JP2000340948A - Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the same - Google Patents
Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the sameInfo
- Publication number
- JP2000340948A JP2000340948A JP15394699A JP15394699A JP2000340948A JP 2000340948 A JP2000340948 A JP 2000340948A JP 15394699 A JP15394699 A JP 15394699A JP 15394699 A JP15394699 A JP 15394699A JP 2000340948 A JP2000340948 A JP 2000340948A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- resin
- tin
- wiring board
- tin alloy
- 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
Links
Landscapes
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅と樹脂との接着
性を向上させる方法およびそれを用いて製造される多層
配線板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for improving the adhesion between copper and a resin, and a multilayer wiring board manufactured using the method.
【０００２】[0002]
【従来の技術】最も一般的な多層配線板は、表面に銅か
らなる導電層を有する内層基板が、プリプレグを挟んで
他の内層基板や銅箔と積層プレスされて製造されてい
る。導電層間は、スルーホールと呼ばれる孔壁が銅めっ
きされた貫通孔により、電気的に接続されている。前記
内層基板の銅表面には、プリプレグとの接着性を向上さ
せるために、ブラックオキサイドやブラウンオキサイド
とよばれる酸化銅の層が形成されている。2. Description of the Related Art The most common multilayer wiring board is manufactured by laminating an inner layer substrate having a conductive layer made of copper on the surface with another inner layer substrate or a copper foil with a prepreg interposed therebetween. The conductive layers are electrically connected to each other by a through-hole, which is called a through-hole, and whose wall is plated with copper. On the copper surface of the inner layer substrate, a layer of copper oxide called black oxide or brown oxide is formed in order to improve the adhesion to the prepreg.
【０００３】前記酸化銅はプリプレグとの接着性に優れ
ているが、スルーホールめっきの工程において酸性液と
接触した場合、溶解して変色し、ハローイングと呼ばれ
る欠陥を生じやすいという問題がある。[0003] The copper oxide is excellent in adhesion to a prepreg, but has a problem that when it comes into contact with an acidic solution in a through-hole plating step, it dissolves and discolors, and easily causes a defect called haloing.
【０００４】そこで、ブラックオキサイドやブラウンオ
キサイドに代わる方法として、ヨーロッパ特許出願第２
１６５３１号明細書や特開平４−２３３７９３号公報に
記載されているように、内層基板の表面にスズ膜を形成
する方法が検討されている。また、特開平１０−２５６
７３６号公報には、銅の変色劣化を防止するために、銅
表面にスズ膜を形成することが記載されている。Accordingly, as an alternative to black oxide and brown oxide, European Patent Application No. 2
As described in JP-A-16531 and JP-A-4-233793, a method of forming a tin film on the surface of an inner substrate has been studied. Also, JP-A-10-256
No. 736 describes that a tin film is formed on a copper surface in order to prevent discoloration and deterioration of copper.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記の
ごとき銅表面にスズ膜を形成する方法は、樹脂との接着
性向上効果が不充分である。However, the method of forming a tin film on a copper surface as described above has an insufficient effect of improving adhesion to a resin.
【０００６】[0006]
【課題を解決するための手段】本発明者らは前記課題を
解決するために鋭意検討を重ねた結果、スズ膜ではな
く、銅スズ合金が絶縁樹脂との接着性を著しく向上させ
ることを見出し、本発明に到達した。すなわち、本発明
は、銅の表面に銅スズ合金を形成したのち樹脂と接着さ
せることを特徴とする銅と樹脂との接着性を向上させる
方法、ならびに銅からなる導電層と絶縁樹脂層とが積層
された多層配線板であって、前記導電層の表面に銅スズ
合金が形成されてなる多層配線板に関する。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that not a tin film but a copper-tin alloy significantly improves the adhesiveness to an insulating resin. Reached the present invention. That is, the present invention provides a method for improving the adhesion between copper and a resin, which comprises forming a copper-tin alloy on the surface of copper and then bonding the resin to a resin, and a method for forming a conductive layer and an insulating resin layer made of copper. The present invention relates to a multilayer wiring board having a multilayer structure in which a copper-tin alloy is formed on a surface of the conductive layer.
