JP2002030452A - Method for producing printed circuit board - Google Patents
Method for producing printed circuit boardInfo
- Publication number
- JP2002030452A JP2002030452A JP2000213371A JP2000213371A JP2002030452A JP 2002030452 A JP2002030452 A JP 2002030452A JP 2000213371 A JP2000213371 A JP 2000213371A JP 2000213371 A JP2000213371 A JP 2000213371A JP 2002030452 A JP2002030452 A JP 2002030452A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper plating
- compounds
- plating solution
- electroless
- 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
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- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、多層プリント配線
板、ビルドアップ基板、ＩＣパッケージ等の種々の電子
部品を製造するのに適した無電解銅めっき方法、これに
用いる無電解銅めっき液及びこの方法を用いた部品の接
着方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless copper plating method suitable for manufacturing various electronic components such as a multilayer printed wiring board, a build-up board, and an IC package, an electroless copper plating solution used for the method, and The present invention relates to a method for bonding components using this method.
【０００２】[0002]
【従来の技術】従来の多層プリント配線板は、絶縁基板
の銅導体パターンの表面を、塩化第二銅又は過硫酸アン
モニウム水溶液等を用いてソフトエッチング処理し、そ
の後に酸化銅皮膜を形成するいわゆる黒化処理を行った
後、この絶縁基板に熱硬化性絶縁樹脂含浸基材（プリプ
レグ）を介して銅箔等を積層接着して製造する。黒化処
理は、過硫酸カリウム又は亜塩素酸ナトリウムを含むア
ルカリ性水溶液により接着する銅表面を処理して酸化第
一銅、酸化第二銅等の酸化銅皮膜を形成する。このよう
な酸化銅皮膜の形成が接着力の向上に有効であるのは、
配位結合又は水素結合により絶縁樹脂に対する銅の化学
的結合力が高まるためと考えられる。2. Description of the Related Art In a conventional multilayer printed wiring board, the surface of a copper conductor pattern of an insulating substrate is soft-etched using an aqueous solution of cupric chloride or ammonium persulfate, and then a so-called black oxide film is formed. After the chemical treatment, a copper foil or the like is laminated and bonded to the insulating substrate via a thermosetting insulating resin-impregnated base material (prepreg). In the blackening treatment, the copper surface to be bonded is treated with an alkaline aqueous solution containing potassium persulfate or sodium chlorite to form a copper oxide film such as cuprous oxide or cupric oxide. The formation of such a copper oxide film is effective for improving the adhesive strength,
It is considered that the coordination bond or the hydrogen bond increases the chemical bonding force of copper to the insulating resin.
【０００３】しかし、一般に酸化銅は酸性水溶液と接触
すると容易に溶解してしまうため、黒化処理後、接着工
程までの間に酸との接触を避ける必要があった。また接
着後も酸処理を行う場合、接着面を貫通するスルーホー
ル内壁に露出した接着界面の酸化銅皮膜が溶解して接着
界面に酸が染み込み酸化銅皮膜が失われるという接着上
好ましくない現象（ハローイング）が起こることが指摘
されていた。この現象は、スルーホール穴明け工程と、
スルーホールめっきの前処理工程である各種酸処理工程
とを有する多層プリント配線板の多層化工程では大きな
問題であった。However, copper oxide generally dissolves easily when it comes into contact with an acidic aqueous solution, so that it was necessary to avoid contact with an acid after the blackening treatment and before the bonding step. In addition, when acid treatment is performed after bonding, the copper oxide film at the bonding interface exposed on the inner wall of the through hole penetrating the bonding surface dissolves, and the acid permeates the bonding interface to lose the copper oxide film. Helloing) was pointed out. This phenomenon is due to the process of drilling through holes,
This was a serious problem in the multilayering process of a multilayer printed wiring board having various acid treatment processes as a pretreatment process for through-hole plating.
【０００４】そこで黒化処理による酸化銅皮膜の形成に
代えて、耐酸性に優る金属銅皮膜をめっきで形成してハ
ローイングを抑制することが提案された。また、絶縁基
板の銅導体パターンには外部と電気的に接続されない独
立パターンが存在するため、めっき法としては無電解銅
めっきを用いることが適している。Therefore, instead of forming a copper oxide film by a blackening treatment, it has been proposed to form a metal copper film having excellent acid resistance by plating to suppress haloing. In addition, since the copper conductor pattern of the insulating substrate includes an independent pattern that is not electrically connected to the outside, it is suitable to use electroless copper plating as a plating method.
