulfonate: 2~10g/L, sodium 1,3,6-naphthalene trisulfonate: 10~30g/L, p-toluenesulfonamide: 0.5~4g/L, sodium saccharin : Any of 0.5 to 5 g/L.
(二次光澤劑) (secondary gloss agent)
其為福馬林：0.5~5g/L、明膠：0.005~0.5g/L、硫脲：0.05~1.0g/L、炔丙醇：0.01~0.3g/L、1,4-丁炔二醇：0.05~0.5g/L、氰乙醇：0.05~0.5g/L中的任一種。 It is fumarin: 0.5~5g/L, gelatin: 0.005~0.5g/L, thiourea: 0.05~1.0g/L, propargyl alcohol: 0.01~0.3g/L, 1,4-butynediol: Any one of 0.05 to 0.5 g/L and cyanoethanol: 0.05 to 0.5 g/L.
在進行鍍鎳等金屬鍍敷後，接著在以下條件下進行(3)鉻酸鹽處理，或在以下條件下進行(4)利用有機物的處理。 After metal plating such as nickel plating, the (3) chromate treatment is carried out under the following conditions, or (4) treatment with an organic substance is carried out under the following conditions.
(3)鉻酸鹽處理 (3) chromate treatment
‧處理液 ‧Processing fluid
鉻：0.5~6.0g/L Chromium: 0.5~6.0g/L
鋅：0.1~2.0g/L Zinc: 0.1~2.0g/L
pH：2.5~5.0 pH: 2.5~5.0
液溫：25~60℃ Liquid temperature: 25~60°C
電流密度：0.1~4A/dm2 Current density: 0.1~4A/dm 2
另外，鉻酸鹽處理的處理液中亦可以含有其它元素。 Further, the chromate-treated treatment liquid may contain other elements.
(4)利用有機物的處理 (4) Treatment with organic matter
‧處理液 ‧Processing fluid
有機物：0.1~20g/L Organic matter: 0.1~20g/L
pH：2~5 pH: 2~5
液溫：20~40℃ Liquid temperature: 20~40°C
浸漬時間：5~30秒 Immersion time: 5~30 seconds
有機物較佳為該有機物、例如含有含氮有機化合物、含硫有機化合物及羧酸中的任一種的有機物。 The organic substance is preferably an organic substance such as an organic substance containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.
[形成中間層後到形成極薄銅層為止所進行的處理] [Processing after forming an intermediate layer until an extremely thin copper layer is formed]
在形成中間層後到形成極薄銅層為止，較佳進一步進行以下加熱處理及/或還原處理。藉由進行此種處理，可以製作如上所述加熱時的水份產 生量得到控制的附載體的銅箔。 It is preferable to further perform the following heat treatment and/or reduction treatment until the formation of the ultra-thin copper layer after the formation of the intermediate layer. By performing such a treatment, it is possible to produce a water product when heated as described above. The controlled amount of copper foil with the carrier is controlled.
(5)加熱處理 (5) Heat treatment
在鉻酸鹽處理或利用有機物的處理後，藉由在鍍銅前於以下條件下進行加熱處理而去除水份。 After the chromate treatment or the treatment with the organic matter, the water is removed by heat treatment under the following conditions before copper plating.
‧例如，利用線上處理以100~200℃、較佳180℃左右加熱1分鐘。並且，若還併用使用IR加熱器的加熱，則更為有效。另外，若一面通入氫氣一面加熱，則還具有還原效果，進一步有效。 ‧ For example, it is heated by an on-line treatment at 100 to 200 ° C, preferably at about 180 ° C for 1 minute. Further, it is more effective if the heating using the IR heater is also used in combination. Further, when heated while passing hydrogen gas, it has a reducing effect and is further effective.
(6)還原處理 (6) Reduction processing
藉由在以下條件下使用還原劑進行後處理，可以減少O(氧)。 O (oxygen) can be reduced by post-treatment using a reducing agent under the following conditions.
‧例如，使用作為還原劑的甲酸(0.1~100g/L)進行浸漬處理。 ‧ For example, immersion treatment is carried out using formic acid (0.1 to 100 g/L) as a reducing agent.
<極薄銅層> <very thin copper layer>
在中間層上設置極薄銅層。亦可以在中間層和極薄銅層之間設置其它層。極薄銅層可以藉由利用硫酸銅、焦磷酸銅、氨基磺酸銅、氰化銅等電解浴的電鍍而形成，從可以利用高電流密度形成銅層的觀點而言，較佳為硫酸銅浴。極薄銅層的厚度並沒有特別限制，通常比載體薄，例如為12μm以下。典型而言為0.5~12μm，更典型而言為1~5μm，進一步更典型而言為1.5~5μm，進一步更典型而言為2~5μm。另外，極薄銅層亦可以設置在載體的雙面。 An extremely thin copper layer is provided on the intermediate layer. It is also possible to provide other layers between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate or copper cyanide. From the viewpoint of forming a copper layer with a high current density, copper sulfate is preferred. bath. The thickness of the ultra-thin copper layer is not particularly limited and is usually thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 1 to 5 μm, further more typically from 1.5 to 5 μm, further more typically from 2 to 5 μm. Alternatively, an extremely thin copper layer may be provided on both sides of the carrier.
可以使用本發明的附載體的銅箔來製作積層體(覆銅箔積層體等)。作為該積層體，例如可以是依序積層“極薄銅層/中間層/載體/樹脂或預浸體”的構成，亦可以是依序積層“載體/中間層/極薄銅層/ 樹脂或預浸體”的構成，亦可以是依序積層“極薄銅層/中間層/載體/樹脂或預浸體/載體/中間層/極薄銅層”的構成，亦可以是依序積層“載體/中間層/極薄銅層/樹脂或預浸體/極薄銅層/中間層/載體”的構成。該樹脂或預浸體只要是下述樹脂層便可，亦可以含有下述樹脂層所使用的樹脂、樹脂硬化劑、化合物、硬化促進劑、介電質、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等。另外，附載體的銅箔亦可以在俯視時小於樹脂或預浸體。 A laminate (copper-clad laminate or the like) can be produced using the copper foil with a carrier of the present invention. As the laminated body, for example, a structure of "extremely thin copper layer/intermediate layer/carrier/resin or prepreg" may be sequentially laminated, or a carrier/intermediate layer/very thin copper layer/layer may be sequentially laminated. The composition of the resin or the prepreg may also be a sequential construction of a "very thin copper layer / intermediate layer / carrier / resin or prepreg / carrier / intermediate layer / very thin copper layer", or may be sequential The structure of the carrier/intermediate layer/very thin copper layer/resin or prepreg/very thin copper layer/intermediate layer/carrier. The resin or prepreg may be the following resin layer, and may also contain The resin used in the resin layer, the resin curing agent, the compound, the curing accelerator, the dielectric, the reaction catalyst, the crosslinking agent, the polymer, the prepreg, the skeleton material, etc. Further, the copper foil with the carrier may also be Less than resin or prepreg in plan view.
<粗化處理及其它表面處理> <Coarsening and other surface treatment>
可以藉由在極薄銅層的表面或載體的表面的任一面或兩面例如為了使和絕緣基板的密合性良好等而實施粗化處理，從而設置粗化處理層。粗化處理例如可以藉由利用銅或銅合金形成粗化粒子而進行。粗化處理亦可以微細。粗化處理層可以是由選自由銅、鎳、鈷、磷、鎢、砷、鉬、鉻及鋅所組成之群中的任一單質或含有任一種以上的合金構成的層等。另外，在利用銅或銅合金形成粗化粒子後，還可以進一步利用鎳、鈷、銅、鋅的單質或合金等進行設置二次粒子或三次粒子的粗化處理。然後，可以利用鎳、鈷、銅、鋅的單質或合金等形成耐熱層及/或防銹層，亦可進一步在其表面實施鉻酸鹽處理、矽烷偶合處理等處理。或者亦可以不進行粗化處理而利用鎳、鈷、銅、鋅的單質或合金等形成耐熱層及/或防銹層，進一步在其表面實施鉻酸鹽處理、矽烷偶合處理等處理。也就是說，可以在粗化處理層的表面形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中的一種以上的層，亦可以在極薄銅層的表面形成選自由耐熱 層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中的一種以上的層。另外，該耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層分別可以形成多層(例如2層以上、3層以上等)。 The roughening treatment layer can be provided by performing roughening treatment on either or both surfaces of the surface of the ultra-thin copper layer or the surface of the carrier, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening process can also be fine. The roughening treatment layer may be any element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or a layer containing any one or more alloys. Further, after the roughened particles are formed of copper or a copper alloy, the secondary particles or the tertiary particles may be further subjected to a roughening treatment using a simple substance such as nickel, cobalt, copper or zinc or an alloy. Then, a heat-resistant layer and/or a rust-preventing layer may be formed using a simple substance such as nickel, cobalt, copper or zinc, or an alloy, or a surface such as a chromate treatment or a decane coupling treatment may be further applied to the surface. Alternatively, the heat-resistant layer and/or the rust-preventing layer may be formed of a single substance or an alloy of nickel, cobalt, copper or zinc without performing the roughening treatment, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be in a very thin copper layer. Surface formation selected from heat resistant One or more layers of the group consisting of a layer, a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer. Further, each of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may be formed in multiple layers (for example, two or more layers, three or more layers, or the like).
此處，鉻酸鹽處理層是指利用含有鉻酸酐、鉻酸、重鉻酸、鉻酸鹽或重鉻酸鹽的液體進行過處理的層。鉻酸鹽處理層亦可以含有鈷、鐵、鎳、鉬、鋅、鉭、銅、鋁、磷、鎢、錫、砷及鈦等元素(可以是金屬、合金、氧化物、氮化物、硫化物等任意形態)。作為鉻酸鹽處理層的具體例，可以列舉利用鉻酸酐或重鉻酸鉀水溶液進行過處理的鉻酸鹽處理層、利用包含鉻酸酐或重鉻酸鉀及鋅的處理液進行過處理的鉻酸鹽處理層等。 Here, the chromate treatment layer means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium (may be metals, alloys, oxides, nitrides, sulfides). Any form). Specific examples of the chromate-treated layer include a chromate-treated layer treated with a chromic acid anhydride or a potassium dichromate aqueous solution, and a chromium treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Acid salt treatment layer, etc.
作為耐熱層、防銹層，可以使用公知的耐熱層、防銹層。例如，耐熱層及/或防銹層可以是含有選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的群中的一種以上的元素的層，亦可以是由選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的群中的一種以上的元素構成的金屬層或合金層。另外，耐熱層及/或防銹層亦可以含有包括選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的群中的一種以上的元素的氧化物、氮化物、矽化物。另外，耐熱層及/或防銹層亦可以是包含鎳-鋅合金的層。另外，耐熱層及/或防銹層亦可以是鎳-鋅合金層。該鎳-鋅合金層除了不可避免的雜質以外，可以含有鎳50wt%~99wt%、鋅50wt%~1wt%。該鎳-鋅合金層的鋅及鎳的總計附著量可以是5~1000mg/m2，較佳為10~500mg/m2，較佳為20~100mg/m2。另外，該含有鎳-鋅合金的層或該鎳-鋅合金層的鎳的附著量和鋅 的附著量的比(=鎳的附著量/鋅的附著量)較佳為1.5~10。另外，該含有鎳-鋅合金的層或該鎳-鋅合金層的鎳的附著量較佳為0.5mg/m2~500mg/m2，更佳為1mg/m2~50mg/m2。在耐熱層及/或防銹層為含有鎳-鋅合金的層的情況下，銅箔和樹脂基板的密合性提升。 As the heat-resistant layer and the rust-preventive layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of more than one element in the group of cerium, which may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum. A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and lanthanum. In addition, the heat-resistant layer and/or the rust-proof layer may also include a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements in the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat resistant layer and/or the rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m 2 , preferably 10 to 500 mg/m 2 , preferably 20 to 100 mg/m 2 . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer and the amount of adhesion of zinc (=the amount of adhesion of nickel/the amount of adhesion of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 0.5 mg/m 2 to 500 mg/m 2 , more preferably 1 mg/m 2 to 50 mg/m 2 . When the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, the adhesion between the copper foil and the resin substrate is improved.
