JPH07138794A - Copper foil having zinc-silica multiple coating film and its production - Google Patents
Copper foil having zinc-silica multiple coating film and its productionInfo
- Publication number
- JPH07138794A JPH07138794A JP30325793A JP30325793A JPH07138794A JP H07138794 A JPH07138794 A JP H07138794A JP 30325793 A JP30325793 A JP 30325793A JP 30325793 A JP30325793 A JP 30325793A JP H07138794 A JPH07138794 A JP H07138794A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- copper foil
- silica
- silica composite
- silane coupling
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、亜鉛−シリカ複合被膜
を具備する銅箔及びその製造方法に関するものであり、
特には粗化面の樹脂との接着性を改善した銅箔及びその
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper foil having a zinc-silica composite coating and a method for producing the same.
In particular, the present invention relates to a copper foil having improved adhesion of a roughened surface to a resin and a method for producing the same.
【０００２】[0002]
【従来の技術】プリント回路用の銅張積層板は銅箔を紙
−フェノール樹脂含浸基材やガラス−エポキシ樹脂含浸
基材等に加熱、加圧して積層して形成され、これをエッ
チングして回路網を形成し、これに半導体装置等の素子
を搭載することにより電子機器用のボードが作られるた
め、銅箔には各種の性能が要求される。たとえば、通常
Ｍ面（粗化面、以下同様）と呼称されている基材と接着
される側には主として基材との接着性、耐薬品性等が要
求され、又Ｍ面の反対側の通常Ｓ面（光沢面、以下同
様）と呼称されている側には主として耐熱性、耐湿性等
が要求されている。又これらＭ面及びＳ面の両面には保
管時に銅箔の酸化変色のないことも要求されている。こ
れらの要求を満たすために、銅箔のＭ面には黄銅層形成
処理（特公昭５１−３５７１１号公報、同５４−６７０
１号公報）、Ｍ，Ｓ双方の面にはクロメート処理、亜鉛
または酸化亜鉛とクロム酸化物とからなる亜鉛−クロム
基混合物被覆処理等（特公昭５８−７０７７号公報）が
行われている。A copper clad laminate for a printed circuit is formed by laminating a copper foil on a paper-phenol resin-impregnated base material or glass-epoxy resin-impregnated base material by heating and pressurizing it. Since a board for electronic equipment is made by forming a circuit network and mounting an element such as a semiconductor device on the circuit network, various performances are required for the copper foil. For example, the side that is usually called the M surface (roughened surface, the same applies below) is mainly required to have adhesiveness with the base material, chemical resistance, etc. Usually, heat resistance, moisture resistance, etc. are required for the side which is usually called the S surface (glossy surface, hereinafter the same). It is also required that the copper foil on both the M-side and the S-side does not undergo oxidative discoloration during storage. In order to meet these requirements, a brass layer forming treatment is performed on the M surface of the copper foil (Japanese Patent Publication Nos. 51-35711 and 54-670).
No. 1), M and S surfaces are subjected to chromate treatment, zinc-chromium group mixture coating treatment comprising zinc or zinc oxide and chromium oxide (Japanese Patent Publication No. 58-7077).
【０００３】ところで、近年プリント配線板の回路の微
細化への要請がますます増大化しているが、これに伴う
エッチング精度の向上に対応するためＭ面にはさらに低
い表面粗さ（ロー・プロファイル）も求められている。
しかし、Ｍ面の表面粗さは一方では基材との接着にあた
ってのアンカー効果をもたらしているので、Ｍ面に対す
るこのロー・プロファイルの要求と接着力の向上とは二
律背反の関係にあり、ロー・プロファイル化によるアン
カー効果の低減分は別の手段による接着力の向上で補償
することが必要である。By the way, in recent years, there is an increasing demand for miniaturization of circuits of printed wiring boards, but in order to cope with the improvement of etching accuracy accompanying this, the M surface has a lower surface roughness (low profile). ) Is also required.
On the other hand, the surface roughness of the M-side, on the other hand, brings about an anchoring effect in bonding with the base material. Therefore, there is a trade-off between the requirement of this low profile and the improvement of the adhesive strength for the M-side. The reduction of the anchor effect due to profiling needs to be compensated by the improvement of the adhesive force by another means.