【０００７】[0007]
【発明の実施の形態】本発明における銅表面は樹脂と接
着させる銅表面であり、例えば樹脂絶縁基板、セラミッ
ク基板、メタルコア基板等の種々の配線板の導電層（電
解銅箔、圧延銅箔、無電解銅めっき膜、電解銅めっき膜
等）等があげられる。BEST MODE FOR CARRYING OUT THE INVENTION The copper surface in the present invention is a copper surface to be bonded to a resin. For example, conductive layers (electrolytic copper foil, rolled copper foil, and the like) of various wiring boards such as a resin insulating board, a ceramic board, and a metal core board. Electroless copper plating film, electrolytic copper plating film, etc.).
【０００８】前記銅表面は、樹脂と積層した際のアンカ
ー効果を得るために、粗化された表面であるのが好まし
い。前記粗化方法としては、例えばマイクロエッチング
法、電気銅めっき法、無電解銅めっき法、ジェットスク
ラブ法、バフ研磨法等があげられる。前記マイクロエッ
チング法としては、例えば硫酸・過酸化水素タイプエッ
チング剤、過硫酸塩タイプエッチング剤、塩化銅タイプ
エッチング剤、塩化鉄タイプエッチング剤、硝酸タイプ
エッチング剤（メック（株）製のＣＺ−５４８０等）、
有機酸タイプエッチング剤（メック（株）製のＣＺ−８
１００等）等を用いる方法があげられる。前記粗化表面
のうちでは、マイクロエッチング法による粗化表面が、
銅スズ合金を形成しやすい活性な銅表面が得られるとい
う点から好ましい。さらに、メック（株）製のＣＺ−８
１００による粗化表面のような、微細なこぶ状の突起が
密に形成されたような深い凹凸のある粗化表面が、樹脂
との接着において高いアンカー効果が得られるという点
から好ましいThe copper surface is preferably a roughened surface in order to obtain an anchor effect when laminated with a resin. Examples of the roughening method include a microetching method, an electrolytic copper plating method, an electroless copper plating method, a jet scrub method, and a buff polishing method. Examples of the microetching method include a sulfuric acid / hydrogen peroxide type etching agent, a persulfate type etching agent, a copper chloride type etching agent, an iron chloride type etching agent, and a nitric acid type etching agent (CZ-5480 manufactured by Mec Co., Ltd.). etc),
Organic acid type etching agent (CZ-8 manufactured by Mec Co., Ltd.)
100 etc.). Among the roughened surfaces, the roughened surface by the micro etching method is
It is preferable in that an active copper surface on which a copper-tin alloy is easily formed can be obtained. Furthermore, CZ-8 manufactured by Mec Co., Ltd.
A roughened surface having deep irregularities such as fine bump-like protrusions densely formed, such as a roughened surface according to 100, is preferable in that a high anchoring effect can be obtained in bonding with a resin.
【０００９】前記銅表面に形成される銅スズ合金は、銅
とスズの合計に対する銅の比率が４５〜９５原子％であ
るのが好ましく、さらに５０〜９０原子％であるのが好
ましく、なかんずく５０〜８５原子％であるのが好まし
い。銅の比率が４５原子％未満の場合や９５原子％を超
える場合、樹脂との接着向上効果が不充分である。な
お、前記銅スズ合金が形成される下地は銅であるため、
表面から深くなるにしたがい、銅スズ合金中の銅が増加
し、スズが少なくなる。前記銅の比率の好ましい範囲
は、銅スズ合金の表面の銅の比率の範囲をいう。この表
面の銅の比率は、オージェ電子分光分析やＥＰＭＡ（電
子プローブＸ線マイクロアナライザ）により測定するこ
とができる。In the copper-tin alloy formed on the copper surface, the ratio of copper to the total of copper and tin is preferably 45 to 95 atomic%, more preferably 50 to 90 atomic%, and especially preferably 50 to 90 atomic%. It is preferably about 85 at%. When the proportion of copper is less than 45 atomic% or more than 95 atomic%, the effect of improving the adhesion to the resin is insufficient. Since the base on which the copper-tin alloy is formed is copper,
As the depth increases from the surface, copper in the copper-tin alloy increases and tin decreases. The preferred range of the copper ratio refers to the range of the copper ratio on the surface of the copper-tin alloy. The ratio of copper on the surface can be measured by Auger electron spectroscopy or EPMA (electron probe X-ray microanalyzer).
