[go: up one dir, main page]

JP2006312265A - Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board - Google Patents

Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board Download PDF

Info

Publication number
JP2006312265A
JP2006312265A JP2005135663A JP2005135663A JP2006312265A JP 2006312265 A JP2006312265 A JP 2006312265A JP 2005135663 A JP2005135663 A JP 2005135663A JP 2005135663 A JP2005135663 A JP 2005135663A JP 2006312265 A JP2006312265 A JP 2006312265A
Authority
JP
Japan
Prior art keywords
copper foil
carrier
layer
wiring board
ultra
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2005135663A
Other languages
Japanese (ja)
Inventor
Akira Kawakami
昭 川上
Akitoshi Suzuki
昭利 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Circuit Foil Co Ltd
Original Assignee
Furukawa Circuit Foil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Circuit Foil Co Ltd filed Critical Furukawa Circuit Foil Co Ltd
Priority to JP2005135663A priority Critical patent/JP2006312265A/en
Publication of JP2006312265A publication Critical patent/JP2006312265A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an extremely thin copper foil with a carrier used at the time of production of a printed wiring board for use in a fine pattern, not scattering a laser absorbing layer or extremely thin copper to the peripheral part of a viahole or not forming the build-up of copper when laser perforating processing is performed in order to form the viahole to a build-up wiring board and extremely easy in wiring processing, the printed wiring board using it and a multilayered printed wiring board. <P>SOLUTION: In the extremely thin copper foil with the carrier, a peel ply and the extremely thin copper foil are formed on one side of the carrier in this order and a layer easy to absorb the beam with a wavelength oscillated by a CO<SB>2</SB>gas laser is formed on the other surface of the carrier. The layer easy to absorb the beam with the wavelength oscillated to by CO<SB>2</SB>gas laser comprises a layer containing at least one kind of an element selected from the group consisting of nickel, cobalt, iron, zinc, manganese, chromium, tin and phosphorus. The printed wiring board and the multilayered printed wiring board are manufactured using this extremely thin copper foil with the carrier. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明はファインパターン用途のプリント配線板製造時に用いるキャリア付き極薄銅箔に関し、特にレーザー穴あけ加工性に優れるキャリア付き極薄銅箔に関するものであり、該極薄銅箔を用いたプリント配線板、多層プリント配線板に関するものである。   TECHNICAL FIELD The present invention relates to an ultrathin copper foil with a carrier used in the production of a printed wiring board for fine pattern use, and particularly relates to an ultrathin copper foil with a carrier excellent in laser drilling workability, and a printed wiring board using the ultrathin copper foil. The present invention relates to a multilayer printed wiring board.

プリント配線基板は、次のようにして製造されている。
まず、ガラスエポキシ樹脂やポリイミド樹脂などから成る電気絶縁性の基板の表面に、表面回路形成用の薄い銅箔を置いたのち、加熱・加圧して銅張り積層板を製造する。
次いで、その銅張り積層板に、スルーホールの穿設、スルーホールめっきを順次行ったのち、該銅張り積層板の表面にある銅箔にエッチング処理を行って所望する線幅と所望する線間ピッチを備えた配線パターンを形成し、最後に、ソルダーレジストの形成やその他の仕上げ処理が行われる。
このときに用いる銅箔に対しては、基板に熱圧着される側の表面を粗化面とし、この粗化面で該基板に対するアンカー効果を発揮させ、もって該基板と銅箔との接合強度を高めてプリント配線板としての信頼性を確保することがなされている。
The printed wiring board is manufactured as follows.
First, a thin copper foil for forming a surface circuit is placed on the surface of an electrically insulating substrate made of glass epoxy resin or polyimide resin, and then heated and pressed to produce a copper-clad laminate.
Next, after drilling through holes and plating through holes in the copper-clad laminate, the copper foil on the surface of the copper-clad laminate is etched to obtain the desired line width and desired line spacing. A wiring pattern having a pitch is formed, and finally, a solder resist is formed and other finishing processes are performed.
For the copper foil used at this time, the surface to be thermocompression bonded to the substrate is a roughened surface, and this roughened surface exerts an anchoring effect on the substrate, so that the bonding strength between the substrate and the copper foil is To ensure the reliability as a printed wiring board.

更に最近では、銅箔の粗化面を予めエポキシ樹脂のような接着用樹脂に貼着し、該接着用樹脂を半硬化状態(Bステージ)の絶縁樹脂層にした樹脂付き銅箔を表面回路形成用の銅箔として用い、その絶縁樹脂層の側を基板(絶縁基板)に熱圧着してプリント配線基板、とりわけビルドアップ配線基板を製造することが行われている。
こうしたビルドアップ配線基板では、各種電子部品を高度に集積化する要望がなされ、これに対応して、配線パターンも高密度化が要求され、微細な線幅や線間ピッチの配線から成る配線パターン、いわゆるファインパターンのプリント配線基板が求められるようになってきている。例えば、線幅や線間ピッチがそれぞれ20μm前後という高密度極微細配線を有するプリント配線基板が要求されている。
More recently, a copper foil with resin, in which the roughened surface of the copper foil is previously attached to an adhesive resin such as an epoxy resin and the adhesive resin is used as an insulating resin layer in a semi-cured state (B stage), is a surface circuit. A printed wiring board, particularly a build-up wiring board, is manufactured by using a copper foil for forming and thermocompression bonding the insulating resin layer side to a board (insulating board).
In such a build-up wiring board, there is a demand for highly integrated various electronic components. Correspondingly, the wiring pattern is also required to have a high density, and the wiring pattern is composed of wiring with a fine line width and line pitch. Therefore, a so-called fine pattern printed circuit board has been demanded. For example, there is a demand for a printed wiring board having high-density ultrafine wiring having a line width and a line-to-line pitch of about 20 μm.

このようなプリント配線を形成する銅箔として厚い銅箔を用いると、回路形成時のエッチングにおいて、銅箔を基材の表面までエッチングするために必要な時間が長くなり、その結果、形成される配線パターンにおける側壁の垂直性が崩れて、次式:
Ef=2H/(B−T)
(ここで、Hは銅箔の厚み、Bは形成された配線パターンのボトム幅、Tは形成された配線パターンのトップ幅である)で示されるエッチングファクター(Ef)が小さくなる。
このような問題は、形成する配線パターンにおける配線の線幅が広い場合にはそれほど深刻な問題にならないが、線幅が狭い配線パターンの場合には断線に結びつくことも起こり得る。
When a thick copper foil is used as the copper foil for forming such a printed wiring, the time required for etching the copper foil to the surface of the base material is increased in the etching at the time of circuit formation, and as a result, formed. The verticality of the side wall in the wiring pattern is broken, and the following formula:
Ef = 2H / (BT)
Here, H is the thickness of the copper foil, B is the bottom width of the formed wiring pattern, and T is the top width of the formed wiring pattern.
Such a problem does not become a serious problem when the line width of the wiring in the wiring pattern to be formed is large. However, in the case of a wiring pattern with a narrow line width, it may be connected to the disconnection.

一方、薄い銅箔の場合はEf値を大きくすることができる。しかしながら、基板との接合強度を確保するためにこの銅箔の基板側の表面は粗化面になっており、この粗化面の突起部が基板に喰い込むため、この喰い込んだ突起部を完全にエッチング除去するためには長時間のエッチング処理が必要とされる。該喰い込んだ突起部を完全に除去しないと、それが残銅となり、配線パターンの線間ピッチが狭い場合には絶縁不良を引き起こすからである。
したがって、該喰い込んだ突起部をエッチング除去する過程で、既に形成されている配線パターンの側壁のエッチングも進行してしまい、結局はEf値が小さくなってしまう。
On the other hand, in the case of a thin copper foil, the Ef value can be increased. However, in order to secure the bonding strength with the substrate, the surface of the copper foil on the substrate side is a roughened surface, and the protrusions on the roughened surface bite into the substrate. A long etching process is required for complete etching removal. This is because if the engulfed protrusion is not completely removed, it becomes a residual copper, and if the pitch between lines of the wiring pattern is narrow, an insulation failure is caused.
Therefore, in the process of removing the biting protrusion, etching of the side wall of the already formed wiring pattern also proceeds, and eventually the Ef value becomes small.