【０００４】また接着力の増強手段としてあるいは前記
したロー・プロファイル化に伴う接着力の増強手段とし
てＭ面にシランカップリング剤を塗布する方法も提案さ
れている（特公平２−１９９９４号公報、特開昭６３−
１８３１７８号公報、特開平２−２６０９７号公報）。A method of applying a silane coupling agent to the M surface has also been proposed as a means for increasing the adhesive force or as a means for increasing the adhesive force associated with the above-mentioned low profile (Japanese Patent Publication No. 2-19994). JP 63-
183178, and JP-A-2-26097).
【０００５】[0005]
【発明が解決しようとする課題】しかしながらシランカ
ップリング剤が加水分解して生成したシラノール基はガ
ラス、シリカ等の表面に対して特異的に強い親和性、反
応性を示すが、反面表面に水酸基をあまり持たない銅箔
及びそれらを表面処理したもの等に対しては、効果を示
しにくい。本発明の課題は、樹脂基材と直接の或いはシ
ランカップリング剤を介しての接着性に優れた銅箔およ
びその製造方法を開発することにある。However, the silanol group formed by hydrolysis of the silane coupling agent shows a strong affinity and reactivity specifically for the surface of glass, silica, etc. The effect is unlikely to be exhibited on copper foils that do not have much, and those whose surface is treated. An object of the present invention is to develop a copper foil having excellent adhesiveness to a resin base material directly or via a silane coupling agent, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者は、鋭意研究を
進めた結果、銅箔の表面上に陰極電解処理によって亜鉛
−シリカ複合めっき被膜を形成し、次いで所望ならシラ
ンカップリング処理を施せば、樹脂基材との接着性を向
上させ得ることを見い出した。この知見に基づいて、本
発明は、（１）銅箔の少なくとも粗化面に亜鉛中にシリ
カが共析・分散した亜鉛−シリカ複合被膜を具備するこ
とを特徴とする銅箔及び（２）前記亜鉛−シリカ複合被
膜上にシランカップリング剤塗布層を有することを特徴
とする上記（１）の銅箔並びに（３）亜鉛塩及び／又は
酸化亜鉛とシリカ粒子を含むめっき液を用いて電気めっ
きを行うことにより、銅箔の少なくとも粗化面に亜鉛−
シリカ複合被膜を共析させることを特徴とする銅箔の製
造方法を提供するものである。本発明において、「亜鉛
−シリカ複合被膜」とは、亜鉛及び／又は酸化亜鉛中に
シリカが共析・分散した被膜を云う。Means for Solving the Problems As a result of intensive studies, the present inventor has formed a zinc-silica composite plating film on the surface of a copper foil by cathodic electrolytic treatment, and then, if desired, silane coupling treatment. It has been found that the adhesiveness with a resin base material can be improved. Based on this finding, the present invention provides (1) a copper foil having a zinc-silica composite coating in which silica is co-deposited and dispersed in zinc on at least a roughened surface of the copper foil, and (2) A zinc-silica composite coating film is provided with a silane coupling agent coating layer, and (3) a copper foil and (3) a zinc salt and / or a plating solution containing zinc oxide and silica particles for electrical By plating, at least the roughened surface of the copper foil is zinc-
The present invention provides a method for producing a copper foil, which comprises depositing a silica composite coating. In the present invention, the “zinc-silica composite coating” means a coating in which silica is co-deposited and dispersed in zinc and / or zinc oxide.
【０００７】鉄鋼材料において、耐食性の向上、塗膜の
接着性向上等を目的として亜鉛とシリカとを含有する被
覆層を形成することは行われているが（例えば特公平５
−５９１１号）、印刷回路用銅箔を対象として樹脂基材
との接着性の改善を目的としてこうした処理が試みられ
たことはない。In iron and steel materials, it has been practiced to form a coating layer containing zinc and silica for the purpose of improving corrosion resistance, improving adhesion of a coating film, etc. (for example, Japanese Patent Publication No.
No. 5911), no such treatment has been attempted for the purpose of improving the adhesiveness to a resin substrate for a copper foil for a printed circuit.