【０００５】このような金属銅皮膜を形成するための無
電解銅めっき液としては、例えば、特開昭５１−１０５
９３２号公報に記載されている無電解銅めっき液が知ら
れている。この無電解銅めっき液は、銅塩、ロッセル塩
等の錯化剤、水酸化アルカリ等のｐＨ調整剤に、２，
２’−ジピリジルや２−（２−ピリジル）ベンズイミダ
ゾール等の添加剤を加えたものである。As an electroless copper plating solution for forming such a metallic copper film, for example, Japanese Patent Application Laid-Open No.
An electroless copper plating solution described in JP-A-932 is known. This electroless copper plating solution is used as a complexing agent such as a copper salt and a rossel salt, and a pH adjusting agent such as an alkali hydroxide.
An additive such as 2′-dipyridyl or 2- (2-pyridyl) benzimidazole is added.
【０００６】また、特開平４−１１６１７６号公報に
は、無電解銅めっき液の還元剤として次亜りん酸化合物
を用い、さらにニッケル、コバルト、パラジウム等の還
元反応開始金属触媒を用いる方法が示されている。Japanese Patent Application Laid-Open No. 4-116176 discloses a method in which a hypophosphorous acid compound is used as a reducing agent for an electroless copper plating solution and a metal catalyst for initiating a reduction reaction such as nickel, cobalt or palladium is used. Have been.
【０００７】[0007]
【発明が解決しようとする課題】上記特開昭５１−１０
５９３２号公報に記載の従来技術は、絶縁基板の銅導体
パターンと絶縁樹脂との接着力については十分な配慮が
されていなかった。また、上記特開平４−１１６１７６
号公報に記載の従来技術は、高価な次亜りん酸化合物を
多量に必要とし、処理コストについて十分な配慮がされ
ていなかった。還元剤である次亜りん酸ナトリウムとホ
ルマリンの価格を比較すると、前者は後者の約２００〜
３００倍になる。SUMMARY OF THE INVENTION The above-mentioned JP-A-51-10
In the prior art described in Japanese Patent No. 5932, sufficient consideration was not given to the adhesive force between the copper conductor pattern of the insulating substrate and the insulating resin. Further, Japanese Patent Application Laid-Open No.
The prior art described in the above publication requires a large amount of an expensive hypophosphorous compound, and the treatment cost has not been sufficiently considered. Comparing the prices of sodium hypophosphite and formalin, which are reducing agents, the former is about 200-
300 times.
【０００８】本発明の第１の目的は、銅導体パターンと
絶縁樹脂との接着力を高めた、信頼性の高い電子部品の
製造することができる無電解銅めっき液を提供すること
にある。本発明の第２の目的は、そのような無電解銅め
っき液を用いた無電解銅めっき方法を提供することにあ
る。本発明の第３の目的は、そのような無電解銅めっき
方法により製造された部品を用いた接着方法を提供する
ことにある。[0008] A first object of the present invention is to provide an electroless copper plating solution capable of producing a highly reliable electronic component having an improved adhesive force between a copper conductor pattern and an insulating resin. A second object of the present invention is to provide an electroless copper plating method using such an electroless copper plating solution. A third object of the present invention is to provide a bonding method using a component manufactured by such an electroless copper plating method.
【０００９】[0009]
【課題を解決するための手段】上記第１の目的を達成す
るために、本発明の無電解銅めっき液は、銅イオン、銅
イオンの錯化剤及び還元剤を含み、さらにＧｅの化合物
及びＳｉの化合物からなる群から選ばれた少なくとも１
種の化合物を含有するようにしたものである。In order to achieve the first object, the electroless copper plating solution of the present invention contains copper ions, a complexing agent for copper ions and a reducing agent, and further contains a compound of Ge and At least one selected from the group consisting of Si compounds
It is intended to contain various kinds of compounds.
【００１０】また、上記第２の目的を達成するために、
本発明の無電解銅めっき方法は、銅イオン、銅イオンの
錯化剤、還元剤並びにＧｅの化合物及びＳｉの化合物か
らなる群から選ばれた少なくとも１種の化合物を含有す
る無電解銅めっき液に被めっき物を浸漬することによ
り、突起を有する銅皮膜を析出させるようにしたもので
ある。In order to achieve the second object,
The electroless copper plating method of the present invention provides an electroless copper plating solution containing copper ions, a complexing agent for copper ions, a reducing agent, and at least one compound selected from the group consisting of Ge compounds and Si compounds. A copper film having protrusions is deposited by immersing the object to be plated in the substrate.
【００１１】また、上記第３の目的を達成するために、
本発明の接着方法は、銅イオン、銅イオンの錯化剤、還
元剤並びにＧｅの化合物及びＳｉの化合物からなる群か
ら選ばれた少なくとも１種の化合物を含有する無電解銅
めっき液に被めっき物を浸漬することにより、突起を有
する銅皮膜を析出させ、その後熱硬化性絶縁樹脂含浸基
材を介して積層接着するようにしたものである。Further, in order to achieve the third object,
The bonding method of the present invention provides plating on an electroless copper plating solution containing copper ions, a complexing agent for copper ions, a reducing agent, and at least one compound selected from the group consisting of Ge compounds and Si compounds. By immersing the object, a copper film having projections is deposited, and then laminated and bonded via a thermosetting insulating resin-impregnated base material.