例如，耐熱層及/或防銹層可以是附著量為1mg/m2~100mg/m2、較佳為5mg/m2~50mg/m2的鎳或鎳合金層和附著量為1mg/m2~80mg/m2、較佳為5mg/m2~40mg/m2的錫層依序積層而成，該鎳合金層可以由鎳-鉬、鎳-鋅、鎳-鉬-鈷中的任一種構成。另外，耐熱層及/或防銹層較佳為鎳或鎳合金和錫的總計附著量為2mg/m2~150mg/m2，更佳10mg/m2~70mg/m2。另外，耐熱層及/或防銹層較佳[鎳或鎳合金中的鎳附著量]/[錫附著量]=0.25~10，更佳為0.33~3。若使用該耐熱層及/或防銹層，則將附載體的銅箔加工成印刷配線板後，電路的剝離強度、該剝離強度的耐化學品性劣化率等變良好。 For example, the heat-resistant layer and/or the rust-preventive layer may be a nickel or nickel alloy layer having an adhesion amount of 1 mg/m 2 to 100 mg/m 2 , preferably 5 mg/m 2 to 50 mg/m 2 , and an adhesion amount of 1 mg/m. The tin layer of 2 to 80 mg/m 2 , preferably 5 mg/m 2 to 40 mg/m 2 , is sequentially laminated, and the nickel alloy layer may be any of nickel-molybdenum, nickel-zinc, and nickel-molybdenum-cobalt. A composition. Further, the heat-resistant layer and/or the rust-preventive layer preferably has a total adhesion amount of nickel or a nickel alloy and tin of 2 mg/m 2 to 150 mg/m 2 , more preferably 10 mg/m 2 to 70 mg/m 2 . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the copper foil with a carrier is processed into a printed wiring board, and the peeling strength of the circuit, the chemical-resistant deterioration rate of the peeling strength, and the like are improved.
再者，用於設置矽烷偶合處理層的矽烷偶合劑可以使用公知的矽烷偶合劑，例如可以使用氨基系矽烷偶合劑或環氧系矽烷偶合劑、巰基系矽烷偶合劑。另外，矽烷偶合劑可以使用乙烯基三甲氧基矽烷、乙烯基苯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、4-縮水甘油基丁基三甲氧基矽烷、γ-氨基丙基三乙氧基矽烷、N-β(氨基乙基)γ-氨基丙基三甲氧基矽烷、N-3-(4-(3-氨基丙氧基)丁氧基)丙基-3-氨基丙基三甲氧基矽烷、咪唑矽烷、三嗪矽烷、γ-巰基丙基三甲氧基矽烷等。 Further, a known decane coupling agent may be used as the decane coupling agent for providing the decane coupling treatment layer. For example, an amino decane coupling agent, an epoxy decane coupling agent or a fluorenyl decane coupling agent may be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxy propyl trimethoxy decane may be used. , 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-(4-( 3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, triazine decane, γ-mercaptopropyltrimethoxydecane, and the like.
該矽烷偶合處理層可以使用環氧系矽烷、氨基系矽烷、甲基 丙烯醯氧基系矽烷、巰基系矽烷等矽烷偶合劑等形成。另外，此種矽烷偶合劑亦可以混合兩種以上使用。其中，較佳使用氨基系矽烷偶合劑或環氧系矽烷偶合劑形成。 The decane coupling treatment layer may be an epoxy decane, an amino decane or a methyl group. It is formed by a decane coupling agent, such as a propylene methoxy oxane and a decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, an amino decane coupling agent or an epoxy decane coupling agent is preferably used.
此處所說的氨基系矽烷偶合劑可以選自由N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷、3-(N-苯乙烯基甲基-2-氨基乙基氨基)丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、雙(2-羥基乙基)-3-氨基丙基三乙氧基矽烷、氨基丙基三甲氧基矽烷、N-甲基氨基丙基三甲氧基矽烷、N-苯基氨基丙基三甲氧基矽烷、N-(3-丙烯醯氧基-2-羥基丙基)-3-氨基丙基三乙氧基矽烷、4-氨基丁基三乙氧基矽烷、(氨基乙基氨基甲基)苯乙基三甲氧基矽烷、N-(2-氨基乙基-3-氨基丙基)三甲氧基矽烷、N-(2-氨基乙基-3-氨基丙基)三(2-乙基己氧基)矽烷、6-(氨基己基氨基丙基)三甲氧基矽烷、氨基苯基三甲氧基矽烷、3-(1-氨基丙氧基)-3,3-二甲基-1-丙烯基三甲氧基矽烷、3-氨基丙基三(甲氧基乙氧基乙氧基)矽烷、3-氨基丙基三乙氧基矽烷、3-氨基丙基三甲氧基矽烷、ω-氨基十一烷基三甲氧基矽烷、3-(2-N-己基氨基乙基氨基丙基)三甲氧基矽烷、雙(2-羥基乙基)-3-氨基丙基三乙氧基矽烷、(N,N-二乙基-3-氨基丙基)三甲氧基矽烷、(N,N-二甲基-3-氨基丙基)三甲氧基矽烷、N-甲基氨基丙基三甲氧基矽烷、N-苯基氨基丙基三甲氧基矽烷、3-(N-苯乙烯基甲基-2-氨基乙基氨基)丙基三甲氧基矽烷、γ-氨基丙基三乙氧基矽烷、N-β(氨基乙基)γ-氨基丙基三甲氧基矽烷、N-3-(4-(3-氨基丙氧基)丁氧基)丙基-3-氨基丙基三甲氧基矽烷所組成之群。 The amino decane coupling agent referred to herein may be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino). Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyltrimethoxydecane, N-methyl Aminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, 4- Aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl-3-aminopropyl)trimethoxynonane, N-(2- Aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl)trimethoxynonane, aminophenyltrimethoxydecane, 3-(1-amino Propoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyltris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxy Decane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N-hexylamine Ethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-aminopropyl)trimethoxydecane (N,N-Dimethyl-3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N- Styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N a group consisting of -3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane.
矽烷偶合處理層理想的是以矽原子換算在0.05mg/m2~ 200mg/m2、較佳為0.15mg/m2~20mg/m2、較佳為0.3mg/m2~2.0mg/m2的範圍內設置。在該範圍內的情況下，可以進一步提高基材和表面處理銅箔的密合性。 The decane coupling treatment layer is preferably 0.05 mg/m 2 to 200 mg/m 2 , preferably 0.15 mg/m 2 to 20 mg/m 2 , preferably 0.3 mg/m 2 to 2.0 mg/m in terms of germanium atom. Set within the range of 2 . In the case of this range, the adhesion between the substrate and the surface-treated copper foil can be further improved.
另外，對極薄銅層、粗化處理層、耐熱層、防銹層、矽烷偶合處理層或鉻酸鹽處理層的表面可以進行國際公開編號WO2008/053878、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、國際公開編號WO2006/134868、日本專利第5046927號、國際公開編號WO2007/105635、日本專利第5180815號、日本特開2013-19056號所記載的表面處理。 Further, the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the decane coupling treatment layer or the chromate-treated layer may be subjected to international publication number WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japan Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, Japanese Patent Publication No. 2013-19056 The surface treatment described in the number.
另外，本發明的附載體的銅箔亦可以在該極薄銅層上、或者該粗化處理層上、或者該耐熱層、防銹層、或者鉻酸鹽處理層、或者矽烷偶合處理層上具備樹脂層。該樹脂層亦可以是絕緣樹脂層。 In addition, the copper foil with a carrier of the present invention may also be on the ultra-thin copper layer, or on the roughened layer, or on the heat-resistant layer, the rust-proof layer, or the chromate-treated layer, or the decane coupling treatment layer. It has a resin layer. The resin layer may also be an insulating resin layer.
該樹脂層可以是黏合劑，亦可以是黏合用的半硬化狀態(B階段狀態)的絕緣樹脂層。半硬化狀態(B階段狀態)包括如下狀態：即使用手指觸摸絕緣樹脂層表面亦沒有黏附感，可以將該絕緣樹脂層重疊保管，若進一步受到加熱處理，則會產生硬化反應。 The resin layer may be a binder or an insulating resin layer in a semi-hardened state (B-stage state) for bonding. The semi-hardened state (B-stage state) includes a state in which the surface of the insulating resin layer is touched with a finger and has no adhesive feeling, and the insulating resin layer can be stacked and stored, and if further heated, a hardening reaction occurs.
另外，該樹脂層可以含有熱硬化性樹脂，亦可以是熱塑性樹脂。另外，該樹脂層亦可以含有熱塑性樹脂。其種類並沒有特別限定，作為適宜的樹脂，例如可以列舉：含有環氧樹脂、聚醯亞胺樹脂、多官能性氰酸酯化合物、馬來醯亞胺化合物、聚乙烯醇縮乙醛樹脂、聚氨酯樹脂、聚醚碸、聚醚碸樹脂、芳香族聚醯胺樹脂、聚醯胺醯亞胺樹脂、橡膠變成環氧樹脂、苯氧基樹脂、羧基改質丙烯腈-丁二烯樹脂、聚苯醚、雙馬來 醯亞胺三嗪樹脂、熱硬化性聚苯醚樹脂、氰酸酯系樹脂、多元羧酸的酐等的樹脂。 Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type of the resin is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polyvinyl acetal resin. Polyurethane resin, polyether oxime, polyether oxime resin, aromatic polyamide resin, polyamidoximine resin, rubber into epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, poly Phenyl ether, double horse A resin such as a quinone imine triazine resin, a thermosetting polyphenylene ether resin, a cyanate resin, or an anhydride of a polyvalent carboxylic acid.
該樹脂層亦可以包含公知的樹脂、樹脂硬化劑、化合物、硬化促進劑、介電質(可以使用包含無機化合物及/或有機化合物的介電質、包含金屬氧化物的介電質等任意介電質)、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等。另外，該樹脂層亦可以使用例如國際公開編號WO2008/004399號、國際公開編號WO2008/053878、國際公開編號WO2009/084533、日本特開平11-5828號、日本特開平11-140281號、日本專利第3184485號、國際公開編號WO97/02728、日本專利第3676375號、日本特開2000-43188號、日本專利第3612594號、日本特開2002-179772號、日本特開2002-359444號、日本特開2003-304068號、日本專利第3992225、日本特開2003-249739號、日本專利第4136509號、日本特開2004-82687號、日本專利第4025177號、日本特開2004-349654號、日本專利第4286060號、日本特開2005-262506號、日本專利第4570070號、日本特開2005-53218號、日本專利第3949676號、日本專利第4178415號、國際公開編號WO2004/005588、日本特開2006-257153號、日本特開2007-326923號、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、日本特開2009-67029號、國際公開編號WO2006/134868、日本專利第5046927號、日本特開2009-173017號、國際公開編號WO2007/105635、日本專利第5180815號、國際公開編號WO2008/114858、國際公開編號WO2009/008471、日本特開2011-14727號、國際公開編號WO2009/001850、國際公開編號WO2009/145179、國 際公開編號WO2011/068157、日本特開2013-19056號所記載的物質(樹脂、樹脂硬化劑、化合物、硬化促進劑、介電質、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等)及/或樹脂層的形成方法、形成裝置來形成。 The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (a dielectric containing an inorganic compound and/or an organic compound, or a dielectric containing a metal oxide may be used. Electrolyte), reaction catalyst, crosslinking agent, polymer, prepreg, framework material, and the like. In addition, as the resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei. No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003 -304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060 Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, and Japanese Special Publication 2009-6 No. 7029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471 , Japan Special Open 2011-14727, International Public Publication No. WO2009/001850, International Public Publication No. WO2009/145179, The materials described in JP 2011/068157 and JP-A-2013-19056 (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton) The material or the like and/or the method of forming the resin layer and the forming device are formed.