【０００８】[0008]
【作用】本発明においては、亜鉛塩及び／又は酸化亜鉛
とシリカ粒子を含むめっき液を用いて電気めっきを行う
ことにより、銅箔の少なくとも粗化面に亜鉛−シリカ複
合被膜が共析により形成される。この亜鉛−シリカ複合
めっき被膜形成用の電気めっき浴は、硫酸浴、塩化浴等
の公知の酸性浴を用いることができる。例えば次の組成
を有する硫酸亜鉛電気めっき浴： 硫酸亜鉛（ZnSO4・7H2O）：５０〜５００ｇ／ｌ 電導度補助剤：１０〜５０ｇ／ｌ ｐＨ緩衝剤 ： ５〜５０ｇ／ｌ ｐＨ ：１〜５．６ を基本浴として、この基本浴にシリカ粒子を添加するこ
とにより調製される。この他、必要に応じて、共析率向
上剤、錯化剤、界面活性剤等を添加することができる。
めっき時の電流密度は１〜２０Ａ／ｄｍ2 の範囲であ
る。In the present invention, electroplating is performed using a plating solution containing zinc salt and / or zinc oxide and silica particles, whereby a zinc-silica composite coating film is formed by co-deposition on at least the roughened surface of the copper foil. To be done. As the electroplating bath for forming the zinc-silica composite plating film, a known acidic bath such as a sulfuric acid bath or a chloride bath can be used. For example, a zinc sulfate electroplating bath having the following composition: Zinc sulfate (ZnSO 4 .7H 2 O): 50 to 500 g / l Conductivity auxiliary agent: 10 to 50 g / l pH buffering agent: 5 to 50 g / l pH: 1 It is prepared by adding .about.5.6 to a basic bath and adding silica particles to the basic bath. In addition to this, if necessary, a eutectoid rate improving agent, a complexing agent, a surfactant, etc. can be added.
The current density during plating is in the range of 1 to 20 A / dm 2 .
【０００９】ｐＨを１〜５．６の範囲と規定したのは、
１未満では共析率が低くなり、他方５．６を超えると電
流効率が低下しそしてめっき浴の安定性が低下するため
である。２．５〜４．５のｐＨ範囲が好ましい。The pH is defined in the range of 1 to 5.6 as follows.
If it is less than 1, the eutectoid ratio will be low, while if it exceeds 5.6, the current efficiency will be lowered and the stability of the plating bath will be lowered. A pH range of 2.5-4.5 is preferred.
【００１０】電導度補助剤は、Na2SO4、(NH4)2SO4 、NH
4Cl 等に代表されるものであり、１０〜５０ｇ／ｌの濃
度で添加される。１０ｇ／ｌ未満では電導度の向上効果
が低く、他方５０ｇ／ｌを超えると効果が飽和し、経済
的でない。The conductivity auxiliary agent is Na 2 SO 4 , (NH 4 ) 2 SO 4 , NH
It is typified by 4 Cl and is added at a concentration of 10 to 50 g / l. If it is less than 10 g / l, the effect of improving the electric conductivity is low, while if it exceeds 50 g / l, the effect is saturated, which is not economical.
【００１１】ｐＨ緩衝剤は、CH3COONa、H3BO4 等に代表
されるものであり、その濃度範囲は５〜５０ｇ／ｌとさ
れる。５ｇ／ｌ未満では緩衝効果が薄く、他方５０ｇ／
ｌを超えると効果が飽和し、経済的でない。The pH buffer agent is represented by CH 3 COONa, H 3 BO 4, etc., and its concentration range is 5 to 50 g / l. If it is less than 5 g / l, the buffering effect is weak, while on the other hand 50 g / l
If it exceeds 1, the effect is saturated and it is not economical.
【００１２】共析率向上剤は、亜鉛−シリカの共析を向
上させるために添加されるものであり、例えば、NO3 -イ
オン、NaNO3 、KNO3、Zn(NO3)2を挙げることができる。
その濃度範囲は、０．０１〜２０ｇ／ｌ、好ましくは
０．１〜１ｇ／ｌとされる。０．０１ｇ／ｌ未満ではシ
リカ共析率が低く、他方２０ｇ／ｌを超えるとシリカ共
析率が高くなり過ぎ、均一なめっき層とならない。[0012] Co-析率improvers zinc - are those which are added to improve the eutectoid silica, for example, NO 3 - ions, NaNO 3, KNO 3, Zn (NO 3) 2 and the like to You can
The concentration range is 0.01 to 20 g / l, preferably 0.1 to 1 g / l. If it is less than 0.01 g / l, the silica eutectoid ratio is low, while if it exceeds 20 g / l, the silica eutectoid ratio is too high, and a uniform plating layer is not formed.