【００１２】銅と絶縁樹脂との接着力は、界面の機械的
な投錨効果によるところが大きいため、粗化した銅表面
の形状が接着力に大きな影響を与える。機械的な投錨効
果を高めて接着力を増加させるためには、めっきによっ
て銅表面に突起を設ける方法が効果的である。これは絶
縁樹脂に対して突起が機械的に食い込むことにより絶縁
樹脂に対する銅の投錨効果が高まり、突起の側面部と絶
縁樹脂との接触面積が大きく確保され、引き剥がしの応
力が分散されるためである。めっき液中にＧｅ及びＳｉ
の化合物の少なくとも１種を含む無電解銅めっき液を用
いるとこのような突起を有する銅表面を得ることがで
き、絶縁基板の銅導体パターンと絶縁樹脂との接着力の
高い、高信頼性の多層プリント配線板等を得ることがで
きる。Since the adhesion between copper and the insulating resin largely depends on the mechanical anchoring effect at the interface, the roughened surface of the copper greatly affects the adhesion. In order to increase the adhesion by increasing the mechanical anchoring effect, it is effective to provide a projection on the copper surface by plating. This is because the protrusion mechanically cuts into the insulating resin, thereby increasing the anchoring effect of copper on the insulating resin, securing a large contact area between the side surface of the protrusion and the insulating resin, and dispersing the peeling stress. It is. Ge and Si in plating solution
By using an electroless copper plating solution containing at least one of the above compounds, it is possible to obtain a copper surface having such protrusions, and to obtain a highly reliable and highly reliable adhesive force between the copper conductor pattern of the insulating substrate and the insulating resin. A multilayer printed wiring board or the like can be obtained.
【００１３】本発明の無電解銅めっき液における基本成
分は、ＣｕＳＯ4、Ｃｕ2Ｏ等の銅イオン源、ＥＤＴＡ
（エチレンジアミンテトラアセテート）、ロッシェル塩
等の錯化剤、ホルマリン、グリオキシル酸等の安価な還
元剤及び下記のＧｅ又はＳｉ化合物である。銅イオンは
０．０１〜０．１ｍｏｌ／ｌ、錯化剤は銅イオンに対す
るｍｏｌ比で１〜５倍、還元剤は０．０２〜０．０６ｍ
ｏｌ／ｌとするのが好ましい。The basic components of the electroless copper plating solution of the present invention include a copper ion source such as CuSO 4 and Cu 2 O, and EDTA.
(Ethylenediaminetetraacetate), complexing agents such as Rochelle salt, inexpensive reducing agents such as formalin and glyoxylic acid, and the following Ge or Si compounds. Copper ion is 0.01 to 0.1 mol / l, complexing agent is 1 to 5 times in molar ratio to copper ion, and reducing agent is 0.02 to 0.06 m.
ol / l is preferred.
【００１４】Ｇｅ又はＳｉ化合物としては酸化物又は水
溶性無機塩を用いることができる。例えば、二酸化ゲル
マニウムＧｅＯ2、メタケイ酸ナトリウムＮａ2ＳｉＯ3
・９Ｈ2Ｏ等が挙げられる。Ｇｅの量としては０．１〜
２ｍｍｏｌ／ｌが望ましく、０．２８〜０．９６ｍｍｏ
ｌ／ｌがより望ましい。ＧｅＯ2に換算すると、約１０
〜２００ｍｇ／ｌ、より好ましくは約３０〜１００ｍｇ
／ｌになる。Ｓｉの量としては０．３５〜３．５ｍｍｏ
ｌ／ｌが望ましい。Ｎａ2ＳｉＯ3・９Ｈ2Ｏに換算する
と約０．１〜１ｇ／ｌになる。めっき液温については本
発明の目的からは特に制限はないが、めっき速度の観点
からは高いほうが望ましい。通常は５０〜７５℃程度で
ある。An oxide or a water-soluble inorganic salt can be used as the Ge or Si compound. For example, germanium dioxide GeO 2 , sodium metasilicate Na 2 SiO 3
9H 2 O and the like. The amount of Ge is 0.1 to
2 mmol / l is desirable, and 0.28 to 0.96 mmol
1 / l is more desirable. When converted to GeO 2 , about 10
~ 200mg / l, more preferably about 30 ~ 100mg
/ L. The amount of Si is 0.35 to 3.5 mmo
1 / l is desirable. In terms of Na 2 SiO 3 .9H 2 O, it is about 0.1 to 1 g / l. The plating solution temperature is not particularly limited for the purpose of the present invention, but is preferably higher from the viewpoint of plating speed. Usually, it is about 50 to 75 ° C.
