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CN105209252B - Copper foil with carrier, the manufacture method using its copper-cover laminated plate, printing distributing board, e-machine and printing distributing board - Google Patents

Copper foil with carrier, the manufacture method using its copper-cover laminated plate, printing distributing board, e-machine and printing distributing board Download PDF

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Publication number
CN105209252B
CN105209252B CN201480012569.8A CN201480012569A CN105209252B CN 105209252 B CN105209252 B CN 105209252B CN 201480012569 A CN201480012569 A CN 201480012569A CN 105209252 B CN105209252 B CN 105209252B
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layer
carrier
copper foil
copper
ultra
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CN105209252A (en
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坂口和彦
佐佐木伸
佐佐木伸一
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0355Metal foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

提供一种适于形成窄间距的附载体铜箔。一种附载体铜箔,其依序具备作为支持体的载体、中间层、极薄铜层,该极薄铜层表面的至少一面以非接触式粗糙度计进行测定而得的Rz在0.5μm以下。

Provided is a copper foil with a carrier suitable for forming a narrow pitch. A copper foil with a carrier, which sequentially includes a carrier as a support, an intermediate layer, and an ultra-thin copper layer, wherein at least one surface of the ultra-thin copper layer has an Rz of 0.5 μm measured by a non-contact roughness meter the following.

Description

附载体铜箔、使用其的覆铜积层板、印刷配线板、电子机器及 印刷配线板的制造方法Copper foil with carrier, copper clad laminate using it, printed wiring board, electronic equipment and Manufacturing method of printed wiring board

技术领域technical field

本发明涉及一种附载体铜箔、使用其的覆铜积层板、印刷配线板、电子机器及印刷配线板的制造方法。The present invention relates to a copper foil with a carrier, a copper-clad laminate using the same, a printed wiring board, an electronic device, and a method for manufacturing the printed wiring board.

背景技术Background technique

印刷配线板通常经过下述步骤而制造:在使绝缘基板与铜箔接着而制成覆铜积层板之后,通过蚀刻而在铜箔面形成导体图案。随着近年来电子机器的小型化、高性能化需求的增大而推展搭载零件的高密度构装化或信号的高频化,从而对印刷配线板要求有导体图案的细微化(窄间距化)或高频应对等。A printed wiring board is usually produced through a process of forming a conductive pattern on the copper foil surface by etching after bonding an insulating substrate and copper foil to form a copper-clad laminate. In recent years, with the miniaturization of electronic equipment and the increase in the demand for high performance, the high-density packaging of mounted parts and the high frequency of signals have been promoted, and the miniaturization of conductor patterns (narrow pitch) is required for printed wiring boards. ) or high-frequency response, etc.

与窄间距化相对应,近来要求厚度在9μm以下、甚至是厚度在5μm以下的铜箔,然而,这种极薄的铜箔其机械强度低,在印刷配线板的制造时易破裂或产生皱折,因此发展出将具有厚度的金属箔用作为载体并隔着剥离层将极薄铜层电沉积在其上而成的附载体铜箔。在将极薄铜层的表面贴合于绝缘基板并进行热压接后,经由剥离层将载体剥离去除。在所露出的极薄铜层上通过抗蚀剂而形成电路图案后,利用硫酸-过氧化氢系蚀刻液来蚀刻去除极薄铜层,通过此手法(MSAP:Modified-Semi-Additive-Process)来形成细微电路。Corresponding to the narrow pitch, copper foil with a thickness of 9 μm or less, and even a thickness of 5 μm or less has recently been required. However, such extremely thin copper foil has low mechanical strength and is prone to cracking or cracking during the manufacture of printed wiring boards. Therefore, a copper foil with a carrier is developed, which uses a thick metal foil as a carrier and deposits an extremely thin copper layer on it through a peeling layer. After bonding the surface of the ultra-thin copper layer to the insulating substrate and performing thermocompression bonding, the carrier is peeled and removed through the release layer. After forming a circuit pattern with a resist on the exposed ultra-thin copper layer, the ultra-thin copper layer is etched and removed with a sulfuric acid-hydrogen peroxide-based etchant (MSAP: Modified-Semi-Additive-Process) to form microscopic circuits.

此处,对于成为与树脂的接着面的附载体铜箔的极薄铜层的表面主要要求极薄铜层与树脂基材的剥离强度充足,且此剥离强度在高温加热、湿式处理、焊接、化学药剂处理等之后也保持为充足。提高极薄铜层与树脂基材间的剥离强度的方法,一般而言是以下述方法为代表:使大量的粗化粒子附着于表面的轮廓(凹凸、粗糙)增大后的极薄铜层上。Here, for the surface of the ultra-thin copper layer of the copper foil with a carrier to be the bonding surface with the resin, it is mainly required that the peel strength between the ultra-thin copper layer and the resin base material is sufficient, and the peel strength is high temperature heating, wet processing, welding, Chemical agent treatment etc. are also kept sufficient afterward. The method of improving the peel strength between the ultra-thin copper layer and the resin base material is generally represented by the method of attaching a large number of roughening particles to the ultra-thin copper layer after the surface contour (concave-convex, roughness) is enlarged superior.

然而,即便是在印刷配线板中,若在具有形成特别细微的电路图案的需要的半导体封装基板使用这种轮廓(凹凸、粗糙)大的极薄铜层,则在电路蚀刻时会残留不需要的铜粒子,会产生电路图案间的绝缘不良等问题。However, even in printed wiring boards, if such an ultra-thin copper layer with a large outline (concave-convex, roughness) is used on a semiconductor package substrate required to form a particularly fine circuit pattern, undesired copper will remain during circuit etching. Necessary copper particles cause problems such as poor insulation between circuit patterns.

因此,在WO2004/005588号(专利文献1)中尝试了使用未在极薄铜层的表面施加粗化处理的附载体铜箔作为以半导体封装基板为首的用于细微电路的附载体铜箔。由于其低轮廓(凹凸、粗糙度、粗糙)的影响,这种未施加粗化处理的极薄铜层与树脂的密合性(剥离强度)与一般的印刷配线板用铜箔相比,有降低的倾向。因此,要求对附载体铜箔作进一步的改善。Therefore, WO2004/005588 (Patent Document 1) attempted to use a copper foil with a carrier that did not roughen the surface of the ultra-thin copper layer as a copper foil with a carrier for fine circuits including semiconductor package substrates. Due to its low profile (concave-convex, roughness, roughness), the adhesion (peel strength) of this ultra-thin copper layer without roughening treatment to resin is lower than that of general copper foil for printed wiring boards. tends to decrease. Therefore, further improvement of the copper foil with a carrier is required.

因此,在日本特开2007-007937号公报(专利文献2)及日本特开2010-006071号公报(专利文献3)中,记载有在附载体极薄铜箔的与聚酰亚胺系树脂基板接触(接着)的面,设置Ni层或/及Ni合金层、设置铬酸盐层、设置Cr层或/及Cr合金层、设置Ni层及铬酸盐层、设置Ni层及Cr层。通过设置该等表面处理层,聚酰亚胺系树脂基板与附载体极薄铜箔的密合强度可不经粗化处理或是降低粗化处理的程度(细微化)即可得到所欲的接着强度。此外,也记载有利用硅烷偶合剂来进行表面处理或施加防锈处理。Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Laid-Open No. 2010-006071 (Patent Document 3), it is described that an ultra-thin copper foil with a carrier and a polyimide-based resin substrate On the contacting (adhering) surface, a Ni layer or/and Ni alloy layer, a chromate layer, a Cr layer or/and Cr alloy layer, a Ni layer and a chromate layer, a Ni layer and a Cr layer are provided. By providing these surface treatment layers, the adhesion strength between the polyimide-based resin substrate and the ultra-thin copper foil with a carrier can be obtained without roughening or by reducing the degree of roughening (micronization). strength. In addition, it is also described that surface treatment or antirust treatment is performed using a silane coupling agent.

[专利文献1]WO2004/005588号[Patent Document 1] WO2004/005588

[专利文献2]日本特开2007-007937号公报[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-007937

[专利文献3]日本特开2010-006071号公报。[Patent Document 3] Japanese Unexamined Patent Publication No. 2010-006071.

发明内容Contents of the invention

发明所要解决的问题The problem to be solved by the invention

在附载体铜箔的开发中,至今为止确保极薄铜层与树脂基材的剥离强度一直被视为重点。因此,仍未对窄间距化进行充分探讨,其仍有改善的空间。故,本发明的目的在于提供一种适于形成窄间距的附载体铜箔。具体而言,本发明的目的在于提供一种附载体铜箔,其可形成比至今为止被认为是利用MSAP而可形成的极限的L(线)/S(间隔)=15μm/15μm更加细微的配线。In the development of copper foil with a carrier, securing the peel strength between the ultra-thin copper layer and the resin substrate has been regarded as an important point until now. Therefore, the narrow pitch has not yet been fully explored, and there is still room for improvement. Therefore, an object of the present invention is to provide a copper foil with a carrier suitable for forming a narrow pitch. Specifically, the object of the present invention is to provide a copper foil with a carrier that can form finer copper foil than L (line)/S (space) = 15 μm/15 μm, which has been considered as the limit of formation using MSAP. Wiring.

为了达成上述目的,本申请发明人重复进行潜心研究,结果发现可使极薄铜层的表面低粗糙度化。然后,发现该附载体铜箔对于形成窄间距极有效果。In order to achieve the above-mentioned object, the inventors of the present application have repeatedly studied intensively, and as a result, found that the surface roughness of the ultra-thin copper layer can be reduced. Then, it was found that this copper foil with a carrier is extremely effective for forming a narrow pitch.

本发明是以上述知识见解为基础而完成的,在一方面中,是一种附载体铜箔,其依序具备作为支持体的载体、中间层、极薄铜层,上述极薄铜层表面的至少一面以非接触式粗糙度计进行测定而得的Rz在0.5μm以下。The present invention is based on the above-mentioned knowledge and knowledge. In one aspect, it is a copper foil with a carrier, which sequentially includes a carrier as a support, an intermediate layer, and an ultra-thin copper layer. The surface of the ultra-thin copper layer is Rz measured with a non-contact roughness meter on at least one side is 0.5 μm or less.

在本发明的附载体铜箔的一实施方案中,上述极薄铜层表面的两面以非接触式粗糙度计进行测定而得的Rz在0.5μm以下。In one Embodiment of the copper foil with a carrier which concerns on this invention, Rz measured with the non-contact roughness meter on both surfaces of the said ultra-thin copper layer surface is 0.5 micrometers or less.

在本发明的附载体铜箔的另一实施方案中,上述极薄铜层表面以非接触式粗糙度计进行测定而得的Ra在0.12μm以下。In another embodiment of the copper foil with a carrier of the present invention, Ra measured with a non-contact roughness meter on the surface of the ultra-thin copper layer is 0.12 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述极薄铜层表面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Rt measured by a non-contact roughness meter on the surface of the ultra-thin copper layer is 1.0 μm or less.

本发明在另一方面中,是一种附载体铜箔,其依序具备作为支持体的载体、中间层、极薄铜层,上述极薄铜层表面的至少一面以非接触式粗糙度计进行测定而得的Ra在0.12μm以下。In another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier as a support, an intermediate layer, and an ultra-thin copper layer, and at least one surface of the ultra-thin copper layer is measured by non-contact roughness. The measured Ra is 0.12 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述极薄铜层表面的两面以非接触式粗糙度计进行测定而得的Ra在0.12μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Ra measured by a non-contact roughness meter on both surfaces of the surface of the ultra-thin copper layer is 0.12 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述极薄铜层表面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Rt measured by a non-contact roughness meter on the surface of the ultra-thin copper layer is 1.0 μm or less.

本发明在再另一方面中,是一种附载体铜箔,其依序具备作为支持体的载体、中间层、极薄铜层,上述极薄铜层表面的至少一面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。In yet another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier as a support, an intermediate layer, and an ultra-thin copper layer, at least one surface of the ultra-thin copper layer is roughened by a non-contact method. The Rt measured by the meter is 1.0 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述极薄铜层表面的两面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Rt measured by a non-contact roughness meter on both surfaces of the ultra-thin copper layer surface is 1.0 μm or less.

在本发明的附载体铜箔的再另一实施方案中,利用膜来形成上述载体。In another one Embodiment of the copper foil with a carrier which concerns on this invention, the said carrier is formed using a film.

在本发明的附载体铜箔的再另一实施方案中,上述载体的上述中间层侧表面的Rz在0.5μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Rz of the surface on the side of the intermediate layer of the carrier is 0.5 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述载体的上述中间层侧表面的Ra在0.12μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Ra of the surface on the side of the intermediate layer of the carrier is 0.12 μm or less.

在本发明的附载体铜箔的再另一实施方案中,上述载体的上述中间层侧表面的Rt在1.0μm以下。In yet another embodiment of the copper foil with a carrier of the present invention, Rt of the surface on the side of the intermediate layer of the carrier is 1.0 μm or less.

在本发明的附载体铜箔的再另一实施方案中,极薄铜层表面的至少一面形成有粗化处理层。In yet another embodiment of the copper foil with a carrier of the present invention, at least one surface of the ultra-thin copper layer is formed with a roughened layer.

在本发明的附载体铜箔的再另一实施方案中,上述粗化处理层为由选自由铜、镍、磷、钨、砷、钼、铬、钴及锌构成的群中的任一单质构成的层,或由含有任一种以上该单质的合金构成的层,或者为含有含任一种以上该单质的合金的层。In yet another embodiment of the copper foil with a carrier of the present invention, the roughening layer is any elemental substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc. The layer constituted is either a layer composed of an alloy containing any one or more of the simple substances, or a layer containing an alloy containing any one or more of the simple substances.

在本发明的附载体铜箔的再另一实施方案中,在上述极薄铜层的表面具有选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层。In yet another embodiment of the copper foil with a carrier of the present invention, the surface of the ultra-thin copper layer has a layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate-treated layer, and a silane coupling-treated layer. More than 1 layer.

在本发明的附载体铜箔的再另一实施方案中,在上述粗化处理层的表面具有选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层。In yet another embodiment of the copper foil with a carrier of the present invention, the surface of the roughened layer has a layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate-treated layer, and a silane coupling-treated layer. More than 1 layer.

在本发明的附载体铜箔的再另一实施方案中,上述该极薄铜层表面具备树脂层。In another one Embodiment of the copper foil with a carrier which concerns on this invention, the surface of the said ultra-thin copper layer is equipped with a resin layer.

在本发明的附载体铜箔的再另一实施方案中,在上述粗化处理层表面具备树脂层。In another one Embodiment of the copper foil with a carrier which concerns on this invention, a resin layer is provided on the surface of the said roughening process layer.

在本发明的附载体铜箔的再另一实施方案中,在上述选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层的表面具备树脂层。In yet another embodiment of the copper foil with a carrier of the present invention, on the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane-coupling-treated layer, With a resin layer.