【００１３】錯化剤は、０．００１〜１０モル／ｌの範
囲で添加される。０．００１モル／ｌ未満ではめっき浴
のｐＨを適切に制御できず、他方１０モル／ｌを超える
と電流効率が低下し、めっき焼けが発生し、品質が劣化
する。この他、界面活性剤も適量添加されうる。The complexing agent is added in the range of 0.001 to 10 mol / l. If it is less than 0.001 mol / l, the pH of the plating bath cannot be properly controlled, while if it exceeds 10 mol / l, the current efficiency decreases, plating burn occurs, and the quality deteriorates. In addition, a surfactant may be added in an appropriate amount.
【００１４】上記した亜鉛−シリカ複合めっき用電気め
っき浴を調製する際において、電気めっき液中に含有さ
せるシリカ粒子の粒径は、１００ｎｍ以下、好ましくは
５０ｎｍ以下、更に好ましくは２０ｎｍ以下であれば亜
鉛−シリカ複合めっきが可能であるが、特にめっき液の
取扱い易さの点から１０〜２０ｎｍのコロイダルシリカ
が好適である。また、めっき液中のシリカの添加量は一
般に０．１〜１００ｇ／ｌの範囲とされる。シリカ量が
０．１ｇ／ｌ未満では、共析率が低く、ピール強度の向
上に効果がない。１００ｇ／ｌを超えると、共析率は高
くなるが、電流効率が低下する。また、めっき液の粘度
が高くなり、めっき液の攪拌が困難となる。When the above-mentioned electroplating bath for zinc-silica composite plating is prepared, the particle size of the silica particles contained in the electroplating solution is 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less. Zinc-silica composite plating is possible, but colloidal silica of 10 to 20 nm is particularly preferable from the viewpoint of easy handling of the plating solution. The amount of silica added to the plating solution is generally in the range of 0.1 to 100 g / l. When the amount of silica is less than 0.1 g / l, the eutectoid ratio is low and the peel strength is not improved. When it exceeds 100 g / l, the eutectoid ratio increases, but the current efficiency decreases. Further, the viscosity of the plating solution becomes high, and it becomes difficult to stir the plating solution.
【００１５】皮膜の厚さは、電流密度、電解時間等の増
加に伴い、厚くなるが、一般的に１〜２０ｍｇ／ｄｍ2
範囲の被覆量が要求される。１ｍｇ／ｄｍ2 未満では均
一なシリカ被膜を形成できず、他方２０ｍｇ／ｄｍ2 を
超えると銅箔の機械的特性に悪影響を及ぼす恐れがあ
る。The thickness of the film becomes thicker as the current density, electrolysis time, etc. increase, but it is generally 1 to 20 mg / dm 2.
A range of coverage is required. If it is less than 1 mg / dm 2 , a uniform silica coating cannot be formed, while if it exceeds 20 mg / dm 2 , the mechanical properties of the copper foil may be adversely affected.
【００１６】シリカ共析比率は、１〜２０重量％が適当
である。１重量％未満では均一なシリカ被膜を形成でき
ず、他方２０重量％を超えるとめっき層の加工性が著し
く劣化する。The silica eutectoid ratio is suitably 1 to 20% by weight. If it is less than 1% by weight, a uniform silica coating cannot be formed, while if it exceeds 20% by weight, the workability of the plating layer is significantly deteriorated.
【００１７】本発明においては、所望なら、形成された
亜鉛−シリカ複合めっき被膜上にシランカップリング剤
が塗布されうる。シランカップリング剤は、一般式：Ｙ
ＲＳｉＸ3 （ここで、Ｙ＝高分子物質と反応する官能
基、Ｒ＝ＹとＳｉとを結合する炭化水素を含む結合基、
そしてＸ＝Ｓｉに結合する加水分解性基）で表わされる
ものであり、代表的にはγ−アミノプロピルトリエトキ
シシラン、Ｎ−２−アミノエチル−３−アミノプロピル
トリメトキシシラン、γ−クロロプロピルトリメトキシ
シラン、γ−グリシドキシプロピルトリメトキシシラ
ン、ビニルトリス（β−メトキシエトキシ）シラン、γ
−メタクリロキシプロピルトリメトキシシラン、β−
（３，４−エポキシ・シクロヘキシル）エチルトリメト
キシシラン等が挙げられる。シランカップリング剤の種
類は、積層する樹脂基材の種類や剥離強度等必要特性の
程度に応じて適宜選択される。In the present invention, if desired, a silane coupling agent may be applied on the formed zinc-silica composite plating film. The silane coupling agent has the general formula: Y
RSiX 3 (where Y = a functional group that reacts with a polymeric substance, R = a bonding group containing a hydrocarbon that bonds Y and Si,
X = hydrolyzable group bonded to Si), and typically γ-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, γ-chloropropyl. Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-Methacryloxypropyltrimethoxysilane, β-
(3,4-epoxy cyclohexyl) ethyltrimethoxysilane and the like can be mentioned. The type of silane coupling agent is appropriately selected according to the type of resin base material to be laminated and the degree of required properties such as peel strength.