薄い銅箔を用いる場合、その表面粗度を小さくすればこのような問題を解消できることは事実であるが、その場合には銅箔と基板との接合強度が小さくなるため信頼性に富むファインな配線パターンのプリント配線基板を製造することは困難である。
また、薄い銅箔の場合は、その機械的強度が低いので、プリント配線基板の製造時に銅箔に皺や折れ目が発生しやすく、更には銅箔が破れたりすることがあり、取り扱いに細心の注意を払わなければならず、作業に高度の熟練を要するという問題もある。
When thin copper foil is used, it is true that such a problem can be solved by reducing the surface roughness, but in that case, the bonding strength between the copper foil and the substrate is reduced, so that the fine and reliable It is difficult to manufacture a printed wiring board having a wiring pattern.
Also, in the case of thin copper foil, its mechanical strength is low, so the copper foil is likely to be wrinkled and creased during the production of the printed wiring board, and the copper foil may be torn. However, there is a problem that a high degree of skill is required for the work.

このように、Ef値が大きく、かつ基板との接合強度も高いファインな配線パターンが形成可能なプリント配線基板を製造することは、実際問題としてかなり困難である。特に、線間や線幅が20μm前後の高密度極微細配線の配線パターンを市販されている銅箔を用いて形成することは事実上不可能であり、それを可能にする銅箔の開発が強く望まれているのが実状である。   Thus, as a practical matter, it is quite difficult to manufacture a printed wiring board capable of forming a fine wiring pattern having a large Ef value and a high bonding strength with the board. In particular, it is practically impossible to form a wiring pattern of high-density ultrafine wiring with a line spacing or line width of around 20 μm using a commercially available copper foil. The real situation is strongly desired.

こうしたファインパターン用途に使われる銅箔としては、厚さ9μm以下、特に5μm以下の銅箔が適している。
このようなファインパターン用途に使われる極薄銅箔として、本願出願人は先に、キャリア付極薄銅箔であって、表面粗さ:Rzが1.5μ以下の銅箔をキャリアとし、その表面に剥離層と極薄銅箔をこの順序に形成し、該極薄銅箔の最外層表面が粗化面とした銅箔(特許文献1参照)、及び銅箔をキャリアとし、その表面に剥離層と極薄銅箔をこの順序に形成したキャリア付き銅箔であって、該キャリア銅箔と該極薄銅箔とがそれらの左右エッジ近傍部分がそれらの中央部に比較して強く結合され、かつ、該極薄銅箔の最外層表面が粗面化であるキャリア付き極薄銅箔(特許文献2参照)を開発した。
なお、ここでキャリア付き極薄銅箔の極薄銅箔とは、通常0.5μmから12μm位の厚さのものを指す。これは0.5μmより薄くなるとピンホールが多くなり実用的でないためである。また12μmを越えるような厚さであるとキャリアを付ける必要がなくなってくるからである。
As a copper foil used for such fine pattern applications, a copper foil having a thickness of 9 μm or less, particularly 5 μm or less is suitable.
As the ultra-thin copper foil used for such fine pattern applications, the applicant of the present application is an ultra-thin copper foil with a carrier, and the surface roughness: Rz is 1.5 μm or less as a carrier, A peeling layer and an ultrathin copper foil are formed in this order on the surface, and the outermost layer surface of the ultrathin copper foil is a roughened surface (see Patent Document 1), and the copper foil is used as a carrier, A copper foil with a carrier in which a peeling layer and an ultra-thin copper foil are formed in this order, and the carrier copper foil and the ultra-thin copper foil are strongly bonded in the vicinity of their left and right edges compared to their center And the ultra-thin copper foil with a carrier (refer patent document 2) whose outermost layer surface of this ultra-thin copper foil is roughened was developed.
In addition, the ultra-thin copper foil of the ultra-thin copper foil with a carrier refers to the thing of thickness of about 0.5 micrometer to 12 micrometers normally here. This is because if the thickness is less than 0.5 μm, the number of pinholes increases, which is not practical. Also, if the thickness exceeds 12 μm, it is not necessary to attach a carrier.

これらのキャリア付き銅箔の具体例を図2に模式図として示す。キャリア付き銅箔は、キャリアとしての銅箔1(以下、「キャリア銅箔」と言う)の片面に、剥離層2と極薄銅箔4がこの順序で形成されている。該極薄銅箔4の表面が粗化面4aとなっている。そして、その粗化面4aをガラスエポキシ基板(図示せず)に重ね合わせたのち全体を熱圧着し、ついでキャリア銅箔1を剥離・除去し、該極薄銅箔の該キャリア銅箔との接合側を表出せしめ、そこに所定の配線パターンを形成するという態様で使用される。
なお、ここでキャリアの材質は銅、SUS、アルミニウム、鋼等から選ぶことが可能である。しかし、取り扱いのしやすさ、キャリア上への剥離層2、極薄銅箔4の形成のしやすさから、銅箔が最も適している。
Specific examples of these copper foils with a carrier are schematically shown in FIG. In the copper foil with a carrier, a release layer 2 and an ultrathin copper foil 4 are formed in this order on one surface of a copper foil 1 (hereinafter referred to as “carrier copper foil”) as a carrier. The surface of the ultrathin copper foil 4 is a roughened surface 4a. Then, after the roughened surface 4a is superposed on a glass epoxy substrate (not shown), the whole is thermocompression bonded, and then the carrier copper foil 1 is peeled and removed, and the ultrathin copper foil and the carrier copper foil are removed. It is used in such a manner that the joining side is exposed and a predetermined wiring pattern is formed there.
Here, the material of the carrier can be selected from copper, SUS, aluminum, steel and the like. However, copper foil is the most suitable because of ease of handling and ease of formation of the release layer 2 and the ultrathin copper foil 4 on the carrier.

キャリア銅箔1は前記の極薄銅箔4を基板と接合するまで極薄銅箔の強度をバックアップする補強材(キャリア)として機能する。更に、剥離層2は、前記の極薄銅箔4と該キャリア銅箔1とを分離する際の剥離をよくするための層であり、該キャリア銅箔1をきれいにかつ容易に剥がすことが出来るようになっている(剥離層2はキャリア銅箔1を銅箔4から剥離除去する際にキャリア銅箔1と一体的に除去される)。   The carrier copper foil 1 functions as a reinforcing material (carrier) that backs up the strength of the ultrathin copper foil until the ultrathin copper foil 4 is bonded to the substrate. Furthermore, the peeling layer 2 is a layer for improving peeling when the ultrathin copper foil 4 and the carrier copper foil 1 are separated, and the carrier copper foil 1 can be peeled cleanly and easily. (The peeling layer 2 is removed together with the carrier copper foil 1 when the carrier copper foil 1 is peeled off from the copper foil 4).

一方ガラスエポキシ基板と張り合わされた極薄銅箔4は、スルーホールの穿設,スルーホールめっきを順次行ったのち、該銅張り積層板の表面にある銅箔にエッチング処理を行って所望する線幅と所望する線間ピッチを備えた配線パターンを形成し、最後に、ソルダーレジストの形成やその他の仕上げ処理が行われる。
こうしたキャリア付き極薄銅箔は、銅箔自体を数μmといったレベルに薄くすることができるため、ファインパターンを切ることが可能であり、しかも、取り扱い時のハンドリング性に優れるという理由から、特にビルドアップ配線基板を製造する際に適した銅箔である。
On the other hand, the ultrathin copper foil 4 bonded to the glass epoxy substrate is subjected to through-hole drilling and through-hole plating in order, and then the copper foil on the surface of the copper-clad laminate is etched to obtain a desired line. A wiring pattern having a width and a desired line pitch is formed, and finally, a solder resist is formed and other finishing processes are performed.
This type of ultra-thin copper foil with a carrier can be thinned to a level of a few micrometers, so it is possible to cut a fine pattern, and it is especially built for its excellent handling when handling. It is a copper foil suitable for manufacturing an up-wiring board.