在本发明的附载体铜箔的再另一实施方案中,上述树脂层含有介电体。In another one Embodiment of the copper foil with a carrier which concerns on this invention, the said resin layer contains a dielectric body.

在本发明的附载体铜箔的再另一实施方案中,是一种附载体铜箔,其可通过使用有极薄铜层的半加成法来形成比线/间隔=15μm/15μm更加细微的电路。In yet another embodiment of the copper foil with a carrier of the present invention, it is a copper foil with a carrier that can be formed finer than line/space = 15 μm/15 μm by using a semi-additive method with an extremely thin copper layer. circuit.

本发明在再另一方面中,是一种覆铜积层板,其是使用本发明的附载体铜箔制造而成者。In still another aspect, the present invention is a copper-clad laminate manufactured using the copper foil with a carrier of the present invention.

本发明在再另一方面中,是一种印刷配线板,其是使用本发明的附载体铜箔制造而成者。This invention is another one side. It is a printed wiring board manufactured using the copper foil with a carrier of this invention.

本发明在再另一方面中,是一种电子机器,其使用有本发明的印刷配线板。In still another aspect, the present invention is an electronic device using the printed wiring board of the present invention.

本发明在再另一方面中,是一种印刷配线板的制造方法,其包含下述步骤:In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;及Laminate the above-mentioned copper foil with carrier and insulating substrate; and

在将上述附载体铜箔与绝缘基板积层后,经将上述附载体铜箔的载体剥离的步骤而形成覆铜积层板,After laminating the above-mentioned copper foil with a carrier and an insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate,

其后,通过半加成法、减成法、部分加成法或改进半加成法(Modified SemiAdditive)中的任一方法形成电路。Thereafter, a circuit is formed by any one of semi-additive method, subtractive method, partial additive method, or modified semi-additive method (Modified SemiAdditive).

本发明在再另一方面中,是一种印刷配线板的制造方法,其包含下述步骤:In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

在本发明的附载体铜箔的上述极薄铜层侧表面形成电路;A circuit is formed on the side surface of the above-mentioned ultra-thin copper layer of the copper foil with a carrier of the present invention;

以埋没该电路的方式在上述附载体铜箔的上述极薄铜层侧表面形成树脂层;forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier so as to bury the circuit;

在上述树脂层上形成电路;forming a circuit on the above-mentioned resin layer;

在上述树脂层上形成电路后,剥离上述载体;及After forming a circuit on the above resin layer, peeling off the above carrier; and

在剥离上述载体后,去除上述极薄铜层,由此使形成在上述极薄铜层侧表面的埋没于上述树脂层的电路露出。After peeling off the carrier, the ultra-thin copper layer is removed, thereby exposing the circuit formed on the side surface of the ultra-thin copper layer buried in the resin layer.

本发明的附载体铜箔适于窄间距形成,例如可形成比被认为是利用MSAP步骤而可形成的极限的线/间隔=15μm/15μm更加细微的配线,例如线/间隔=10μm/10μm的细微配线。The copper foil with a carrier of the present invention is suitable for narrow-pitch formation, for example, finer wiring can be formed than line/space = 15 μm/15 μm, which is considered to be the limit that can be formed by the MSAP process, for example, line/space = 10 μm/10 μm fine wiring.

附图说明Description of drawings

图1:本发明的附载体铜箔的结构的一例。FIG. 1 : An example of the structure of the copper foil with a carrier of this invention.

图2:A~C是使用了本发明的附载体铜箔的印刷配线板的制造方法的具体实施例的至电路镀敷-去除光阻剂为止的步骤中的配线板剖面的示意图。2 : A to C are schematic cross-sectional diagrams of wiring boards in steps from circuit plating to photoresist removal in a specific embodiment of the method of manufacturing a printed wiring board using copper foil with a carrier according to the present invention.

图3:D~F是使用了本发明的附载体铜箔的印刷配线板的制造方法的具体实施例的自积层树脂及第2层附载体铜箔至雷射开孔为止的步骤中的配线板剖面的示意图。Figure 3: D to F are the steps from the lamination resin and the second layer of copper foil with a carrier to the laser opening of the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of the present invention A schematic diagram of a patch panel cross-section.

图4:G~I是使用了本发明的附载体铜箔的印刷配线板的制造方法的具体实施例的自形成通孔填充物至剥离第1层载体为止的步骤中的配线板剖面的示意图。Fig. 4: G to I are the cross sections of the printed wiring board in the steps from the formation of the through-hole filling to the peeling of the first layer carrier in the specific example of the manufacturing method of the printed wiring board using the copper foil with carrier of the present invention schematic diagram.

图5:J~K是使用了本发明的附载体铜箔的印刷配线板的制造方法的具体实施例的自快速蚀刻至形成凸块-铜柱为止的步骤中的配线板剖面的示意图。5: J to K are schematic cross-sectional views of the wiring board in the steps from flash etching to bump-copper pillar formation in a specific example of the method of manufacturing the printed wiring board using the copper foil with carrier of the present invention. .

具体实施方式detailed description

<载体><Carrier>

本发明的载体,优选为使用中间层侧表面的Rz为0.5μm以下的。通过此种构成,可容易地将形成于载体上的中间层的一个表面或两表面的Rz控制在0.5μm以下。载体的中间层侧表面的Rz更优选为0.3μm以下,再更优选为0.1μm以下。As the carrier of the present invention, it is preferable to use one whose Rz of the side surface of the intermediate layer is 0.5 μm or less. With such a configuration, Rz of one or both surfaces of the intermediate layer formed on the carrier can be easily controlled to 0.5 μm or less. Rz of the intermediate layer side surface of the carrier is more preferably 0.3 μm or less, still more preferably 0.1 μm or less.

又,本发明的载体,优选为使用中间层侧表面的Ra为0.12μm以下的。通过此种构成,可容易地将形成于载体上的中间层的一个表面或两表面的Ra控制在0.12μm以下。载体的中间层侧表面的Ra更优选为0.1μm以下,再更优选为0.08μm以下,再更优选为0.05μm以下。In addition, it is preferable to use the carrier of the present invention having an Ra of the surface on the side of the intermediate layer of 0.12 μm or less. With such a configuration, Ra of one surface or both surfaces of the intermediate layer formed on the carrier can be easily controlled to 0.12 μm or less. Ra of the intermediate layer side surface of the support is more preferably 0.1 μm or less, still more preferably 0.08 μm or less, still more preferably 0.05 μm or less.

又,本发明的载体,优选为使用中间层侧表面的Rt为1.0μm以下的。通过此种构成,可容易地将形成于载体上的中间层的一个表面或两表面的Rt控制在1.0μm以下。载体的中间层侧表面的Rt更优选为0.5μm以下,再更优选为0.3μm以下。Also, it is preferable to use the carrier of the present invention having an Rt of 1.0 μm or less on the side surface of the intermediate layer. With such a configuration, it is possible to easily control the Rt of one surface or both surfaces of the intermediate layer formed on the carrier to 1.0 μm or less. The Rt of the intermediate layer side surface of the support is more preferably 0.5 μm or less, still more preferably 0.3 μm or less.

作为本发明的载体,例如优选为使用树脂膜等膜,特优选为使用具有表面平滑性的膜。作为此种膜载体,一般而言,优选为可承受干式表面处理或湿式表面处理时,或者是基板制作时的积层压制时的热负载的耐热膜,可使用聚酰亚胺膜等。As the carrier of the present invention, for example, a film such as a resin film is preferably used, and a film having a smooth surface is particularly preferably used. Generally speaking, such a film carrier is preferably a heat-resistant film that can withstand thermal load during dry surface treatment or wet surface treatment, or during lamination and pressing during substrate production, and polyimide films and the like can be used. .

使用为聚酰亚胺膜的材料并无特别限制。例如现正上市中的宇部兴产制造的Upilex、DuPont/DU PONT-TORAY制造的Kapton、KANEKA制造的Apical等,任何的聚酰亚胺膜皆可应用。又,可应用于本发明的载体的膜并不限定于上述的特定品种。The material used as the polyimide film is not particularly limited. For example, Upilex manufactured by Ube Industries, Kapton manufactured by DuPont/DU PONT-TORAY, Apical manufactured by KANEKA etc. which are currently on the market, any polyimide film can be applied. In addition, the film applicable to the carrier of the present invention is not limited to the above-mentioned specific ones.

在使用聚酰亚胺膜的情形,可通过对该膜表面进行电浆处理,来进行去除膜表面的污染物质与表面改质。电浆处理后的聚酰亚胺膜的表面的Rz虽会受材质的不同与初期表面粗糙度的不同影响,但可在Rz=2.5~500nm的范围、Ra=1~100nm的范围,或Rt=5~800nm的范围内调整。又,通过预先取得电浆处理条件与表面粗糙度的关系,而可在特定的条件进行电浆处理从而获得具有所欲的表面粗糙度的聚酰亚胺膜。In the case of using a polyimide membrane, removal of contaminants on the membrane surface and surface modification can be performed by subjecting the membrane surface to plasma treatment. Although the Rz of the surface of the polyimide film after plasma treatment will be affected by different materials and initial surface roughness, it can be in the range of Rz=2.5-500nm, Ra=1-100nm, or Rt = Adjust within the range of 5-800nm. Also, by obtaining the relationship between plasma treatment conditions and surface roughness in advance, it is possible to perform plasma treatment under specific conditions to obtain a polyimide film having desired surface roughness.

又,作为本发明的载体,可使用金属箔。作为金属箔,可使用铜箔、镍箔、镍合金箔、铝箔、铝合金箔、铁箔、铁合金箔、锌箔、锌合金箔、不锈钢箔等。又,作为本发明的载体,可使用铜箔。铜箔典型而言以压延铜箔或电解铜箔的型态提供。一般而言,电解铜箔是自硫酸铜镀浴中使铜电解析出于钛或不锈钢的滚筒上而制造,压延铜箔是重复利用压延辊的塑性加工与热处理而制造。作为铜箔的材料,除了可使用精铜(JIS H3100;合金编号C1100)或无氧铜(JIS H3100;合金编号C1020)等高纯度铜以外,也可使用例如像是掺Sn的铜、掺Ag的铜、添加有Cr、Zr或Mg等的铜合金、添加有Ni及Si等的卡逊系铜合金般的铜合金。再者,本说明书中单独使用用语“铜箔”时也包含铜合金箔。Moreover, metal foil can be used as a carrier of this invention. As the metal foil, copper foil, nickel foil, nickel alloy foil, aluminum foil, aluminum alloy foil, iron foil, iron alloy foil, zinc foil, zinc alloy foil, stainless steel foil, etc. can be used. Moreover, copper foil can be used as a carrier of this invention. Copper foil is typically provided in the form of rolled copper foil or electrolytic copper foil. Generally speaking, electrolytic copper foil is produced by electrolytically desorbing copper from a copper sulfate plating bath on a titanium or stainless steel roll, and rolled copper foil is produced by repeating plastic processing and heat treatment of rolling rolls. As the material of copper foil, in addition to high-purity copper such as refined copper (JIS H3100; alloy number C1100) or oxygen-free copper (JIS H3100; alloy number C1020), for example, Sn-doped copper, Ag-doped copper, etc. can also be used. Copper alloys such as copper, copper alloys with Cr, Zr or Mg added, and copper alloys such as Cason-based copper alloys with Ni and Si added. In addition, copper alloy foil is also included when the term "copper foil" is used independently in this specification.

用作为本发明的载体的压延铜箔可通过高光泽压延来生产。The rolled copper foil used as a support in the present invention can be produced by high-gloss rolling.

再者,高光泽压延可通过将以下的式中所规定的油膜当量设为13000~24000以下而进行。再者,在欲进一步减小表面处理后的铜箔的表面粗糙度(Rz)(例如Rz=0.20μm)的情形时,可通过将以下式中所规定的油膜当量设为12000以上且24000以下而进行高光泽压延。In addition, high-gloss rolling can be performed by making the oil film equivalent prescribed|regulated by the following formula into 13000-24000 or less. Furthermore, when it is desired to further reduce the surface roughness (Rz) of the surface-treated copper foil (for example, Rz = 0.20 μm), the oil film equivalent specified in the following formula can be set to 12000 or more and 24000 or less And carry out high-gloss calendering.

油膜当量={(压延油粘度[cSt])×(通板速度[mpm]+辊周边速度[mpm])}/{(辊的咬入角[rad])×(材料的降伏应力[kg/mm2])}Oil film equivalent={(rolling oil viscosity [cSt])×(passing plate speed [mpm]+roll peripheral speed [mpm])}/{(roller bite angle [rad])×(material yield stress [kg/ mm 2 ])}

压延油粘度[cSt]为于40℃的动粘度。The rolling oil viscosity [cSt] is the dynamic viscosity at 40°C.

为了将油膜当量设为12000~24000,只要使用低粘度的压延油、或使用减缓通板速度等公知的方法即可。In order to set the oil film equivalent to 12,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing down the plate-passing speed may be used.

又,将用作为本发明的载体的电解铜箔的制造条件的一实施例表示如下。Moreover, an example of the manufacturing conditions of the electrolytic copper foil used as a carrier of this invention is shown below.

<电解液组成><Electrolyte composition>

铜:90~110g/LCopper: 90~110g/L

硫酸:90~110g/LSulfuric acid: 90~110g/L

氯:50~100mg/LChlorine: 50~100mg/L

调平剂1(双(3-磺丙基)二硫醚):10~50mg/LLeveling agent 1 (bis(3-sulfopropyl) disulfide): 10~50mg/L

调平剂2(含有二烷基胺基的聚合物):10~50mg/LLeveling agent 2 (polymer containing dialkylamine group): 10~50mg/L

上述含有二烷基胺基的聚合物例如可使用以下化学式的含有二烷基胺的聚合物。As the dialkylamine group-containing polymer, for example, a dialkylamine-containing polymer of the following chemical formula can be used.

[化学式1][chemical formula 1]

(上述化学式中,R1及R2为选自由羟烷基、醚基、芳基、经芳香族取代的烷基、不饱和烃基、烷基组成的群)( In the above chemical formula , R1 and R2 are selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups)

<制造条件><Manufacturing conditions>

电流密度:70~100A/dm2 Current density: 70~100A/ dm2

电解液温度:50~60℃Electrolyte temperature: 50~60℃

电解液线速:3~5m/secElectrolyte line speed: 3~5m/sec

电解时间:0.5~10分钟Electrolysis time: 0.5 to 10 minutes

又,作为可用于本发明中的电解铜箔,可列举JX日矿日石金属股份有限公司制造的HLP箔。Moreover, as an electrolytic copper foil which can be used for this invention, the HLP foil by JX Nikko Nippon Metal Co., Ltd. is mentioned.