【００１８】また、シランカップリング剤を亜鉛−シリ
カ複合めっき被膜上に塗布する方法としては、そのまま
塗布してもよいが、水、メタノール、エタノール等のア
ルコール類、更には、アセトン、酢酸エチル、トルエン
等の溶剤で０．００１〜２０重量％になるように希釈
し、浸漬またはスプレーによる吹き付け等が簡便で好ま
しい。なお、シランカップリング剤は単独で用いてもよ
いが、複数のシランカップリング剤と混合して用いても
よい。As a method for applying the silane coupling agent onto the zinc-silica composite plating film, it may be applied as it is, but water, alcohols such as methanol and ethanol, and further acetone, ethyl acetate, Diluting with a solvent such as toluene to 0.001 to 20% by weight, and dipping or spraying with a spray are simple and preferable. The silane coupling agent may be used alone, or may be used as a mixture with a plurality of silane coupling agents.
【００１９】[0019]
【実施例】回転ドラムを陰極として電気分解反応により
連続的に銅をドラム上に電着させて、３３μｍの銅箔を
製造した。次いで下記の組成からなる亜鉛電気めっき
浴： 硫酸亜鉛 ：１５０ｇ／ｌ 硫酸ナトリウム： １５ｇ／ｌ 酢酸ナトリウム： ６ｇ／ｌ ｐＨ ：５ を基本浴として、この基本浴に表１に示した粒径および
濃度のシリカ粒子を添加し、亜鉛−シリカ複合めっき用
電気めっき浴を調製した。このめっき浴を使用して、上
記銅箔に２．２Ａ／ｄｍ2 の電流密度で陰極電解処理を
施して、銅箔の表面上に亜鉛−シリカ複合めっき被膜を
作成した（実施例１〜１０）。シリカ共析率を表１に併
せて示した。EXAMPLE A copper foil having a thickness of 33 μm was produced by continuously electrodepositing copper on the drum by an electrolysis reaction using a rotating drum as a cathode. Then, a zinc electroplating bath having the following composition: zinc sulfate: 150 g / l sodium sulfate: 15 g / l sodium acetate: 6 g / l pH: 5 as a basic bath, and the particle size and concentration shown in Table 1 in this basic bath. Silica particles were added to prepare an electroplating bath for zinc-silica composite plating. Using this plating bath, the copper foil was subjected to cathodic electrolysis at a current density of 2.2 A / dm 2 to form a zinc-silica composite plating film on the surface of the copper foil (Examples 1 to 10). ). The silica eutectoid rate is also shown in Table 1.
【００２０】これら作成した亜鉛−シリカ複合めっき被
膜を有する銅箔をガラス繊維クロスにエポキシ樹脂を含
浸させた基材に接着し、ＪＩＳ Ｃ ６４８１に規定す
る方法により常態ピール強度を測定した。比較のため、
亜鉛めっきのみを施した銅箔及び未処理の銅箔について
も同様の方法で接着性を試験した。これらの結果も表１
に併せて示した（比較例１及び２）。The copper foil having the zinc-silica composite plating film thus prepared was adhered to a base material in which glass fiber cloth was impregnated with an epoxy resin, and the normal peel strength was measured by the method specified in JIS C6481. For comparison,
Adhesiveness was tested by the same method for a copper foil which was only galvanized and an untreated copper foil. These results are also shown in Table 1.
(Comparative Examples 1 and 2).