しかし、その一方で以下のような問題点が顕在化してきた。
ビルドアップ配線板のビア形成には、高生産性等の理由からCO ガスレーザーによるレーザービア法が主流となっている。しかし、従来のキャリア付き極薄箔にCO ガスレーザーを用いる場合、CO ガスレーザーの波長は10,600nm前後の赤外線の領域であるため、銅箔表面はこの領域の光及び電磁波のほとんどを反射してしまい、したがって直接穴明け加工ができず、そのため、ビア形成部分の銅箔を前もってエッチングにて除去し、基材に穴明け加工を行うコンフォーマルマスク法が行われている。
However, on the other hand, the following problems have become apparent.
For via formation of the build-up wiring board, a laser via method using a CO 2 gas laser has become the mainstream for reasons such as high productivity. However, when a CO 2 gas laser is used for a conventional ultra-thin foil with a carrier, the wavelength of the CO 2 gas laser is in the infrared region around 10,600 nm, so the surface of the copper foil absorbs most of the light and electromagnetic waves in this region. Therefore, a direct drilling process cannot be performed. Therefore, a conformal mask method is performed in which a copper foil in a via forming portion is removed in advance by etching and a drilling process is performed on a base material.

コンフォーマルマスク法は、図2の極薄銅箔4のビヤホールを開けたい部分にエッチングレジストを被覆せず、他の部分にはエッチングレジストを被覆し、前もって極薄銅箔をエッチングしてからCO ガスレーザーで基板(樹脂部分)に穴あけ加工をするという煩雑なやり方をとる。これに対してCO ガスレーザーを用いて、極薄銅箔と樹脂部分が同時に穴あけ加工が出来れば、穴あけ加工を簡略化することが可能となる。 In the conformal mask method, the etching resist is not coated on the portion of the ultrathin copper foil 4 shown in FIG. 2 where the via hole is to be opened, and the other portion is coated with the etching resist. The complicated method of drilling a substrate (resin portion) with a two- gas laser is used. On the other hand, if an ultra-thin copper foil and a resin part can be drilled simultaneously using a CO 2 gas laser, the drilling process can be simplified.

この問題に対して本願出願人はキャリアの表面に、剥離層と、拡散防止層と、極薄銅箔をこの順序に形成し、前記剥離層がクロム層であり、前記拡散防止層がCO ガスレーザーが発振する波長の光を吸収しやすい層であり、極薄銅箔の表面が粗面化されているキャリア付き極薄銅箔を開発した(特許文献3参照)。
これは、CO ガスレーザーが発振する波長の光を吸収しやすい層は、ニッケル、コバルト、鉄、クロム、モリブデン、タングステン、銅、アルミニウム、及びリンからなる群から選ばれる元素からなり、単一金属の層、2種以上の金属の合金層または1種以上の金属酸化物層であるキャリア付き極薄銅箔である。
特願平11−073803号公報 特願平11−137983号公報 特願2002−528488号
For this problem, the applicant of the present invention forms a release layer, a diffusion prevention layer, and an ultrathin copper foil in this order on the surface of the carrier, the release layer is a chromium layer, and the diffusion prevention layer is CO 2. An ultrathin copper foil with a carrier, which is a layer that easily absorbs light having a wavelength oscillated by a gas laser and whose surface is roughened, has been developed (see Patent Document 3).
This is because the layer that easily absorbs light of the wavelength oscillated by the CO 2 gas laser is composed of an element selected from the group consisting of nickel, cobalt, iron, chromium, molybdenum, tungsten, copper, aluminum, and phosphorus. An ultrathin copper foil with a carrier, which is a metal layer, an alloy layer of two or more metals, or one or more metal oxide layers.
Japanese Patent Application No. 11-073803 Japanese Patent Application No. 11-137983 Japanese Patent Application No. 2002-528488

しかし、この極薄銅箔を使った場合、以下の問題点が顕在化してきた。
(1)ビルドアップ配線板でレーザー穴あけ加工を行う際に、穴周辺部に前記CO ガスレーザーが発振する波長の光を吸収しやすい層及び極薄銅が飛び散り、銅の盛り上がりが生成する。通常、それを過酸化水素−硫酸系のソフトエッチング液により溶解除去しないと、その後に行うスルーホールめっきが正常にめっきできない。すなわち、穴周囲の銅盛り上がりの上にさらに銅めっきがなされると、他の部分に比較して、その部分だけ銅めっきの厚さが厚くなってしまう。従って銅の盛り上がりをソフトエッチングにより除去しているが、銅の盛り上がり部分だけを選択的に除去することは困難である。
(2)レーザー穴あけ加工後、スルーホール銅めっきを行う際、回路部分にも同時に銅めっきを行うが、CO ガスレーザーが発振する波長の光を吸収しやすい層であるニッケルあるいはコバルト等の金属層が存在したままでは、銅めっきの密着性が悪くなる。このため、ニッケルあるいはコバルト等の金属層をエッチングにより溶解除去する。ここで、通常使用されている過酸化水素−硫酸系のソフトエッチング液は、ニッケル、コバルト金属層とともに銅も溶解し、極薄銅箔の厚さにばらつきが生じる。さらには、エッチング条件が悪い場合には極薄銅箔が全て溶解してしまうといった問題がある。
However, when this ultra-thin copper foil is used, the following problems have become apparent.
(1) When laser drilling is performed with a build-up wiring board, a layer that easily absorbs light having a wavelength oscillated by the CO 2 gas laser and ultrathin copper are scattered around the hole, and a copper swell is generated. Usually, unless it is dissolved and removed by a hydrogen peroxide-sulfuric acid based soft etching solution, subsequent through-hole plating cannot be performed normally. That is, when copper plating is further performed on the copper bulge around the hole, the thickness of the copper plating is increased only in that portion compared to other portions. Therefore, although the copper bulge is removed by soft etching, it is difficult to selectively remove only the copper bulge.
(2) When through-hole copper plating is performed after laser drilling, copper is also applied to the circuit portion at the same time, but a metal such as nickel or cobalt which is a layer that easily absorbs light having a wavelength oscillated by a CO 2 gas laser. If the layer is still present, the adhesion of copper plating will be poor. Therefore, a metal layer such as nickel or cobalt is dissolved and removed by etching. Here, the commonly used hydrogen peroxide-sulfuric acid based soft etching solution dissolves copper together with the nickel and cobalt metal layers, and the thickness of the ultrathin copper foil varies. Furthermore, when etching conditions are bad, there exists a problem that all the ultrathin copper foil will melt | dissolve.

本発明はファインパターン用途のプリント配線基板の製造時に用いるキャリア付き極薄銅箔であって、上記2つの問題点を解決したキャリア付き極薄銅箔である。
本発明は、キャリアの一方の面に、剥離層、極薄銅箔とがこの順序に形成されたキャリア付き極薄銅箔であり、キャリアのもう一方の面にCOガスレーザーが発振する波長の光を吸収しやすい層が形成されているキャリア付き極薄銅箔である。
なお、本発明における「COガスレーザーが発振する波長の光を吸収しやすい層」を以下「レーザー吸収層」と表現する。
好ましくは前記レーザー吸収層を、ニッケル、コバルト、鉄、亜鉛、マンガン、クロム、錫、リンからなる群より選ばれた1種以上の元素を含有する層で,或いは銅の酸化物で形成する。
The present invention is an ultrathin copper foil with a carrier used in the production of a printed wiring board for fine pattern use, and is an ultrathin copper foil with a carrier that solves the above two problems.
The present invention is an ultrathin copper foil with a carrier in which a release layer and an ultrathin copper foil are formed in this order on one surface of a carrier, and a wavelength at which a CO 2 gas laser oscillates on the other surface of the carrier. It is an ultrathin copper foil with a carrier in which a layer that easily absorbs light is formed.
In the present invention, “a layer that easily absorbs light having a wavelength oscillated by a CO 2 gas laser” is hereinafter referred to as a “laser absorption layer”.
Preferably, the laser absorption layer is formed of a layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, zinc, manganese, chromium, tin, and phosphorus, or a copper oxide.

好ましくは前記剥離層を、クロム、ニッケル、コバルト、鉄、モリブデン、チタン、タングステン、リン又は/及びこれら元素の2種以上の元素を含有する層又はこれら元素の水和酸化物層、又は有機被膜で形成する。   Preferably, the release layer is formed of chromium, nickel, cobalt, iron, molybdenum, titanium, tungsten, phosphorus, and / or a layer containing two or more of these elements, or a hydrated oxide layer of these elements, or an organic coating. Form with.

本発明は、前記記載のキャリア付き極薄銅箔により高密度微細配線を施したことを特徴とするプリント配線板であり、該プリント配線板を複数枚積層した多層プリント配線板である。   The present invention is a printed wiring board in which high-density fine wiring is performed by the ultrathin copper foil with a carrier described above, and a multilayer printed wiring board in which a plurality of the printed wiring boards are laminated.