將這些樹脂例如溶解於甲基乙基酮(MEK)、甲苯等溶劑而製成樹脂液，將其例如利用輥塗法等塗布在該極薄銅層上、或者該耐熱層、防銹層、或者該鉻酸鹽皮膜層、或者該矽烷偶合劑層上，接著根據需要加熱乾燥而去除溶劑，製成B階段狀態。乾燥只要使用例如熱風乾燥爐便可，乾燥溫度為100~250℃、較佳130~200℃便可。 The resin is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin liquid, and is applied to the ultra-thin copper layer, for example, by a roll coating method, or the heat-resistant layer, the rust-proof layer, or the like. Alternatively, the chromate coating layer or the decane coupling agent layer may be heated and dried as needed to remove the solvent to form a B-stage state. Drying can be carried out, for example, by using a hot air drying oven, and the drying temperature is 100 to 250 ° C, preferably 130 to 200 ° C.
具備該樹脂層的附載體的銅箔(附樹脂的附載體的銅箔)是以如下形態使用：將該樹脂層和基材重疊後，將整體進行熱壓接而使該樹脂層熱硬化，接著將載體剝離而露出極薄銅層(當然，露出的是該極薄銅層的中間層側的表面)，並在極薄銅層形成特定的配線圖案。 The copper foil with a carrier (the resin-attached copper foil with a resin layer) which has this resin layer is used after superposing this resin layer and a base material, and thermo-com Next, the carrier is peeled off to expose an extremely thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed on the ultra-thin copper layer.
若使用該附樹脂的附載體的銅箔，則可以減少製造多層印刷配線基板時的預浸體材料的使用片數。而且，可以將樹脂層的厚度設為能夠確保層間絕緣的厚度，或者即便完全不使用預浸體材料亦可以製造覆銅積層板。另外，此時在基材的表面亦可以底塗絕緣樹脂來進一步改善表面的平滑性。 When the copper foil with a carrier attached to the resin is used, the number of sheets of the prepreg material used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be set to a thickness that can ensure interlayer insulation, or a copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, an insulating resin may be undercoated on the surface of the substrate to further improve the smoothness of the surface.
另外，在不使用預浸體材料的情況下，有如下優點：節約預浸體材料的材料成本，而且積層步驟亦變簡略，所以經濟上有利，此外，以預浸體材料的厚度製造的多層印刷配線基板的厚度變薄，可以製造1層的厚度為100μm以下之極薄的多層印刷配線基板。 Further, in the case where the prepreg material is not used, there is an advantage in that the material cost of the prepreg material is saved, and the lamination step is also simplified, so that it is economically advantageous, and further, the multilayer is manufactured in the thickness of the prepreg material. The thickness of the printed wiring board is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.
該樹脂層的厚度較佳為0.1~80μm。若樹脂層的厚度薄於0.1μm，則有如下情況：黏合力降低，在不介隔預浸體材料而將該附樹脂的附載體的銅箔積層在具備內層材料的基材時，難以確保和內層材料的電路間的層間絕緣。 The thickness of the resin layer is preferably from 0.1 to 80 μm. When the thickness of the resin layer is thinner than 0.1 μm, the adhesive strength is lowered, and it is difficult to laminate the copper foil with the carrier attached to the resin without interposing the prepreg material on the substrate having the inner layer material. Ensure interlayer insulation between the circuits of the inner material.
另一方面，若將樹脂層的厚度設為厚於80μm，則難以利用1次塗布步驟形成目標厚度的樹脂層，會花費多餘的材料費和工時，所以經濟上不利。並且，有如下情況：形成的樹脂層的可撓性差，所以操作時容易產生龜裂等，而且和內層材料熱壓接時會產生過多的樹脂流動，難以順利地積層。 On the other hand, when the thickness of the resin layer is made thicker than 80 μm, it is difficult to form a resin layer having a target thickness by one application step, which requires extra material cost and man-hours, and is therefore economically disadvantageous. Further, there is a case where the resin layer formed is inferior in flexibility, so that cracks or the like are likely to occur during handling, and excessive resin flow occurs when the inner layer material is thermocompression bonded, and it is difficult to laminate smoothly.
並且，作為該附樹脂的附載體的銅箔的另一產品形態，亦可以在該極薄銅層上、或者該耐熱層、防銹層、或者該鉻酸鹽處理層、或者該矽烷偶合處理層上利用樹脂層進行被覆，並製成半硬化狀態後，接著剝離載體，以不存在載體的附樹脂的銅箔的形態製造。 Further, another product form of the copper foil as the carrier with the resin may be applied to the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromate-treated layer, or the decane coupling treatment. The layer was coated with a resin layer and formed into a semi-hardened state, and then the carrier was peeled off, and it was produced in the form of a resin-attached copper foil in which no carrier was present.
以下，列舉一些使用本發明的附載體的銅箔的印刷配線板的製造步驟的例子。 Hereinafter, an example of a manufacturing procedure of a printed wiring board using the copper foil with a carrier of the present invention will be described.
在本發明的印刷配線板的製造方法的一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；及將該附載體的銅箔和絕緣基板以極薄銅層側和絕緣基板相對向的方式積層後，經過剝離該附載體的銅箔的載體的步驟而形成覆銅積層板，然後藉由半加成法、改良半加成法、部分加成法及減成法中的任一種方法形成電路。絕緣基板亦可以設為設置了內層電路的絕緣基板。 In an embodiment of the method of manufacturing a printed wiring board of the present invention, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil and the insulating substrate with the carrier; The copper foil of the carrier and the insulating substrate are laminated such that the ultra-thin copper layer side and the insulating substrate face each other, and then the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then by a semi-additive method, The circuit is formed by any one of a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate may be an insulating substrate provided with an inner layer circuit.
在本發明中，半加成法是指在絕緣基板或銅箔籽晶層上進行 薄的無電鍍敷，形成圖案後，使用電鍍及蝕刻形成導體圖案的方法。 In the present invention, the semi-additive method refers to performing on an insulating substrate or a copper foil seed layer. A thin electroless plating method, after forming a pattern, a method of forming a conductor pattern by electroplating and etching.
因此，在使用半加成法的本發明的印刷配線板的製造方法的一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；將剝離該載體所露出的極薄銅層利用使用酸等腐蝕溶液的蝕刻或等離子等方法全部去除；在藉由利用蝕刻去除該極薄銅層而露出的該樹脂設置通孔或/及盲孔；對含有該通孔或/及盲孔的區域進行除膠渣處理；在含有該樹脂及該通孔或/及盲孔的區域設置無電鍍層；在該無電鍍層上設置抗鍍敷劑；對該抗鍍敷劑進行曝光，然後去除供電路形成的區域的抗鍍敷劑；在去除了該抗鍍敷劑的該供電路形成的區域設置電解鍍層；去除該抗鍍敷劑；及利用快速蝕刻等去除該供電路形成的區域以外的區域上的無電鍍層。 Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and insulating the copper foil of the carrier The substrate is laminated; the copper foil with the carrier and the insulating substrate are laminated, and the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is etched using an etching solution using an acid or the like, plasma, or the like. The method is completely removed; a through hole or/and a blind hole is provided in the resin exposed by removing the ultra-thin copper layer by etching; a desmear treatment is performed on a region containing the through hole or/and the blind hole; An electroless plating layer is disposed on a region of the resin and the through hole or/and the blind hole; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resist for the region formed by the circuit is removed Providing an electrolytic plating layer in a region where the supply circuit for removing the plating resist is formed; removing the plating resist; and removing an electroless plating layer on a region other than the region where the circuit is formed by rapid etching or the like.
在使用半加成法的本發明的印刷配線板的製造方法的另一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層； 將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；將剝離該載體所露出的極薄銅層利用使用酸等腐蝕溶液的蝕刻或等離子等方法全部去除；在藉由利用蝕刻去除該極薄銅層而露出的該樹脂的表面設置無電鍍層；在該無電鍍層上設置抗鍍敷劑；對該抗鍍敷劑進行曝光，然後去除供電路形成的區域的抗鍍敷劑；在去除了該抗鍍敷劑的該供電路形成的區域設置電解鍍層；去除該抗鍍敷劑；利用快速蝕刻等去除該供電路形成的區域以外的區域上的無電鍍層及極薄銅層。 In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and providing the carrier with a copper foil and an insulating substrate Carry out the layering; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by the carrier is removed by etching or plasma using an etching solution such as acid; An electroless plating layer is disposed on a surface of the resin exposed by removing the ultra-thin copper layer by etching; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the circuit is formed. a plating resist in the region; an electrolytic plating layer is provided in a region where the plating circuit is removed from the supply circuit; the plating resist is removed; and the region other than the region formed by the circuit is removed by rapid etching or the like Electroplated layer and very thin copper layer.
在本發明中，改良半加成法是指如下方法：在絕緣層上積層金屬箔，利用抗鍍敷劑保護非電路形成部，利用電解鍍敷在電路形成部鍍銅，然後去除抗鍍敷劑，利用(快速)蝕刻去除該電路形成部以外的金屬箔，由此在絕緣層上形成電路。 In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion with a plating resist, plating copper in the circuit forming portion by electrolytic plating, and then removing the plating resistance. The metal foil other than the circuit forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.
因此，在使用改良半加成法的本發明的印刷配線板的製造方法的一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體； 在剝離該載體而露出的極薄銅層和絕緣基板設置通孔或/及盲孔；對含有該通孔或/及盲孔的區域進行除膠渣處理；在含有該通孔或/及盲孔的區域設置無電鍍層；在剝離該載體而露出的極薄銅層表面設置抗鍍敷劑；設置該抗鍍敷劑後，利用電解鍍敷形成電路；去除該抗鍍敷劑；利用快速蝕刻去除藉由去除該抗鍍敷劑而露出的極薄銅層。 Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and using the copper foil of the carrier and The insulating substrate is laminated; the copper foil with the carrier and the insulating substrate are laminated, and then the carrier of the copper foil with the carrier is peeled off; Providing a through hole or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; performing desmear treatment on the region containing the through hole or/and the blind hole; and containing the through hole or/and blind An electroless plating layer is disposed in a region of the hole; a plating resist is disposed on a surface of the ultra-thin copper layer exposed by peeling off the carrier; after the plating resist is disposed, a circuit is formed by electrolytic plating; the plating resist is removed; Etching removes an extremely thin copper layer exposed by removing the plating resist.
在使用改良半加成法的本發明的印刷配線板的製造方法的另一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；在剝離該載體所露出的極薄銅層上設置抗鍍敷劑；對該抗鍍敷劑進行曝光，然後去除供電路形成的區域的抗鍍敷劑；在去除了該抗鍍敷劑的該供電路形成的區域設置電解鍍層；去除該抗鍍敷劑；利用快速蝕刻等去除該供電路形成的區域以外的區域上的無電鍍層及極薄銅層。 In another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and insulating the copper foil of the carrier The substrate is laminated; after the copper foil with the carrier and the insulating substrate are laminated, the carrier of the copper foil with the carrier is peeled off; and a plating resist is provided on the extremely thin copper layer exposed by peeling the carrier; The coating agent is exposed, and then the plating resist for the region formed by the circuit is removed; the electrolytic plating layer is disposed in a region where the supply circuit for removing the plating resist is removed; the plating resist is removed; and the etching is removed by rapid etching or the like. An electroless plating layer and an extremely thin copper layer on a region other than the region where the circuit is formed.