【００１５】なお、本発明の無電解銅めっき液では既述
の成分以外に、必要に応じて種々の成分を添加できる。
例えばｐＨ調整剤として苛性ソーダ等の水酸化アルカリ
を用いることができ、めっき液温２５℃で測定したｐＨ
値としては１１〜１４が望ましい。また界面活性剤とし
てポリアルキレンオキシド（ＰＥＧ１０００等）等が添
加できる。In the electroless copper plating solution of the present invention, various components other than the above-mentioned components can be added as required.
For example, an alkali hydroxide such as caustic soda can be used as a pH adjuster, and the pH measured at a plating solution temperature of 25 ° C.
A value of 11 to 14 is desirable. Further, a polyalkylene oxide (such as PEG1000) can be added as a surfactant.
【００１６】突起形成のためのめっき厚さとしては、厚
い方の限界については接着性の観点からは特に制限はな
く、むしろ銅導体パターンの寸法仕様によって定めるこ
とが好ましい。幅１００μｍ以下の微細パターンにあっ
ては通常５〜１０μｍが上限である。The plating thickness for forming the protrusions is not particularly limited from the viewpoint of adhesiveness, but rather is preferably determined by the dimensional specifications of the copper conductor pattern. The upper limit is usually 5 to 10 μm for a fine pattern having a width of 100 μm or less.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施形態を実施例
により具体的に説明するが、本発明はこれらの実施例に
限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
【００１８】〈実施例１〉 工程１：ガラス布基材ポリイミド樹脂銅張積層板の銅箔
を、フォトレジストをマスクとするエッチングにより銅
導体パターンを形成した。次いで、銅導体パターン上の
フォトレジストを除去した。Example 1 Step 1: A copper conductor pattern was formed by etching a copper foil of a glass cloth substrate polyimide resin copper clad laminate using a photoresist as a mask. Next, the photoresist on the copper conductor pattern was removed.
【００１９】工程２：前記試料を水洗した後、液温７２
℃の下記組成（Ｉ）の無電解銅めっき液に浸漬して、銅
厚５μｍの無電解銅めっきを行い、突起が不規則に配列
した銅表面を得た。なお、この無電解銅めっき液のｐＨ
は１２．５である。 組成（Ｉ） ＣｕＳＯ4・５Ｈ2Ｏ………………１０ｇ／ｌ ＥＤＴＡ・２Ｎａ・２Ｈ2Ｏ…… ３５ｇ／ｌ ＧｅＯ2………………………… ７０ｍｇ／ｌ ＰＥＧ１０００………………………１ｇ／ｌ ホルマリン（３７％）………２．５ｍｌ／ｌ 工程３:以上の処理を行った銅張積層板を水洗し、乾燥
した後、ガラス布にポリイミド樹脂を含浸させたプリプ
レグを介して積層し、２００℃で３０ｋｇ／ｃｍ2の圧
力を１２０分間かけて接着した。Step 2: After the sample has been washed with water, a liquid temperature of 72
It was immersed in an electroless copper plating solution having the following composition (I) at a temperature of 5 ° C. to perform electroless copper plating with a copper thickness of 5 μm to obtain a copper surface having projections arranged irregularly. In addition, pH of this electroless copper plating solution
Is 12.5. Composition (I) CuSO 4 .5H 2 O 10 g / l EDTA 2Na 2H 2 O 35 g / l GeO 2 70 mg / l PEG1000 ………………………………………………………………………………………………………………………………………………………………………………………… ………………………………………………………………………………………………………………………………… Have a great deal? The layers were laminated via the prepreg and bonded at 200 ° C. under a pressure of 30 kg / cm 2 for 120 minutes.
【００２０】こうして製造されるプリント配線板の製造
工程を図面を用いて説明する。図１（ａ）は、ガラス布
基材ポリイミド樹脂２の両面に銅箔１が設けられた銅張
積層板の断面模式図、図１（ｂ）は、銅張積層板の銅箔
１をエッチングすることにより、銅導体パターン３が形
成された銅張積層板の断面模式図、図１（ｃ）は無電解
銅めっきにより形成した突起を表面に有する銅めっき層
４を持つ銅張積層板の断面模式図である。The manufacturing process of the printed wiring board thus manufactured will be described with reference to the drawings. FIG. 1A is a schematic cross-sectional view of a copper-clad laminate in which copper foils 1 are provided on both sides of a glass cloth base polyimide resin 2, and FIG. 1B is an illustration of etching the copper foil 1 of the copper-clad laminate. By doing so, a schematic cross-sectional view of the copper-clad laminate having the copper conductor pattern 3 formed thereon, FIG. 1C shows a copper-clad laminate having a copper plating layer 4 having projections formed on the surface by electroless copper plating. It is a cross section schematic diagram.