【００１０】また、銅スズ合金中には、空気との接触等
により酸素原子が含まれているが、酸素原子が存在して
も樹脂との接着性に悪影響を及ぼさない。したがって、
本発明の効果は、銅スズ合金の酸化が促進されるような
加熱等の処理を経た後であっても維持される。また、銅
スズ合金中には、種々の汚染源からの他種の原子が含ま
れている場合もある。[0010] The copper-tin alloy contains oxygen atoms due to contact with air or the like, but the presence of oxygen atoms does not adversely affect the adhesion to the resin. Therefore,
The effect of the present invention is maintained even after a treatment such as heating that promotes oxidation of the copper-tin alloy. The copper-tin alloy may also contain other types of atoms from various sources.
【００１１】前記銅表面に銅スズ合金を形成する方法に
特に限定はないが、例えば銅表面にスズ膜を形成し、銅
との間で銅スズ合金を形成し、次にこの銅スズ合金を残
してその上のスズを剥離する方法があげられる。前記ス
ズ膜の形成法としては、例えば置換スズめっき法、無電
解スズめっき法（還元剤使用）、電気スズめっき法、溶
融スズ浸漬法などがあげられる。前記スズを剥離する方
法としては、例えば市販されているスズ剥離液により、
銅表面上からスズを選択的に剥離する方法があげられ
る。前記スズを選択的に剥離し得る剥離液としては、例
えばメック（株）製のメックリムーバーＳ−６５１Ａ等
を使用することができる。The method of forming the copper-tin alloy on the copper surface is not particularly limited. For example, a tin film is formed on the copper surface, a copper-tin alloy is formed with copper, and then the copper-tin alloy is formed. There is a method of removing the tin on it while leaving it. Examples of the method for forming the tin film include a displacement tin plating method, an electroless tin plating method (using a reducing agent), an electrotin plating method, and a molten tin immersion method. As a method of peeling the tin, for example, with a commercially available tin peeling liquid,
There is a method of selectively peeling tin off from the copper surface. As the stripper capable of selectively stripping the tin, for example, Mechmover S-651A manufactured by Mec Co., Ltd. or the like can be used.
【００１２】また、合金形成置換スズめっき法によって
直接的に銅の表面に銅スズ合金を形成することもでき
る。この方法に用いられる合金形成置換スズめっき液と
しては、例えばメック（株）製のメックゾールＴ−９９
００があげられる。Further, a copper-tin alloy can be formed directly on the surface of copper by an alloy-forming displacement tin plating method. Examples of the alloy-forming substitution tin plating solution used in this method include Mecsol T-99 manufactured by Mec Corporation.
00 is given.
【００１３】前記の表面に銅スズ合金が形成された銅と
接着させる樹脂に特に限定はなく、例えばＡＳ樹脂、Ａ
ＢＳ樹脂、フッ素樹脂、ポリアミド、ポリエチレン、ポ
リエチレンテレフタレート、ポリ塩化ビニリデン、ポリ
塩化ビニル、ポリカーボネート、ポリスチレン、ポリサ
ルホン、ポリプロピレン、液晶ポリマー等の熱可塑性樹
脂や、エポキシ樹脂、フェノール樹脂、ポリイミド、ポ
リウレタン、ビスマレイミド・トリアジン樹脂、変性ポ
リフェニレンエーテル等の熱硬化性樹脂等があげられ
る。本発明の方法は、このような種々の樹脂と銅との接
着性を向上させることができる。The resin to be bonded to copper having a copper-tin alloy formed on the surface is not particularly limited. For example, AS resin, A resin
Thermoplastic resins such as BS resin, fluororesin, polyamide, polyethylene, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, liquid crystal polymer, epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide -Thermosetting resins such as triazine resins and modified polyphenylene ethers. The method of the present invention can improve the adhesion between such various resins and copper.
【００１４】したがって、本発明の方法は、例えば配線
板の導電層の銅と層間絶縁樹脂（プリプレグ、無電解め
っき用接着剤、フィルム状樹脂、液状樹脂、感光性樹
脂、熱硬化性樹脂、熱可塑性樹脂）、ソルダーレジス
ト、導電性樹脂、導電性ペースト、導電性接着剤、穴埋
め用樹脂、フレキシブルカバーレイフィルム等との接着
に有効である。Therefore, the method of the present invention can be applied, for example, to a method of forming a conductive layer of a wiring board with copper and an interlayer insulating resin (prepreg, adhesive for electroless plating, film-like resin, liquid resin, photosensitive resin, thermosetting resin, (Plastic resin), a solder resist, a conductive resin, a conductive paste, a conductive adhesive, a filling resin, a flexible coverlay film, and the like.