在本發明中，部分加成法是指如下方法：在設置導體層而成的基板、根據需要打通通孔或穿孔用的孔而成的基板上賦予催化劑核，進行蝕刻而形成導體電路，根據需要設置阻焊劑或抗鍍敷劑後，在該導體電 路上對通孔或穿孔等利用無電鍍敷處理進行鍍敷，由此製造印刷配線板。 In the present invention, the partial addition method refers to a method in which a catalyst core is provided on a substrate obtained by providing a conductor layer, a via hole or a hole for perforation, and etching is performed to form a conductor circuit. After the solder resist or anti-plating agent needs to be set, the conductor is electrically A through-hole or a perforation is plated by an electroless plating treatment to produce a printed wiring board.
因此，在使用部分加成法的本發明的印刷配線板的製造方法的一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；在剝離該載體所露出的極薄銅層和絕緣基板設置通孔或/及盲孔；對含有該通孔或/及盲孔的區域進行除膠渣處理；對含有該通孔或/及盲孔的區域賦予催化劑核；在剝離該載體而露出的極薄銅層表面設置抗蝕劑；對該抗蝕劑進行曝光而形成電路圖案；將該極薄銅層及該催化劑核利用使用酸等腐蝕溶液的蝕刻或等離子等方法去除而形成電路；去除該抗蝕劑；在將該極薄銅層及該催化劑核利用使用酸等腐蝕溶液的蝕刻或等離子等方法去除而露出的該絕緣基板表面設置阻焊劑或抗鍍敷劑；在沒有設置該阻焊劑或抗鍍敷劑的區域設置無電鍍層。 Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the partial addition method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and insulating the copper foil of the carrier The substrate is laminated; after the copper foil with the carrier and the insulating substrate are laminated, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer and the insulating substrate exposed by the carrier are provided with through holes or/and blind holes. And removing the region containing the through hole or/and the blind hole; applying a catalyst core to the region containing the through hole or/and the blind hole; and providing a resist on the surface of the extremely thin copper layer exposed by peeling the carrier Exposing the resist to form a circuit pattern; forming the circuit by removing the ultra-thin copper layer and the catalyst core by etching or plasma using an etching solution such as an acid; removing the resist; The ultra-thin copper layer and the catalyst core are provided with a solder resist or a plating resist on the surface of the insulating substrate exposed by etching or plasma removal using an etching solution such as an acid; the solder resist or the anti-etching agent is not provided. Cataplasm region provided electroless plating.
在本發明中，減成法是指利用蝕刻等選擇性地去除覆銅積層板上的銅箔之不需要的部分而形成導體圖案的方法。 In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like.
因此，在使用減成法的本發明的印刷配線板的製造方法的一實施方式中，包括如下步驟： 準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；在剝離該載體而露出的極薄銅層和絕緣基板設置通孔或/及盲孔；對含有該通孔或/及盲孔的區域進行除膠渣處理；在含有該通孔或/及盲孔的區域設置無電鍍層；在該無電鍍層的表面設置電解鍍層；在該電解鍍層或/及該極薄銅層的表面設置抗蝕劑；對該抗蝕劑進行曝光，形成電路圖案；將該極薄銅層及該無電鍍層及該電解鍍層利用使用酸等腐蝕溶液的蝕刻或等離子等方法去除而形成電路；去除該抗蝕劑。 Therefore, in an embodiment of the method of manufacturing a printed wiring board of the present invention using the subtractive method, the following steps are included: Preparing the copper foil and the insulating substrate with a carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and then peeling off the carrier of the copper foil with the carrier; Providing a through hole or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; performing desmear treatment on the region containing the through hole or/and the blind hole; and containing the through hole or/and blind An electroless plating layer is disposed on a surface of the electroless plating layer; a resist is disposed on the surface of the electroless plating layer and/or the ultra-thin copper layer; and the resist is exposed to form a circuit pattern; The ultra-thin copper layer, the electroless plating layer, and the electrolytic plating layer are removed by etching or plasma using an etching solution such as an acid to form a circuit; and the resist is removed.
在使用減成法的本發明的印刷配線板的製造方法的另一實施方式中，包括如下步驟：準備本發明的附載體的銅箔和絕緣基板；將該附載體的銅箔和絕緣基板進行積層；將該附載體的銅箔和絕緣基板進行積層後，剝離該附載體的銅箔的載體；在剝離該載體所露出的極薄銅層和絕緣基板設置通孔或/及盲孔；對含有該通孔或/及盲孔的區域進行除膠渣處理；在含有該通孔或/及盲孔的區域設置無電鍍層； 在該無電鍍層的表面形成遮罩；在沒有形成遮罩的該無電鍍層的表面設置電解鍍層；在該電解鍍層或/及該極薄銅層的表面設置抗蝕劑；對該抗蝕劑進行曝光而形成電路圖案；將該極薄銅層及該無電鍍層利用使用酸等腐蝕溶液的蝕刻或等離子等方法去除而形成電路；去除該抗蝕劑。 In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and performing the copper foil and the insulating substrate of the carrier Laminating; laminating the copper foil with the carrier and the insulating substrate, and then peeling off the carrier of the copper foil with the carrier; and providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by the carrier; The area containing the through hole or/and the blind hole is subjected to desmear treatment; an electroless plating layer is disposed in a region containing the through hole or/and the blind hole; Forming a mask on the surface of the electroless plating layer; providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; providing a resist on the surface of the electrolytic plating layer and/or the ultra-thin copper layer; The agent is exposed to form a circuit pattern; the ultra-thin copper layer and the electroless plated layer are removed by etching or plasma using an etching solution such as an acid to form a circuit; and the resist is removed.
亦可以不進行設置通孔或/及盲孔的步驟及其後的除膠渣步驟。 It is also possible not to perform the step of providing a through hole or/and a blind hole and the subsequent desmear step.
此處，使用圖式對使用本發明的附載體的銅箔的印刷配線板的製造方法的具體例進行詳細說明。另外，此處，以在極薄銅層表面形成了粗化處理層的附載體的銅箔為例進行說明，但亦可以不形成粗化處理層。 Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail using a drawing. Here, the copper foil with a carrier having a roughened layer formed on the surface of the ultra-thin copper layer will be described as an example, but the roughened layer may not be formed.
首先，如圖1-A所示，準備具有表面形成了粗化處理層的極薄銅層的附載體的銅箔(第1層)。 First, as shown in FIG. 1-A, a copper foil (first layer) with a carrier having an extremely thin copper layer having a roughened layer formed thereon is prepared.
接著，如圖1-B所示，在極薄銅層的粗化處理層上塗布抗鍍敷劑，並進行曝光、顯影，將抗鍍敷劑蝕刻成特定的形狀。 Next, as shown in FIG. 1-B, a plating resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the anti-plating agent is etched into a specific shape.
接著，如圖1-C所示，在形成電路用鍍層後，去除抗鍍敷劑，由此形成特定形狀的電路鍍層。 Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the plating resist is removed, thereby forming a circuit plating of a specific shape.
接著，如圖2-D所示，以覆蓋電路鍍層的方式(以埋沒電路鍍層的方式)在極薄銅層上設置填埋樹脂而積層樹脂層，接著從極薄銅層側黏合另一片附載體的銅箔(第2層)。 Next, as shown in FIG. 2-D, a resin layer is laminated on the ultra-thin copper layer to cover the circuit plating layer (in the form of a buried circuit plating layer), and then another film is bonded from the side of the ultra-thin copper layer. Carrier copper foil (layer 2).
接著，如圖2-E所示，從第2層附載體的銅箔剝離載體。 Next, as shown in Fig. 2-E, the carrier is peeled off from the copper foil of the second layer with a carrier.
接著，如圖2-F所示，在樹脂層的特定位置進行雷射開孔，露出電路鍍層而形成盲孔。 Next, as shown in FIG. 2-F, a laser opening is formed at a specific position of the resin layer to expose a circuit plating layer to form a blind hole.
接著，如圖3-G所示，在盲孔填埋銅而形成通孔填充物。 Next, as shown in FIG. 3-G, copper is filled in the blind via hole to form a via fill.
接著，如圖3-H所示，在通孔填充物上以該圖1-B及圖1-C的方式形成電路鍍層。 Next, as shown in FIG. 3-H, a circuit plating layer is formed on the via fill in the manner of FIG. 1-B and FIG. 1-C.
接著，如圖3-I所示，從第1層附載體的銅箔剝離載體。 Next, as shown in FIG. 3-I, the carrier is peeled off from the copper foil of the first layer with a carrier.
接著，如圖4-J所示，利用快速蝕刻去除兩表面的極薄銅層，露出樹脂層內的電路鍍層的表面。 Next, as shown in FIG. 4-J, the ultra-thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.
接著，如圖4-K所示，在樹脂層內的電路鍍層上形成凸塊，在該焊料上形成銅柱。以如上所述的方式製作使用本發明的附載體的銅箔的印刷配線板。 Next, as shown in FIG. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced as described above.
該另外的附載體的銅箔(第2層)可以使用本發明的附載體的銅箔，亦可以使用以往的附載體的銅箔，進而亦可以使用通常的銅箔。另外，亦可以在圖3-H所示的第2層電路上進而形成1層或多層電路，亦可以藉由半加成法、減成法、部分加成法或改良半加成法中的任一種方法形成這些電路。 The copper foil with a carrier of the present invention (the second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil with a carrier may be used, and a general copper foil may be used. Alternatively, a layer 1 or a multilayer circuit may be further formed on the second layer circuit shown in FIG. 3-H, or may be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method forms these circuits.
另外，該第1層所使用的附載體的銅箔亦可以在該附載體的銅箔的載體側表面具有基板。藉由具有該基板，第1層所使用的附載體的銅箔受到支撐，不易產生皺褶，所以有生產性提升的優點。另外，該基板只要具有支撐該第1層所使用的附載體之銅箔的效果，則可以使用所有基板。例如，作為該基板，可以使用本案說明書所記載的載體、預浸體、樹脂層或公知的載體、預浸體、樹脂層、金屬板、金屬箔、無機化合物的板、 無機化合物的箔、有機化合物的板、有機化合物的箔。 Further, the copper foil with a carrier used for the first layer may have a substrate on the carrier side surface of the copper foil with the carrier. By having such a substrate, the copper foil with a carrier used for the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, as long as the substrate has an effect of supporting the copper foil with a carrier used for the first layer, all of the substrates can be used. For example, as the substrate, a carrier, a prepreg, a resin layer, a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, or the like described in the specification can be used. A foil of an inorganic compound, a plate of an organic compound, or a foil of an organic compound.
關於在載體側表面形成基板的時點並沒有特別限制，但必須在剝離載體前形成。尤其較佳於在該附載體的銅箔的該極薄銅層側表面形成樹脂層的步驟前形成，更佳於在附載體的銅箔的該極薄銅層側表面形成電路的步驟前形成。 The time at which the substrate is formed on the side surface of the carrier is not particularly limited, but it must be formed before the carrier is peeled off. It is particularly preferable to form the resin layer before the step of forming the resin layer on the side surface of the ultra-thin copper layer of the copper foil with the carrier, more preferably before the step of forming a circuit on the side surface of the ultra-thin copper layer of the copper foil of the carrier. .