本発明はファインパターン用途のプリント配線基板の製造時に用いるキャリア付き極薄銅箔であって、ビルドアップ配線板のビア形成でレーザー穴あけ加工を行う際に、ビアホール周辺部にレーザー吸収層及び極薄銅が飛び散り、或いは銅の盛り上がりが生成することがなく、配線加工が極めて容易な極薄銅箔、および該極薄銅箔を用いたプリント配線板、多層プリント配線板を提供することができる。   The present invention is an ultra-thin copper foil with a carrier for use in the production of printed wiring boards for fine pattern use. When laser drilling is performed for via formation of a build-up wiring board, a laser absorbing layer and an ultra-thin layer are formed around the via hole. It is possible to provide an ultrathin copper foil that is extremely easy to process without copper scattering or copper swell, and a printed wiring board and multilayer printed wiring board using the ultrathin copper foil.

図1は本発明の一実施形態を示すキャリア付き極薄銅箔の模式図である。
キャリア銅箔1の一方の面には、剥離層2、極薄銅箔4とがこの順序に形成されている。キャリア銅箔1のもう一方の面にはレーザー吸収層3が形成されている。
FIG. 1 is a schematic view of an ultrathin copper foil with a carrier showing an embodiment of the present invention.
On one surface of the carrier copper foil 1, a release layer 2 and an ultrathin copper foil 4 are formed in this order. A laser absorption layer 3 is formed on the other surface of the carrier copper foil 1.

前記レーザー吸収層3は、ニッケル、コバルト、鉄、亜鉛、マンガン、クロム、錫、リンからなる群より選ばれた1種以上の元素を含有する層で形成する。
前記レーザー吸収層3の形成方法は、電気めっき、無電解めっき、スパッタリング等の方法で形成できるが、電気めっきで形成するのが最も低コストで実用的である。
また、レーザー吸収層3は銅の酸化物等で形成することもできる。銅の酸化物の形成は、化成処理、陽極電解酸化等により形成することができる。
上記レーザー吸収層3は、0.01〜50mg/dm付着させるのが良い。これは0.01mg/dmより少ない付着量ではCO ガスレーザーが発振する波長の光を吸収する効果が充分でなく、50mg/dmより多くしても効果が飽和してしまうためである。
レーザー吸収層3にCO ガスレーザーが発振する波長の光を照射した場合、レーザー光の吸収率が良いためキャリア及び極薄銅箔、樹脂基板と連続して穴あけが可能である。
The laser absorption layer 3 is formed of a layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, zinc, manganese, chromium, tin, and phosphorus.
The laser absorption layer 3 can be formed by electroplating, electroless plating, sputtering, or the like, but it is most practical and inexpensive to form by electroplating.
The laser absorption layer 3 can also be formed of copper oxide or the like. The copper oxide can be formed by chemical conversion treatment, anodic electrolytic oxidation, or the like.
The laser absorbing layer 3, it is preferable to 0.01 to 50 mg / dm 2 deposited. This is because the in less coating weight than 0.01 mg / dm 2 not sufficient effect of absorbing light having a wavelength CO 2 gas laser is oscillated, the effect even if more than 50 mg / dm 2 is saturated .
When the laser absorption layer 3 is irradiated with light having a wavelength oscillated by a CO 2 gas laser, since the absorption rate of the laser light is good, the carrier, the ultrathin copper foil, and the resin substrate can be continuously drilled.

前記剥離層2は、クロム、ニッケル、コバルト、鉄、モリブデン、チタン、タングステン、リン又は/及びこれら元素の2種以上の元素を含有する層又はこれら元素の水和酸化物層で形成する。又は有機被膜で形成してもよい。   The peeling layer 2 is formed of chromium, nickel, cobalt, iron, molybdenum, titanium, tungsten, phosphorus, and / or a layer containing two or more of these elements or a hydrated oxide layer of these elements. Or you may form with an organic film.

前記剥離層2の上に極薄銅箔4を電気めっきにより形成する。次いで、電解銅めっきで形成した極薄銅箔4の表面を粗化面4aとする。具体的には、極薄銅箔4を電解銅めっきで形成する最終段階で、浴組成や浴温、電流密度や電解時間などを変化させることにより、既に形成されている銅めっき層の表面に0.2〜2.0μm程度の銅粒子を突起物として析出させる粗化処理を行う。このような粗化処理によって極薄銅箔の最外層表面を粗化面とするのは、極薄銅箔を樹脂基材に熱圧着したときに樹脂基材との間の接合強度を高めるためである。   An ultrathin copper foil 4 is formed on the release layer 2 by electroplating. Next, the surface of the ultrathin copper foil 4 formed by electrolytic copper plating is a roughened surface 4a. Specifically, in the final stage of forming the ultrathin copper foil 4 by electrolytic copper plating, by changing the bath composition, bath temperature, current density, electrolysis time, etc., the surface of the copper plating layer already formed is changed. A roughening treatment is performed to precipitate copper particles of about 0.2 to 2.0 μm as protrusions. The reason why the surface of the outermost layer of the ultrathin copper foil is roughened by such a roughening treatment is to increase the bonding strength between the ultrathin copper foil and the resin base material when the ultrathin copper foil is thermocompression bonded to the resin base material. It is.

粗化面4aの上に更にニッケル層、亜鉛層をこの順序で形成することが好ましい。
この亜鉛層は、極薄銅箔と樹脂基板を熱圧着したときに、極薄銅箔4と基板樹脂との反応による該基板樹脂の劣化や極薄銅箔4の表面酸化を防止して基板との接合強度を高める働きをする。またニッケル層は、樹脂基板への熱圧着時に該亜鉛層の亜鉛が極薄銅箔(電解銅めっき層)側へ熱拡散することを防止し、もって亜鉛層の上記機能を有効に発揮させる働きをする。
なお、これらのニッケル層や亜鉛層は、公知の電解めっき法や無電解めっき法を適用して形成することができる。また、該ニッケル層は純ニッケルで形成してもよいし、含リンニッケルで形成してもよい。
It is preferable to further form a nickel layer and a zinc layer in this order on the roughened surface 4a.
This zinc layer prevents the deterioration of the substrate resin due to the reaction between the ultrathin copper foil 4 and the substrate resin and the surface oxidation of the ultrathin copper foil 4 when the ultrathin copper foil and the resin substrate are thermocompression bonded. It works to increase the joint strength. The nickel layer also prevents the zinc in the zinc layer from thermally diffusing to the ultrathin copper foil (electrolytic copper plating layer) side during thermocompression bonding to the resin substrate, thereby effectively exerting the above functions of the zinc layer. do.
In addition, these nickel layers and zinc layers can be formed by applying a known electrolytic plating method or electroless plating method. The nickel layer may be formed of pure nickel or may be formed of phosphorus-containing nickel.

また、亜鉛層の表面に更にクロメート処理を行うと、該表面に酸化防止層が形成されるので好ましい。適用するクロメート処理としては、公知の方法に従えばよく、例えば、特開昭60−86894号公報に開示されている方法をあげることができる。クロム量に換算して0.01〜0.3mg/dm程度のクロム酸化物とその水和物などを付着させることにより、銅箔に優れた防錆能を付与することができる。
また、前記のクロメート処理した表面に対し更にシランカップリング剤を用いた表面処理を行うと、極薄銅箔表面(基板との接合側の表面)には接着剤との親和力の強い官能基が付与されるので、該銅箔と基板との接合強度は一層向上し、銅箔の防錆性,吸湿耐熱性を更に向上するので好適である。
Further, it is preferable to further perform chromate treatment on the surface of the zinc layer because an antioxidant layer is formed on the surface. As the chromate treatment to be applied, a known method may be used, and examples thereof include a method disclosed in JP-A-60-86894. By attaching a chromium oxide of about 0.01 to 0.3 mg / dm 2 and its hydrate in terms of the amount of chromium, an excellent rust prevention ability can be imparted to the copper foil.
Moreover, when the surface treatment using a silane coupling agent is further performed on the chromate-treated surface, a functional group having a strong affinity for the adhesive is present on the surface of the ultrathin copper foil (surface on the side bonded to the substrate). Therefore, the bonding strength between the copper foil and the substrate is further improved, and the rust prevention and moisture absorption heat resistance of the copper foil are further improved, which is preferable.