【００１５】次に本発明の多層配線板を説明する。本発
明の多層配線板は、銅からなる導電層と絶縁樹脂層とが
積層され、前記導電層の表面に銅スズ合金が形成された
ものである。Next, the multilayer wiring board of the present invention will be described. The multilayer wiring board of the present invention has a structure in which a conductive layer made of copper and an insulating resin layer are laminated, and a copper-tin alloy is formed on a surface of the conductive layer.
【００１６】前記導電層の回路は、例えば絶縁基材に張
合わされた銅箔を回路を残してエッチングするサブトラ
クティブ法、はんだ剥離法等や、絶縁基材上に無電解銅
めっきにより回路を形成するアディティブ法等によって
形成される。サブトラクティブ法により回路を形成する
場合、銅箔上への銅スズ合金の形成は、回路形成前に行
ってもよく、回路形成後に行ってもよい。The circuit of the conductive layer is formed by, for example, a subtractive method in which a copper foil bonded to an insulating base material is etched while leaving the circuit, a solder peeling method, or the like, or a circuit formed by electroless copper plating on the insulating base material. It is formed by an additive method or the like. When a circuit is formed by the subtractive method, the formation of the copper-tin alloy on the copper foil may be performed before the circuit is formed, or may be performed after the circuit is formed.
【００１７】前記絶縁樹脂層に特に限定はないが、例え
ばフェノール樹脂、エポキシ樹脂、耐熱エポキシ樹脂、
ポリイミド、ビスマレイミド・トリアジン樹脂、ポリフ
ェニレンエーテル等があげられる。これらの樹脂はフィ
ラーを含有している場合もある。また、これらの樹脂を
ガラス布、アラミド布等の基材に含浸させたものがあげ
られる。Although the insulating resin layer is not particularly limited, for example, a phenol resin, an epoxy resin, a heat-resistant epoxy resin,
Examples thereof include polyimide, bismaleimide / triazine resin, and polyphenylene ether. These resins may contain fillers in some cases. In addition, those obtained by impregnating a base material such as a glass cloth and an aramid cloth with these resins may be used.
【００１８】導電層と絶縁樹脂層との積層方法にも特に
限定はなく、例えば絶縁樹脂層がガラス布基材エポキシ
樹脂含浸プリプレグの場合、表面に導電層を有する内層
基板が、プレプレグを挟んで他の内層基板や銅箔と積層
プレスされる。また前記内層基板に液状樹脂を塗布する
方法、フィルム状樹脂を積層する方法、樹脂付き銅箔を
積層する方法等があげられる。The method of laminating the conductive layer and the insulating resin layer is not particularly limited. For example, when the insulating resin layer is a prepreg impregnated with a glass cloth base epoxy resin, an inner layer substrate having a conductive layer on the surface sandwiches the prepreg. It is laminated and pressed with another inner layer substrate and copper foil. Examples of the method include a method of applying a liquid resin to the inner layer substrate, a method of laminating a film-like resin, and a method of laminating a copper foil with a resin.
【００１９】次に実施例により、本発明をさらに具体的
に説明する。 実施例１ 両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポ
キシ樹脂含浸銅張積層板（ＦＲ−４グレード）の銅箔
を、メック（株）製のＣＺ−８１００によりマイクロエ
ッチングして粗化した。エッチング量（銅の重量減少か
ら算出）は１μｍであった。次にホウフッ化スズ０．１
ｍｏｌ／リットルおよびチオ尿素１ｍｏｌ／リットルを
含有し、ホウフッ酸でｐＨが１．２になるように調整し
た合金形成置換スズめっき液に、前記積層板を４５℃、
３０秒の条件で浸漬したのち水洗、乾燥し、銅箔表面に
銅スズ合金を形成した。得られた表面の原子組成をオー
ジェ分光分析により調べたところ、銅とスズの合計に対
する銅の比率は５６原子％であった。またこの表面の色
調は濃い灰色であった。次に、得られた積層板の銅箔と
樹脂との接着性を評価した。前記積層板の両面にガラス
布エポキシ樹脂含浸プリプレグ（ＦＲ−４グレード）を
積層プレスした後、周辺部を切り取り、テストピースを
作製した。次に得られたテストピースにプレッシャーク
ッカーにて１２１℃、１００％ＲＨ、２気圧、８時間の
負荷を与えた後、ＪＩＳ Ｃ ６４８１に準じて溶融は
んだ浴中に１分間浸漬した。銅箔とプリプレグの剥離
（プリプレグのふくれ）は全く生じなかった。Next, the present invention will be described more specifically with reference to examples. Example 1 A copper foil of a glass cloth epoxy resin-impregnated copper-clad laminate (FR-4 grade) having 18 μm-thick copper foil laminated on both sides was micro-etched and roughened by CZ-8100 manufactured by MEC Corporation. did. The etching amount (calculated from the weight loss of copper) was 1 μm. Next, tin borofluoride 0.1
mol / l and 1 mol / l of thiourea, and the laminated plate was placed at 45 ° C. in an alloy-forming substitution tin plating solution adjusted to have a pH of 1.2 with borofluoric acid.