另外，填埋樹脂(resin)可以使用公知的樹脂、預浸體。例如可以使用BT(雙馬來醯亞胺三嗪)樹脂或作為含浸了BT樹脂的玻璃布的預浸體、Ajinomoto Fine-Techno股份有限公司製造的ABF膜或ABF。另外，該填埋樹脂可以含有熱硬化性樹脂，亦可以是熱塑性樹脂。另外，該填埋樹脂亦可以含有熱塑性樹脂。該填埋樹脂的種類並沒有特別限定，作為適宜的樹脂，例如可以列舉：含有環氧樹脂、聚醯亞胺樹脂、多官能性氰酸酯化合物、馬來醯亞胺化合物、聚乙烯醇縮乙醛樹脂、聚氨酯樹脂、嵌段共聚合聚醯亞胺樹脂、嵌段共聚合聚醯亞胺樹脂、聚醚碸、聚醚碸樹脂、芳香族聚醯胺樹脂、聚醯胺醯亞胺樹脂、橡膠變成環氧樹脂、苯氧基樹脂、羧基改質丙烯腈-丁二烯樹脂、聚苯醚、雙馬來醯亞胺三嗪樹脂、熱硬化性聚苯醚樹脂、氰酸酯系樹脂、多元羧酸的酐等的樹脂；或紙基材酚樹脂、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/玻璃無紡布複合基材環氧樹脂及玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺膜、液晶聚合物膜、氟樹脂膜等。另外，該填埋樹脂(resin)可以使用本說明書所記載的樹脂層及/或樹脂及/或預浸體。 Further, a well-known resin or prepreg can be used as the resin. For example, a BT (Bismaleimide Triazine) resin or a prepreg which is a glass cloth impregnated with a BT resin, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF can be used. Further, the filling resin may contain a thermosetting resin or a thermoplastic resin. Further, the filling resin may also contain a thermoplastic resin. The type of the resin to be filled is not particularly limited, and examples of the suitable resin include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polyvinyl alcohol. Acetaldehyde resin, polyurethane resin, block copolymerized polyimine resin, block copolymerized polyimide resin, polyether oxime, polyether oxime resin, aromatic polyamide resin, polyamidoximine resin , rubber into epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide triazine resin, thermosetting polyphenylene ether resin, cyanate resin a resin such as a polycarboxylic acid anhydride; or a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, a glass cloth/paper composite substrate epoxy resin, a glass cloth/glass non-woven fabric Cloth composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film, and the like. Further, as the resin, a resin layer and/or a resin and/or a prepreg described in the present specification can be used.
並且，藉由在本發明的印刷配線板搭載電子零件類，從而完成印刷電路板。在本發明中，“印刷配線板”亦包括如此搭載了電子零件 類的印刷配線板及印刷電路板及印刷基板。 Further, the printed circuit board is completed by mounting electronic components on the printed wiring board of the present invention. In the present invention, the "printed wiring board" also includes the electronic components thus mounted. Printed wiring boards, printed circuit boards and printed boards.
另外，可以使用該印刷配線板製作電子機器，亦可以使用該搭載了電子零件類的印刷電路板製作電子機器，亦可以使用該搭載了電子零件類的印刷基板製作電子機器。 In addition, an electronic device can be produced using the printed wiring board, and an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted.
另外，本發明的印刷配線板的製造方法亦可為包括如下步驟的印刷配線板的製造方法(無芯法)：將本發明的附載體的銅箔的該極薄銅層側表面或該載體側表面和樹脂基板進行積層；在與該和樹脂基板積層的極薄銅層側表面或該載體側表面為相反側的附載體的銅箔的表面至少設置1次樹脂層和電路之兩層；及在形成該樹脂層及電路之兩層後，從該附載體的銅箔剝離該載體或該極薄銅層。關於該無芯法，作為具體的例子，首先，將本發明的附載體的銅箔的極薄銅層側表面或載體側表面和樹脂基板進行積層。然後，在與和樹脂基板積層的極薄銅層側表面或該載體側表面為相反側的附載體的銅箔的表面形成樹脂層。亦可以在形成於載體側表面或極薄銅層側表面的樹脂層從載體側或極薄銅層側進而積層另一片附載體的銅箔。在此情況下，成為如下構成：以樹脂基板為中心，在該樹脂基板的兩表面側以載體/中間層/極薄銅層的順序或以極薄銅層/中間層/載體的順序積層附載體的銅箔。亦可以在兩端的極薄銅層或載體所露出的表面設置另一樹脂層，並進而設置銅層或金屬層，然後對該銅層或金屬層進行加工，由此形成電路。亦可以進而將另一樹脂層以填埋該電路的方式設置在該電路上。另外，亦可以將此種電路及樹脂層的形成進行1次以上(增層法)。並且，關於以上述方式形成的積層體(以下亦稱為積層體B)，可以將各附載體的銅箔的極薄銅層或載體從載體或極薄銅層剝離而製作無芯基 板。另外，在製作該無芯基板時，亦可以使用2個附載體的銅箔，製作下述具有極薄銅層/中間層/載體/載體/中間層/極薄銅層的構成的積層體、或具有載體/中間層/極薄銅層/極薄銅層/中間層/載體的構成的積層體、或具有載體/中間層/極薄銅層/載體/中間層/極薄銅層的構成的積層體，並將該積層體用於中心。可以在這些積層體(以下亦稱為積層體A)的兩側的極薄銅層或載體的表面設置1次以上樹脂層及電路之兩層，在設置1次以上樹脂層及電路之兩層後，將各附載體的銅箔的極薄銅層或載體從載體或極薄銅層剝離而製作無芯基板。該積層體在極薄銅層的表面、載體的表面、載體和載體之間、極薄銅層和極薄銅層之間、極薄銅層和載體之間亦可以具有其它層。另外，本說明書中，“極薄銅層的表面”、“極薄銅層側表面”、“載體的表面”、“載體側表面”、“積層體的表面”當極薄銅層、載體、積層體在極薄銅層表面、載體表面、積層體表面具有其它層的情況下，是設為包括該其它層的表面(最表面)的概念。另外，積層體較佳具有極薄銅層/中間層/載體/載體/中間層/極薄銅層的構成。這是由於：在使用該積層體制作無芯基板時，因為在無芯基板側配置極薄銅層，所以容易使用改良半加成法在無芯基板上形成電路。另外，是由於：因為極薄銅層的厚度薄，所以容易去除該極薄銅層，去除極薄銅層後容易使用半加成法在無芯基板上形成電路。 Further, the method for producing a printed wiring board of the present invention may be a method for producing a printed wiring board including the following steps (coreless method): the extremely thin copper layer side surface of the copper foil with a carrier of the present invention or the carrier The side surface and the resin substrate are laminated; at least one resin layer and two layers of the circuit are provided on the surface of the copper foil with the carrier on the side opposite to the extremely thin copper layer side surface or the carrier side surface of the resin substrate; And after forming the two layers of the resin layer and the circuit, the carrier or the ultra-thin copper layer is peeled off from the copper foil of the carrier. In the coreless method, as a specific example, first, the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate are laminated. Then, a resin layer is formed on the surface of the copper foil with a carrier on the side opposite to the extremely thin copper layer side surface or the carrier side surface laminated with the resin substrate. It is also possible to laminate another copper foil with a carrier from the side of the carrier or the side of the ultra-thin copper layer on the resin layer formed on the side surface of the carrier side or the side surface of the ultra-thin copper layer. In this case, the resin substrate is centered on the both surface sides of the resin substrate in the order of the carrier/intermediate layer/very thin copper layer or in the order of the ultra-thin copper layer/intermediate layer/carrier. Carrier copper foil. It is also possible to provide another resin layer on the surface of the extremely thin copper layer or the carrier exposed at both ends, and further to provide a copper layer or a metal layer, and then process the copper layer or the metal layer, thereby forming an electric circuit. It is also possible to further arrange another resin layer on the circuit in such a manner as to fill the circuit. Further, the formation of such a circuit and the resin layer may be performed once or more (growth method). Further, with respect to the laminate (hereinafter also referred to as laminate B) formed as described above, the ultra-thin copper layer or carrier of the copper foil with the carrier can be peeled off from the carrier or the ultra-thin copper layer to form a coreless base. board. Further, in the production of the coreless substrate, it is also possible to use two copper foils with a carrier to produce a laminate having a structure of an extremely thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer, Or a laminate having a carrier/intermediate layer/very thin copper layer/very thin copper layer/intermediate layer/carrier, or a composition having a carrier/intermediate layer/very thin copper layer/carrier/intermediate layer/very thin copper layer The laminate is used and the laminate is used for the center. One or more resin layers and two layers of the circuit may be provided on the surface of the ultra-thin copper layer or the carrier on both sides of the laminated body (hereinafter also referred to as the laminated body A), and the resin layer and the two layers of the circuit may be provided one time or more. Thereafter, the ultra-thin copper layer or carrier of each of the copper foils with the carrier is peeled off from the carrier or the ultra-thin copper layer to form a coreless substrate. The laminate may have other layers between the surface of the ultra-thin copper layer, the surface of the carrier, the carrier and the carrier, between the ultra-thin copper layer and the ultra-thin copper layer, and between the ultra-thin copper layer and the carrier. In addition, in the present specification, "the surface of the ultra-thin copper layer", the "very thin copper layer side surface", the "carrier surface", the "carrier side surface", and the "layer surface" are extremely thin copper layers, carriers, In the case where the laminate has other layers on the surface of the ultra-thin copper layer, the surface of the carrier, and the surface of the laminate, the concept is to include the surface (the outermost surface) of the other layer. Further, the laminate preferably has a very thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer. This is because when the coreless substrate is produced using the laminated body, since the ultra-thin copper layer is disposed on the coreless substrate side, it is easy to form a circuit on the coreless substrate by the improved semi-additive method. In addition, since the ultra-thin copper layer is thin, it is easy to remove the ultra-thin copper layer, and after removing the ultra-thin copper layer, it is easy to form a circuit on the coreless substrate by using a semi-additive method.
另外，在本說明書中，沒有特別記載成“積層體A”或“積層體B”的“積層體”表示至少包括積層體A及積層體B的積層體。 In the present specification, the "layered body" which is not particularly described as "layered body A" or "layered body B" means a layered body including at least the layered body A and the layered body B.