シランカップリング剤としては、ビニル系シラン、エポキシ系シラン、スチリル系シラン、メタクリロキシ系シラン、アクリロキシ系シラン、アミノ系シラン、ウレイド系シラン、クロロプロピル系シラン、メルカプト系シラン、スルフィド系シラン、イソシアネート系シランなどをあげることができる。これらのシランカップリング剤は通常0.001〜5%の水溶液にし、これを銅箔の表面に塗布したのちそのまま加熱乾燥すればよい。なお、シランカップリング剤に代えて、チタネート系,ジルコネート系などのカップリング剤を用いても同様の効果を得ることができる。   Silane coupling agents include vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, mercapto silane, sulfide silane, isocyanate silane Examples include silane. These silane coupling agents are usually made into 0.001 to 5% aqueous solution, which is applied to the surface of the copper foil and then dried by heating as it is. In addition, it can replace with a silane coupling agent, and the same effect can be acquired even if it uses coupling agents, such as a titanate type and a zirconate type.

次に、本発明のキャリア付き極薄銅箔の使用方法を説明する。
最初にガラスエポキシ樹脂やポリイミド樹脂などから成る電気絶縁性の基板の表面に、キャリア付き極薄銅箔の極薄銅箔面を重ねて置き、加熱・加圧してキャリア付き銅張り積層板を製造する。
次いで、該キャリア付き銅張り積層板のキャリア側にCOガスレーザーを照射して穴あけを行う。すなわち、キャリアのレーザー吸収層が形成されている面からCOガスレーザーを照射してキャリア及び極薄銅箔、樹脂基板を貫通する穴あけ加工を行う。
Next, the usage method of the ultra-thin copper foil with a carrier of this invention is demonstrated.
First, the ultrathin copper foil surface of the ultrathin copper foil with carrier is placed on the surface of an electrically insulating substrate made of glass epoxy resin or polyimide resin, and then heated and pressed to produce a copper clad laminate with carrier. To do.
Next, the carrier side of the copper-clad laminate with a carrier is irradiated with a CO 2 gas laser to make a hole. That is, a hole is formed through the carrier, the ultrathin copper foil and the resin substrate by irradiating a CO 2 gas laser from the surface where the laser absorption layer of the carrier is formed.

従来のキャリア付き極薄銅箔(図2参照)では、キャリアが純銅であるためCOガスレーザーが発振する波長の光を反射してしまい、キャリア及び極薄銅箔、樹脂基板を連続して穴あけ加工を行うには高エネルギーを必要として、穴あけ加工が殆ど不可能であった。
これに対して本発明におけるキャリア付き極薄銅箔では、キャリアにレーザー吸収層が形成してあるので、COガスレーザーが発振する波長の光に対して反射が少なく、エネルギー損失が少ないため容易にキャリア及び極薄銅箔、樹脂基板を連続して貫通する穴あけ加工が可能である。
In the conventional ultra-thin copper foil with a carrier (see FIG. 2), the carrier is pure copper, so the light of the wavelength oscillated by the CO 2 gas laser is reflected, and the carrier, the ultra-thin copper foil, and the resin substrate are successively Drilling requires high energy, and drilling is almost impossible.
On the other hand, in the ultrathin copper foil with a carrier in the present invention, since a laser absorption layer is formed on the carrier, it is easy because there is little reflection with respect to the light of the wavelength oscillated by the CO 2 gas laser and there is little energy loss In addition, it is possible to perform drilling that continuously penetrates the carrier, the ultrathin copper foil, and the resin substrate.

また、穴あけを行ったときの穴周辺部へのレーザー吸収層の形成素材が飛び散っても、飛び散った素材はキャリア部分で受け止められ、また、銅の盛り上がりは、キャリア部分で発生するのみで極薄銅箔では発生しない。吸収層の飛び散りや銅の盛り上がりはレーザー穴あけ加工後にキャリア箔は引き剥がされるので、極薄銅箔表面の穴周囲には飛び散りや銅の盛り上がりは全くなく、極薄銅箔表面の穴周囲は清潔で平滑な面を保てる。従って、次工程で穴周囲の盛り上がりをエッチングする必要は全くなく。極薄銅箔表面をソフトエッチング後銅めっきを行うことが可能で、極薄銅箔の厚さバラつきが従来とは比較にならないほどに小さい。   Even if the material for forming the laser absorption layer around the hole when it is drilled is scattered, the scattered material is received by the carrier part, and the copper bulge occurs only at the carrier part and is extremely thin. It does not occur with copper foil. Since the carrier foil is peeled off after laser drilling for scattering of the absorbing layer and copper swell, there is no splatter or copper swell around the hole on the surface of the ultrathin copper foil, and the area around the hole on the surface of the ultrathin copper foil is clean And keep a smooth surface. Therefore, there is no need to etch the bulge around the hole in the next process. It is possible to perform copper plating after soft etching of the ultrathin copper foil surface, and the thickness variation of the ultrathin copper foil is so small that it cannot be compared with the conventional one.

以下実施例により本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail by way of examples.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次の条件でレーザー吸収層3としてNiめっき層を形成した。
レーザー吸収層:
NiSO・7HO : 240〜330g/L
NiCl・6HO : 45g/L
BO : 30〜40g/L
pH : 4.5〜5.5
電流密度 : 2〜10A/dm
次いで剥離層2として、前記キャリア銅箔のS面にクロムの電解めっきを連続的に行って厚み0.005μmのクロムめっき層を形成した。
次いで、形成された剥離層2上に極薄銅箔4を硫酸銅めっき液で下記の条件で5μmめっきした。
極薄銅箔:
銅 : 80g/L
硫酸 : 160g/L
電流密度 : 55A/dm
前記極薄銅箔の製箔終了時点で従来公知の方法により粗化処理を施し銅の粒子を付着させた粗化面4aを形成した。
最後に、粗化処理が施された極薄銅層上に従来公知の方法により、亜鉛めっき及びクロメート処理を行い、更に、ビニルトリス(2−メトキシエトキシ)シラン2g/Lの水溶液に5秒間浸漬したのち取り出し、温度100℃の温風で乾燥してシランカップリング剤処理を行い図1に示すキャリア銅箔付き極薄銅箔を製造した。
An Ni plating layer was formed as a laser absorption layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following conditions.
Laser absorption layer:
NiSO 4 · 7H 2 O: 240 to 330 g / L
NiCl 2 · 6H 2 O: 45 g / L
H 3 BO 3 : 30 to 40 g / L
pH: 4.5-5.5
Current density: 2 to 10 A / dm 2
Next, as the release layer 2, electrolytic plating of chromium was continuously performed on the S surface of the carrier copper foil to form a chromium plating layer having a thickness of 0.005 μm.
Next, 5 μm of an ultrathin copper foil 4 was plated on the formed release layer 2 with a copper sulfate plating solution under the following conditions.
Ultra-thin copper foil:
Copper: 80 g / L
Sulfuric acid: 160 g / L
Current density: 55 A / dm 2
At the end of the production of the ultrathin copper foil, a roughening treatment was performed by a conventionally known method to form a roughened surface 4a to which copper particles were adhered.
Finally, galvanization and chromate treatment were performed on the ultrathin copper layer subjected to the roughening treatment by a conventionally known method, and further immersed in an aqueous solution of vinyltris (2-methoxyethoxy) silane 2 g / L for 5 seconds. Thereafter, it was taken out and dried with hot air at a temperature of 100 ° C. and treated with a silane coupling agent to produce an ultrathin copper foil with a carrier copper foil shown in FIG.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてCoめっき層を形成した。
レーザー吸収層:
CoSO・7HO : 55g/L
・3HO : 390g/L
KCl : 7〜8g/L
ブチンジオール : 0.1g/L
pH : 9.5〜10
電流密度 : 1〜3A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Co plating layer was formed as a laser absorption layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
CoSO 4 · 7H 2 O: 55 g / L
K 2 P 2 O 7 · 3H 2 O: 390g / L
KCl: 7-8 g / L
Butynediol: 0.1 g / L
pH: 9.5-10
Current density: 1 to 3 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてNi−Co合金層を形成した。
レーザー吸収層:
NiSO・7HO :130〜140g/L
CoSO・7HO :110〜120g/L
BO :20〜30g/L
pH :4.0〜5.0
電流密度 :10〜15A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Ni—Co alloy layer was formed as a laser absorption layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
NiSO 4 · 7H 2 O: 130 to 140 g / L
CoSO 4 · 7H 2 O: 110~120g / L
H 3 BO 3: 20~30g / L
pH: 4.0-5.0
Current density: 10-15 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてFe−Ni合金層を形成した。
レーザー吸収層:
NiSO・7HO : 70g/L
FeSO・7HO : 15g/L
・3HO : 250g/L
NHCl : 50g/L
ブチンジオール : 0.1g/L
pH : 5〜7
電流密度 : 1〜7A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
An Fe—Ni alloy layer was formed as a laser absorption layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
NiSO 4 · 7H 2 O: 70 g / L
FeSO 4 · 7H 2 O: 15g / L
K 4 P 2 O 7 · 3H 2 O: 250g / L
NH 4 Cl: 50 g / L
Butynediol: 0.1 g / L
pH: 5-7
Current density: 1 to 7 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてZn−Sn合金層を形成した。
レーザー吸収層:
NaSnO : 50〜65g/L
NaZnO : 5〜7g/L
NaOH : 4〜6g/L
電流密度 : 1〜3A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Zn—Sn alloy layer was formed as the laser absorption layer 3 on the M surface of the electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
Na 2 SnO 3 : 50 to 65 g / L
Na 2 ZnO 2 : 5 to 7 g / L
NaOH: 4-6 g / L
Current density: 1 to 3 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてCo−Mn合金層を形成した。
レーザー吸収層:
CoCl・6HO : 0.2〜12g/L
MnCl・4HO : 140〜280g/L
NHCl : 30〜60g/L
ジメチルスルホキシド : 2.5〜15g/L
pH : 1.6〜4.0
電流密度 : 1〜40A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Co—Mn alloy layer was formed as a laser absorption layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
CoCl 2 .6H 2 O: 0.2 to 12 g / L
MnCl 2 .4H 2 O: 140-280 g / L
NH 4 Cl: 30~60g / L
Dimethyl sulfoxide: 2.5 to 15 g / L
pH: 1.6-4.0
Current density: 1 to 40 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてCr−Ni合金層を形成した。
レーザー吸収層:
NiSO・7HO : 20〜50g/L
CrO : 40〜60g/L
MgSO・7HO : 20〜50g/L
pH : 0.6〜1.0
電流密度 : 15〜30A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Cr—Ni alloy layer was formed as a laser absorbing layer 3 on the M surface of an electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
NiSO 4 · 7H 2 O: 20 to 50 g / L
CrO 3 : 40-60 g / L
MgSO 4 .7H 2 O: 20 to 50 g / L
pH: 0.6 to 1.0
Current density: 15-30 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