【００２１】また実施例５〜９の亜鉛−シリカ複合めっ
き銅箔にシラン処理として０．４容積％γ−グリシドキ
シプロピルトリメトキシシラン水溶液を塗布し、余分な
液を落とした後１００℃の乾燥器中で５分間乾燥した。
これらシラン処理した亜鉛−シリカ複合めっき銅箔を上
記と同様の方法で接着性を試験した。この結果を表２に
示した（実施例１１〜１５とする）。また比較のため、
亜鉛めっきのみを施した銅箔及び未処理の銅箔について
も同様なシランカップリング剤処理を行ない、接着性を
試験した。これらの結果も表２に併せて示した（比較例
３及び４）。Further, 0.4% by volume of γ-glycidoxypropyltrimethoxysilane aqueous solution was applied as a silane treatment to the zinc-silica composite plated copper foils of Examples 5 to 9 to remove excess liquid, and then 100 ° C. It was dried in a dryer for 5 minutes.
These silane-treated zinc-silica composite plated copper foils were tested for adhesion in the same manner as above. The results are shown in Table 2 (Examples 11 to 15). For comparison,
The same silane coupling agent treatment was carried out on the copper foil which was only galvanized and the untreated copper foil, and the adhesion was tested. These results are also shown in Table 2 (Comparative Examples 3 and 4).
【００２２】さらに実施例７の亜鉛−シリカ複合めっき
銅箔およびその銅箔に２．０ｖｏｌ％γ−グリシドキシ
プロピルトリメトキシシラン水溶液処理した銅箔をガラ
スクロス基材エポキシ樹脂板に積層接着し、沸とう水に
２時間浸漬後のピール強度を０．２ｍｍ巾の回路で測定
し、沸とう水浸漬前後の劣化率（％）を求めた。この結
果を実施例１６及び１７としてそれぞれ表３に示した。
また比較のため、亜鉛めっき銅箔及びそのシラン処理銅
箔について同様の評価を行なった。この結果も表３に併
せて示した（比較例５及び６）。Furthermore, the zinc-silica composite plated copper foil of Example 7 and the copper foil treated with 2.0 vol% γ-glycidoxypropyltrimethoxysilane aqueous solution were laminated and adhered to a glass cloth base epoxy resin plate. The peel strength after immersion in boiling water for 2 hours was measured with a circuit having a width of 0.2 mm to determine the deterioration rate (%) before and after immersion in boiling water. The results are shown in Table 3 as Examples 16 and 17, respectively.
For comparison, the same evaluation was performed on the galvanized copper foil and its silane-treated copper foil. The results are also shown in Table 3 (Comparative Examples 5 and 6).
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】これらの結果を表４に整理してまとめて示
す。The results are summarized in Table 4 and summarized.
【００２７】[0027]
【表４】 [Table 4]
【００２８】以上の結果から、本発明の亜鉛−シリカ複
合めっき銅箔は常態ピール強度および沸とう水に浸漬後
のピール強度に優れていることが確認された。また、シ
ランカップリング剤を処理することにより、これら強度
が一層改善されることが確認された。From the above results, it was confirmed that the zinc-silica composite plated copper foil of the present invention is excellent in normal state peel strength and peel strength after immersion in boiling water. In addition, it was confirmed that these strengths were further improved by treating with a silane coupling agent.
【００２９】[0029]
【発明の効果】樹脂基材と直接或いはシランカップリン
グ剤を介しての接着性に優れた銅箔を提供する。The present invention provides a copper foil having excellent adhesiveness with a resin substrate directly or through a silane coupling agent.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１月１４日[Submission date] January 14, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】 ｐＨを１〜５．６の範囲と規定したの
は、１未満では共析率が低くなり、他方５．６を超える
と電流効率が低下しそしてめっき浴の安定性が低下する
ためである。２．５〜５．０のｐＨ範囲が好ましい。The pH is defined to be in the range of 1 to 5.6 because when it is less than 1, the eutectoid ratio is low, and when it exceeds 5.6, the current efficiency is lowered and the stability of the plating bath is lowered. Is. A pH range of 2.5 to 5.0 is preferred.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２１】 また実施例５〜９の亜鉛−シリカ複合め
っき銅箔にシラン処理として０．４ｖｏｌ％γ−グリシ
ドキシプロピルトリメトキシシラン水溶液を塗布し、余
分な液を落とした後１００℃の乾燥器中で５分間乾燥し
た。これらシラン処理した亜鉛−シリカ複合めっき銅箔
を上記と同様の方法で接着性を試験した。この結果を表
２に示した（実施例１１〜１５とする）。また比較のた
め、亜鉛めっきのみを施した銅箔及び未処理の銅箔につ
いても同様なシランカップリング剤処理を行ない、接着
性を試験した。これらの結果も表２に併せて示した（比
較例３及び４）。Further, a 0.4 vol% γ-glycidoxypropyltrimethoxysilane aqueous solution was applied as a silane treatment to the zinc-silica composite plated copper foils of Examples 5 to 9 to remove excess liquid, and then dried at 100 ° C. Dry in the oven for 5 minutes. These silane-treated zinc-silica composite plated copper foils were tested for adhesion in the same manner as above. The results are shown in Table 2 (Examples 11 to 15). Further, for comparison, the same silane coupling agent treatment was performed on the copper foil only plated with zinc and the untreated copper foil, and the adhesion was tested. These results are also shown in Table 2 (Comparative Examples 3 and 4).