可用于本发明的载体的厚度并无特别限制,只要基于可发挥作为载体的效果来适当调节成适当厚度即可,例如可设为25μm以上。但是,若过厚则生产成本变高,因此一般优选为设为50μm以下。因此,载体的厚度典型而言为12~300μm,更典型为12~150μm,再更典型为12~100μm,再更典型为25~50μm,再更典型为25~38μm。The thickness of the support that can be used in the present invention is not particularly limited, as long as it can be adjusted to an appropriate thickness based on the effect as a support can be exhibited, for example, it can be set to 25 μm or more. However, if it is too thick, the production cost will increase, so it is generally preferable to set it to 50 μm or less. Thus, the thickness of the carrier is typically 12-300 μm, more typically 12-150 μm, still more typically 12-100 μm, still more typically 25-50 μm, still more typically 25-38 μm.

<中间层><Middle layer>

在载体上设置中间层。在载体与中间层之间也可设置其它层。作为中间层,可在附载体铜箔中利用干式表面处理或湿式表面处理而制成任意的中间层。例如,中间层优选为由含有Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、或其等的合金、或其等的水和物、或其等的氧化物或有机物中的任一种以上的层所形成。中间层也可以多个层来构成。An intermediate layer is provided on the carrier. Further layers may also be arranged between the carrier and the intermediate layer. As the intermediate layer, any intermediate layer can be formed by dry surface treatment or wet surface treatment on the copper foil with a carrier. For example, the intermediate layer is preferably made of alloys containing Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or the like, or hydrates of the same, or oxides or organic substances of the like. Any one of the above layers is formed. The intermediate layer can also be composed of multiple layers.

在本发明的一实施方案中,中间层是自载体侧由下述两种层所构成,第一种层是由选自Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al的元素群中的任一种元素构成的单一金属层,或由选自Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al的元素群中的一种以上的元素构成的合金层;第二种层是形成在其上的由选自Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al的元素群中的一种以上的元素的水和物或氧化物构成的层。In one embodiment of the present invention, the intermediate layer is composed of the following two layers from the carrier side, the first layer is selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, A single metal layer composed of any element in the element group of Al, or composed of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al The alloy layer; the second layer is formed on it by water and substance of more than one element selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al or oxide layers.

中间层优选为以金属层或合金层与形成在其上的氧化物层此2层来构成。在此情形,分别以金属层或合金层与和膜载体的界面相接,氧化物层与和极薄铜层的界面相接的方式来形成。The intermediate layer is preferably constituted by two layers of a metal layer or an alloy layer and an oxide layer formed thereon. In this case, the metal layer or the alloy layer is formed in contact with the interface with the film carrier, and the oxide layer is formed in contact with the interface with the ultra-thin copper layer, respectively.

中间层例如可通过溅镀、CVD及PVD之类的干式表面处理,或电镀、无电解镀敷及浸渍镀敷之类的湿式表面处理而获得。The intermediate layer can be obtained by, for example, dry surface treatment such as sputtering, CVD, and PVD, or wet surface treatment such as electroplating, electroless plating, and dip plating.

<极薄铜层><Extremely thin copper layer>

在中间层上设置极薄铜层。也可在中间层与极薄铜层间设置其他层。极薄铜层可通过干式镀敷,或利用有硫酸铜、焦磷酸铜、胺磺酸铜、氰化铜等电解浴的电镀(湿式镀敷)来形成,优选为硫酸铜浴,其原因在于可在一般的电解铜箔中使用,且可在高电流密度下形成铜箔。再者,在利用湿式镀敷形成极薄铜层的情形时,必须使用含有氯、作为调平剂的有机硫化合物、作为调平剂的有机氮化合物的铜镀浴来形成极薄铜层。例如,在本申请中可用于湿式镀敷的铜镀浴的组成、镀敷条件如以下所述。An extremely thin copper layer is provided on the intermediate layer. It is also possible to arrange other layers between the intermediate layer and the ultra-thin copper layer. The extremely thin copper layer can be formed by dry plating, or electroplating (wet plating) using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., preferably a copper sulfate bath. The reason It can be used in general electrolytic copper foil, and copper foil can be formed under high current density. Furthermore, when forming an ultra-thin copper layer by wet plating, it is necessary to form an ultra-thin copper layer using a copper plating bath containing chlorine, an organic sulfur compound as a leveling agent, and an organic nitrogen compound as a leveling agent. For example, the composition and plating conditions of the copper plating bath which can be used for wet plating in this application are as follows.

·铜镀浴·Copper plating bath

铜浓度:30~120g/LCopper concentration: 30~120g/L

H2SO4浓度:20~120g/LH 2 SO 4 concentration: 20~120g/L

Cl浓度:30~80mg/LCl concentration: 30~80mg/L

二硫双(3-磺丙基)二钠浓度:10~50mg/LConcentration of dithiobis(3-sulfopropyl) disodium: 10~50mg/L

以下述结构式表示的含有二烷基胺基的聚合物:10~50mg/LPolymers containing dialkylamine groups represented by the following structural formula: 10-50 mg/L

[化学式2][chemical formula 2]

·镀铜条件·Copper plating conditions

电解液温度:20~80℃Electrolyte temperature: 20~80℃

电流密度:10~100A/dm2 Current density: 10 ~100A/dm2

极薄铜层的厚度并无特别限制,一般而言比载体薄,例如为12μm以下。典型而言为0.5~12μm,更典型而言为2~5μm。再者,极薄铜层也可设置在载体的两面。The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. Typically, it is 0.5 to 12 μm, and more typically, it is 2 to 5 μm. Furthermore, an extremely thin copper layer can also be provided on both sides of the carrier.

<粗化处理以及其他表面处理><Roughening treatment and other surface treatment>

在极薄铜层的表面,例如为了使其与绝缘基板的密合性变得良好等,通过施予粗化处理来设置粗化处理层。粗化处理例如可通过利用铜或铜合金来形成粗化粒子来进行。粗化处理层由形成窄间距的观点而言以细微的粒子来构成为优选。On the surface of the ultra-thin copper layer, for example, in order to improve the adhesion with an insulating substrate, a roughening treatment layer is provided by giving roughening treatment. The roughening treatment can be performed, for example, by forming roughened particles using copper or a copper alloy. From the viewpoint of forming a narrow pitch, the roughening treatment layer is preferably composed of fine particles.

粗化处理层可为由选自由铜、镍、磷、钨、砷、钼、铬、钴及锌所组成的群中的任一单质构成的层,或者由包含该等单质的任一种以上的合金构成的层,或具备包含该等单质的任一种以上的合金的层来构成。The roughening treatment layer may be a layer composed of any elemental substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or any one or more elements containing these elemental substances. A layer composed of an alloy, or a layer containing any one or more alloys of these simple substances.

又,在粗化处理后,利用镍、钴、铜、锌的单质或合金等形成二次粒子或三次粒子及/或耐热层及/或防锈层,也可进一步对其表面施加铬酸盐处理、硅烷偶合处理等处理。即,可在粗化处理层的表面形成选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层所构成的群中的1种以上的层,也可在极薄铜层的表面形成选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层所构成的群中的一种以上的层。Also, after the roughening treatment, secondary particles or tertiary particles and/or a heat-resistant layer and/or an anti-rust layer are formed using nickel, cobalt, copper, zinc, or an alloy, etc., and chromic acid can be further applied to the surface. Salt treatment, silane coupling treatment, etc. That is, one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, and an ultra-thin copper layer may be formed. One or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate-treated layer, and a silane coupling-treated layer are formed on the surface.

此处所谓铬酸盐处理层,意指经利用含有铬酸酐、铬酸、重铬酸、铬酸盐或重铬酸盐的液体处理的层。铬酸盐处理层也可含有钴、铁、镍、钼、锌、钽、铜、铝、磷、钨、锡、砷及钛等元素(可为金属、合金、氧化物、氮化物、硫化物等任何形态)。作为铬酸盐处理层的具体实施例,可列举经铬酸酐或重铬酸钾水溶液处理的铬酸盐处理层,或是经含有铬酸酐或重铬酸钾及锌的处理液处理的铬酸盐处理层等。Here, the chromate-treated layer means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer can also contain elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (which can be metal, alloy, oxide, nitride, sulfide any other form). Specific examples of the chromate treatment layer include chromate treatment layers treated with chromic anhydride or potassium dichromate aqueous solution, or chromic acid treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc. Salt treatment layer, etc.

作为耐热层、防锈层,可使用公知的耐热层、防锈层。例如,耐热层及/或防锈层也可为含有选自镍、锌、锡、钴、钼、铜、钨、磷、砷、铬、钒、钛、铝、金、银、铂族元素、铁、钽的群中的一种以上的元素的层,也可为由选自镍、锌、锡、钴、钼、铜、钨、磷、砷、铬、钒、钛、铝、金、银、铂族元素、铁、钽的群中的一种以上的元素构成的金属层或合金层。又,耐热层及/或防锈层也可含有包含选自镍、锌、锡、钴、钼、铜、钨、磷、砷、铬、钒、钛、铝、金、银、铂族元素、铁、钽的群中的一种以上的元素的氧化物、氮化物、硅化物。又,耐热层及/或防锈层也可为含有镍-锌合金的层。又,耐热层及/或防锈层也可为镍-锌合金层。上述镍-锌合金层可为除不可避免的杂质以外,含有镍50wt%~99wt%、锌50wt%~1wt%者。上述镍-锌合金层的锌及镍的合计附着量为5~1000mg/m2,优选为10~500mg/m2,优选也可为20~100mg/m2。又,上述含有镍-锌合金的层或上述镍-锌合金层的镍附着量与锌附着量之比(=镍的附着量/锌的附着量)优选为1.5~10。又,上述含有镍-锌合金的层或上述镍-锌合金层的镍附着量优选为0.5mg/m2~500mg/m2,更优选为1mg/m2~50mg/m2。在耐热层及/或防锈层为含有镍-锌合金的层的情形时,通孔(through hole)或通路孔(via hole)等的内壁部与除胶渣(desmear)液接触时铜箔与树脂基板的界面难以被除胶渣液腐蚀,铜箔与树脂基板的密合性会提升。As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and/or rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. , iron, tantalum group of more than one element layer, can also be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, A metal layer or an alloy layer composed of one or more elements in the group of silver, platinum group elements, iron, and tantalum. In addition, the heat-resistant layer and/or rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. Oxides, nitrides, and silicides of one or more elements in the group of , iron, and tantalum. In addition, the heat-resistant layer and/or the rust-proof layer may be a layer containing a nickel-zinc alloy. Also, the heat-resistant layer and/or the rust-proof layer may be a nickel-zinc alloy layer. The above-mentioned nickel-zinc alloy layer may contain 50 wt % to 99 wt % of nickel and 50 wt % to 1 wt % of zinc in addition to unavoidable impurities. The total deposition amount of zinc and nickel in the nickel-zinc alloy layer is 5 to 1000 mg/m 2 , preferably 10 to 500 mg/m 2 , preferably 20 to 100 mg/m 2 . In addition, it is preferable that the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer has a ratio of nickel adhesion to zinc adhesion (=nickel adhesion/zinc adhesion) of 1.5-10. Also, the nickel deposition amount of the layer containing nickel-zinc alloy 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 rust-proof layer is a layer containing a nickel-zinc alloy, when the inner wall of a through hole or a via hole comes into contact with a desmear liquid, copper The interface between the foil and the resin substrate is less likely to be corroded by the desmear solution, and the adhesion between the copper foil and the resin substrate will be improved.

例如耐热层及/或防锈层可为将附着量为1mg/m2~100mg/m2、优选为5mg/m2~50mg/m2的镍或镍合金层、与附着量为1mg/m2~80mg/m2、优选为5mg/m2~40mg/m2的锡层依序积层而成,上述镍合金层也可由镍-钼、镍-锌、镍-钼-钴中的任一种构成。又,耐热层及/或防锈层的镍或镍合金与锡的合计附着量优选为2mg/m2~150mg/m2,更优选为10mg/m2~70mg/m2。又,耐热层及/或防锈层优选为[镍或镍合金中的镍附着量]/[锡附着量]=0.25~10,更优选为0.33~3。若使用该耐热层及/或防锈层,则将附载体铜箔加工成印刷配线板以后的电路的剥离强度、该剥离强度的耐化学品性劣化率等会变得良好。For example, the heat-resistant layer and/or rust-proof layer can be a nickel or nickel alloy layer with 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 2 m 2 to 80mg/m 2 , preferably 5mg/m 2 to 40mg/m 2 tin layers are sequentially laminated. The nickel alloy layer can also be made of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt any composition. Also, the total adhesion amount of nickel or nickel alloy and tin in the heat-resistant layer and/or rust-proof layer is preferably 2 mg/m 2 to 150 mg/m 2 , more preferably 10 mg/m 2 to 70 mg/m 2 . In addition, the heat-resistant layer and/or the antirust layer are preferably [Ni deposition amount in nickel or nickel alloy]/[Sn deposition amount]=0.25-10, more preferably 0.33-3. Using the heat-resistant layer and/or the rust-proof layer will improve the peel strength of the circuit after the copper foil with a carrier is processed into a printed wiring board, the chemical resistance deterioration rate of the peel strength, and the like.

再者,硅烷偶合处理所使用的硅烷偶合剂可使用公知的硅烷偶合剂,例如可使用胺系硅烷偶合剂或环氧系硅烷偶合剂、巯基系硅烷偶合剂。又,硅烷偶合剂也可使用乙烯基三甲氧基硅烷、乙烯基苯基三甲氧基硅烷、γ-甲基丙烯氧基丙基三甲氧基硅烷(γ-methacryloxypropyltrimethoxysilane)、γ-环氧丙氧基丙基三甲氧基硅烷(γ-glycidoxypropyltrimethoxysilane)、4-环氧丙基丁基三甲氧基硅烷、γ-胺基丙基三乙氧基硅烷、N-β(胺基乙基)γ-胺基丙基三甲氧基硅烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基硅烷、咪唑硅烷、三嗪硅烷、γ-巯基丙基三甲氧基硅烷等。In addition, a well-known silane coupling agent can be used for the silane coupling agent used for a silane coupling process, For example, an amine type silane coupling agent, an epoxy type silane coupling agent, and a mercapto type silane coupling agent can be used. In addition, the silane coupling agent can also use vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane (γ-methacryloxypropyltrimethoxysilane), γ-glycidoxy Propyltrimethoxysilane (γ-glycidoxypropyltrimethoxysilane), 4-epoxypropylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-amino Propyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazine silane, γ- Mercaptopropyltrimethoxysilane, etc.