另外，在該無芯基板的製造方法中，藉由利用樹脂覆蓋附載體的銅箔或積層體(積層體A)的端面的一部分或全部，在利用增層法製 造印刷配線板時，可以防止藥液滲入到中間層或構成積層體的一片附載體的銅箔和另一片附載體的銅箔之間，可以防止由藥液的滲入所導致的極薄銅層和載體的分離或附載體的銅箔的腐蝕，可以提升良率。作為此處所使用的“覆蓋附載體的銅箔之端面的一部分或全部的樹脂”或“覆蓋積層體之端面的一部分或全部的樹脂”，可以使用能夠用於樹脂層的樹脂。另外，在該無芯基板的製造方法中，在對附載體的銅箔或積層體進行俯視時，附載體的銅箔或積層體的積層部分(載體和極薄銅層的積層部分、或一片附載體的銅箔和另一片附載體的銅箔的積層部分)的外周的至少一部分可以由樹脂或預浸體覆蓋。另外，利用該無芯基板的製造方法所形成的積層體(積層體A)亦可以是使一對附載體的銅箔相互以可分離的方式接觸而構成。另外，在對該附載體的銅箔進行俯視時，亦可以由樹脂或預浸體覆蓋附載體的銅箔或積層體的積層部分(載體和極薄銅層的積層部分、或一片附載體的銅箔和另一片附載體的銅箔的積層部分)的外周整體。藉由設為此種構成，在俯視附載體的銅箔或積層體時，附載體的銅箔或積層體的積層部分由樹脂或預浸體覆蓋，可以防止其它部件從該部分側向、亦就是相對於積層方向橫向的方向碰撞，結果，可以減少操作中載體和極薄銅層或附載體的銅箔彼此的剝離。另外，藉由以不露出附載體的銅箔或積層體的積層部分的外周的方式利用樹脂或預浸體進行覆蓋，可以防止如上所述藥液處理步驟中藥液向該積層部分的介面的滲入，可以防止附載體的銅箔的腐蝕或侵蝕。另外，在從積層體的一對附載體的銅箔分離一片附載體的銅箔時，或分離附載體的銅箔的載體和銅箔(極薄銅層)時，必須藉由切斷等去除利用樹脂或預浸體覆蓋的附載體的銅箔或積層體的積層部分(載體 和極薄銅層的積層部分、或一片附載體的銅箔和另一片附載體的銅箔的積層部分)。 Further, in the method for producing a coreless substrate, a part or the whole of the end faces of the copper foil or the laminated body (layered body A) of the carrier is covered with a resin, and is formed by a build-up method. When the printed wiring board is formed, it is possible to prevent the chemical solution from infiltrating into the intermediate layer or a piece of the copper foil with the carrier constituting the laminated body and the copper foil with the other carrier, and the extremely thin copper layer caused by the penetration of the chemical liquid can be prevented. Separation from the carrier or corrosion of the copper foil with the carrier can increase the yield. As the "resin covering a part or all of the end surface of the copper foil with a carrier" or "resin covering a part or all of the end faces of the laminated body", a resin which can be used for the resin layer can be used. In the method of manufacturing the coreless substrate, when the copper foil or the laminated body with the carrier is viewed in plan, the copper foil of the carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultra-thin copper layer, or one piece) At least a part of the outer circumference of the copper foil with the carrier and the laminated portion of the copper foil with the other carrier may be covered with a resin or a prepreg. Further, the laminate (layered product A) formed by the method for producing a coreless substrate may be configured such that a pair of copper foils with a carrier are detachably connected to each other. Further, when the copper foil with the carrier is viewed in plan, the copper foil of the carrier or the laminated portion of the laminate (the laminated portion of the carrier and the ultra-thin copper layer, or a carrier with a carrier) may be covered with a resin or a prepreg. The entire outer circumference of the copper foil and the laminated portion of the copper foil with the other carrier. With such a configuration, when the copper foil or the laminated body with the carrier is viewed in a plan view, the laminated portion of the copper foil or the laminated body with the carrier is covered with the resin or the prepreg, and it is possible to prevent other members from being laterally oriented from the portion. That is, collision in a direction transverse to the lamination direction, and as a result, peeling of the carrier and the ultra-thin copper layer or the copper foil with the carrier in operation can be reduced. In addition, by covering with the resin or the prepreg so as not to expose the outer periphery of the laminated portion of the copper foil or the laminated body with the carrier, it is possible to prevent the interface of the chemical solution to the laminated portion in the chemical liquid processing step as described above. Infiltration can prevent corrosion or erosion of the copper foil with the carrier. Further, when a piece of copper foil with a carrier is separated from a pair of copper foils with a carrier of a laminate, or when a carrier of a copper foil with a carrier and a copper foil (very thin copper layer) are separated, it is necessary to remove and utilize it by cutting or the like. a copper foil or a laminate of a laminate covered with a resin or a prepreg (carrier) And a laminated portion of an extremely thin copper layer, or a laminated portion of a copper foil with a carrier and another copper foil with a carrier).
亦可以將本發明的附載體的銅箔從載體側或極薄銅層側積層在另一片本發明的附載體的銅箔的載體側或極薄銅層側而構成積層體。另外，可以是該一片附載體的銅箔的該載體側表面或該極薄銅層側表面和該另一片附載體的銅箔的該載體側表面或該極薄銅層側表面，根據需要經由黏合劑直接積層而獲得的積層體。另外，亦可以將該一片附載體的銅箔的載體或極薄銅層和該另一片附載體的銅箔的載體或極薄銅層連接。此處，該“連接”在載體或極薄銅層具有表面處理層的情況下，亦包括經由該表面處理層相互連接的形態。另外，亦可以被樹脂覆蓋該積層體的端面的一部分或全部。 The copper foil with a carrier of the present invention may be laminated from the side of the carrier or the side of the ultra-thin copper layer to the side of the carrier or the ultra-thin copper layer of the copper foil of the other carrier of the present invention to form a laminate. In addition, it may be the carrier side surface of the copper foil with the carrier or the side surface of the ultra-thin copper layer and the carrier side surface of the copper foil of the other sheet carrier or the side surface of the ultra-thin copper layer, as needed A laminate obtained by directly laminating a binder. Alternatively, the carrier or the ultra-thin copper layer of the copper foil with a carrier may be connected to the carrier or the ultra-thin copper layer of the copper foil of the other carrier. Here, the "connection" also includes a form in which the carrier or the ultra-thin copper layer has a surface treatment layer, and also includes a state in which the surface treatment layer is connected to each other. Further, a part or all of the end faces of the laminate may be covered with a resin.
載體彼此的積層除了單純地重疊以外，例如可以利用以下方法進行。 The laminate of the carriers can be carried out, for example, by the following method, except for simply overlapping.
(a)冶金連接方法：焊接(電弧焊接、TIG(tungsten inert gas，鎢-惰性氣體)焊接、MIG(metal inert gas，金屬-惰性氣體)焊接、電阻焊接、縫焊接、點焊接)、壓接(超音波焊接、摩擦攪拌焊接)、針焊；(b)機械連接方法：斂縫、利用鉚釘的連接(利用自沖鉚的連接、利用鉚釘的連接)、裝訂機；(c)物理連接方法：黏合劑、(雙面)膠帶 (a) Metallurgical joining method: welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), crimping (ultrasonic welding, friction stir welding), needle welding; (b) mechanical connection method: caulking, connection by rivet (connection by self-piercing riveting, connection by rivet), binding machine; (c) physical connection method : adhesive, (double sided) tape
藉由將一載體的一部分或全部和另一載體的一部分或全部使用該連接方法進行連接，可以製造將一載體和另一載體積層，使載體彼此以可分離的方式接觸而構成的積層體。若一載體和另一載體較弱地連 接，則在將一載體和另一載體積層的情況下，即使不去除一載體和另一載體的連接部，亦可以將一載體和另一載體分離。另外，在一載體和另一載體較強地連接的情況下，藉由將一載體和另一載體連接的部位利用切斷或化學研磨(蝕刻等)、機械研磨等去除，可以分離一載體和另一載體。 By connecting a part or all of a carrier to a part or all of another carrier using the joining method, it is possible to manufacture a laminate in which one carrier and another carrier layer are brought into contact with each other in a separable manner. If one carrier and another carrier are weakly connected Alternatively, in the case of one carrier and another carrier layer, one carrier can be separated from the other carrier even without removing the connection between one carrier and the other carrier. In addition, in the case where one carrier and the other carrier are strongly connected, a carrier and a portion to which the other carrier is connected may be separated by cutting or chemical polishing (etching, etc.), mechanical polishing, or the like, thereby separating a carrier and Another carrier.
另外，可以藉由實施如下步驟而製作印刷配線板：在以上述方式構成的積層體至少設置1次樹脂層和電路之兩層；及在至少形成1次該樹脂層及電路之兩層後，從該積層體的附載體的銅箔剝離該極薄銅層或載體。另外，亦可以在該積層體的一個表面或兩個表面設置樹脂層和電路之兩層。 Further, a printed wiring board can be produced by performing the following steps: at least one layer of the resin layer and the circuit is provided in the laminated body configured as described above; and after at least one layer of the resin layer and the circuit is formed once, The ultra-thin copper layer or carrier is peeled off from the copper foil with the carrier of the laminate. Further, it is also possible to provide two layers of a resin layer and a circuit on one surface or both surfaces of the laminate.
[實施例] [Examples]
以下，基於實施例及比較例進行說明。另外，本實施例只不過是一例，並不僅限定於該例。 Hereinafter, description will be made based on examples and comparative examples. In addition, this embodiment is only an example, and is not limited to this example.
1.製造附載體的銅箔 1. Manufacturing copper foil with carrier
作為銅箔載體，準備厚度35μm的長條的電解銅箔(JX日礦日石金屬公司製造的JTC)及厚度33μm的壓延銅箔(JX日礦日石金屬公司製造的C1100)。對該銅箔的光澤面(亮面)在以下條件下利用輥一輥型的連續鍍敷線進行鍍鎳(Ni)或鍍鈷(Co)作為金屬鍍敷後，進行BTA處理作為鉻酸鹽處理或利用有機物的處理，由此形成中間層。另外，表1的“脫脂”、“酸洗”表示分別利用以下條件對載體的將要鍍鎳或鍍鈷一側的表面進行鍍鎳(Ni)的前處理。並且，表1的“光澤劑”表示在以下鍍鎳(Ni)處理中在鍍液中含有光澤劑(一次光澤劑及二次光澤劑)。另外，對於實施例1、 3、5、9、11，在鉻酸鹽處理後進行加熱處理。將此時的加熱溫度(乾燥溫度)示於表1。另外，對載體的表面依序進行脫脂、酸洗處理。將該脫脂條件及酸洗條件示於下文。 As a copper foil carrier, a long electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm and a rolled copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 33 μm were prepared. The shiny surface (bright side) of the copper foil was subjected to nickel plating (Ni) or cobalt plating (Co) as a metal plating by a roll-roll type continuous plating line under the following conditions, and then subjected to BTA treatment as a chromate. The treatment of the organic matter is treated or utilized, thereby forming an intermediate layer. In addition, "defatting" and "pickling" of Table 1 indicate that the surface of the carrier to be plated with nickel or cobalt is subjected to nickel plating (Ni) pretreatment by the following conditions. Further, the "gloss agent" in Table 1 indicates that a gloss agent (primary gloss agent and secondary gloss agent) is contained in the plating solution in the following nickel plating (Ni) treatment. In addition, for the embodiment 1, 3, 5, 9, and 11, after the chromate treatment, heat treatment. The heating temperature (drying temperature) at this time is shown in Table 1. Further, the surface of the carrier is sequentially subjected to degreasing and pickling treatment. The degreasing conditions and pickling conditions are shown below.
[脫脂] [degreased]
使用以下脫脂處理液，在以下條件下進行電解脫脂。 Electrolytic degreasing was carried out under the following conditions using the following degreasing treatment liquid.
‧脫脂處理液：氫氧化鈉水溶液(氫氧化鈉濃度70g/L) ‧Degreasing treatment solution: aqueous sodium hydroxide solution (sodium hydroxide concentration 70g/L)
‧電解脫脂：在以下條件下進行陰極電解脫脂，然後進行陽極電解脫脂，然後再次進行陰極電解脫脂。 ‧ Electrolytic degreasing: Cathodic electrolytic degreasing is carried out under the following conditions, followed by anodic electrolytic degreasing, followed by cathodic electrolysis degreasing again.