【００２１】図２は、図１（ｃ）の銅張積層板を用いた
多層プリント配線板の断面模式図である。図１（ｃ）の
銅張積層板を、絶縁樹脂層５を介在させて、ガラス布基
材ポリイミド樹脂２に銅箔１が設けられた銅張積層板と
積層接着し、次いで常法に従ってスルーホール６を形成
し、スルーホールをめっき銅７により層間接続し、多層
プリント配線板が形成された。FIG. 2 is a schematic sectional view of a multilayer printed wiring board using the copper-clad laminate of FIG. 1C. The copper-clad laminate of FIG. 1C is laminated and bonded to a glass-clad laminate 2 provided with a copper foil 1 on a glass cloth base polyimide resin 2 with an insulating resin layer 5 interposed therebetween. Holes 6 were formed, and the through holes were interconnected with plated copper 7 to form a multilayer printed wiring board.
【００２２】この多層プリント配線板の機械的強度を調
べるため、銅箔の幅が１ｃｍになるように試料を作製
し、樹脂から銅箔を垂直方向に引き剥がすときの引張速
度を５ｃｍ／分として銅箔と絶縁樹脂層との間のピール
強度を測定したところ、０．８ｋｇｆ／ｃｍであった。
一方、耐酸性を調べるため、工程３の多層化接着後、ス
ルーホール６を開け、１７．５％濃度の塩酸に浸漬し
た。その結果、３時間以上浸漬してもスルーホール内壁
からの接着界面への塩酸の染み込みは見られなかった。In order to examine the mechanical strength of this multilayer printed wiring board, a sample was prepared so that the width of the copper foil was 1 cm, and the tensile speed when peeling the copper foil from the resin in the vertical direction was set at 5 cm / min. When the peel strength between the copper foil and the insulating resin layer was measured, it was 0.8 kgf / cm.
On the other hand, in order to check the acid resistance, a through hole 6 was opened after the multi-layer bonding in the step 3 and immersed in 17.5% hydrochloric acid. As a result, even when immersed for 3 hours or more, no permeation of hydrochloric acid from the inner wall of the through hole to the adhesive interface was observed.
【００２３】なお、銅めっき液中のＧｅＯ2量を３０〜
１５０ｍｇ／ｌの範囲で変えてもほぼ同等のピール強度
と、同様の耐塩酸性が得られた。また、ＧｅＯ2量を１
０ｍｇ／ｌ以上、３０ｍｇ／ｌ未満及び１５０ｍｇ／ｌ
を超え、２００ｍｇ／ｌ以下の範囲で変えても、同様の
耐塩酸性が得られた。ピール強度はやや低下したが下記
の比較例１のピール強度を超える値が得られた。The amount of GeO 2 in the copper plating solution is 30 to
Even when changed in the range of 150 mg / l, almost the same peel strength and the same hydrochloric acid resistance were obtained. In addition, the amount of GeO 2 is 1
0 mg / l or more, less than 30 mg / l and 150 mg / l
Even when it was changed within the range of 200 mg / l or less, similar hydrochloric acid resistance was obtained. Although the peel strength was slightly lowered, a value exceeding the peel strength of Comparative Example 1 described below was obtained.
【００２４】また、本実施例により製造した多層プリン
ト配線板を２６０℃又は２８８℃の溶融半田に浮かべて
半田耐熱性試験を行った。試料の銅導体パターン部分の
断面を顕微鏡観察し、銅導体パターンと絶縁樹脂との剥
離、絶縁樹脂のクラックの有無を観察した。その結果を
表１に示す。２８８℃の半田に６０秒浮かべて半田耐熱
性を調べても、銅と絶縁樹脂層間の剥離、絶縁樹脂のク
ラックは見られなかった。Further, the multilayer printed wiring board manufactured according to the present embodiment was floated on molten solder at 260 ° C. or 288 ° C., and a solder heat resistance test was performed. The cross section of the copper conductor pattern portion of the sample was observed under a microscope, and the peeling of the copper conductor pattern from the insulating resin and the presence or absence of cracks in the insulating resin were observed. Table 1 shows the results. Even when the sample was floated on 288 ° C. solder for 60 seconds and examined for heat resistance, no peeling between copper and the insulating resin layer and no cracking of the insulating resin were observed.