上述硅烷偶合处理层也可使用环氧系硅烷、胺系硅烷、甲基丙烯氧基系硅烷、巯基系硅烷等硅烷偶合剂等而形成。再者,此种硅烷偶合剂也可将两种以上混合使用。其中,优选为使用胺系硅烷偶合剂或环氧系硅烷偶合剂所形成者。The above-mentioned silane coupling treatment layer can also be formed using silane coupling agents such as epoxy-based silanes, amine-based silanes, methacryloxy-based silanes, and mercapto-based silanes. In addition, such a silane coupling agent can also be used in mixture of 2 or more types. Among them, those formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

此处所谓的胺系硅烷偶合剂也可为选自由如下物质所组成的群者:N-(2-胺基乙基)-3-胺基丙基三甲氧基硅烷、3-(N-苯乙烯基甲基-2-胺基乙基胺基)丙基三甲氧基硅烷、3-胺基丙基三乙氧基硅烷、双(2-羟基乙基)-3-胺基丙基三乙氧基硅烷、胺基丙基三甲氧基硅烷、N-甲基胺基丙基三甲氧基硅烷、N-苯基胺基丙基三甲氧基硅烷、N-(3-丙烯氧基-2-羟基丙基)-3-胺基丙基三乙氧基硅烷、4-胺基丁基三乙氧基硅烷、(胺基乙基胺基甲基)苯乙基三甲氧基硅烷、N-(2-胺基乙基-3-胺基丙基)三甲氧基硅烷、N-(2-胺基乙基-3-胺基丙基)三(2-乙基己氧基)硅烷、6-(胺基己基胺基丙基)三甲氧基硅烷、胺基苯基三甲氧基硅烷、3-(1-胺基丙氧基)-3,3-二甲基-1-丙烯基三甲氧基硅烷、3-胺基丙基三(甲氧基乙氧基乙氧基)硅烷、3-胺基丙基三乙氧基硅烷、3-胺基丙基三甲氧基硅烷、ω-胺基十一烷基三甲氧基硅烷、3-(2-N-苄基胺基乙基胺基丙基)三甲氧基硅烷、双(2-羟基乙基)-3-胺基丙基三乙氧基硅烷、(N,N-二乙基-3-胺基丙基)三甲氧基硅烷、(N,N-二甲基-3-胺基丙基)三甲氧基硅烷、N-甲基胺基丙基三甲氧基硅烷、N-苯基胺基丙基三甲氧基硅烷、3-(N-苯乙烯基甲基-2-胺基乙基胺基)丙基三甲氧基硅烷、γ-胺基丙基三乙氧基硅烷、N-β(胺基乙基)γ-胺基丙基三甲氧基硅烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基硅烷。The so-called amine silane coupling agent here can also be selected from the group consisting of the following substances: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N-phenyl Vinylmethyl-2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethyl Oxysilane, Aminopropyltrimethoxysilane, N-Methylaminopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, N-(3-Propyloxy-2- Hydroxypropyl)-3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-( 2-aminoethyl-3-aminopropyl)trimethoxysilane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)silane, 6- (Aminohexylaminopropyl)trimethoxysilane, Aminophenyltrimethoxysilane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxy Silane, 3-aminopropyltri(methoxyethoxyethoxy)silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminodeca Monoalkyltrimethoxysilane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxy Silane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, N-methylamino Propyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, γ-amine N-3-(4-(3-aminopropoxy)butoxy)propyl -3-Aminopropyltrimethoxysilane.

硅烷偶合处理层较理想为以硅原子换算设为0.05mg/m2~200mg/m2、优选为0.15mg/m2~20mg/m2、优选为0.3mg/m2~2.0mg/m2的范围。在上述范围的情形时,可使基材树脂与表面处理铜箔的密合性更加提升。The silane coupling treatment layer is preferably 0.05 mg/m 2 to 200 mg/m 2 in terms of silicon atoms, preferably 0.15 mg/m 2 to 20 mg/m 2 , preferably 0.3 mg/m 2 to 2.0 mg/m 2 range. In the case of the said range, the adhesiveness of a base resin and a surface-treated copper foil can be further improved.

又,可对极薄铜层、粗化处理层、耐热层、防锈层、硅烷偶合处理层或铬酸盐处理层的表面进行下述专利所记载的表面处理:国际公开编号WO2008/053878、日本特开2008-111169号、日本专利第5024930号、国际公开编号WO2006/028207、日本专利第4828427号、国际公开编号WO2006/134868、日本专利第5046927号、国际公开编号WO2007/105635、日本专利第5180815号、日本特开2013-19056号。In addition, the surface treatment described in the following patent can be carried out on the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, anti-rust layer, silane coupling layer or chromate layer: International Publication No. WO2008/053878 , Japanese Patent Application No. 2008-111169, Japanese 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 Laid-Open No. 2013-19056.

施予粗化处理等的各种表面处理后的极薄铜层的表面(再者,在本发明中,在极薄铜层的表面施予粗化处理等的各种表面处理的情形时,“极薄铜层的表面”及“极薄铜层表面”是指施予粗化处理等各种表面处理后的极薄铜层的表面)在一方面中,在利用非接触式粗糙度计对至少一面,优选为两面进行测定时,将Rz(十点平均粗糙度)设为0.5μm以下在形成窄间距的观点上极为有利。Rz优选为0.3μm以下、更优选为0.1μm以下。然而,Rz若变得过小,则与树脂的密合力会降低,故而必须根据所使用的基板的与树脂的组合来进行适当选择。再者,Rz的下限不需特别设定,例如Rz为0.0001μm以上,例如为0.0005μm以上,例如为0.0010μm以上,例如为0.005μm以上,例如为0.007μm以上。The surface of the ultra-thin copper layer after various surface treatments such as roughening treatment (Furthermore, in the present invention, when various surface treatments such as roughening treatment are applied to the surface of the ultra-thin copper layer, "The surface of the ultra-thin copper layer" and "the surface of the ultra-thin copper layer" refer to the surface of the ultra-thin copper layer subjected to various surface treatments such as roughening) When measuring on at least one side, preferably both sides, it is very advantageous from the viewpoint of forming a narrow pitch to set Rz (ten-point average roughness) to 0.5 μm or less. Rz is preferably 0.3 μm or less, more preferably 0.1 μm or less. However, if Rz is too small, since the adhesive force with resin will fall, it must select suitably according to the combination with resin of the board|substrate to be used. The lower limit of Rz does not need to be particularly set, for example, Rz is 0.0001 μm or more, for example 0.0005 μm or more, for example 0.0010 μm or more, for example 0.005 μm or more, for example 0.007 μm or more.

施予粗化处理等各种表面处理后的极薄铜层的表面在另一方面中,在利用非接触式粗糙度计对至少一面,优选为两面进行测定时,将Ra(算术平均粗糙度)设为0.12μm以下在形成窄间距的观点上极为有利。Ra优选为0.10μm以下、更优选为0.08μm以下,再更优选为0.05μm以下。然而,Ra若变得过小,则与树脂的密合力会降低,故而必须根据所使用的基板的与树脂的组合来进行适当选择。再者,Ra的下限不需特别设定,例如Ra为0.0001μm以上,例如为0.0005μm以上,例如为0.0010μm以上,例如为0.005μm以上,例如为0.007μm以上。On the other hand, the surface of the ultra-thin copper layer subjected to various surface treatments such as roughening treatment is measured by Ra (arithmetic mean roughness ) to be 0.12 μm or less is extremely advantageous from the viewpoint of forming a narrow pitch. Ra is preferably 0.10 μm or less, more preferably 0.08 μm or less, still more preferably 0.05 μm or less. However, if Ra becomes too small, since the adhesive force with resin will fall, it must select suitably according to the combination with resin of the board|substrate to be used. Note that the lower limit of Ra does not need to be set in particular, for example, Ra is 0.0001 μm or more, for example 0.0005 μm or more, for example 0.0010 μm or more, for example 0.005 μm or more, for example 0.007 μm or more.

施予粗化处理等各种表面处理后的极薄铜层的表面在另一方面中,在利用非接触式粗糙度计对至少一面,优选为两面进行测定时,将Rt设为1.0μm以下在形成窄间距的观点上极为有利。Rt优选为0.5μm以下、更优选为0.3μm以下。然而,Rt若变得过小,则与树脂的密合力会降低,故而必须根据所使用的基板的与树脂的组合来进行适当选择。再者,Rt的下限不需特别设定,例如Rt为0.0001μm以上,例如为0.0005μm以上,例如为0.0010μm以上,例如为0.005μm以上,例如为0.007μm以上。On the other hand, when the surface of the ultra-thin copper layer subjected to various surface treatments such as roughening treatment is measured with a non-contact roughness meter on at least one side, preferably both sides, Rt is set to be 1.0 μm or less It is extremely advantageous from the viewpoint of forming a narrow pitch. Rt is preferably 0.5 μm or less, more preferably 0.3 μm or less. However, if Rt is too small, since the adhesive force with resin will fall, it must select suitably according to the combination of the board|substrate used and resin. The lower limit of Rt does not need to be set in particular, for example, Rt is 0.0001 μm or more, for example 0.0005 μm or more, for example 0.0010 μm or more, for example 0.005 μm or more, for example 0.007 μm or more.

上述极薄铜层表面并非如上述般分别单独地控制Rz、Ra、Rt的粗糙度,而是通过控制Rz与Ra、Ra与Rt,或是Rz与Ra与Rt而可更良好地形成窄间距。The surface of the above-mentioned ultra-thin copper layer does not control the roughness of Rz, Ra, and Rt separately as mentioned above, but by controlling Rz and Ra, Ra and Rt, or Rz and Ra and Rt, a narrower pitch can be formed more preferably .

在本发明中,关于极薄铜层表面的Rz,是根据JIS B0601-1994利用非接触式粗糙度计来进行测定,关于Ra、Rt的粗糙度参数,是根据JIS B0601-2001利用非接触式粗糙度计来进行测定。In the present invention, Rz on the surface of the ultra-thin copper layer is measured with a non-contact roughness meter according to JIS B0601-1994, and the roughness parameters of Ra and Rt are measured with a non-contact roughness meter according to JIS B0601-2001. Roughness meter to measure.

由此,极薄铜层表面的Rz、Ra、及/或Rt的粗糙度经控制的本发明的附载体铜箔适于形成窄间距,例如可形成比被认为是利用MSAP步骤而可形成的极限的线/间隔=15μm/15μm更加细微的配线,例如线/间隔=10μm/10μm的细微配线。Therefore, the copper foil with a carrier of the present invention whose roughness of Rz, Ra, and/or Rt on the surface of the ultra-thin copper layer is controlled is suitable for forming a narrow pitch, for example, it can be formed compared to that which can be formed by using the MSAP step. The limit line/space=15 μm/15 μm is finer wiring, for example, line/space=10 μm/10 μm finer wiring.

<树脂层><Resin layer>

本发明的附载体铜箔的极薄铜层(在极薄铜层经表面处理的情形时,通过该表面处理而形成在极薄铜层上的表面处理层)上也可具备树脂层。上述树脂层也可为绝缘树脂层。The ultra-thin copper layer (when the ultra-thin copper layer is surface-treated, the surface-treated layer formed on the ultra-thin copper layer by the surface treatment) of the copper foil with a carrier of the present invention may include a resin layer. The aforementioned resin layer may also be an insulating resin layer.

上述树脂层也可为接着用树脂,即接着剂,也可为接着用半硬化状态(B阶段状态)的绝缘树脂层。所谓半硬化状态(B阶段状态),包含如下状态:即便用手指触摸其表面也无粘着感,可重迭地保管该绝缘树脂层,若进一步进行加热处理,则会引起硬化反应。The above-mentioned resin layer may be an adhesive resin, that is, an adhesive, or may be an insulating resin layer in a semi-cured state (B-stage state) for adhesive. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stored in a stacked state without sticky feeling even when touched with a finger, and further heat-treated to cause a hardening reaction.

又,上述树脂层也可含有热硬化性树脂,也可为热塑性树脂。又,上述树脂层也可含有热塑性树脂。上述树脂层可含有公知的树脂、树脂硬化剂、化合物、硬化促进剂、介电体、反应催化剂、交联剂、聚合物、预浸体、骨架材料等。又,上述树脂层例如可使用如下文献中所记载的物质(树脂、树脂硬化剂、化合物、硬化促进剂、介电体、反应催化剂、交联剂、聚合物、预浸体、骨架材料等)及/或树脂层的形成方法、形成装置而形成,该文献是:国际公开编号WO2008/004399号、国际公开编号WO2008/053878、国际公开编号WO2009/084533、日本特开平11-5828号、日本特开平11-140281号、日本专利第3184485号、国际公开编号WO97/02728、日本专利第3676375号、日本特开2000-43188号、日本专利第3612594号、日本特开2002-179772号、日本特开2002-359444号、日本特开2003-304068号、日本专利第3992225号、日本特开2003-249739号、日本专利第4136509号、日本特开2004-82687号、日本专利第4025177号、日本特开2004-349654号、日本专利第4286060号、日本特开2005-262506号、日本专利第4570070号、日本特开2005-53218号、日本专利第3949676号、日本专利第4178415号、国际公开编号WO2004/005588、日本特开2006-257153号、日本特开2007-326923号、日本特开2008-111169号、日本专利第5024930号、国际公开编号WO2006/028207、日本专利第4828427号、日本特开2009-67029号、国际公开编号WO2006/134868、日本专利第5046927号、日本特开2009-173017号、国际公开编号WO2007/105635、日本专利第5180815号、国际公开编号WO2008/114858、国际公开编号WO2009/008471、日本特开2011-14727号、国际公开编号WO2009/001850、国际公开编号WO2009/145179、国际公开编号WO2011/068157、日本特开2013-19056号。In addition, the above-mentioned resin layer may contain a thermosetting resin, or may be a thermoplastic resin. Moreover, the said resin layer may contain a thermoplastic resin. The resin layer may contain known resins, resin hardeners, compounds, hardening accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, and the like. In addition, for the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, frame material, etc.) can be used. And/or the forming method and forming device of the resin layer. The documents are: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application No. Kaihei No. 11-140281, Japanese Patent No. 3184485, 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, JP 2003-304068, JP 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 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, JP 2006-257153, JP 2007-326923, JP 2008-111169, JP 5024930, International Publication No. WO2006/028207, JP 4828427, JP 2009- No. 67029, 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 , Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

<附载体铜箔><Copper foil with carrier>

如此,制造具备载体、积层于载体上的剥离层、及积层于剥离层上的极薄铜层的附载体铜箔。Thus, the copper foil with a carrier provided with the carrier, the peeling layer laminated|stacked on a carrier, and the ultra-thin copper layer laminated|stacked on a peeling layer was manufactured.

将本发明的附载体铜箔的结构的一实施例示于图1。图1所示的本发明的附载体铜箔依序具备膜载体、中间层与极薄铜层。极薄铜层是以通过溅镀而形成的溅镀铜层及通过电镀而形成的电解铜层来构成。又,将附载体铜箔自极薄铜层侧贴合于树脂基板并剥离载体后的极薄铜层表面区分为剥离面侧与树脂面侧。One example of the structure of the copper foil with a carrier of this invention is shown in FIG. 1. The copper foil with a carrier of the present invention shown in FIG. 1 includes a film carrier, an intermediate layer, and an ultra-thin copper layer in this order. The ultra-thin copper layer is composed of a sputtered copper layer formed by sputtering and an electrolytic copper layer formed by electroplating. Moreover, the surface of the ultra-thin copper layer after bonding the copper foil with a carrier to the resin substrate from the ultra-thin copper layer side and peeling off the carrier is divided into a peeling surface side and a resin surface side.