厚み12μmの電解銅箔(キャリア銅箔1)のM面に、次のめっき条件でレーザー吸収層3としてNi−P合金層を形成した。
レーザー吸収層:
NiSO・7HO : 240g/L
(NHSO : 45g/L
NiCl・6HO : 45g/L
BO : 30g/L
PO : 5〜50g/L
pH : 1〜3
電流密度 : 2A/dm
次いで、剥離層2、極薄銅箔4、粗化処理、防錆処理及び表面処理を実施例1と同じに施しキャリア銅箔付き極薄銅箔を製造した。
A Ni—P alloy layer was formed as the laser absorption layer 3 on the M surface of the electrolytic copper foil (carrier copper foil 1) having a thickness of 12 μm under the following plating conditions.
Laser absorption layer:
NiSO 4 · 7H 2 O: 240 g / L
(NH 4 ) 2 SO 4 : 45 g / L
NiCl 2 · 6H 2 O: 45 g / L
H 3 BO 3 : 30 g / L
H 3 PO 3 : 5 to 50 g / L
pH: 1-3
Current density: 2 A / dm 2
Next, the peeling layer 2, the ultrathin copper foil 4, the roughening treatment, the rust prevention treatment, and the surface treatment were performed in the same manner as in Example 1 to produce an ultrathin copper foil with a carrier copper foil.

<比較例1>
厚み12μmの電解銅箔(キャリア銅箔)のM面に、何のめっきも行わず、S面に実施例1と同じ製法で剥離層、極薄銅箔、粗化処理、防錆処理及び表面処理を設け、キャリア銅箔付き極薄銅箔を製造した。
<Comparative Example 1>
No plating is performed on the M surface of the electrolytic copper foil (carrier copper foil) having a thickness of 12 μm, and the release surface, the ultrathin copper foil, the roughening treatment, the rust prevention treatment, and the surface are applied to the S surface by the same manufacturing method as in Example 1. A treatment was provided to produce an ultrathin copper foil with a carrier copper foil.

<比較例2>
図2に示すキャリア付き極薄銅箔を製造した。
製造は、厚み12μmの電解銅箔(キャリア銅箔)1のM面に、何のめっきも行わず、S面に実施例1と同じ条件で剥離層2をめっきした後、それに続いて、実施例1と同様の方法によりNiめっきを行い、剥離層2の上にレーザー吸収層5を形成し、該レーザー吸収層5の上に、極薄銅箔4を電解銅めっきで形成し、粗化処理、防錆処理及び表面処理を施し、キャリア付き極薄銅箔とした。
<Comparative Example 2>
The ultrathin copper foil with a carrier shown in FIG. 2 was produced.
The production was carried out after plating the release layer 2 on the S surface under the same conditions as in Example 1 without performing any plating on the M surface of the electrolytic copper foil (carrier copper foil) 1 having a thickness of 12 μm. Ni plating is performed in the same manner as in Example 1, a laser absorption layer 5 is formed on the release layer 2, and an ultrathin copper foil 4 is formed on the laser absorption layer 5 by electrolytic copper plating, and roughened. Treatment, rust prevention treatment and surface treatment were performed to obtain an ultrathin copper foil with a carrier.

各実施例、比較例で製造したキャリア付き極薄銅箔につき、COレーザーによる穴あけ試験を実施し、評価した。
評価試料の作成
片面銅張り積層板の作成(レーザー穴あけ用):
実施例1〜8、比較例1〜2で製造したキャリア付き極薄銅箔を、縦250mm,横250mmに切断したのち、厚み1mmのガラス繊維エポキシプレプリグシート(FR−4)の上に粗化面4aが対向するように配置し、全体を2枚の平滑なステンレス鋼板で挟み、温度170℃,圧力5MPa/mで60分間熱圧着し、片面銅張り積層板を製造した。
With respect to the ultrathin copper foil with carrier manufactured in each example and comparative example, a drilling test using a CO 2 laser was performed and evaluated.
Preparation of evaluation sample Preparation of single-sided copper-clad laminate (for laser drilling):
After cutting the ultra-thin copper foil with a carrier manufactured in Examples 1 to 8 and Comparative Examples 1 and 2 into a length of 250 mm and a width of 250 mm, it was rough on a glass fiber epoxy prepreg sheet (FR-4) having a thickness of 1 mm. The single-sided copper-clad laminate was manufactured by placing the entire surface between two smooth stainless steel plates and thermocompression bonding at a temperature of 170 ° C. and a pressure of 5 MPa / m 2 for 60 minutes.