【００２５】[0025]
【表１】 [Table 1]
【００２６】〈比較例１〉 工程４:実施例１の工程１の処理をした試料を水洗した
後、工程２の無電解銅めっきに代えて、工程４として液
温４０℃の下記組成（II）の水溶液に１分間浸漬してソ
フトエッチングした。 組成（II) ＣｕＣｌ2・２Ｈ2Ｏ……………４０ｇ／ｌ ＨＣｌ（３５％）………………５００ｍｌ／ｌ 工程５:前記試料を水洗した後、液温７５℃の下記組成
（III）の水溶液に１分間浸漬して、銅表面に酸化銅皮
膜を形成し、黒化処理を行った。<Comparative Example 1> Step 4: After the sample treated in Step 1 of Example 1 was washed with water, the following composition (II) at a liquid temperature of 40 ° C. was used in Step 4 instead of the electroless copper plating in Step 2. ) Was immersed in the aqueous solution for 1 minute to perform soft etching. Composition (II) CuCl 2 .2H 2 O 40 g / l HCl (35%) 500 ml / l Step 5: After washing the sample with water, the following composition at a liquid temperature of 75 ° C. It was immersed in the aqueous solution of III) for 1 minute to form a copper oxide film on the copper surface, and blackened.
【００２７】組成（III） ＮａＣｌＯ2………………………９０ｇ／ｌ Ｎａ3ＰＯ4・１２Ｈ2Ｏ…………３０ｇ／ｌ ＮａＯＨ………………………… １５ｇ／ｌ 以後は実施例１の工程３と同様にして多層プリント配線
板を得た。耐酸性を調べるため、多層化接着後にスルー
ホールをあけ１７．５％濃度の塩酸に浸漬したところ、
約１０分後にスルーホール内壁から接着界面へ塩酸が染
み込み、ハローイングが発生した。また実施例１の場合
と同様にして得られたピール強度は０．５ｋｇｆ／ｃｍ
であった。Composition (III) NaClO 2 ········· 90 g / l Na 3 PO 4 .12H 2 O ····· 30 g / l NaOH ················ 15 g / l Thereafter, a multilayer printed wiring board was obtained in the same manner as in Step 3 of Example 1. In order to check the acid resistance, a through hole was opened after the multi-layer bonding and immersed in 17.5% hydrochloric acid.
About 10 minutes later, hydrochloric acid permeated from the inner wall of the through hole to the bonding interface, and haloing occurred. The peel strength obtained in the same manner as in Example 1 was 0.5 kgf / cm.
Met.
【００２８】〈実施例２〉実施例１の無電解銅めっき液
中のＧｅＯ2に代えて、Ｎａ2ＳｉＯ3・９Ｈ2Ｏを１ｇ／
ｌ加え、銅厚５μｍの無電解銅めっきを行い、他は実施
例１と同様にして多層プリント配線板を得た。銅めっき
後の銅表面には突起が形成され、ピール強度は０．７ｋ
ｇｆ／ｃｍであった。Example 2 Instead of GeO 2 in the electroless copper plating solution of Example 1, 1 g / Na 2 SiO 3 .9H 2 O was used.
In addition, a multilayer printed wiring board was obtained in the same manner as in Example 1 except that electroless copper plating with a copper thickness of 5 μm was performed. A projection is formed on the copper surface after copper plating, and the peel strength is 0.7 k.
gf / cm.
【００２９】〈実施例３〉実施例１で用いたガラス布基
材ポリイミド樹脂に代えてガラス布基材エポキシ樹脂を
用い、またポリイミド樹脂に代えてエポキシ樹脂プリプ
レグを用い、これ以外は実施例１と同様に処理した後、
１７０℃で３０ｋｇｆ／ｃｍ2の圧力で１２０分かけて
接着した。Example 3 A glass cloth base epoxy resin was used in place of the glass cloth base polyimide resin used in Example 1, and an epoxy resin prepreg was used in place of the polyimide resin. After processing in the same way as
Bonding was performed at 170 ° C. under a pressure of 30 kgf / cm 2 for 120 minutes.
【００３０】銅箔と絶縁樹脂層との間のピール強度を測
定した結果、１．６ｋｇｆ／ｃｍであった。また、耐酸
性を調べるため、多層化接着後にスルーホールをあけ１
７．５％濃度の塩酸に３時間以上浸漬してもスルーホー
ル内壁からの接着界面への塩酸の染み込みは見られなか
った。The measured peel strength between the copper foil and the insulating resin layer was 1.6 kgf / cm. In order to check the acid resistance, a through hole was drilled after multi-layer bonding.
Even when immersed in 7.5% hydrochloric acid for 3 hours or more, no permeation of hydrochloric acid from the inner wall of the through hole to the adhesive interface was observed.