附载体铜箔本身的使用方法为本领域技术人员所周知,例如可将极薄铜层的表面贴合于纸基材酚树脂、纸基材环氧树脂、合成纤维布基材环氧树脂、玻璃布-纸复合基材环氧树脂、玻璃布-玻璃不织布复合基材环氧树脂及玻璃布基材环氧树脂、聚酯膜、聚酰亚胺膜等绝缘基板并进行热压接后,剥离载体而形成覆铜积层板,将接着于绝缘基板的极薄铜层蚀刻为目标导体图案,最后制造印刷配线板。进一步,通过在印刷配线板搭载电子零件类,而完成印刷电路板。在本发明中,“印刷配线板”也形成为含有此种搭载有电子零件类的印刷配线板及印刷电路板及印刷基板。The use method of copper foil with carrier itself is well known to those skilled in the art, for example, the surface of the ultra-thin copper layer can be attached to paper base material phenolic resin, paper base material epoxy resin, synthetic fiber cloth base material 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 and other insulating substrates are thermally bonded, The carrier is peeled off to form a copper-clad laminate, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board is manufactured. Furthermore, a printed wiring board is completed by mounting electronic components on a printed wiring board. In the present invention, the "printed wiring board" is also formed to include such printed wiring boards, printed wiring boards, and printed circuit boards on which such electronic components are mounted.

又,也可使用该印刷配线板而制作电子机器,也可使用搭载有该电子零件类的印刷配线板来制作电子机器,也可使用搭载有该电子零件类的印刷基板来制作电子机器。以下,表示若干使用有本发明的附载体铜箔的印刷配线板的制造步骤的实施例。Furthermore, electronic equipment can also be produced using the printed wiring board, electronic equipment can also be produced using the printed wiring board on which the electronic components are mounted, and electronic equipment can also be produced using the printed circuit board on which the electronic components are mounted. . Some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier of this invention are shown below.

在本发明的印刷配线板的制造方法的一实施方案中,包含下述步骤:准备本发明的附载体铜箔与绝缘基板;将上述附载体铜箔与绝缘基板积层;以使极薄铜层侧与绝缘基板对向的方式将上述附载体铜箔与绝缘基板积层后,经将上述附载体铜箔的载体剥离的步骤而形成覆铜积层板,其后,通过半加成法、改进半加成法、部分加成法及减成法中任一方法形成电路。绝缘基板也可设为内层电路入口。In one embodiment of the method for manufacturing a printed wiring board of the present invention, the following steps are included: preparing the copper foil with a carrier and the insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the above-mentioned copper foil with a carrier and the insulating substrate in such a way that the copper layer side faces the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate. Method, improved semi-additive method, partial additive method and subtractive method to form a circuit. The insulating substrate can also be used as the entrance of the inner layer circuit.

本发明中,所谓半加成法,是指在绝缘基板或铜箔晶种层上进行较薄的无电解镀敷,形成图案后,使用电镀及蚀刻形成导体图案的方法。In the present invention, the so-called semi-additive method refers to a method in which thin electroless plating is performed on an insulating substrate or a copper foil seed layer to form a pattern, and then electroplating and etching are used to form a conductive pattern.

因此,在使用半加成法的本发明的印刷配线板的制造方法的一实施方案中,包含下述步骤:Therefore, in one embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

通过使用有酸等腐蚀溶液的蚀刻或电浆等方法将剥离上述载体而露出的极薄铜层完全去除;The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by using etching or plasma with a corrosive solution such as acid;

在通过利用蚀刻去除上述极薄铜层而露出的上述树脂设置通孔或/及盲孔;providing through holes or/and blind holes in the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching;

对含有上述通孔或/及盲孔的区域进行除胶渣处理;Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

在上述树脂及含有上述通孔或/及盲孔的区域设置无电解镀敷层;An electroless plating layer is provided on the above-mentioned resin and the area containing the above-mentioned through hole or/and blind hole;

在上述无电解镀敷层之上设置镀敷阻剂;disposing a plating resist on the electroless plating layer;

对上述镀敷阻剂进行曝光,其后,去除形成有电路的区域的镀敷阻剂;Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

在去除了上述镀敷阻剂的形成有上述电路的区域设置电镀层;An electroplating layer is provided in the region where the above-mentioned circuit is formed where the above-mentioned plating resist is removed;

去除上述镀敷阻剂;及removing said plating resist; and

通过快速蚀刻等去除形成有上述电路的区域以外的区域的无电解镀敷层。The electroless plating layer is removed by flash etching or the like in regions other than the regions where the above-mentioned circuits are formed.

在使用半加成法的本发明的印刷配线板的制造方法的另一实施方案中,包含下述步骤:In another embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

通过使用有酸等腐蚀溶液的蚀刻或电浆等方法将剥离上述载体而露出的极薄铜层完全去除;The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by using etching or plasma with a corrosive solution such as acid;

在通过利用蚀刻去除上述极薄铜层而露出的上述树脂的表面设置无电解镀敷层;providing an electroless plating layer on the surface of the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching;

在上述无电解镀敷层之上设置镀敷阻剂;disposing a plating resist on the electroless plating layer;

对上述镀敷阻剂进行曝光,其后,去除形成有电路的区域的镀敷阻剂;Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

在去除了上述镀敷阻剂的形成有上述电路的区域设置电镀层;An electroplating layer is provided in the region where the above-mentioned circuit is formed where the above-mentioned plating resist is removed;

去除上述镀敷阻剂;及removing said plating resist; and

通过快速蚀刻等去除形成有上述电路的区域以外的区域的无电解镀敷层及极薄铜层。The electroless plated layer and the ultra-thin copper layer are removed by flash etching or the like in areas other than the areas where the above-mentioned circuits are formed.

本发明中,所谓改进半加成法,是指在绝缘层上积层金属箔,利用镀敷阻剂保护非电路形成部,通过电镀增厚电路形成部的铜层后,去除光阻剂,利用(快速)蚀刻去除上述电路形成部以外的金属箔,由此在绝缘层上形成电路的方法。In the present invention, the so-called improved semi-additive method refers to laminating metal foil on the insulating layer, using a plating resist to protect the non-circuit forming part, and removing the photoresist after thickening the copper layer of the circuit forming part by electroplating. A method of forming a circuit on an insulating layer by (snap) etching to remove the metal foil other than the above-mentioned circuit forming part.

因此,在使用改进半加成法的本发明的印刷配线板的制造方法的一实施方案中,包含下述步骤:Therefore, in one embodiment of the manufacturing method of the printed wiring board of the present invention using the improved semi-additive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

在剥离上述载体而露出的极薄铜层与绝缘基板设置通孔或/及盲孔;Provide through holes or/and blind holes on the extremely thin copper layer exposed by peeling off the above-mentioned carrier and the insulating substrate;

对含有上述通孔或/及盲孔的区域进行除胶渣处理;Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

在含有上述通孔或/及盲孔的区域设置无电解镀敷层;Provide an electroless plating layer in the area containing the above-mentioned through holes or/and blind holes;

在剥离上述载体而露出的极薄铜层表面设置镀敷阻剂;A plating resist is provided on the surface of the ultra-thin copper layer exposed by peeling off the above-mentioned carrier;

在设置上述镀敷阻剂后,通过电镀形成电路;After the above-mentioned plating resist is provided, a circuit is formed by electroplating;

去除上述镀敷阻剂;及removing said plating resist; and

利用快速蚀刻去除通过去除上述镀敷阻剂而露出的极薄铜层。The very thin copper layer exposed by removing the above-mentioned plating resist is removed by flash etching.

在使用改进半加成法的本发明的印刷配线板的制造方法的另一实施方案中,包含下述步骤:In another embodiment of the manufacturing method of the printed wiring board of the present invention using the improved semi-additive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

在剥离上述载体而露出的极薄铜层之上设置镀敷阻剂;disposing a plating resist on the extremely thin copper layer exposed by peeling off the above-mentioned carrier;

对上述镀敷阻剂进行曝光,其后,去除形成有电路的区域的镀敷阻剂;Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

在去除了上述镀敷阻剂的形成有上述电路的区域设置电镀层;An electroplating layer is provided in the region where the above-mentioned circuit is formed where the above-mentioned plating resist is removed;

去除上述镀敷阻剂;及removing said plating resist; and

通过快速蚀刻等去除形成有上述电路的区域以外的区域的无电解镀敷层及极薄铜层。The electroless plated layer and the ultra-thin copper layer are removed by flash etching or the like in areas other than the areas where the above-mentioned circuits are formed.

本发明中,所谓部分加成法,是指在设置导体层而成的基板、视需要穿过通孔或通路孔用的孔而成的基板上赋予催化剂核,进行蚀刻而形成导体电路,视需要设置阻焊剂或镀敷阻剂后,在上述导体电路上通过无电解镀敷处理对通孔或通路孔等进行增厚,由此制造印刷配线板的方法。In the present invention, the so-called partial addition method means that a catalyst nucleus is provided on a substrate provided with a conductor layer, or a substrate formed by passing through holes or holes for via holes as needed, and etched to form a conductor circuit. It is necessary to provide a solder resist or a plating resist, and then increase the thickness of through holes or via holes on the above-mentioned conductive circuit by electroless plating, thereby manufacturing a printed wiring board.

因此,在使用部分加成法的本发明的印刷配线板的制造方法的一实施方案中,包含下述步骤:Therefore, in one embodiment of the manufacturing method of the printed wiring board of the present invention using the partial additive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

在剥离上述载体而露出的极薄铜层与绝缘基板设置通孔或/及盲孔;Provide through holes or/and blind holes on the extremely thin copper layer exposed by peeling off the above-mentioned carrier and the insulating substrate;

对含有上述通孔或/及盲孔的区域进行除胶渣处理;Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

对含有上述通孔或/及盲孔的区域赋予催化剂核;Giving a catalyst core to the region containing the above-mentioned through holes or/and blind holes;

在剥离上述载体而露出的极薄铜层表面设置蚀刻阻剂;Etching resist is provided on the surface of the ultra-thin copper layer exposed by peeling off the above-mentioned carrier;

对上述蚀刻阻剂进行曝光,形成电路图案;Exposing the above etching resist to form a circuit pattern;

通过使用有酸等腐蚀溶液的蚀刻或电浆等方法去除上述极薄铜层及上述催化剂核,而形成电路;Forming a circuit by removing the above-mentioned extremely thin copper layer and the above-mentioned catalyst core by using etching or plasma with a corrosive solution such as acid;

去除上述蚀刻阻剂;removing the above etching resist;

在通过使用有酸等腐蚀溶液的蚀刻或电浆等方法去除上述极薄铜层及上述催化剂核而露出的上述绝缘基板表面,设置阻焊剂或镀敷阻剂;及A solder resist or a plating resist is provided on the surface of the above-mentioned insulating substrate exposed by removing the above-mentioned ultra-thin copper layer and the above-mentioned catalyst core by etching or plasma using a corrosive solution such as acid; and

在未设置上述阻焊剂或镀敷阻剂的区域设置无电解镀敷层。An electroless plating layer is provided in a region where the above-mentioned solder resist or plating resist is not provided.

本发明中,所谓减成法,是指通过蚀刻等选择性地去除覆铜积层板上的铜箔的不需要的部分,而形成导体图案的方法。In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper-clad laminate by etching or the like to form a conductor pattern.

因此,在使用减成法的本发明的印刷配线板的制造方法的一实施方案中,包含下述步骤:Therefore, in one embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

在剥离上述载体而露出的极薄铜层与绝缘基板设置通孔或/及盲孔;Provide through holes or/and blind holes on the extremely thin copper layer exposed by peeling off the above-mentioned carrier and the insulating substrate;

对含有上述通孔或/及盲孔的区域进行除胶渣处理;Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

在含有上述通孔或/及盲孔的区域设置无电解镀敷层;Provide an electroless plating layer in the area containing the above-mentioned through holes or/and blind holes;

在上述无电解镀敷层的表面设置电镀层;An electroplating layer is provided on the surface of the above-mentioned electroless plating layer;

在上述电镀层或/及上述极薄铜层的表面设置蚀刻阻剂;setting an etching resist on the surface of the electroplating layer or/and the above-mentioned ultra-thin copper layer;

对上述蚀刻阻剂进行曝光,形成电路图案;Exposing the above etching resist to form a circuit pattern;

通过使用有酸等腐蚀溶液的蚀刻或电浆等方法去除上述极薄铜层及上述无电解镀敷层及上述电镀层,而形成电路;及A circuit is formed by removing the above-mentioned ultra-thin copper layer, the above-mentioned electroless plating layer, and the above-mentioned electroplating layer by methods such as etching or plasma using a corrosive solution such as acid; and

去除上述蚀刻阻剂。The above etching resist is removed.

在使用减成法的本发明的印刷配线板的制造方法的另一实施方案中,包含下述步骤:In another embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method, the following steps are included:

准备本发明的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate of the present invention;

将上述附载体铜箔与绝缘基板积层;Laminate the above copper foil with carrier and insulating substrate;

在将上述附载体铜箔与绝缘基板积层后,将上述附载体铜箔的载体剥离;After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

在剥离上述载体而露出的极薄铜层与绝缘基板设置通孔或/及盲孔;Provide through holes or/and blind holes on the extremely thin copper layer exposed by peeling off the above-mentioned carrier and the insulating substrate;

对含有上述通孔或/及盲孔的区域进行除胶渣处理;Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

在含有上述通孔或/及盲孔的区域设置无电解镀敷层;Provide an electroless plating layer in the area containing the above-mentioned through holes or/and blind holes;

在上述无电解镀敷层的表面形成遮罩;Forming a mask on the surface of the electroless plating layer;

在未形成遮罩的上述无电解镀敷层的表面设置电镀层;An electroplating layer is provided on the surface of the above-mentioned electroless plating layer that does not form a mask;

在上述电镀层或/及上述极薄铜层的表面设置蚀刻阻剂;setting an etching resist on the surface of the electroplating layer or/and the above-mentioned ultra-thin copper layer;

对上述蚀刻阻剂进行曝光,形成电路图案;Exposing the above etching resist to form a circuit pattern;

通过使用有酸等腐蚀溶液的蚀刻或电浆等方法去除上述极薄铜层及上述无电解镀敷层,而形成电路;及A circuit is formed by removing the above-mentioned ultra-thin copper layer and the above-mentioned electroless plating layer by methods such as etching or plasma using a corrosive solution such as acid; and

去除上述蚀刻阻剂。The above etching resist is removed.

也可不进行设置通孔或/及盲孔的步骤、及其后的除胶渣步骤。The step of providing through holes and/or blind holes and the subsequent step of removing smear may also be omitted.