特性評価
レーザー穴あけ:
各実施例と比較例1のサンプルについては、評価試料作成の方法により作成した片面銅張り積層板を、以下の条件によりCOガスレーザーにより穴あけ加工を行った。結果を表1に示した。
比較例2については、評価試料作成後、キャリアを剥離し、レーザー吸収層5の上からレーザーを照射して穴あけを行った。結果を表1に併記した。
レーザー加工条件(穴あけ条件):
装置 :COガスレーザー穴あけ加工機
マスク :φ1.8mm
パルス幅 :40,60μsec
パルスエネルギー :20,35mJ
ショット数 :1ショット
Characterization laser drilling:
About the sample of each Example and the comparative example 1, the single-sided copper clad laminated board created by the method of preparation of an evaluation sample was drilled with a CO 2 gas laser under the following conditions. The results are shown in Table 1.
In Comparative Example 2, after the evaluation sample was prepared, the carrier was peeled off, and a laser was applied from above the laser absorption layer 5 to make a hole. The results are also shown in Table 1.
Laser processing conditions (drilling conditions):
Equipment: CO 2 gas laser drilling machine Mask: φ1.8mm
Pulse width: 40, 60 μsec
Pulse energy: 20, 35 mJ
Number of shots: 1 shot

Figure 2006312265
Figure 2006312265

表1から明らかはように、実施例1〜8で製造したキャリア付き極薄銅箔では、COガスレーザーで穴あけ加工を行う際に、ビアホール周辺部にレーザー吸収層形成素材や極薄銅が飛び散り、或いは銅の盛り上がりが生成することなく、綺麗な穴を空ける(ビア形成)ことができた。
これに対し、比較例2ではビアホール周辺部にレーザー吸収層形成素材や極薄銅の飛び散りが見られ、銅の盛り上がりが形成された。
一方、レーザー穴あけ加工性は、各実施例ではレーザーエネルギー20mJで50〜60μmと目的とする穴あけができたにもかかわらず、比較例1では穴が空けられず、比較例2では70μmを越える大きさになった。比較例2は、レーザー穴あけ加工性という点だけに関して言えば、良好であると言える。しかし、穴周囲にレーザー穴あけ時のレーザー吸収層形成素材や極薄銅が飛び散り、穴周囲に盛り上がりができてしまった。このため、後工程のスルーホールめっきを行う際に、ソフトエッチング液によりその盛り上がりを除去しなければ、正常なスルーホールめっきを行うことができなかった。すなわち、本発明による銅箔を使う場合に比較して製造工程が1工程増えてしまうことになる。
またレーザーエネルギー35mJでは目的とする80〜90μmの穴あけができたが、比較例1では62μmと小さく、また、比較例2では、100μm程度の穴となった。
この場合も、比較例2では穴周囲にレーザー穴あけ時のレーザー吸収層形成素材や極薄銅が飛び散り、穴周囲に盛り上がりができてしまった。
As is clear from Table 1, in the ultrathin copper foil with carrier manufactured in Examples 1 to 8, when drilling with a CO 2 gas laser, the laser absorbing layer forming material and ultrathin copper are formed around the via hole. It was possible to make a beautiful hole (via formation) without scattering or generating copper swell.
On the other hand, in Comparative Example 2, scattering of the laser absorption layer forming material and ultrathin copper was seen around the via hole, and a copper swell was formed.
On the other hand, the laser drilling workability was 50-60 μm at the laser energy of 20 mJ in each example, but the hole was not drilled in Comparative Example 1, and the size exceeding 70 μm in Comparative Example 2 That's right. Comparative Example 2 can be said to be good only in terms of laser drilling workability. However, the laser-absorbing layer forming material and ultra-thin copper at the time of laser drilling scattered around the hole, resulting in a swell around the hole. For this reason, when through-hole plating in the subsequent process is performed, normal through-hole plating cannot be performed unless the bulge is removed with a soft etching solution. That is, the number of manufacturing steps is increased by one compared with the case of using the copper foil according to the present invention.
Moreover, although the target 80-90 micrometers drilling was able to be performed with laser energy 35mJ, in Comparative Example 1, it was as small as 62 micrometers, and in Comparative Example 2, it became a hole about 100 micrometers.
Also in this case, in Comparative Example 2, the material for forming the laser absorption layer and ultra-thin copper at the time of laser drilling scattered around the hole, and the swelled around the hole.

本発明は上述したように、ファインパターン用途のプリント配線基板の製造時に用いるキャリア付き極薄銅箔であり、ビルドアップ配線板のビア形成でレーザー穴あけ加工を行っても、ビアホール周辺部にレーザー吸収層の素材や極薄銅が飛び散り、或いは銅の盛り上がりが生成するようなことはなく、配線加工が極めて容易な極薄銅箔であり、該極薄銅箔を用いることで、極薄微細配線のプリント配線板、多層プリント配線板を製造し提供できる、優れた効果を有するものである。   As described above, the present invention is an ultra-thin copper foil with a carrier for use in the production of printed wiring boards for fine pattern applications. Even if laser drilling is performed in via formation of a build-up wiring board, laser absorption is performed around the via hole. Layer material and ultra-thin copper are not scattered or copper bulges are generated, and it is an ultra-thin copper foil that is extremely easy to process. By using this ultra-thin copper foil, ultra-thin fine wiring The printed wiring board and the multilayer printed wiring board can be manufactured and provided, and have excellent effects.

本発明のキャリア付き極薄銅箔の断面模式図である。It is a cross-sectional schematic diagram of the ultra-thin copper foil with a carrier of this invention. 従来のキャリア付き極薄銅箔の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the conventional ultra-thin copper foil with a carrier. 従来のキャリア付き極薄銅箔の他の例を示す断面模式図である。It is a cross-sectional schematic diagram which shows the other example of the conventional ultra-thin copper foil with a carrier.

符号の説明Explanation of symbols

1:キャリア
2:剥離層
3:CO ガスレーザーが発振する波長の光を吸収しやすい層(レーザー吸収層)
4:極薄銅箔
4a:粗化面
5:レーザー吸収層
1: Carrier 2: Release layer 3: Layer that easily absorbs light having a wavelength oscillated by a CO 2 gas laser (laser absorption layer)
4: Ultra-thin copper foil 4a: Roughened surface 5: Laser absorption layer

Claims (6)

キャリアの一方の面に、剥離層、極薄銅箔とがこの順序に形成され、キャリアのもう一方の面にCOガスレーザーが発振する波長の光を吸収しやすい層が形成されているキャリア付き極薄銅箔。 A carrier in which a release layer and an ultrathin copper foil are formed in this order on one surface of the carrier, and a layer that easily absorbs light having a wavelength oscillated by a CO 2 gas laser is formed on the other surface of the carrier. With ultra-thin copper foil. 前記COガスレーザーが発振する波長の光を吸収しやすい層が、ニッケル、コバルト、鉄、亜鉛、マンガン、クロム、錫、リンからなる群より選ばれた1種以上の元素を含有する層である請求項1に記載のキャリア付き極薄銅箔。 The layer that easily absorbs light having a wavelength oscillated by the CO 2 gas laser is a layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, zinc, manganese, chromium, tin, and phosphorus. The ultrathin copper foil with a carrier according to claim 1. 前記COガスレーザーが発振する波長の光を吸収しやすい層が、銅の酸化物である請求項1に記載のキャリア付き極薄銅箔。 The ultrathin copper foil with a carrier according to claim 1, wherein the layer that easily absorbs light having a wavelength oscillated by the CO 2 gas laser is a copper oxide. 前記剥離層が、クロム、ニッケル、コバルト、鉄、モリブデン、チタン、タングステン、リン又は/及びこれら元素の2種以上の元素を含有する層又はこれら元素の水和酸化物層、又は有機被膜である請求項1乃至3のいずれかに記載のキャリア付き極薄銅箔。   The release layer is chromium, nickel, cobalt, iron, molybdenum, titanium, tungsten, phosphorus, and / or a layer containing two or more of these elements, or a hydrated oxide layer of these elements, or an organic coating. The ultra-thin copper foil with a carrier in any one of Claims 1 thru | or 3. キャリアの一方の面に、剥離層、極薄銅箔とがこの順序に形成され、キャリアのもう一方の面にCOガスレーザーが発振する波長の光を吸収しやすい層が形成されているキャリア付き極薄銅箔の前記極薄銅箔を基板に張り合わせ、前記COガスレーザーが発振する波長の光を吸収しやすい層からCOガスレーザーにより極薄銅箔に所定の回路を形成してキャリアを基板から剥離し、露出した極薄銅箔に高密度極薄微細配線を施したプリント配線板。 A carrier in which a release layer and an ultrathin copper foil are formed in this order on one surface of the carrier, and a layer that easily absorbs light having a wavelength oscillated by a CO 2 gas laser is formed on the other surface of the carrier the ultra-thin copper foil attached ultrathin copper foil laminated to the substrate, the CO 2 gas laser to form a predetermined circuit in ultra-thin copper foil by CO 2 gas laser from easily absorbing layer to light of a wavelength oscillated A printed wiring board in which the carrier is peeled off the substrate, and the exposed ultra-thin copper foil is coated with high-density ultra-thin and fine wiring. キャリアの一方の面に、剥離層、極薄銅箔とがこの順序に形成され、キャリアのもう一方の面にCOガスレーザーが発振する波長の光を、純銅に比較して吸収しやすい層が形成されているキャリア付き極薄銅箔の前記極薄銅箔を基板に張り合わせ、前記COガスレーザーが発振する波長の光を吸収しやすい層からCOガスレーザーにより極薄銅箔に所定の回路を形成してキャリアを基板から剥離し、露出した極薄銅箔に必要とする高密度極薄微細配線を施したことを特徴とするプリント配線板を複数枚積層してなる多層プリント配線板。 A release layer and an ultrathin copper foil are formed in this order on one side of the carrier, and the layer on the other side of the carrier that absorbs light of a wavelength oscillated by a CO 2 gas laser is easier than pure copper. given the ultra-thin copper foil ultra-thin copper foil with a carrier but is formed laminated on a substrate, the CO 2 gas ultra-thin copper foil by CO 2 gas laser from easily absorbing layer to light of a wavelength that the laser oscillation A multilayer printed wiring consisting of a plurality of printed wiring boards, in which the circuit is formed, the carrier is peeled from the substrate, and the exposed ultrathin copper foil is provided with the necessary high density ultrathin fine wiring Board.
JP2005135663A 2005-05-09 2005-05-09 Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board Pending JP2006312265A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005135663A JP2006312265A (en) 2005-05-09 2005-05-09 Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005135663A JP2006312265A (en) 2005-05-09 2005-05-09 Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board