【００３１】〈比較例２〉実施例１の無電解銅めっき液
中のＧｅＯ2の７０ｍｇ／ｌに代えて、２，２’−ジピ
リジルを３０ｍｇ／ｌ加え、銅厚５μｍの無電解銅めっ
きを行い、他は実施例１と同様にして多層プリント配線
板を得た。銅めっき後の銅表面形状は比較的平滑であ
り、突起は形成されていなかった。ピール強度は０．３
ｋｇｆ／ｃｍであった。Comparative Example 2 Instead of 70 mg / l of GeO 2 in the electroless copper plating solution of Example 1, 30 mg / l of 2,2′-dipyridyl was added, and electroless copper plating having a copper thickness of 5 μm was performed. Then, a multilayer printed wiring board was obtained in the same manner as in Example 1 except for the above. The copper surface shape after copper plating was relatively smooth, and no protrusion was formed. Peel strength is 0.3
kgf / cm.
【００３２】また、この方法により製造した多層プリン
ト配線板を実施例１と同様に半田耐熱試験を行い、銅導
体パターンと絶縁樹脂間の剥離、絶縁樹脂のクラックの
有無を観察した。その結果、表１に示したように、半田
に浮かせる時間が３０秒以上の場合に剥離、クラックが
観察された。The multilayer printed wiring board manufactured by this method was subjected to a soldering heat test in the same manner as in Example 1, and the peeling between the copper conductor pattern and the insulating resin and the presence or absence of cracks in the insulating resin were observed. As a result, as shown in Table 1, peeling and cracking were observed when the floating time on the solder was 30 seconds or more.
【００３３】なお、図３は多層プリント配線板の半田耐
熱性試験後の状態を示す概略断面図である。符号２、
３、５は図２と同義であり、符号８は銅導体パターンと
絶縁樹脂との剥離部分、符号９は絶縁樹脂のクラックを
意味する。FIG. 3 is a schematic sectional view showing a state after the solder heat resistance test of the multilayer printed wiring board. Code 2,
Reference numerals 3 and 5 have the same meanings as in FIG. 2, reference numeral 8 denotes a peeled portion between the copper conductor pattern and the insulating resin, and reference numeral 9 denotes a crack in the insulating resin.
【００３４】[0034]
【発明の効果】本発明によれば、銅導体パターン表面に
無電解銅めっきにより突起を形成でき、その投錨効果に
より絶縁樹脂層との間の接着力が向上する。また、黒化
処理による酸化銅皮膜形成に代わり、耐酸性に優る金属
銅皮膜を形成するため、ハローイングの発生を抑制でき
る。According to the present invention, projections can be formed on the surface of the copper conductor pattern by electroless copper plating, and the anchoring effect improves the adhesive strength between the copper conductor pattern and the insulating resin layer. Further, instead of forming a copper oxide film by the blackening treatment, a metal copper film having excellent acid resistance is formed, so that occurrence of haloing can be suppressed.
【図１】本発明の実施例１で処理する銅張積層板の断面
模式図。FIG. 1 is a schematic cross-sectional view of a copper-clad laminate processed in Example 1 of the present invention.
【図２】本発明の一実施例の多層プリント配線板の断面
模式図。FIG. 2 is a schematic sectional view of a multilayer printed wiring board according to one embodiment of the present invention.
【図３】比較例の多層プリント配線板の半田耐熱性試験
後の状態を示す断面模式図。FIG. 3 is a schematic cross-sectional view showing a state after a solder heat resistance test of a multilayer printed wiring board of a comparative example.
１…銅箔 ２…ガラス布基材ポリイミド樹脂 ３…銅導体パターン ４…突起を表面に有する銅めっき層 ５…絶縁樹脂層 ６…スルーホール ７…めっき銅 ８…剥離部分 ９…クラック DESCRIPTION OF SYMBOLS 1 ... Copper foil 2 ... Glass cloth base polyimide resin 3 ... Copper conductor pattern 4 ... Copper plating layer which has a protrusion on the surface 5 ... Insulating resin layer 6 ... Through hole 7 ... Plated copper 8 ... Peeling part 9 ... Crack
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上田 佳功 神奈川県秦野市堀山下１番地 株式会社日 立製作所エンタープライズサーバ事業部内 (72)発明者 川口 雅己 神奈川県秦野市堀山下１番地 株式会社日 立製作所エンタープライズサーバ事業部内 (72)発明者 村川 聡 神奈川県秦野市堀山下１番地 株式会社日 立製作所エンタープライズサーバ事業部内 Ｆターム(参考） 4K022 AA02 AA42 BA08 BA35 DA01 DB01 DB04 DB06 DB07 DB08 5E343 AA15 AA18 BB24 BB67 CC78 DD33 DD76 ER18 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshiko Ueda 1st Horiyamashita, Hadano-shi, Kanagawa Prefecture Hitachi Server Corporation Enterprise Server Division (72) Inventor Masami Kawaguchi 1st Horiyamashita, Hadano-shi, Kanagawa Japan Co., Ltd. (72) Inventor Satoshi Murakawa 1st Horiyamashita, Hadano-shi, Kanagawa F-term in Enterprise Server Division, Hitachi Ltd. 4K022 AA02 AA42 BA08 BA35 DA01 DB01 DB04 DB06 DB07 DB08 5E343 AA15 AA18 BB24 BB67 CC78 DD33 DD76 ER18
Claims (3)
含む無電解銅めっき液において、該無電解銅めっき液
は、Ｇｅの化合物及びＳｉの化合物からなる群から選ば
れた少なくとも１種の化合物を含有することを特徴とす
る無電解銅めっき液。1. An electroless copper plating solution containing copper ions, a copper ion complexing agent and a reducing agent, wherein the electroless copper plating solution is at least one selected from the group consisting of Ge compounds and Si compounds. An electroless copper plating solution containing a kind of compound.