此处,利用图式详细地说明使用本发明的附载体铜箔的印刷配线板的制造方法的具体实施例。再者,此处,以具有形成有粗化处理层的极薄铜层的附载体铜箔为例进行说明,但并不限于此,使用具有未形成粗化处理层的极薄铜层的附载体铜箔,也可同样地进行下述印刷配线板的制造方法。Here, the specific Example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, here, a copper foil with a carrier having an ultra-thin copper layer on which a roughening treatment layer is formed is described as an example. Carrier copper foil can also perform the manufacturing method of the following printed wiring board in the same manner.

首先,如图2-A所示,准备表面具有形成有粗化处理层的极薄铜层的附载体铜箔(第1层)。First, as shown in FIG. 2-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed in the surface is prepared.

其次,如图2-B所示,在极薄铜层的粗化处理层上涂布光阻剂,进行曝光、显影,将光阻剂蚀刻为既定的形状。Next, as shown in Fig. 2-B, a photoresist is applied on the roughened layer of the ultra-thin copper layer, exposed and developed, and the photoresist is etched into a predetermined shape.

继而,如图2-C所示,在形成电路用镀敷后,去除光阻剂,由此形成特定的形状的电路镀层。Next, as shown in FIG. 2-C , after the plating for circuit formation, the photoresist is removed to form a circuit plating layer of a specific shape.

继而,如图3-D所示,以被覆电路镀层的方式(以埋没电路镀层的方式)在极薄铜层上设置埋入树脂而积层树脂层,继而,自极薄铜层侧接着另一附载体铜箔(第2层)。Next, as shown in Fig. 3-D, an embedding resin is provided on the ultra-thin copper layer to form a laminated resin layer in such a way as to cover the circuit plating layer (by burying the circuit plating layer), and then another One copper foil with carrier (2nd layer).

继而,如图3-E所示,自第2层的附载体铜箔剥离载体。Next, as shown in FIG. 3-E , the carrier is peeled off from the second-layer copper foil with a carrier.

继而,如图3-F所示,在树脂层的既定位置进行雷射开孔,使电路镀层露出而形成盲孔。Then, as shown in FIG. 3-F , laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating layer and form a blind hole.

继而,如图4-G所示,在盲孔中埋入铜,形成通孔填充物。Then, as shown in Figure 4-G, copper is buried in the blind hole to form a via filling.

继而,如图4-H所示,在通孔填充物上,以上述图2-B及图2-C的方式形成电路镀层。Next, as shown in FIG. 4-H, a circuit plating layer is formed on the through-hole filling in the manner of the above-mentioned FIG. 2-B and FIG. 2-C.

继而,如图4-I所示,自第1层的附载体铜箔剥离载体。Next, as shown in FIG. 4-I , the carrier is peeled off from the first-layer copper foil with a carrier.

继而,如图5-J所示,通过快速蚀刻去除两表面的极薄铜层,使树脂层内的电路镀层的表面露出。Then, as shown in Fig. 5-J, the extremely thin copper layers on both surfaces are removed by rapid etching, so that the surface of the circuit plating layer in the resin layer is exposed.

继而,如图5-K所示,在树脂层内的电路镀层上形成凸块,在该焊料上形成铜柱。如此制作使用本发明的附载体铜箔的印刷配线板。Next, as shown in FIG. 5-K , bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board which used the copper foil with a carrier of this invention was produced.

上述另一附载体铜箔(第2层)可使用本发明的附载体铜箔,也可使用现有的附载体铜箔,进而也可使用通常的铜箔。又,可在图4-H所表示的第2层的电路上进一步形成1层或多个层电路,可通过半加成法、减成法、部分加成法或改进半加成法中的任一方法形成该等电路。The copper foil with a carrier of this invention may be used for said another copper foil with a carrier (2nd layer), the existing copper foil with a carrier may be used, and a normal copper foil may be used further. In addition, one or more layers of circuits can be further formed on the circuit of the second layer shown in Figure 4-H, which can be achieved by semi-additive method, subtractive method, partial additive method or improved semi-additive method. Either method forms the circuits.

本发明的附载体铜箔优选为以满足以下(1)的方式控制极薄铜层表面的色差。本发明中,所谓“极薄铜层表面的色差”是表示极薄铜层的表面的色差,或在实施粗化处理等各种表面处理的情形时表示其表面处理层表面的色差。即,本发明的附载体铜箔优选为以满足以下(1)的方式控制极薄铜层或粗化处理层或耐热层或防锈层或铬酸盐处理层或硅烷偶合层的表面的色差。It is preferable that the copper foil with a carrier of this invention controls the color difference of the ultra-thin copper layer surface so that the following (1) may be satisfied. In the present invention, the "color difference on the surface of the ultra-thin copper layer" means the color difference on the surface of the ultra-thin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention is preferably such that the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling layer is controlled so that the following (1) is satisfied. chromatic aberration.

(1)极薄铜层或粗化处理层或耐热层或防锈层或铬酸盐处理层或硅烷偶合处理层的表面的基在JISZ8730的色差ΔE*ab为45以上。(1) The color difference ΔE*ab of the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, rust-proof layer, chromate-treated layer, or silane coupling-treated layer based on JISZ8730 is 45 or more.

此处,色差ΔL、Δa、Δb是分别以色差计进行测定,采取黑/白/红/绿/黄/蓝,而使用基于JIS Z8730的L﹡a﹡b表色是统表示的综合指标,且表示为ΔL:白黑、Δa:红绿、Δb:黄蓝。又,ΔE*ab是使用该等色差以下述式表示。Here, the color difference ΔL, Δa, and Δb are respectively measured by a color difference meter, and black/white/red/green/yellow/blue are used, and L*a*b color based on JIS Z8730 is used as a comprehensive indicator for statistical representation. And expressed as ΔL: white and black, Δa: red and green, Δb: yellow and blue. In addition, ΔE*ab is represented by the following formula using these color differences.

[数学式1][mathematical formula 1]

上述色差可通过提高极薄铜层形成时的电流密度、降低镀敷液中的铜浓度、提高镀敷液的线流速而进行调整。The above-mentioned color difference can be adjusted by increasing the current density when forming the ultra-thin copper layer, reducing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.

又,上述色差也可通过在极薄铜层的表面实施粗化处理并设置粗化处理层而进行调整。在设置粗化处理层的情形时,可通过如下而进行调整:使用含有选自由铜及镍、钴、钨、钼所组成的群中的一种以上元素的电解液,较现有进一步提高电流密度(例如40~60A/dm2),缩短处理时间(例如0.1~1.3秒)。在极薄铜层的表面未设置粗化处理层的情形时,可通过如下而完成:使用使Ni的浓度为其他元素的2倍以上的镀浴,在极薄铜层或耐热层或防锈层或铬酸盐处理层或硅烷偶合处理层的表面,以设定较现有低的电流密度(0.1~1.3A/dm2)且增加处理时间(20秒~40秒)的方式对镀Ni合金(例如镀Ni-W合金、镀Ni-Co-P合金、镀Ni-Zn合金)进行处理。In addition, the above-mentioned color difference can also be adjusted by roughening the surface of the ultra-thin copper layer and providing a roughened layer. When the roughening treatment layer is provided, it can be adjusted by using an electrolyte solution containing one or more elements selected from the group consisting of copper, nickel, cobalt, tungsten, and molybdenum, and further increasing the current Density (eg 40-60A/dm 2 ), shorten processing time (eg 0.1-1.3 seconds). When the roughening treatment layer is not provided on the surface of the ultra-thin copper layer, it can be completed as follows: use a plating bath whose Ni concentration is more than twice that of other elements, and coat the ultra-thin copper layer or the heat-resistant layer or the anti-corrosion layer. On the surface of the rust layer, chromate treatment layer or silane coupling treatment layer, the current density (0.1-1.3A/dm 2 ) is set lower than the existing one and the treatment time is increased (20 seconds to 40 seconds). Ni alloy (such as Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) for treatment.

若极薄铜层表面的基于JISZ8730的色差ΔE*ab为45以上,则在例如附载体铜箔的极薄铜层表面形成电路时,极薄铜层与电路的对比度清晰,结果视认性变得良好,可精度良好地进行电路的位置对准。极薄铜层表面的基于JISZ8730的色差ΔE*ab优选为50以上,更优选为55以上,再更优选为60以上。If the color difference ΔE*ab based on JISZ8730 on the surface of the ultra-thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer of copper foil with a carrier, the contrast between the ultra-thin copper layer and the circuit will be clear, resulting in poor visibility. The position of the circuit can be aligned with good accuracy. The color difference ΔE*ab based on JISZ8730 of the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more.

在如上所述般控制极薄铜层或粗化处理层或耐热层或防锈层或铬酸盐处理层或硅烷偶合层的表面的色差的情形时,与电路镀层的对比度变得清晰,视认性良好。因此,在如上所述的印刷配线板的例如图2-C所表示的制造步骤中,可精度良好地在既定的位置形成电路镀层。又,通过如上所述的印刷配线板的制造方法,形成使电路镀层埋入于树脂层的构成,因此在例如图5-J所表示的通过快速蚀刻去除极薄铜层时,利用树脂层保护电路镀层,并保持其形状,由此容易形成细微电路。又,因利用树脂层保护电路镀层,而提高耐迁移性,良好地抑制电路的配线的导通。因此,容易形成细微电路。又,在如图5-J及图5-K所表示般通过快速蚀刻去除极薄铜层时,电路镀层的露出面形成为自树脂层凹陷的形状,因此容易分别在该电路镀层上形成凸块,进而在其上形成铜柱,而提高制造效率。In the case of controlling the color difference of the surface of the ultra-thin copper layer or the roughening treatment layer or the heat-resistant layer or the rust-proof layer or the chromate treatment layer or the silane coupling layer as described above, the contrast with the circuit plating layer becomes clear, Good visibility. Therefore, in the manufacturing process shown, for example in FIG. 2-C of the above-mentioned printed wiring board, a circuit plating layer can be formed in a predetermined position with high precision. In addition, the above-mentioned printed wiring board manufacturing method forms a structure in which the circuit plating layer is embedded in the resin layer. Therefore, when removing the ultra-thin copper layer by rapid etching as shown in FIG. 5-J, for example, the resin layer Protects the circuit plating and maintains its shape, making it easy to form fine circuits. In addition, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit is favorably suppressed. Therefore, it is easy to form a fine circuit. Also, when the extremely thin copper layer is removed by rapid etching as shown in Fig. 5-J and Fig. 5-K, the exposed surface of the circuit plating layer is formed in a shape recessed from the resin layer, so it is easy to form protrusions on the circuit plating layer respectively. Block, and then form copper pillars on it, and improve manufacturing efficiency.

再者,埋入树脂(Resin)可使用公知的树脂、预浸体。可使用例如BT(双马来亚酰胺三嗪)树脂或含浸BT树脂的玻璃布即预浸体、Ajinomoto Fine-Techno股份有限公司制造的ABF膜或ABF。又,上述埋入树脂(Resin)可使用本说明书中所记载的树脂层及/或树脂及/或预浸体。In addition, well-known resin and prepreg can be used for embedding resin (Resin). For example, a BT (bismaleimide triazine) resin or a prepreg which is a glass cloth impregnated with a BT resin, an ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. can be used. Moreover, the above-mentioned embedding resin (Resin) can use the resin layer and/or resin and/or prepreg described in this specification.

又,上述第一层所使用的附载体铜箔也可在该附载体铜箔的载体表面具有基板或树脂层。通过具有该基板或树脂层,使用在第一层的附载体铜箔被支持,变得难以生成皱折,故具有生产性提高的优点。再者,上述基板或树脂层只要为具有支持上述第一层所使用的附载体铜箔的效果者,则无特别限制。例如,作为上述基板或树脂层,可使用本申请说明书中所记载的载体、预浸体、树脂层或周知的载体、预浸体、树脂层、金属板、金属箔、无机化合物的板、无机化合物的箔、有机化合物的板、有机化合物的箔。Moreover, the copper foil with a carrier used for the said 1st layer may have a board|substrate or a resin layer on the carrier surface of this copper foil with a carrier. By having such a substrate or a resin layer, the copper foil with a carrier used as the first layer is supported, and it becomes difficult to generate wrinkles, so there is an advantage that productivity improves. In addition, it will not specifically limit if the said board|substrate or resin layer has the effect of supporting the copper foil with a carrier used for the said 1st layer. For example, as the above-mentioned substrate or resin layer, the carrier, prepreg, resin layer described in the specification of this application, or a well-known carrier, prepreg, resin layer, metal plate, metal foil, plate of inorganic compound, inorganic compound can be used. Foil of compound, plate of organic compound, foil of organic compound.

实施例Example

以下,通过实施例对本发明进一步进行详细说明,但本发明并不因这些实施例而受到任何限定。Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited by these examples.

1.附载体铜箔的制造1. Manufacture of copper foil with carrier

<实施例1><Example 1>

将聚酰亚胺膜(宇部兴产公司制造的Upilex-S膜;厚度:35μm)安装于真空装置内,真空排气后使用氧实施电浆处理。A polyimide film (Upilex-S film manufactured by Ube Industries, Ltd.; thickness: 35 μm) was installed in a vacuum apparatus, and plasma treatment was performed using oxygen after vacuum exhaust.

接着,通过Cr溅镀而在电浆处理后的膜的一面形成Cr层10nm。之后,在氧气气氛的腔室中处理Cr溅镀层,在表面形成铬氧化物,形成中间层。Next, a Cr layer of 10 nm was formed on one surface of the plasma-treated film by Cr sputtering. Afterwards, the Cr sputtered layer is processed in an oxygen atmosphere chamber to form chromium oxide on the surface to form an intermediate layer.

再来,对Cr中间层的表面进行Cu溅镀而形成厚5μm的Cu溅镀层。溅镀条件设为在使用Cu靶的Ar气体中,放电电压为500V,放电电流为15A,真空度为5×10-2Pa。Next, Cu sputtering was performed on the surface of the Cr intermediate layer to form a Cu sputtering layer with a thickness of 5 μm. The sputtering conditions were set to a discharge voltage of 500 V, a discharge current of 15 A, and a vacuum degree of 5×10 −2 Pa in Ar gas using a Cu target.

接着,对于此5μm的Cu溅镀层的表面,对极薄铜层表面依序进行以下的粗化处理1、粗化处理2、耐热处理、铬酸盐处理及硅烷偶合处理。Next, on the surface of the 5 μm Cu sputtered layer, the following roughening treatment 1, roughening treatment 2, heat resistance treatment, chromate treatment, and silane coupling treatment were sequentially performed on the surface of the ultra-thin copper layer.