陰極(電解)脫脂(電流密度10A/dm2)：20秒 Cathode (electrolysis) degreasing (current density 10A/dm 2 ): 20 seconds
陽極(電解)脫脂(電流密度5A/dm2)：20秒 Anode (electrolysis) degreasing (current density 5A/dm 2 ): 20 seconds
陰極(電解)脫脂(電流密度10A/dm2)：20秒 Cathode (electrolysis) degreasing (current density 10A/dm 2 ): 20 seconds
[酸洗] [pickling]
‧酸洗處理液：硫酸水溶液(硫酸濃度：50mL/L) ‧ Pickling treatment solution: aqueous sulfuric acid solution (sulfuric acid concentration: 50mL / L)
浸漬時間：20秒 Dipping time: 20 seconds
[鍍鎳(Ni)] [Ni-plated (Ni)]
‧鍍液 ‧ plating solution
鎳：20~200g/L Nickel: 20~200g/L
硼酸：5~60g/L Boric acid: 5~60g/L
液溫：40~65℃ Liquid temperature: 40~65°C
pH：1.5~5.0 pH: 1.5~5.0
‧電流密度：0.5~20A/dm2 ‧ Current density: 0.5~20A/dm 2
‧通電時間：1~20秒 ‧ Power-on time: 1~20 seconds
‧攪拌(液迴圈量)：100~1000L/分鐘 ‧Stirring (liquid circulation): 100~1000L/min
‧運送速度：2~30m/分鐘 ‧Transport speed: 2~30m/min
‧添加劑：一次光澤劑(糖精鈉：0.5~5g/L)、二次光澤劑(硫脲：0.05~1g/L) ‧Additives: one-time brightener (sodium saccharin: 0.5~5g/L), secondary brightener (thiourea: 0.05~1g/L)
[鍍鈷(Co)] [Cobalt plating (Co)]
‧鍍液 ‧ plating solution
鈷：20~200g/L Cobalt: 20~200g/L
硼酸：5~60g/L Boric acid: 5~60g/L
液溫：40~65℃ Liquid temperature: 40~65°C
pH：1.5~5.0 pH: 1.5~5.0
‧電流密度：0.5~20A/dm2 ‧ Current density: 0.5~20A/dm 2
‧通電時間：1~20秒 ‧ Power-on time: 1~20 seconds
‧攪拌(液迴圈量)：100~1000L/分鐘 ‧Stirring (liquid circulation): 100~1000L/min
‧運送速度：2~30m/分鐘 ‧Transport speed: 2~30m/min
‧添加劑：一次光澤劑(糖精鈉：0.5~5g/L)、二次光澤劑(硫脲：0.05~1g/L) ‧Additives: one-time brightener (sodium saccharin: 0.5~5g/L), secondary brightener (thiourea: 0.05~1g/L)
[鉻酸鹽處理] [chromate treatment]
‧處理液 ‧Processing fluid
鉻：0.5~6.0g/L Chromium: 0.5~6.0g/L
鋅：0.1~2.0g/L Zinc: 0.1~2.0g/L
液溫：25~60℃ Liquid temperature: 25~60°C
pH：2.5~5.0 pH: 2.5~5.0
‧電流密度：0.1~4A/dm2 ‧ Current density: 0.1~4A/dm 2
‧通電時間：1~30秒 ‧ Power-on time: 1~30 seconds
[BTA處理] [BTA processing]
‧BTA處理：使用苯併***的防銹處理 ‧BTA treatment: anti-rust treatment with benzotriazole
‧處理液 ‧Processing fluid
苯併***：0.1~20g/L Benzotriazole: 0.1~20g/L
pH：2~5 pH: 2~5
液溫：20~40℃ Liquid temperature: 20~40°C
浸漬時間：5~30秒 Immersion time: 5~30 seconds
接著，藉由在輥-輥型的連續鍍敷線上，在以下條件下進行電鍍而在中間層上形成表1所記載的厚度的極薄銅層，從而製作附載體的銅箔。 Next, an ultra-thin copper layer having the thickness shown in Table 1 was formed on the intermediate layer on a roll-roll type continuous plating line under the following conditions to produce a copper foil with a carrier.
‧極薄銅層 ‧ very thin copper layer
銅濃度：90~120g/L Copper concentration: 90~120g/L
H2SO4濃度：20~120g/L H 2 SO 4 concentration: 20~120g/L
電解液溫度：20~80℃ Electrolyte temperature: 20~80°C
電流密度：10~70A/dm2 Current density: 10~70A/dm 2
鍍液線流速：1.0m/s Plating line flow rate: 1.0m / s
關於這些實施例及比較例，對所有極薄銅層的表面依序進行以下的粗化處理、防銹處理、鉻酸鹽處理及矽烷偶合處理。 In these examples and comparative examples, the following roughening treatment, rust prevention treatment, chromate treatment, and decane coupling treatment were sequentially performed on the surfaces of all the ultra-thin copper layers.
‧粗化處理 ‧ roughening
Cu：10~20g/L Cu: 10~20g/L
Co：5~15g/L Co: 5~15g/L
Ni：5~15g/L Ni: 5~15g/L
pH：1~4 pH: 1~4
溫度：40~50℃ Temperature: 40~50°C
電流密度Dk：40~50A/dm2 Current density Dk: 40~50A/dm 2
時間：0.5秒~2秒 Time: 0.5 seconds to 2 seconds
Cu附著量：15~40mg/dm2 Cu adhesion: 15~40mg/dm 2
Co附著量：100~3000μg/dm2 Co adhesion: 100~3000μg/dm 2
Ni附著量：100~1000μg/dm2 Ni adhesion: 100~1000μg/dm 2
‧防銹處理 ‧Anti-rust treatment
Zn：0~20g/L Zn: 0~20g/L
Ni：0~5g/L Ni: 0~5g/L
pH：3.5 pH: 3.5
溫度：40℃ Temperature: 40 ° C
電流密度Dk：0~1.7A/dm2 Current density Dk: 0~1.7A/dm 2
時間：1秒 Time: 1 second
Zn附著量：5~250μg/dm2 Zn adhesion: 5~250μg/dm 2
Ni附著量：5~300μg/dm2 Ni adhesion: 5~300μg/dm 2
‧鉻酸鹽處理 ‧Chromate treatment
處理液組成： Treatment liquid composition:
K2Cr2O7 K 2 Cr 2 O 7
(Na2Cr2O7或CrO3)：2~10g/L (Na 2 Cr 2 O 7 or CrO 3 ): 2~10g/L
NaOH或KOH：10~50g/L NaOH or KOH: 10~50g/L
ZnO或ZnSO47H2O：0.05~10g/L ZnO or ZnSO 4 7H 2 O: 0.05~10g/L
pH：7~13 pH: 7~13
浴溫：20~80℃ Bath temperature: 20~80°C
電流密度：0.05~5A/dm2 Current density: 0.05~5A/dm 2
時間：5~30秒 Time: 5~30 seconds
Cr附著量：10~150μg/dm2 Cr adhesion: 10~150μg/dm 2
‧矽烷偶合處理 ‧decane coupling treatment
乙烯基三乙氧基矽烷水溶液 Vinyl triethoxy decane aqueous solution
(乙烯基三乙氧基矽烷濃度：0.1~1.4wt%) (Vinyl triethoxy decane concentration: 0.1~1.4wt%)
pH：4~5 pH: 4~5
時間：5~30秒 Time: 5~30 seconds
2.附載體的銅箔的評估 2. Evaluation of copper foil with carrier
對以如上所述的方式製作的實施例及比較例的各樣品如下該進行各種評估。 Each of the samples of the examples and the comparative examples produced as described above was subjected to various evaluations as follows.
‧中間層的金屬附著量 ‧ metal adhesion in the middle layer
鎳附著量及鈷附著量是將樣品利用濃度20品質%的硝酸溶解，並使用SII公司製造的ICP發射光譜分析裝置(型號：SPS3100)利用ICP發光分析進行測量，鋅、鉻附著量是藉由將樣品利用濃度7品質%的鹽酸溶解，使用VARIAN公司製造的原子吸光分光光度計(型號：AA240FS)利用原子吸光法進行定量分析而測量。另外，該鎳、鈷、鋅、鉻附著量的測量是利用以下方式進行。首先，從附載體的銅箔剝離極薄銅層後，只溶解極薄銅層的中間層側的表面附近(在極薄銅層的厚度為1.4μm以上的情況下，只溶解距極薄銅層的中間層側的表面0.5μm厚度，在極薄銅層的厚度未達1.4μm的情況下，只溶解從極薄銅層的中間層側的表面起到極薄銅層厚度的20%)，測量極薄銅層的中間層側的表面的附著量。另外，在剝離極薄銅層後，只溶解載體的中間層側的表面附近(距表面0.5μm厚度)，測量載體的中間層側的表面的附著量。並且，將對極薄銅層的中間層側的表面的附著量和載體的中間層側的表面的附著量總計所得之值設為中間層的金屬附著量。 The nickel adhesion amount and the cobalt adhesion amount were obtained by dissolving the sample in a concentration of 20% by mass of nitric acid, and measuring it by ICP emission analysis using an ICP emission spectrometer (Model: SPS3100) manufactured by SII Corporation. The sample was dissolved in hydrochloric acid having a concentration of 7% by mass, and was measured by atomic absorption spectrometry using an atomic absorption spectrophotometer (Model: AA240FS) manufactured by VARIAN Co., Ltd. Further, the measurement of the adhesion amount of nickel, cobalt, zinc, and chromium was carried out in the following manner. First, after the ultra-thin copper layer is peeled off from the copper foil with a carrier, only the vicinity of the surface of the intermediate layer side of the ultra-thin copper layer is dissolved (in the case where the thickness of the ultra-thin copper layer is 1.4 μm or more, only the extremely thin copper is dissolved) The surface of the intermediate layer side of the layer has a thickness of 0.5 μm, and in the case where the thickness of the ultra-thin copper layer is less than 1.4 μm, only the surface from the intermediate layer side of the ultra-thin copper layer is dissolved to 20% of the thickness of the extremely thin copper layer) The amount of adhesion of the surface on the intermediate layer side of the ultra-thin copper layer was measured. Further, after the ultra-thin copper layer was peeled off, only the vicinity of the surface on the intermediate layer side of the carrier (0.5 μm thick from the surface) was dissolved, and the amount of adhesion of the surface on the intermediate layer side of the carrier was measured. In addition, the value obtained by totaling the adhesion amount of the surface of the ultra-thin copper layer on the intermediate layer side and the adhesion amount of the surface of the carrier on the intermediate layer side is the metal adhesion amount of the intermediate layer.
‧蝕刻性 ‧ etchability
將附載體的銅箔貼附到BT樹脂基板、或FR-4基板並以220℃進行2小時熱壓，然後以220℃進行4小時熱處理。接著，將極薄銅層從銅箔載體 剝離。接著，在基板上的極薄銅層表面塗布感光性抗鍍敷劑後，利用曝光、顯影步驟形成50條L/S=10μm/10μm寬的抗鍍敷劑圖案，在以下的噴霧蝕刻條件下去除銅層不需要的部分。 The copper foil with a carrier was attached to the BT resin substrate or the FR-4 substrate, and hot pressed at 220 ° C for 2 hours, and then heat treated at 220 ° C for 4 hours. Next, the ultra-thin copper layer is removed from the copper foil carrier Stripped. Next, after applying a photosensitive anti-plating agent to the surface of the ultra-thin copper layer on the substrate, 50 strips of L/S=10 μm/10 μm-resistant plating resist pattern were formed by exposure and development steps under the following spray etching conditions. Remove unwanted portions of the copper layer.
(噴霧蝕刻條件) (spray etching conditions)
液溫：60℃ Liquid temperature: 60 ° C
噴霧壓：2.0Mpa Spray pressure: 2.0Mpa
繼續蝕刻，測量電路頂寬成為4μm的時間，進而評估此時的電路底寬(底辺X的長度)及蝕刻係數。在蝕刻成扇形時(產生塌邊時)，在假定電路垂直地蝕刻的情況下從銅箔上表面引下垂線，將從垂線和樹脂基板的交點起的塌邊的長度的距離設為a的情況下，蝕刻係數表示該a和銅箔的厚度b的比：b/a，該數值越大，意味著傾斜角越大，越不殘留蝕刻殘渣，塌邊越小。在圖5中表示電路圖案的寬度方向的橫截面的示意圖，並表示使用該示意圖的蝕刻係數的計算方法的概略。該a藉由從電路上方進行SEM觀察而測量，算出蝕刻係數(EF=b/a)。另外，利用b=(X(μm)-4(μm))/2進行計算。藉由使用該蝕刻係數，可以簡單地判定蝕刻性是否良好。在本發明中，將蝕刻係數為2.5以上設為蝕刻性良好，將未達2.5或無法算出(包括在底邊部分，鄰接的電路間短路的情況)判定為蝕刻異常，評估每1dm2的蝕刻異常數。 The etching was continued, and the top width of the measuring circuit was measured to be 4 μm, and the circuit bottom width (the length of the bottom 辺X) and the etching coefficient at this time were evaluated. When etching into a fan shape (when a sag occurs), a vertical line is drawn from the upper surface of the copper foil assuming that the circuit is vertically etched, and the distance from the length of the sag from the intersection of the vertical line and the resin substrate is set to a. In the case, the etching coefficient indicates the ratio of the thickness b of the a to the copper foil: b/a, and the larger the value, the larger the inclination angle, the less the etching residue remains, and the smaller the collapse. FIG. 5 is a schematic view showing a cross section of the circuit pattern in the width direction, and shows an outline of a calculation method of the etching coefficient using the schematic diagram. This a is measured by SEM observation from the upper side of the circuit, and the etching coefficient (EF = b / a) is calculated. Further, calculation was performed using b = (X (μm) - 4 (μm))/2. By using this etching coefficient, it is possible to easily determine whether or not the etching property is good. In the present invention, the etching coefficient is preferably 2.5 or more, and the etching property is good, and it is determined that the etching is abnormal, and it is impossible to calculate (including the case where the bottom side portion is short-circuited between adjacent circuits), and the etching is evaluated every 1 dm 2 . The number of exceptions.