にＧｅの化合物及びＳｉの化合物からなる群から選ばれ
た少なくとも１種の化合物を含有する無電解銅めっき液
に被めっき物を浸漬することにより、突起を有する銅皮
膜を析出させることを特徴とする無電解銅めっき方法。2. An electroless copper plating solution containing copper ions, a complexing agent for copper ions, a reducing agent, and at least one compound selected from the group consisting of Ge compounds and Si compounds. An electroless copper plating method characterized by depositing a copper film having protrusions by immersion.
にＧｅの化合物及びＳｉの化合物からなる群から選ばれ
た少なくとも１種の化合物を含有する無電解銅めっき液
に被めっき物を浸漬することにより、突起を有する銅皮
膜を析出させ、その後熱硬化性絶縁樹脂含浸基材を介し
て積層接着する方法。3. An electroless copper plating solution containing copper ions, a complexing agent for copper ions, a reducing agent, and at least one compound selected from the group consisting of Ge compounds and Si compounds. A method in which a copper film having protrusions is deposited by immersion, and then laminated and bonded via a thermosetting insulating resin-impregnated base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213371A JP2002030452A (en) | 2000-07-10 | 2000-07-10 | Method for producing printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213371A JP2002030452A (en) | 2000-07-10 | 2000-07-10 | Method for producing printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002030452A true JP2002030452A (en) | 2002-01-31 |
Family
ID=18709134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000213371A Pending JP2002030452A (en) | 2000-07-10 | 2000-07-10 | Method for producing printed circuit board |
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| Country | Link |
|---|---|
| JP (1) | JP2002030452A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003098985A1 (en) * | 2002-05-17 | 2003-11-27 | Japan Science And Technology Corporation | Method for forming multilayer circuit structure and base having multilayer circuit structure |
| JP2010524227A (en) * | 2007-04-02 | 2010-07-15 | エルジー・ケム・リミテッド | Electromagnetic wave shielding glass with conductive pattern blackened and method for producing the same |
| KR20200055963A (en) * | 2018-11-14 | 2020-05-22 | 와이엠티 주식회사 | Plating laminate and printed circuit board |
-
2000
- 2000-07-10 JP JP2000213371A patent/JP2002030452A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003098985A1 (en) * | 2002-05-17 | 2003-11-27 | Japan Science And Technology Corporation | Method for forming multilayer circuit structure and base having multilayer circuit structure |
| CN100435603C (en) * | 2002-05-17 | 2008-11-19 | 独立行政法人科学技术振兴机构 | Method for forming multilayer circuit structure and base having multilayer circuit structure |
| JP2010524227A (en) * | 2007-04-02 | 2010-07-15 | エルジー・ケム・リミテッド | Electromagnetic wave shielding glass with conductive pattern blackened and method for producing the same |
| KR20200055963A (en) * | 2018-11-14 | 2020-05-22 | 와이엠티 주식회사 | Plating laminate and printed circuit board |
| WO2020101183A1 (en) * | 2018-11-14 | 2020-05-22 | 와이엠티 주식회사 | Plated laminate and printed circuit board |
| KR102124324B1 (en) * | 2018-11-14 | 2020-06-18 | 와이엠티 주식회사 | Plating laminate and printed circuit board |
| CN112969819A (en) * | 2018-11-14 | 2021-06-15 | Ｙｍｔ股份有限公司 | Electroplating laminate and printed wiring board |
| JP2021517933A (en) * | 2018-11-14 | 2021-07-29 | ワイエムティー カンパニー リミテッド | Plated laminate and printed circuit board |
| EP3760761A4 (en) * | 2018-11-14 | 2022-03-30 | YMT Co. Ltd. | Plated laminate and printed circuit board |
| US11499233B2 (en) | 2018-11-14 | 2022-11-15 | Ymt Co., Ltd. | Plated laminate and printed circuit board |
| JP7205027B2 (en) | 2018-11-14 | 2023-01-17 | ワイエムティー カンパニー リミテッド | Plated laminates and printed circuit boards |
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