·粗化处理1·Coarsening treatment 1

(液体组成1)(liquid composition 1)

Cu:10~30g/LCu: 10~30g/L

H2SO4:10~150g/L H2SO4 : 10 ~150g/L

W:0~50mg/LW: 0~50mg/L

十二烷基硫酸钠:0~50mg/LSodium lauryl sulfate: 0~50mg/L

As:0~200mg/LAs: 0~200mg/L

(电镀条件1)(plating condition 1)

温度:30~70℃Temperature: 30~70℃

电流密度:25~110A/dm2 Current density: 25 ~110A/dm2

粗化库伦量:50~500As/dm2 Coarse Coulomb quantity: 50~500As/dm 2

镀敷时间:0.5~20秒Plating time: 0.5 to 20 seconds

·粗化处理2·Coarsening 2

(液体组成2)(liquid composition 2)

Cu:20~80g/LCu: 20~80g/L

H2SO4:50~200g/L H2SO4 : 50~200g/L

(电镀条件2)(plating condition 2)

温度:30~70℃Temperature: 30~70℃

电流密度:5~50A/dm2 Current density: 5 ~50A/dm2

粗化库伦量:50~300As/dm2 Coarse Coulomb quantity: 50~300As/dm 2

镀敷时间:1~60秒Plating time: 1 to 60 seconds

·耐热处理·Heat-resistant treatment

(液体组成)(liquid composition)

NaOH:40~200g/LNaOH: 40~200g/L

NaCN:70~250g/LNaCN: 70~250g/L

CuCN:50~200g/LCuCN: 50~200g/L

Zn(CN)2:2~100g/LZn(CN) 2 : 2~100g/L

As2O3:0.01~1g/LAs 2 O 3 : 0.01~1g/L

(液温)(liquid temperature)

40~90℃40~90℃

(电流条件)(current condition)

电流密度:1~50A/dm2 Current density: 1 ~50A/dm2

镀敷时间:1~20秒Plating time: 1 to 20 seconds

·铬酸盐处理·Chromate treatment

K2Cr2O7(Na2Cr2O7或CrO3):2~10g/LK 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2~10g/L

NaOH或KOH:10~50g/LNaOH or KOH: 10~50g/L

ZnOH或ZnSO4·7H2O:0.05~10g/LZnOH or ZnSO 4 ·7H 2 O: 0.05~10g/L

pH:7~13pH: 7~13

浴温:20~80℃Bath temperature: 20~80℃

电流密度:0.05~5A/dm2 Current density: 0.05~5A/ dm2

时间:5~30秒Time: 5-30 seconds

·硅烷偶合处理·Silane coupling treatment

喷涂0.1vol%~0.3vol%的3-环氧丙氧基丙基三甲氧基硅烷水溶液后,在100~200℃的空气中进行干燥-加热0.1~10秒钟。After spraying 0.1vol%-0.3vol% 3-glycidoxypropyltrimethoxysilane aqueous solution, dry-heat in air at 100-200°C for 0.1-10 seconds.

<实施例2><Example 2>

以与实施例1相同的步骤、方法、条件在聚酰亚胺膜载体上形成5μm的Cu溅镀的极薄铜层后,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。After forming the ultra-thin copper layer of 5 μm Cu sputtering on the polyimide film carrier with the same steps, methods and conditions as in Example 1, the heat-resistant treatment of Example 1, chromate treatment, and Silane coupling treatment.

<实施例3><Example 3>

以与实施例1相同的步骤、方法、条件在聚酰亚胺载体上形成1μm的Cu溅镀层后,接着,在辊对辊型的连续镀敷线上,通过电镀而在Cu溅镀层上形成2μm的镀Cu层,以下述的条件进行电镀,由此形成总铜厚为3μm的极薄铜层,制造附载体铜箔。After forming a Cu sputtering layer of 1 μm on the polyimide carrier with the same steps, methods, and conditions as in Example 1, then, on a roll-to-roll continuous plating line, form a sputtering layer on the Cu sputtering layer by electroplating. The Cu plated layer of 2 μm was electroplated under the following conditions to form an ultra-thin copper layer with a total copper thickness of 3 μm, and to manufacture a copper foil with a carrier.

·电镀Cu层·Electroplating Cu layer

铜浓度:30~120g/LCopper concentration: 30~120g/L

H2SO4浓度:20~120g/LH 2 SO 4 concentration: 20~120g/L

Cl浓度:30~80mg/LCl concentration: 30~80mg/L

二硫双(3-磺丙基)二钠浓度:10~50mg/LConcentration of dithiobis(3-sulfopropyl) disodium: 10~50mg/L

含有二烷基胺基的聚合物(重量平均分子量8500):10~50mg/LPolymers containing dialkylamine groups (weight average molecular weight 8500): 10~50mg/L

电解液温度:20~80℃Electrolyte temperature: 20~80℃

电流密度:10~100A/dm2 Current density: 10 ~100A/dm2

在形成极薄铜层后,接着在极薄铜层表面依序进行与实施例1相同的粗化处理1、粗化处理2、耐热处理、铬酸盐处理及硅烷偶合处理。After forming the ultra-thin copper layer, the same roughening treatment 1, roughening treatment 2, heat-resistant treatment, chromate treatment and silane coupling treatment as in Example 1 were sequentially performed on the surface of the ultra-thin copper layer.

<实施例4><Example 4>

以与实施例3相同的步骤、方法、条件在聚酰亚胺膜载体上形成中间层及极薄铜层。接着,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。The intermediate layer and the ultra-thin copper layer were formed on the polyimide film carrier with the same steps, methods, and conditions as in Example 3. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<实施例5><Example 5>

使用压延铜箔(JX日矿日石金属制造的精铜(JIS H3100;合金编号C1100)箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成1μm的Cu溅镀层后,接着,在辊对辊型的连续镀敷线上,通过电镀而在Cu溅镀层上形成2μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Use rolled copper foil (refined copper (JIS H3100; alloy number C1100) foil manufactured by JX Japan Mining Nippon Metal; thickness 18 μm) to replace the polyimide carrier of Example 4, and perform the same steps as Example 4 , method, conditions After forming a 1 μm Cu sputtering layer, then, on a roll-to-roll continuous plating line, a 2 μm Cu plating layer is formed on the Cu sputtering layer by electroplating, thereby obtaining a total copper thickness of 3 μm. thin copper layer. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<实施例6><Example 6>

使用电解铜箔(JX日矿日石金属制造的HLP箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成1μm的Cu溅镀层后,接着,在辊对辊型的连续镀敷线上,通过电镀而在Cu溅镀层上形成2μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Use electrolytic copper foil (HLP foil manufactured by JX Japan Mining Japan Metal; thickness 18 μm) to replace the polyimide carrier of Example 4, and form a Cu splash of 1 μm with the same steps, methods and conditions as in Example 4. After the plating, a 2 μm Cu plated layer was formed on the Cu sputtered layer by electroplating on a roll-to-roll continuous plating line to obtain an ultra-thin copper layer with a total copper thickness of 3 μm. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<实施例7><Example 7>

使用压延铜箔(JX日矿日石金属制造的精铜(JIS H3100;合金编号C1100)箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成中间层后,接着,在辊对辊型的连续镀敷线上,以与实施例4相同的方法、条件通过电镀而在中间层上形成3μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Use rolled copper foil (refined copper (JIS H3100; alloy number C1100) foil manufactured by JX Japan Mining Nippon Metal; thickness 18 μm) to replace the polyimide carrier of Example 4, and perform the same steps as Example 4 , method, condition After forming the intermediate layer, then, on the continuous plating line of roll-to-roll type, form a 3 μm Cu plating layer on the intermediate layer by electroplating with the same method and conditions as in Example 4, thereby obtaining the total An extremely thin layer of copper with a copper thickness of 3 μm. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<实施例8><Example 8>

使用电解铜箔(JX日矿日石金属制造的HLP箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成中间层后,接着,在辊对辊型的连续镀敷线上,通过电镀而在中间层上形成3μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Electrolytic copper foil (HLP foil manufactured by JX Nippon Mining Metal; thickness 18 μm) was used to replace the polyimide carrier in Example 4, and after the intermediate layer was formed in the same steps, methods and conditions as in Example 4, Next, a Cu plating layer of 3 μm was formed on the intermediate layer by electroplating on a roll-to-roll continuous plating line to obtain an ultra-thin copper layer with a total copper thickness of 3 μm. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<实施例9><Example 9>

使用压延铜箔(JX日矿日石金属制造的精铜(JIS H3100;合金编号C1100)箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成中间层后,接着,在辊对辊型的连续镀敷线上,以与实施例4相同的方法、条件通过电镀而在中间层上形成3μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,在进行以下的粗化处理3后,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Use rolled copper foil (refined copper (JIS H3100; alloy number C1100) foil manufactured by JX Japan Mining Nippon Metal; thickness 18 μm) to replace the polyimide carrier of Example 4, and perform the same steps as Example 4 , method, condition After forming the intermediate layer, then, on the continuous plating line of roll-to-roll type, form a 3 μm Cu plating layer on the intermediate layer by electroplating with the same method and conditions as in Example 4, thereby obtaining the total An extremely thin layer of copper with a copper thickness of 3 μm. Next, after the following roughening treatment 3 was performed, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

·粗化处理3·Coarsening treatment 3

(液体组成3)(liquid composition 3)

Cu:10~20g/LCu: 10~20g/L

Ni:5~15g/LNi: 5~15g/L

Co:5~15g/LCo: 5~15g/L

(电镀条件3)(plating condition 3)

温度:25~60℃Temperature: 25~60℃

电流密度:35~55A/dm2 Current density: 35~55A/ dm2

粗化库伦量:5~50As/dm2 Coarse Coulomb quantity: 5~50As/dm 2

镀敷时间:0.1~1.4秒Plating time: 0.1 to 1.4 seconds

<实施例10><Example 10>

使用电解铜箔(JX日矿日石金属制造的HLP箔;厚度18μm)取代实施例4的聚酰亚胺载体,并对其以与实施例4相同的步骤、方法、条件形成中间层后,接着,在辊对辊型的连续镀敷线上,通过电镀而在中间层上形成3μm的镀Cu层,从而得到总铜厚为3μm的极薄铜层。接着,在进行实施例9的粗化处理3后,依序进行实施例1的耐热处理、铬酸盐处理、及硅烷偶合处理。Electrolytic copper foil (HLP foil manufactured by JX Nippon Mining Metal; thickness 18 μm) was used to replace the polyimide carrier in Example 4, and after the intermediate layer was formed in the same steps, methods and conditions as in Example 4, Next, a Cu plating layer of 3 μm was formed on the intermediate layer by electroplating on a roll-to-roll continuous plating line to obtain an ultra-thin copper layer with a total copper thickness of 3 μm. Next, after the roughening treatment 3 of Example 9, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were sequentially performed.

<比较例1><Comparative example 1>

以电解铜箔(JX日矿日石金属制造的JTC箔;厚度18μm)取代实施例1的聚酰亚胺载体,对其上的光泽面利用以下条件在辊对辊型的连续镀敷线上,通过电镀而形成附着量4000μg/dm2的Ni层。Electrolytic copper foil (JTC foil manufactured by JX Nippon Mining Metal; thickness 18 μm) was used to replace the polyimide carrier in Example 1, and the glossy surface on it was used on a roll-to-roll continuous plating line under the following conditions , A Ni layer with an adhesion amount of 4000 μg/dm 2 was formed by electroplating.

·Ni层·Ni layer

硫酸镍:250~300g/LNickel sulfate: 250~300g/L

氯化镍:35~45g/LNickel chloride: 35~45g/L

乙酸镍:10~20g/LNickel acetate: 10~20g/L

柠檬酸三钠:15~30g/LTrisodium citrate: 15~30g/L

光泽剂:糖精、丁炔二醇等Gloss agent: saccharin, butynediol, etc.

十二烷基硫酸钠:30~100ppmSodium lauryl sulfate: 30~100ppm

pH:4~6pH: 4~6

浴温:50~70℃Bath temperature: 50~70℃

电流密度:3~15A/dm2 Current density: 3 ~15A/dm2

在水洗及酸洗后,接着在辊对辊型的连续镀敷线上,利用以下条件通过电解铬酸盐处理而使附着量为11μg/dm2的Cr层附着在Ni层上。After washing with water and pickling, a Cr layer with an adhesion amount of 11 μg/dm 2 was deposited on the Ni layer by electrolytic chromate treatment on a roll-to-roll continuous plating line under the following conditions.

·电解铬酸盐处理·Electrolytic chromate treatment

液体组成:重铬酸钾1~10g/L、锌0~5g/LLiquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH:3~4pH: 3~4

液温:50~60℃Liquid temperature: 50~60℃

电流密度:0.1~2.6A/dm2 Current density: 0.1~2.6A/ dm2

库伦量:0.5~30A·s/dm2 Coulomb capacity: 0.5~30A·s/dm 2

在辊对辊型的连续镀敷线上,利用以下条件通过电镀而在Cr层上形成厚度3μm的极薄铜层,从而制得附载体铜箔。On a roll-to-roll type continuous plating line, an ultra-thin copper layer with a thickness of 3 μm was formed on the Cr layer by electroplating under the following conditions, and a copper foil with a carrier was produced.

·极薄铜层·Extremely thin copper layer

铜浓度:30~120g/LCopper concentration: 30~120g/L

H2SO4浓度:20~120g/LH 2 SO 4 concentration: 20~120g/L

电解液温度:20~80℃Electrolyte temperature: 20~80℃

电流密度:5~9A/dm2 Current density: 5 ~9A/dm2

·粗化处理1·Coarsening treatment 1

(液体组成1)(liquid composition 1)

Cu:10~30g/LCu: 10~30g/L

H2SO4:10~150g/L H2SO4 : 10 ~150g/L

As:0~200mg/LAs: 0~200mg/L

(电镀条件1)(plating condition 1)

温度:30~70℃Temperature: 30~70℃

电流密度:25~110A/dm2 Current density: 25 ~110A/dm2

粗化库伦量:50~500As/dm2 Coarse Coulomb quantity: 50~500As/dm 2

镀敷时间:0.5~20秒Plating time: 0.5 to 20 seconds

·粗化处理2·Coarsening 2

(液体组成2)(liquid composition 2)

Cu:20~80g/LCu: 20~80g/L

H2SO4:50~200g/L H2SO4 : 50~200g/L

(电镀条件2)(plating condition 2)

温度:30~70℃Temperature: 30~70℃

电流密度:5~50A/dm2 Current density: 5 ~50A/dm2

粗化库伦量:50~300As/dm2 Coarse Coulomb quantity: 50~300As/dm 2

镀敷时间:1~60秒Plating time: 1 to 60 seconds

·耐热处理·Heat-resistant treatment

(液体组成)(liquid composition)

NaOH:40~200g/LNaOH: 40~200g/L

NaCN:70~250g/LNaCN: 70~250g/L

CuCN:50~200g/LCuCN: 50~200g/L

Zn(CN)2:2~100g/LZn(CN) 2 : 2~100g/L

As2O3:0.01~1g/LAs 2 O 3 : 0.01~1g/L

(液温)(liquid temperature)

40~90℃40~90℃

(电流条件)(current condition)

电流密度:1~50A/dm2 Current density: 1 ~50A/dm2

镀敷时间:1~20秒Plating time: 1 to 20 seconds

·铬酸盐处理·Chromate treatment

K2Cr2O7(Na2Cr2O7或CrO3):2~10g/LK 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2~10g/L

NaOH或KOH:10~50g/LNaOH or KOH: 10~50g/L

ZnOH或ZnSO4·7H2O:0.05~10g/LZnOH or ZnSO 4 ·7H 2 O: 0.05~10g/L

pH:7~13pH: 7~13

浴温:20~80℃Bath temperature: 20~80℃

电流密度:0.05~5A/dm2 Current density: 0.05~5A/ dm2

时间:5~30秒Time: 5-30 seconds

·硅烷偶合处理·Silane coupling treatment

喷涂0.1vol%~0.3vol%的3-环氧丙氧基丙基三甲氧基硅烷水溶液后,在100~200℃的空气中进行干燥-加热0.1~10秒钟。After spraying 0.1vol%-0.3vol% 3-glycidoxypropyltrimethoxysilane aqueous solution, dry-heat in air at 100-200°C for 0.1-10 seconds.