After being immersed in the condition for 30 seconds, it was washed with water and dried to form a copper-tin alloy on the surface of the copper foil. When the atomic composition of the obtained surface was examined by Auger spectroscopy, the ratio of copper to the total of copper and tin was 56 atomic%. The color of this surface was dark gray. Next, the adhesiveness between the copper foil and the resin of the obtained laminate was evaluated. After laminating and pressing a prepreg impregnated with glass cloth epoxy resin (FR-4 grade) on both sides of the laminate, the periphery was cut off to produce a test piece. Next, after applying a load of 121 ° C., 100% RH, 2 atm, and 8 hours with a pressure cooker to the obtained test piece, the test piece was immersed in a molten solder bath for 1 minute according to JIS C6481. Peeling of the copper foil and the prepreg (bulging of the prepreg) did not occur at all.
【００２０】実施例２ 実施例１と同様に銅張積層板の銅箔をマイクロエッチン
グし、表面を粗化した。実施例１で用いた合金形成置換
スズめっき液に、ホウフッ化銅を銅濃度が２ｇ／リット
ル含有されるように添加しためっき液を調製した。この
めっき液に、前記積層板を４５℃、３０秒の条件で浸漬
したのち水洗、乾燥し、銅箔表面に銅スズ合金を形成し
た。得れられた表面の銅とスズの合計に対する銅の比率
は８４原子％であった。また、この表面の色調は赤みを
帯びた濃い灰色であった。次に銅箔と樹脂との接着性を
実施例１と同様に評価したが、銅箔とプリプレグの剥離
は全く生じなかった。Example 2 As in Example 1, the copper foil of the copper-clad laminate was microetched to roughen the surface. A plating solution was prepared by adding copper borofluoride to the alloy-forming substitution tin plating solution used in Example 1 so that the copper concentration was 2 g / liter. The laminate was immersed in the plating solution at 45 ° C. for 30 seconds, washed with water and dried to form a copper-tin alloy on the surface of the copper foil. The ratio of copper to the total of copper and tin on the obtained surface was 84 atomic%. The color of this surface was reddish dark gray. Next, the adhesion between the copper foil and the resin was evaluated in the same manner as in Example 1, but no peeling of the copper foil and the prepreg occurred.
【００２１】実施例３ 両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポ
キシ樹脂含浸銅張積層板（ＦＲ−４グレード）の銅箔を
バフ研磨したのち、電気スズめっきを行い、厚さ約１０
μｍのスズを被覆した。得られた表面は光沢のある銀色
であった。この積層板を約１年間放置し、スズ中に銅を
拡散させた。次に、メック（株）製のメックリムーバー
Ｓ−６５１Ａを用い、スズ層を剥離し、表面に銅スズ合
金を露出させた。得られた表面の銅とスズの合計に対す
る銅の比率は６０原子％であった。この表面の色調は濃
い灰色であった。次に銅箔と樹脂との接着性を実施例１
と同様に評価したが、銅箔とプリプレグの剥離は全く生
じなかった。Example 3 After buffing a copper foil of a glass cloth epoxy resin impregnated copper-clad laminate (FR-4 grade) having 18 μm-thick copper foil laminated on both sides, electro-tin plating was performed to a thickness of about 10
μm of tin was coated. The resulting surface was shiny silver. The laminate was left for about one year to diffuse copper into the tin. Next, the tin layer was peeled off using a Mech Mover S-651A manufactured by Mec Corporation to expose the copper-tin alloy on the surface. The ratio of copper to the total of copper and tin on the obtained surface was 60 atomic%. The color of this surface was dark gray. Next, the adhesion between the copper foil and the resin was measured in Example 1.
Was evaluated in the same manner as in the above, but no peeling of the copper foil and the prepreg occurred.