‧銅以外的元素的被覆率 ‧The coverage rate of elements other than copper
對附載體的銅箔在載體/極薄銅層間進行剝離，將載體側浸漬於硫化銨水溶液。硫化銨具有使Cu變黑的性質，只有銅載體基材之沒有被Ni鍍 層或Co鍍層等由銅以外的金屬形成的金屬鍍層、或者鉻酸鹽處理層、有機物層等層覆蓋的部分變黑。 The copper foil with the carrier was peeled off between the carrier/very thin copper layer, and the carrier side was immersed in an aqueous solution of ammonium sulfide. Ammonium sulfide has the property of blackening Cu, and only the copper carrier substrate is not Ni plated. A metal plating layer made of a metal other than copper such as a layer or a Co plating layer, or a portion covered with a layer such as a chromate treatment layer or an organic layer is blackened.
‧硫化銨水溶液 ‧Ammonium sulfide aqueous solution
硫化銨：5~20vol% Ammonium sulfide: 5~20vol%
液溫：20~30℃ Liquid temperature: 20~30°C
浸漬時間：30秒~2分鐘 Immersion time: 30 seconds to 2 minutes
然後，用掃描器掃描載體剝離層側，將其圖像用“2灰階化”加工成黑白。將圖像的白和黑的“閾值”設定為70(白：0、黑：255)，將白色部分的面積率定義為銅以外的元素的被覆率。 Then, the carrier peeling layer side was scanned with a scanner, and the image was processed into black and white by "2 gray-scale". The white and black "threshold value" of the image is set to 70 (white: 0, black: 255), and the area ratio of the white portion is defined as the coverage ratio of the elements other than copper.
‧水份產生量(將附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量) ‧ Moisture production (the amount of water produced when the carrier's copper foil is heated to 500 ° C at 30 ° C / min)
在經氬氣置換的手套箱內，將附載體的銅箔切取成
水份產生量(將附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量)(ppm/g)=水份產生量A(品質(g))/所測量的附載體的銅箔的樣品的品質(g)×106 Moisture yield (amount of water produced when the copper foil with a carrier is heated to 500 ° C at 30 ° C / min) (ppm / g) = moisture production A (quality (g)) / measured carrier The quality of the copper foil sample (g) × 10 6
‧鼓出的個數 ‧The number of bulges
將附載體的銅箔在220℃的大氣加熱爐內加熱4小時。加熱後，利用光學顯微鏡用目視數出每1dm2的鼓出的個數。另外，將附載體的銅箔在400℃的大氣加熱爐內加熱10分鐘。加熱後，利用光學顯微鏡用目視數出每1dm2的鼓出的個數。 The copper foil with the carrier was heated in an atmospheric heating furnace at 220 ° C for 4 hours. After heating, the number of bulging per 1 dm 2 was visually observed by an optical microscope. Further, the copper foil with a carrier was heated in an air oven at 400 ° C for 10 minutes. After heating, the number of bulging per 1 dm 2 was visually observed by an optical microscope.
將該試驗條件及試驗結果示於表1。 The test conditions and test results are shown in Table 1.
(評估結果) (evaluation result)
實施例1~12將附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量皆為160ppm/g以下，鼓出的產生及蝕刻產生率皆被良好地抑制。 In Examples 1 to 12, when the copper foil with a carrier was heated at 30 ° C / min to 500 ° C, the amount of water generated was 160 ppm / g or less, and the generation of bulging and the etching yield were well suppressed.
另外，實施例1~12將附載體的銅箔以220℃加熱4小時時所產生的鼓出皆為20個/dm2以下，水份的產生及蝕刻產生率皆被良好地抑制。 Further, in Examples 1 to 12, when the copper foil with a carrier was heated at 220 ° C for 4 hours, the bulging was 20 / dm 2 or less, and the generation of moisture and the etching yield were well suppressed.
比較例1~3將附載體的銅箔以30℃/分鐘加熱到500℃時所產生的水份量皆超過160ppm/g，鼓出的產生皆多，蝕刻產生率皆不良。 In Comparative Examples 1 to 3, when the copper foil with a carrier was heated at 30 ° C / min to 500 ° C, the amount of water generated exceeded 160 ppm / g, and the generation of bulging was excessive, and the etching yield was poor.
另外，比較例1~3將附載體的銅箔以220℃加熱4小時時所產生的鼓出皆超過20個/dm2，水份的產生皆多，蝕刻產生率皆不良。 Further, 1 to 3, a copper foil with a carrier bulging upon heating at 220 ℃ 4 hour period are generated Comparative Example over 20 / dm 2, the produced water are more etch rate are undesirable generation.
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| JP6570430B2 (en) * | 2015-11-12 | 2019-09-04 | Ｊｘ金属株式会社 | Method for producing copper foil with carrier, method for producing printed wiring board, and method for producing electronic device |
| JP2017124533A (en) * | 2016-01-13 | 2017-07-20 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, method for manufacturing copper foil with carrier, method for manufacturing printed wiring board, and method for manufacturing electric equipment |
| CN105704948B (en) * | 2016-03-28 | 2018-05-29 | 上海美维电子有限公司 | The production method of ultra-thin printed circuit board and ultra-thin printed circuit board |
| JP2017177610A (en) * | 2016-03-30 | 2017-10-05 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device |
| JP2017177611A (en) * | 2016-03-30 | 2017-10-05 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device |
| JP6391621B2 (en) * | 2016-03-31 | 2018-09-19 | Ｊｘ金属株式会社 | Titanium copper foil, copper products, electronic equipment parts and autofocus camera module |
| KR101881287B1 (en) * | 2017-01-16 | 2018-07-27 | 일진머티리얼즈 주식회사 | Copper foil attached to the carrier foil |
| CN107623990A (en) * | 2017-07-26 | 2018-01-23 | 珠海亚泰电子科技有限公司 | Thicken copper base and preparation technology |
| CN108093572A (en) * | 2017-12-15 | 2018-05-29 | 上海美维科技有限公司 | A kind of production method of the printed circuit board with no porose disc blind hole structure |
| JP6462940B1 (en) * | 2018-03-23 | 2019-01-30 | 三井金属鉱業株式会社 | Copper foil with carrier, copper-clad laminate and printed wiring board |
| CN112423982A (en) * | 2018-07-18 | 2021-02-26 | 昭和电工材料株式会社 | Copper-clad laminate, printed wiring board, semiconductor package, and method for manufacturing copper-clad laminate |
| JP7328671B2 (en) * | 2019-05-09 | 2023-08-17 | ナミックス株式会社 | laminate |
| US10697082B1 (en) * | 2019-08-12 | 2020-06-30 | Chang Chun Petrochemical Co., Ltd. | Surface-treated copper foil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200808145A (en) * | 2006-03-24 | 2008-02-01 | Ube Industries | Process for producing copper wiring polyimide film and copper wiring polyimide film |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0818401B2 (en) * | 1989-05-17 | 1996-02-28 | 福田金属箔粉工業株式会社 | Composite foil and its manufacturing method |
| JP4160131B2 (en) * | 1994-12-26 | 2008-10-01 | 日立化成工業株式会社 | Method for producing metal foil for printed wiring board |
| JP2001127429A (en) * | 1999-10-25 | 2001-05-11 | Hitachi Chem Co Ltd | Method for producing multilayer printed wiring board |
| JP2002026475A (en) * | 2000-07-07 | 2002-01-25 | Mitsui Mining & Smelting Co Ltd | Copper foil circuit with carrier foil, method of manufacturing printed wiring board, using the same, and printed wiring board |
| US7691487B2 (en) | 2002-07-04 | 2010-04-06 | Mitsui Mining & Smelting Co., Ltd. | Electrodeposited copper foil with carrier foil |
| JP4701735B2 (en) * | 2004-07-09 | 2011-06-15 | 株式会社豊田自動織機 | Sliding member |
| JP4429979B2 (en) | 2005-06-29 | 2010-03-10 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier and method for producing ultra-thin copper foil with carrier |
| JP4927503B2 (en) * | 2005-12-15 | 2012-05-09 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier and printed wiring board |
| JP2010006071A (en) | 2009-08-21 | 2010-01-14 | Furukawa Electric Co Ltd:The | Surface treatment copper foil, extremely thin copper foil with carrier, flexible copper clad laminate, and polyimide based flexible printed wiring board |
| US8329315B2 (en) * | 2011-01-31 | 2012-12-11 | Nan Ya Plastics Corporation | Ultra thin copper foil with very low profile copper foil as carrier and its manufacturing method |
| TWI511633B (en) * | 2011-03-30 | 2015-12-01 | Mitsui Mining & Smelting Co | Method of manufacturing multi-layer printed wiring board and multi-layer printed wiring board obtained by the manufacturing method |
| JP2013001993A (en) * | 2011-06-21 | 2013-01-07 | Meltex Inc | Ultrathin copper foil with carrier foil and method of manufacturing the same |
| KR101614624B1 (en) * | 2011-08-31 | 2016-04-29 | 제이엑스 킨조쿠 가부시키가이샤 | Copper foil with carrier |
| JP5413693B2 (en) * | 2012-02-06 | 2014-02-12 | 日立化成株式会社 | Circuit forming support substrate and method of manufacturing semiconductor device mounting package substrate |
| JP5156873B1 (en) * | 2012-07-25 | 2013-03-06 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| KR101391811B1 (en) * | 2012-08-17 | 2014-05-07 | 일진머티리얼즈 주식회사 | Copper foil attached to the carrier foil, copper-clad laminate and printed circuit board using the same |
| JP5481577B1 (en) * | 2012-09-11 | 2014-04-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| JP5521099B1 (en) * | 2013-09-02 | 2014-06-11 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method |
-
2015
- 2015-03-24 TW TW104109351A patent/TWI613940B/en active
- 2015-03-30 KR KR1020150044261A patent/KR101705969B1/en active IP Right Grant
- 2015-03-31 JP JP2015074348A patent/JP6342356B2/en active Active
- 2015-03-31 CN CN201510147943.1A patent/CN104943270B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200808145A (en) * | 2006-03-24 | 2008-02-01 | Ube Industries | Process for producing copper wiring polyimide film and copper wiring polyimide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6342356B2 (en) | 2018-06-13 |
| TW201542047A (en) | 2015-11-01 |
| KR20150113901A (en) | 2015-10-08 |
| JP2015199355A (en) | 2015-11-12 |
| CN104943270A (en) | 2015-09-30 |
| KR101705969B1 (en) | 2017-02-10 |
| CN104943270B (en) | 2017-10-31 |
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