<比较例2><Comparative example 2>

使用电解铜箔(JX日矿日石金属制造的JTC箔;厚度18μm)取代实施例4的聚酰亚胺膜载体,在该电解铜箔上的光泽面形成1μm的镀Cu层,除此之外,进行与实施例4相同的处理。Electrolytic copper foil (JTC foil manufactured by JX Nippon Mining Metal; thickness 18 μm) was used instead of the polyimide film carrier of Example 4, and a 1 μm Cu plating layer was formed on the glossy surface of the electrolytic copper foil. Otherwise, the same treatment as in Example 4 was carried out.

2.评价附载体铜箔的特性2. Evaluation of the characteristics of copper foil with carrier

关于以上述方式而得的附载体铜箔,通过以下方法来实施特性评价。About the copper foil with a carrier obtained as mentioned above, the characteristic evaluation was implemented by the following method.

(表面粗糙度)(Surface roughness)

对于形成有中间层的载体,使用非接触式粗糙度测定机(Olympus制造的LEXTOLS4000),且Ra、Rt依据JIS B0601-2001、Rz依据JIS B0601-1994对该中间层的表面粗糙度(载体的中间层形成侧的表面粗糙度)进行测定。又,使用非接触式粗糙度测定机(Olympus制造的LEXT OLS4000),且Ra、Rt依据JIS B0601-2001、Rz依据JIS B0601-1994也对极薄铜层的中间层侧及树脂侧的表面粗糙度进行测定。For the carrier formed with the intermediate layer, use a non-contact roughness measuring machine (LEXTOLS4000 manufactured by Olympus), and Ra, Rt are based on JIS B0601-2001, and Rz is based on JIS B0601-1994 The surface roughness of the intermediate layer (carrier Surface roughness on the side where the intermediate layer was formed) was measured. In addition, using a non-contact roughness measuring machine (LEXT OLS4000 manufactured by Olympus), Ra and Rt are based on JIS B0601-2001, and Rz is based on JIS B0601-1994. degree is measured.

<测定条件><Measurement conditions>

截断值:无Cutoff: None

基准长度:257.9μmReference length: 257.9μm

基准面积:66524μm2 Reference area: 66524μm 2

测定环境温度:23~25℃Measuring ambient temperature: 23~25℃

(电路形成性)(circuit formation)

将各附载体铜箔积层压制于环氧系树脂,接着,剥离除去载体。通过软蚀刻将露出的极薄铜层表面去除0.3μm。之后,在进行洗净、干燥后,在极薄铜层上层迭涂布干膜光阻(日立化成工业制造,商品名RY-3625)。以15mJ/cm2的条件曝光,使用显影液(碳酸钠)于38℃进行1分钟的液体喷射摇动,形成各种线/间隔的光阻图案。接着,使用硫酸铜镀浴(JCU制造的CUBRITE21)镀敷成总铜厚为15μm后,使用剥离液(氢氧化钠)剥离干膜光阻。之后,利用硫酸-过氧化氢系蚀刻剂(Mitsubishi Gas Chemical制造的CPE-800)蚀刻去除极薄铜层而形成各种线/间距的配线。将结果示于表1。Each copper foil with a carrier was laminated and pressed on an epoxy-based resin, and then, the carrier was peeled off and removed. The surface of the exposed ultra-thin copper layer was removed by 0.3 μm by soft etching. Thereafter, after cleaning and drying, a dry film photoresist (manufactured by Hitachi Chemical Industry, trade name RY-3625) is laminated and coated on the ultra-thin copper layer. Exposure was performed at 15 mJ/cm 2 , and liquid jet shaking was performed at 38° C. for 1 minute using a developer solution (sodium carbonate) to form various line/space photoresist patterns. Next, after plating to a total copper thickness of 15 μm using a copper sulfate plating bath (CUBRITE 21 manufactured by JCU), the dry film resist was peeled off using a stripping solution (sodium hydroxide). Thereafter, the ultra-thin copper layer was etched and removed with a sulfuric acid-hydrogen peroxide-based etchant (CPE-800 manufactured by Mitsubishi Gas Chemical) to form wirings of various lines and pitches. The results are shown in Table 1.

(评价结果)(Evaluation results)

实施例1~10皆为极薄铜层表面的至少一面的Rz在0.5μm以下,可形成比线/间距=15μm/15μm更加细微的配线。又,实施例1~10皆为极薄铜层表面的至少一面的Ra在0.12μm以下。又,实施例1~10皆为极薄铜层表面的至少一面的Rt在1.0μm以下。In Examples 1 to 10, Rz of at least one side of the surface of the ultra-thin copper layer is 0.5 μm or less, and finer wiring can be formed than line/space = 15 μm/15 μm. In addition, in Examples 1 to 10, the Ra of at least one surface of the ultra-thin copper layer was 0.12 μm or less. In addition, in Examples 1 to 10, the Rt of at least one surface of the ultra-thin copper layer was 1.0 μm or less.

比较例1、2皆为极薄铜层的两表面的Rz超过0.5μm,无法形成比线/间距=15μm/15μm更加细微的配线。又,比较例1、2皆为极薄铜层的两表面的Ra超过0.12μm,且极薄铜层表面的两表面的Rt超过1.0μm。In Comparative Examples 1 and 2, Rz on both surfaces of the ultra-thin copper layer exceeded 0.5 μm, and finer wiring than line/space = 15 μm/15 μm could not be formed. In addition, in Comparative Examples 1 and 2, the Ra of both surfaces of the ultra-thin copper layer exceeded 0.12 μm, and the Rt of both surfaces of the ultra-thin copper layer surface exceeded 1.0 μm.

Claims (26)

1.一种附载体铜箔,依序具备作为支持体的载体、中间层、极薄铜层,所述极薄铜层表面的至少一面以非接触式粗糙度计进行测定而得的Rz在0.5μm以下,所述极薄铜层表面的一面或两面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。1. A copper foil with a carrier, which is sequentially provided with a carrier as a support, an intermediate layer, and an ultra-thin copper layer, wherein at least one surface of the ultra-thin copper layer has an Rz measured by a non-contact roughness meter at 0.5 μm or less, and Rt measured on one or both sides of the ultra-thin copper layer surface by a non-contact roughness meter is 1.0 μm or less. 2.根据权利要求1所述的附载体铜箔,所述极薄铜层表面的一面或两面以非接触式粗糙度计进行测定而得的Ra在0.12μm以下。2 . The copper foil with a carrier according to claim 1 , wherein Ra measured on one or both surfaces of the surface of the ultra-thin copper layer by a non-contact roughness meter is 0.12 μm or less. 3.一种附载体铜箔,依序具备作为支持体的载体、中间层、极薄铜层,所述极薄铜层表面的两面以非接触式粗糙度计进行测定而得的Rz在0.5μm以下,所述极薄铜层表面的一面或两面以非接触式粗糙度计进行测定而得的Rt在1.0μm以下。3. A copper foil with a carrier, which is sequentially provided with a carrier as a support, an intermediate layer, and an ultra-thin copper layer, and the Rz measured by a non-contact roughness meter on both sides of the ultra-thin copper layer is 0.5 μm or less, the Rt measured on one or both surfaces of the ultra-thin copper layer surface by a non-contact roughness meter is 1.0 μm or less. 4.根据权利要求3所述的附载体铜箔,其中,所述极薄铜层表面的一面或两面以非接触式粗糙度计进行测定而得的Ra在0.12μm以下。4 . The copper foil with a carrier according to claim 3 , wherein Ra measured by a non-contact roughness meter on one or both surfaces of the ultra-thin copper layer is 0.12 μm or less. 5.根据权利要求1至4中任一项所述的附载体铜箔,其中,利用膜来形成所述载体。5. The copper foil with a carrier according to any one of claims 1 to 4, wherein the carrier is formed of a film. 6.根据权利要求1至4中任一项所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Rz在0.5μm以下。The copper foil with a carrier according to any one of claims 1 to 4, wherein Rz of the side surface of the intermediate layer of the carrier is 0.5 μm or less. 7.根据权利要求5所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Rz在0.5μm以下。7 . The copper foil with a carrier according to claim 5 , wherein Rz of the intermediate layer side surface of the carrier is 0.5 μm or less. 8.根据权利要求1至4中任一项所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Ra在0.12μm以下。8 . The copper foil with a carrier according to claim 1 , wherein Ra of the intermediate layer side surface of the carrier is 0.12 μm or less. 9.根据权利要求5所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Ra在0.12μm以下。9 . The copper foil with a carrier according to claim 5 , wherein Ra of the intermediate layer side surface of the carrier is 0.12 μm or less. 10.根据权利要求1至4中任一项所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Rt在1.0μm以下。10 . The copper foil with a carrier according to claim 1 , wherein Rt of the intermediate layer side surface of the carrier is 1.0 μm or less. 11 . 11.根据权利要求5所述的附载体铜箔,其中,所述载体的所述中间层侧表面的Rt在1.0μm以下。11. The copper foil with a carrier according to claim 5, wherein Rt of the intermediate layer side surface of the carrier is 1.0 μm or less. 12.根据权利要求1至4中任一项所述的附载体铜箔,其中,极薄铜层表面的至少一面形成有粗化处理层。12. The copper foil with a carrier according to any one of claims 1 to 4, wherein a roughening treatment layer is formed on at least one surface of the ultra-thin copper layer. 13.根据权利要求12所述的附载体铜箔,其中,所述粗化处理层为由选自由铜、镍、磷、钨、砷、钼、铬、钴及锌构成的群中的任一单质构成的层,或由含有任一种以上所述单质的合金构成的层。13. The copper foil with a carrier according to claim 12, wherein the roughening treatment layer is any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc. A layer composed of a single substance, or a layer composed of an alloy containing any one of the above-mentioned simple substances. 14.根据权利要求1至4中任一项所述的附载体铜箔,其中,在所述极薄铜层的表面具有选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层。14. The copper foil with a carrier according to any one of claims 1 to 4, wherein the surface of the ultra-thin copper layer has a layer selected from a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling layer. One or more types of layers in a group consisting of layers are processed. 15.根据权利要求12所述的附载体铜箔,其中,在所述粗化处理层的表面具有选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层。15. The copper foil with a carrier according to claim 12, wherein the surface of the roughening treatment layer has a layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer. more than 1 layer. 16.根据权利要求1至4中任一项所述的附载体铜箔,其中,在所述极薄铜层表面具备树脂层。The copper foil with a carrier as described in any one of Claims 1-4 provided with the resin layer on the surface of the said ultra-thin copper layer. 17.根据权利要求12所述的附载体铜箔,其中,在所述粗化处理层表面具备树脂层。17. The copper foil with a carrier according to claim 12, wherein a resin layer is provided on the surface of the roughened layer. 18.根据权利要求14所述的附载体铜箔,其中,在所述选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层的表面具备树脂层。18. The copper foil with a carrier according to claim 14, wherein one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer are The surface has a resin layer. 19.根据权利要求15所述的附载体铜箔,其中,在所述选自由耐热层、防锈层、铬酸盐处理层及硅烷偶合处理层构成的群中的1种以上的层的表面具备树脂层。19. The copper foil with a carrier according to claim 15, wherein one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate-treated layer, and a silane coupling-treated layer The surface has a resin layer. 20.根据权利要求19所述的附载体铜箔,其中,所述树脂层含有介电体。20. The copper foil with a carrier according to claim 19, wherein the resin layer contains a dielectric. 21.根据权利要求1至4中任一项所述的附载体铜箔,其可通过使用有极薄铜层的半加成法来形成比线/间隔=15μm/15μm更加细微的电路。21. The copper foil with a carrier according to any one of claims 1 to 4, which can form a circuit finer than line/space=15 μm/15 μm by using a semi-additive method with an ultra-thin copper layer. 22.一种覆铜积层板,其是使用权利要求1至21中任一项所述的附载体铜箔制造而成。22. A copper-clad laminate manufactured using the copper foil with a carrier according to any one of claims 1 to 21. 23.一种印刷配线板,其是使用权利要求1至21中任一项所述的附载体铜箔制造而成。The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-21. 24.一种电子机器,其使用有权利要求23所述的印刷配线板。24. An electronic device using the printed wiring board according to claim 23. 25.一种印刷配线板的制造方法,其包含下述步骤:25. A method of manufacturing a printed wiring board, comprising the steps of: 准备权利要求1至21中任一项所述的附载体铜箔与绝缘基板;Prepare the copper foil with carrier and insulating substrate according to any one of claims 1 to 21; 将所述附载体铜箔与绝缘基板积层;及Laminating the copper foil with carrier and insulating substrate; and 在将所述附载体铜箔与绝缘基板积层后,经将所述附载体铜箔的载体剥离的步骤而形成覆铜积层板,After laminating the copper foil with a carrier and an insulating substrate, the step of peeling off the carrier of the copper foil with a carrier is performed to form a copper-clad laminate, 其后,通过半加成法、减成法、部分加成法或改进半加成法中的任一方法形成电路。Thereafter, a circuit is formed by any one of semi-additive method, subtractive method, partial additive method, or modified semi-additive method. 26.一种印刷配线板的制造方法,其包含下述步骤:26. A method of manufacturing a printed wiring board, comprising the steps of: 在权利要求1至21中任一项所述的附载体铜箔的所述极薄铜层侧表面形成电路;forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier according to any one of claims 1 to 21; 以埋没所述电路的方式在所述附载体铜箔的所述极薄铜层侧表面形成树脂层;forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier in such a manner as to bury the circuit; 在所述树脂层上形成电路;forming a circuit on the resin layer; 在所述树脂层上形成电路后,剥离所述载体;及after forming a circuit on the resin layer, peeling off the carrier; and 在剥离所述载体后,去除所述极薄铜层,由此使形成在所述极薄铜层侧表面的埋没于所述树脂层的电路露出。After peeling off the carrier, the ultra-thin copper layer is removed, thereby exposing the circuit formed on the side surface of the ultra-thin copper layer buried in the resin layer.
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