【００２２】実施例４ 実施例１と同様に銅張積層板の銅箔をマイクロエッチン
グし、表面を粗化した。次にメック（株）製のメックゾ
ールＴ−９９００に４℃、３０秒の条件で浸漬したのち
水洗、乾燥し、銅箔表面に銅スズ合金を形成した。得ら
れた表面の銅とスズの合計に対する銅の比率は６５原子
％であった。また、この表面の色調は濃い灰色であっ
た。次に銅箔と樹脂との接着性を実施例１と同様に評価
したが、銅箔とプリプレグの剥離は全く生じなかった。Example 4 In the same manner as in Example 1, the copper foil of the copper clad laminate was microetched to roughen the surface. Next, it was immersed in Mecsol T-9900 manufactured by Mec Corporation at 4 ° C. for 30 seconds, washed with water and dried to form a copper-tin alloy on the copper foil surface. The ratio of copper to the total of copper and tin on the obtained surface was 65 atomic%. The color of this surface was dark gray. Next, the adhesion between the copper foil and the resin was evaluated in the same manner as in Example 1, but no peeling of the copper foil and the prepreg occurred.
【００２３】実施例５ 両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポ
キシ樹脂含浸銅張積層板（ＦＲ−４グレード）の銅箔
を、塩化銅２０重量％および塩酸１５重量％を含有する
水溶液によりマイクロエッチングして粗化した。エッチ
ング量（銅の重量減少から算出）は１μｍであった。次
に、実施例１と同様に合金形成置換スズめっきを行い、
銅箔表面に銅スズ合金を形成した。得られた表面の銅と
スズの合計に対する銅の比率は５８原子％であった。こ
の表面の色調は濃い灰色であった。次に銅箔と樹脂との
接着性を実施例１と同様に評価したが、銅箔とプリプレ
グの剥離は全く生じなかった。Example 5 A copper foil of a glass cloth epoxy resin-impregnated copper-clad laminate (FR-4 grade) having 18 μm-thick copper foil laminated on both sides contains 20% by weight of copper chloride and 15% by weight of hydrochloric acid. Roughening was performed by microetching with an aqueous solution. The etching amount (calculated from the weight loss of copper) was 1 μm. Next, in the same manner as in Example 1, alloy forming displacement tin plating was performed.
A copper-tin alloy was formed on the copper foil surface. The ratio of copper to the total of copper and tin on the obtained surface was 58 atomic%. The color of this surface was dark gray. Next, the adhesion between the copper foil and the resin was evaluated in the same manner as in Example 1, but no peeling of the copper foil and the prepreg occurred.
【００２４】比較例１ 実施例５と同様に銅張積層板の銅箔をマイクロエッチン
グして表面を粗化した。次に、一般に使用されている置
換スズめっき液（シプレイ（株）製のティンポジットＬ
Ｔ−３４）に、前記積層板を４５℃、３０秒の条件で浸
漬したのち水洗、乾燥し、銅箔表面にスズ膜を形成し
た。この表面の色調は光沢のある銀色であった。次に銅
箔と樹脂との接着性を実施例１と同様に評価したとこ
ろ、プリプレグの一部が銅箔から剥がれ、激しいふくれ
が生じた。Comparative Example 1 In the same manner as in Example 5, the copper foil of the copper-clad laminate was microetched to roughen the surface. Next, a commonly used substituted tin plating solution (Tymposit L manufactured by Shipley Co., Ltd.)
In T-34), the laminate was immersed at 45 ° C. for 30 seconds, washed with water and dried to form a tin film on the surface of the copper foil. The color of this surface was shiny silver. Next, when the adhesiveness between the copper foil and the resin was evaluated in the same manner as in Example 1, a part of the prepreg was peeled off from the copper foil and severe blistering occurred.
【００２５】比較例２ 実施例５と同様に銅張積層板の銅箔をマイクロエッチン
グし、表面を粗化した。次に銅箔と樹脂との接着性を実
施例１と同様に評価したところ、プリプレグの一部が銅
箔から剥がれ、激しいふくれが生じた。Comparative Example 2 In the same manner as in Example 5, the copper foil of the copper-clad laminate was microetched to roughen the surface. Next, when the adhesiveness between the copper foil and the resin was evaluated in the same manner as in Example 1, a part of the prepreg was peeled off from the copper foil and severe blistering occurred.