Publications (1)

Publication Number Publication Date
JP2006312265A true JP2006312265A (en) 2006-11-16

Family

ID=37533958

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005135663A Pending JP2006312265A (en) 2005-05-09 2005-05-09 Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board

Country Status (1)

Country Link
JP (1) JP2006312265A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010201804A (en) * 2009-03-04 2010-09-16 Fukuda Metal Foil & Powder Co Ltd Composite metal foil, method for producing the same, and printed wiring board
JP2010201805A (en) * 2009-03-04 2010-09-16 Fukuda Metal Foil & Powder Co Ltd Composite metal foil, method for producing the same, and printed wiring board
JP2013089863A (en) * 2011-10-20 2013-05-13 Hitachi Chemical Co Ltd Manufacturing method of printed wiring board
JP2013110408A (en) * 2011-11-18 2013-06-06 Samsung Electro-Mechanics Co Ltd Printed circuit board and manufacturing method therefor
US8530749B2 (en) 2007-12-28 2013-09-10 Iljin Copper Foil Co., Ltd. Copper foil attached to the carrier foil, a method for preparing the same and printed circuit board using the same
JPWO2015151935A1 (en) * 2014-03-31 2017-04-13 三井金属鉱業株式会社 Copper foil with carrier foil, copper-clad laminate and printed wiring board manufacturing method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6199596A (en) * 1984-10-22 1986-05-17 Hitachi Ltd How to drill holes in the board
JP2001217516A (en) * 2000-02-03 2001-08-10 Nikko Materials Co Ltd Copper foil with superior laser boring property and its manufacturing method
WO2002024444A1 (en) * 2000-09-22 2002-03-28 Circuit Foil Japan Co., Ltd. Copper foil for high-density ultrafine wiring board
JP2004087697A (en) * 2002-08-26 2004-03-18 Shinko Electric Ind Co Ltd Manufacturing method of wiring board
JP2004281872A (en) * 2003-03-18 2004-10-07 Mitsubishi Gas Chem Co Inc Hole making method by laser
JP2004289109A (en) * 2003-03-05 2004-10-14 Shinko Electric Ind Co Ltd Laser processing method and metal foil with carrier used therefor
JP2004314568A (en) * 2003-04-21 2004-11-11 Fukuda Metal Foil & Powder Co Ltd Copper foil for printed wiring boards

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6199596A (en) * 1984-10-22 1986-05-17 Hitachi Ltd How to drill holes in the board
JP2001217516A (en) * 2000-02-03 2001-08-10 Nikko Materials Co Ltd Copper foil with superior laser boring property and its manufacturing method
WO2002024444A1 (en) * 2000-09-22 2002-03-28 Circuit Foil Japan Co., Ltd. Copper foil for high-density ultrafine wiring board
JP2004087697A (en) * 2002-08-26 2004-03-18 Shinko Electric Ind Co Ltd Manufacturing method of wiring board
JP2004289109A (en) * 2003-03-05 2004-10-14 Shinko Electric Ind Co Ltd Laser processing method and metal foil with carrier used therefor
JP2004281872A (en) * 2003-03-18 2004-10-07 Mitsubishi Gas Chem Co Inc Hole making method by laser
JP2004314568A (en) * 2003-04-21 2004-11-11 Fukuda Metal Foil & Powder Co Ltd Copper foil for printed wiring boards

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530749B2 (en) 2007-12-28 2013-09-10 Iljin Copper Foil Co., Ltd. Copper foil attached to the carrier foil, a method for preparing the same and printed circuit board using the same
JP2010201804A (en) * 2009-03-04 2010-09-16 Fukuda Metal Foil & Powder Co Ltd Composite metal foil, method for producing the same, and printed wiring board
JP2010201805A (en) * 2009-03-04 2010-09-16 Fukuda Metal Foil & Powder Co Ltd Composite metal foil, method for producing the same, and printed wiring board
JP2013089863A (en) * 2011-10-20 2013-05-13 Hitachi Chemical Co Ltd Manufacturing method of printed wiring board
JP2013110408A (en) * 2011-11-18 2013-06-06 Samsung Electro-Mechanics Co Ltd Printed circuit board and manufacturing method therefor
JPWO2015151935A1 (en) * 2014-03-31 2017-04-13 三井金属鉱業株式会社 Copper foil with carrier foil, copper-clad laminate and printed wiring board manufacturing method

Similar Documents

Publication Publication Date Title
KR100937291B1 (en) Manufacturing method of printed wiring board
JP3628585B2 (en) Copper-clad laminate and method for drilling copper-clad laminate with laser
CN1466517B (en) Copper foil for high-density ultra-fine circuit boards
CN109072472B (en) Surface-treated copper foil, copper foil with carrier, and copper-clad laminate and printed wiring board manufacturing method using same
CN103266335B (en) Copper foil for printed circuit and copper-clad laminate
JP6314085B2 (en) Manufacturing method of printed wiring board and copper foil for laser processing
JP4087369B2 (en) Ultra-thin copper foil with carrier and printed wiring board
JP2010100942A (en) Ultra-thin copper foil with carrier, method of manufacturing the same and printed circuit board
US6548153B2 (en) Composite material used in making printed wiring boards
JP2004169181A (en) Ultra-thin copper foil with carrier, method for producing the same, printed wiring board using ultra-thin copper foil with carrier
JP4217786B2 (en) Ultra-thin copper foil with carrier and wiring board using ultra-thin copper foil with carrier
JP5653876B2 (en) Copper foil with laser absorbing layer, copper-clad laminate and printed wiring board using the copper foil
JP6247829B2 (en) Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate and printed wiring board manufacturing method
JP2006312265A (en) Extremely thin copper foil with carrier, printed wiring board using it and multilayered printed wiring board
JP3615973B2 (en) Novel composite foil and manufacturing method thereof, copper-clad laminate
JP6425399B2 (en) Carrier-coated copper foil, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP4748519B2 (en) Ultra thin copper foil with carrier, manufacturing method thereof, printed wiring board using ultra thin copper foil with carrier
JP2009235580A (en) Copper foil sheet for opening laser-drilled hole
JP2010058325A (en) Copper foil and multilayered wiring board
JP6304829B2 (en) Copper foil for laser processing, copper foil for laser processing with carrier foil, copper-clad laminate, and method for producing printed wiring board
JP3785022B2 (en) Resin laminate with excellent laser drilling capability
JP2017133105A (en) Copper foil with carrier, printed wiring board, printed circuit, copper clad laminate and manufacturing method of printed wiring board
KR101400778B1 (en) Copper foil for laser hole drilling, copper-clad laminate and preparation method of the foil
JP2000196226A (en) Composite material for forming electric circuit and its use

Legal Events

Date Code Title Description
RD02 Notification of acceptance of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7422

Effective date: 20080624

RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20080703

RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20080801

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080815

A072 Dismissal of procedure

Free format text: JAPANESE INTERMEDIATE CODE: A073

Effective date: 20090106

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20090120

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20091027