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Name of item to be corrected] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２２】 さらに実施例７の亜鉛−シリカ複合めっ
き銅箔およびその銅箔に２．０ｖｏｌ％γ−グリシドキ
シプロピルトリメトキシシラン水溶液処理した銅箔をガ
ラスクロス基材エポキシ樹脂板に積層接着し、沸とう水
に２時間浸漬後のピール強度を０．２ｍｍ巾１０本の回
路で測定し、沸とう水浸漬前後の劣化率（％）を求め
た。この結果を実施例１６及び１７としてそれぞれ表３
に示した。また比較のため、亜鉛めっき銅箔及びそのシ
ラン処理銅箔について同様の評価を行なった。この結果
も表３に併せて示した（比較例５及び６）。Further, the zinc-silica composite plated copper foil of Example 7 and the copper foil treated with a 2.0 vol% γ-glycidoxypropyltrimethoxysilane aqueous solution were laminated and adhered to a glass cloth base epoxy resin plate. The peel strength after immersion in boiling water for 2 hours was measured with a circuit having a width of 0.2 mm and 10 pieces to determine the deterioration rate (%) before and after the immersion in boiling water. The results are shown in Table 3 as Examples 16 and 17, respectively.
It was shown to. For comparison, the same evaluation was performed on the galvanized copper foil and its silane-treated copper foil. The results are also shown in Table 3 (Comparative Examples 5 and 6).
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２７[Name of item to be corrected] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２７】[0027]
【表４】 [Table 4]
Claims (3)
カが共析・分散した亜鉛−シリカ複合被膜を具備するこ
とを特徴とする銅箔。1. A copper foil comprising a zinc-silica composite coating in which silica is co-deposited and dispersed in zinc on at least a roughened surface of the copper foil.
ップリング剤塗布層を有することを特徴とする請求項１
の銅箔。2. A silane coupling agent coating layer is provided on the zinc-silica composite coating film.
Copper foil.
を含むめっき液を用いて電気めっきを行うことにより、
銅箔の少なくとも粗化面に亜鉛−シリカ複合被膜を共析
させることを特徴とする銅箔の製造方法。3. Electroplating using a plating solution containing a zinc salt and / or zinc oxide and silica particles,
A method for producing a copper foil, which comprises depositing a zinc-silica composite coating on at least a roughened surface of the copper foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30325793A JPH07138794A (en) | 1993-11-10 | 1993-11-10 | Copper foil having zinc-silica multiple coating film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30325793A JPH07138794A (en) | 1993-11-10 | 1993-11-10 | Copper foil having zinc-silica multiple coating film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07138794A true JPH07138794A (en) | 1995-05-30 |
Family
ID=17918780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30325793A Pending JPH07138794A (en) | 1993-11-10 | 1993-11-10 | Copper foil having zinc-silica multiple coating film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07138794A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004107833A1 (en) * | 2003-05-29 | 2004-12-09 | Iljin Copper Foil Co., Ltd. | Method for manufacturing copper foilfor printed circuit board |
| JP2010180454A (en) * | 2009-02-05 | 2010-08-19 | Hitachi Cable Ltd | Surface-treated copper foil, method for manufacturing the same and copper-clad laminate |
-
1993
- 1993-11-10 JP JP30325793A patent/JPH07138794A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004107833A1 (en) * | 2003-05-29 | 2004-12-09 | Iljin Copper Foil Co., Ltd. | Method for manufacturing copper foilfor printed circuit board |
| JP2010180454A (en) * | 2009-02-05 | 2010-08-19 | Hitachi Cable Ltd | Surface-treated copper foil, method for manufacturing the same and copper-clad laminate |
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