【００２６】[0026]
【発明の効果】以上説明したように、本発明によれば、
銅表面に銅スズ合金を形成した後、樹脂を接着させるこ
とにより、両者の接着をより強固にして、例えば導電層
とプリプレグとを積層してなる多層配線板におけるプリ
プレグの剥離を防止することができるAs described above, according to the present invention,
After forming a copper-tin alloy on the copper surface, by bonding the resin, the bonding between the two is strengthened, and for example, it is possible to prevent peeling of the prepreg in a multilayer wiring board formed by laminating a conductive layer and a prepreg. it can
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河口 睦行 兵庫県尼崎市東初島町１番地 メック株式 会社内 (72)発明者 井戸本 昌也 兵庫県尼崎市東初島町１番地 メック株式 会社内 (72)発明者 戸田 健次 兵庫県尼崎市東初島町１番地 メック株式 会社内 Ｆターム(参考） 5E343 AA12 AA15 AA17 AA22 BB24 BB54 BB55 DD33 GG02 5E346 AA12 AA15 AA32 AA35 BB01 CC32 CC33 CC57 DD02 DD03 EE02 EE09 EE18 GG27 HH11 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mutsugu Kawaguchi 1 Higashi Hatsushima-cho, Amagasaki City, Hyogo Prefecture Inside the MEC Corporation (72) Inventor Masaya Ido 1 Higashi-Hatsushima Town, Amagasaki City, Hyogo Prefecture Inside the MEC Corporation (72) Inventor Kenji Toda 1 Higashi-Hatsushima-cho, Amagasaki-shi, Hyogo FEC term (reference) 5E343 AA12 AA15 AA17 AA22 BB24 BB54 BB55 DD33 GG02 5E346 AA12 AA15 AA32 AA35 BB01 CC32 CC33 CC57 DD02 DD03 EE18 GG02H
Claims (2)
脂と接着させることを特徴とする銅と樹脂との接着性を
向上させる方法。1. A method for improving the adhesion between copper and a resin, comprising forming a copper-tin alloy on the surface of copper and then bonding it to a resin.
された多層配線板であって、前記導電層の表面に銅スズ
合金が形成されてなる多層配線板。2. A multilayer wiring board in which a conductive layer made of copper and an insulating resin layer are laminated, wherein the copper-tin alloy is formed on the surface of the conductive layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15394699A JP2000340948A (en) | 1999-06-01 | 1999-06-01 | Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15394699A JP2000340948A (en) | 1999-06-01 | 1999-06-01 | Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000340948A true JP2000340948A (en) | 2000-12-08 |
Family
ID=15573544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15394699A Pending JP2000340948A (en) | 1999-06-01 | 1999-06-01 | Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000340948A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7029761B2 (en) | 2003-04-30 | 2006-04-18 | Mec Company Ltd. | Bonding layer for bonding resin on copper surface |
| US7156904B2 (en) | 2003-04-30 | 2007-01-02 | Mec Company Ltd. | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby |
| DE102009005691A1 (en) | 2008-02-01 | 2009-08-06 | MEC COMPANY LTD., Amagasaki | Electrically conductive layer, laminate using same and manufacturing method therefor |
| JP2011049289A (en) * | 2009-08-26 | 2011-03-10 | Kyocera Corp | Wiring board and manufacturing method thereof |
| US8314340B2 (en) | 2008-09-30 | 2012-11-20 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| EP2603064A1 (en) * | 2011-12-08 | 2013-06-12 | Atotech Deutschland GmbH | Multilayer printed circuit board manufacture |
| US8633400B2 (en) | 2008-09-30 | 2014-01-21 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| CN113170585A (en) * | 2020-06-02 | 2021-07-23 | Mec股份有限公司 | Microetching agent and method for producing wiring board |
| WO2021245964A1 (en) * | 2020-06-02 | 2021-12-09 | メック株式会社 | Microetching agent and method for producing wiring board |
-
1999
- 1999-06-01 JP JP15394699A patent/JP2000340948A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7156904B2 (en) | 2003-04-30 | 2007-01-02 | Mec Company Ltd. | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby |
| CN100363175C (en) * | 2003-04-30 | 2008-01-23 | 美格株式会社 | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby |
| DE102004019877B4 (en) * | 2003-04-30 | 2009-06-25 | MEC Co., Ltd., Amagasaki | Adhesive layer for bonding resin to a copper surface |
| DE102004019878B4 (en) * | 2003-04-30 | 2009-09-17 | MEC Co., Ltd., Amagasaki | A method of forming an adhesive layer on a copper surface by depositing a tin alloy and a layered product formed therefrom |
| US7029761B2 (en) | 2003-04-30 | 2006-04-18 | Mec Company Ltd. | Bonding layer for bonding resin on copper surface |
| US8828554B2 (en) | 2008-02-01 | 2014-09-09 | Mec Company Ltd. | Electroconductive layer, laminate using the same, and producing processes thereof |
| DE102009005691A1 (en) | 2008-02-01 | 2009-08-06 | MEC COMPANY LTD., Amagasaki | Electrically conductive layer, laminate using same and manufacturing method therefor |
| US9038266B2 (en) | 2008-09-30 | 2015-05-26 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| US8633400B2 (en) | 2008-09-30 | 2014-01-21 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| US8661665B2 (en) | 2008-09-30 | 2014-03-04 | Ibiden Co., Ltd. | Method for manufacturing multilayer printed wiring board |
| US8314340B2 (en) | 2008-09-30 | 2012-11-20 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| JP2011049289A (en) * | 2009-08-26 | 2011-03-10 | Kyocera Corp | Wiring board and manufacturing method thereof |
| EP2603064A1 (en) * | 2011-12-08 | 2013-06-12 | Atotech Deutschland GmbH | Multilayer printed circuit board manufacture |
| CN113170585A (en) * | 2020-06-02 | 2021-07-23 | Mec股份有限公司 | Microetching agent and method for producing wiring board |
| WO2021245964A1 (en) * | 2020-06-02 | 2021-12-09 | メック株式会社 | Microetching agent and method for producing wiring board |
| JP2021188100A (en) * | 2020-06-02 | 2021-12-13 | メック株式会社 | Microetching agent and method for manufacturing wiring board |
| KR20210151835A (en) * | 2020-06-02 | 2021-12-14 | 멕크 가부시키가이샤 | Method for manufacturing micro etchant and wiring board |
| KR102404620B1 (en) | 2020-06-02 | 2022-06-15 | 멕크 가부시키가이샤 | Method for manufacturing micro etchant and wiring board |
| CN113170585B (en) * | 2020-06-02 | 2023-04-04 | Mec股份有限公司 | Microetching agent and method for producing wiring board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3990926A (en) | Method for the production of material for printed circuits | |
| JP5392732B2 (en) | Copper surface-to-resin adhesive layer, wiring board, and adhesive layer forming method | |
| US10244635B2 (en) | Production method for copper-clad laminate plate | |
| US3936548A (en) | Method for the production of material for printed circuits and material for printed circuits | |
| TWI808183B (en) | Coarse treatment of copper foil, copper-clad laminates and printed wiring boards | |
| KR20120135197A (en) | Surface-treated copper foil, method for producing same and copper clad laminated board | |
| EP1194021A2 (en) | Method of producing multilayer printed wiring board and multilayer printed wiring board | |
| JP4865381B2 (en) | Film metal laminate, method for producing the same, circuit board using the film metal laminate, and method for producing the circuit board | |
| JP2000340948A (en) | Method of improving adhesion between copper and resin, and multilayered wiring board manufactured using the same | |
| US7156904B2 (en) | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby | |
| JPWO2019188837A1 (en) | Manufacturing method of surface-treated copper foil, copper-clad laminate, and printed wiring board | |
| JPH11214846A (en) | Multilayer printed wiring board | |
| JP2755058B2 (en) | Metal foil for printed wiring board, method of manufacturing the same, and method of manufacturing wiring board using the metal foil | |
| JP4572363B2 (en) | Adhesive layer forming liquid between copper and resin for wiring board and method for producing adhesive layer between copper and resin for wiring board using the liquid | |
| JP2004349693A (en) | Resin adhesive layer on surface of copper | |
| JPWO2017150043A1 (en) | Method for producing copper clad laminate | |
| JP3373406B2 (en) | Printed wiring board and method of manufacturing the same | |
| JP2010080702A (en) | Multilayer printed wiring board | |
| CN111757607A (en) | Surface-treated copper foil, copper-clad laminate, and printed wiring board | |
| JPH0573359B2 (en) | ||
| JP4734875B2 (en) | Insulator for additive plating, substrate with additive plating metal film | |
| TWI853007B (en) | Metal foil for printed wiring board, carrier metal foil and metal-clad laminate, and method for producing printed wiring board using the same | |
| JPH09321443A (en) | Manufacture of multilayer board | |
| JP2003115663A (en) | Multilayer printed wiring board | |
| JP2000049440A (en) | Manufacture of printed wiring multilayer board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060327 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20060425 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20071129 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081001 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081112 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20090331 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090722 |