JP3067672B2 - Copper foil for printed wiring board and method for producing the same - Google Patents
Copper foil for printed wiring board and method for producing the sameInfo
- Publication number
- JP3067672B2 JP3067672B2 JP9029364A JP2936497A JP3067672B2 JP 3067672 B2 JP3067672 B2 JP 3067672B2 JP 9029364 A JP9029364 A JP 9029364A JP 2936497 A JP2936497 A JP 2936497A JP 3067672 B2 JP3067672 B2 JP 3067672B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- copper foil
- printed wiring
- mixture
- wiring board
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はプリント配線板用銅
箔及びその製造方法に関する。更に詳しくは、銅張積層
板とした後、銅箔と樹脂基材間の引き剥し強さに優れる
とともに、耐湿性（ＰＣＴ後劣化率）に優れるプリント
配線板用銅箔及びその製造方法に関する。The present invention relates to a copper foil for a printed wiring board and a method for producing the same. More specifically, the present invention relates to a copper foil for a printed wiring board having excellent peeling strength between a copper foil and a resin substrate after being formed into a copper-clad laminate, and also having excellent moisture resistance (deterioration rate after PCT) and a method for producing the same.
【０００２】[0002]
【従来の技術】プリント配線板は、それに組み込まれる
電子部品等の小型化、高性能化、高信頼性化に伴い、急
速な技術的進歩を遂げている。そのような中でプリント
配線板の構成材料となる銅箔に要求される性能も厳しさ
を増している。2. Description of the Related Art Printed wiring boards have made rapid technological progress with the miniaturization, high performance, and high reliability of electronic components incorporated therein. In such a situation, the performance required for the copper foil as a constituent material of the printed wiring board is becoming more severe.
【０００３】この要求性能の代表的なものとして銅箔と
樹脂基材間の引き剥し強さがある。この引き剥し強さ
は、プリント配線板を作製する過程で、熱処理工程、酸
やアルカリなどの液に接触させる工程など、いくつかの
異質な工程を通過することから、これらの工程を経た後
でも初期時の引き剥し強さを保持することが重要とな
る。A typical example of the required performance is the peel strength between the copper foil and the resin substrate. This peeling strength, in the process of manufacturing a printed wiring board, through a number of different steps, such as a heat treatment step, a step of contacting with a liquid such as acid or alkali, even after passing through these steps It is important to maintain the initial peel strength.
【０００４】そこで、一般に樹脂基材と積層する銅箔面
（被接着面）は、例えば予め酸性銅めっき浴等を使用し
て粗化処理が施されている。これにより銅箔と樹脂基材
間の引き剥し強さが物理的に高められる。また、熱処理
工程等に耐久性を持たせるために、引き続き防錆層を含
めた各種の表面処理層が設けられている。Therefore, a copper foil surface (adhered surface) to be laminated with a resin substrate is generally subjected to a roughening treatment using, for example, an acidic copper plating bath in advance. This physically increases the peel strength between the copper foil and the resin substrate. Further, various surface treatment layers including a rust-preventive layer are continuously provided in order to impart durability to the heat treatment step and the like.
【０００５】粗化処理に引き続いて実施される前記の表
面処理層の形成は、一般にＣｒ、Ｚｎ、Ｓｎ、Ｎｉ、Ｍ
ｏ、Ｃｏ、Ｉｎ、Ｃｕなどの金属から選ばれる１種以上
の金属をイオン源とする水溶液を使用して浸漬処理又は
電解処理により、各種の金属層、合金層、酸化物層、水
酸化物層を少なくとも一層以上形成することが行われて
いる。[0005] The formation of the above-mentioned surface treatment layer, which is carried out subsequent to the roughening treatment, is generally carried out by using Cr, Zn, Sn, Ni, M
Various metal layers, alloy layers, oxide layers, and hydroxides by immersion or electrolytic treatment using an aqueous solution containing one or more metals selected from metals such as o, Co, In, and Cu as an ion source. At least one layer is formed.
【０００６】一方これらの金属を主体とする形成層の他
に有機系の表面処理層、例えば、ベンゾトリアゾール、
イミダゾール、シランカップリング剤等による表面処理
層を設けることも知られている。On the other hand, in addition to the formation layer mainly composed of these metals, an organic surface treatment layer such as benzotriazole,
It is also known to provide a surface treatment layer using imidazole, a silane coupling agent, or the like.
【０００７】そこで、要求特性に応じて粗化処理を施し
た後に、前記の金属系形成層と有機系表面処理層を組み
合わせて形成することにより、耐熱性、耐化学薬品性な
どの特性を向上させることも行われている。Therefore, after performing a roughening treatment in accordance with required characteristics, by forming the above-mentioned metal-based forming layer and an organic-based surface treatment layer in combination, characteristics such as heat resistance and chemical resistance are improved. It is also performed.
【０００８】しかしながら、近年、銅箔回路幅やその回
路間隙は狭小化傾向が著しく、更に優れた性能と高信頼
性が要求され、前記する耐熱性、耐薬品性に加えて、耐
湿性に優れた銅箔が要求されるようになってきている。However, in recent years, the copper foil circuit width and the circuit gap have been remarkably narrowed, and further excellent performance and high reliability have been demanded. In addition to the above-mentioned heat resistance and chemical resistance, they have excellent moisture resistance. Copper foil is required.
【０００９】従来の表面処理層銅箔は、常態の引き剥し
強さは改善されても、耐湿性（ＰＣＴ後の引き剥し強さ
の劣化率）については、十分な特性が得られなかった。Although the conventional surface-treated copper foil has improved peel strength under normal conditions, it has not been able to obtain sufficient moisture resistance (rate of deterioration of peel strength after PCT).
【００１０】[0010]
【発明が解決しようとする課題】本発明は、銅箔の被接
着面に樹脂基材を積層し、銅張積層板としたとき、銅箔
と樹脂基材間の引き剥し強さを高く保持すると共に、耐
湿性に優れたプリント配線板用銅箔とその好適な製造方
法を提供するものである。SUMMARY OF THE INVENTION According to the present invention, when a resin base material is laminated on a surface to be bonded of a copper foil to form a copper-clad laminate, the peel strength between the copper foil and the resin base material is kept high. In addition, the present invention provides a copper foil for a printed wiring board excellent in moisture resistance and a suitable production method thereof.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、 銅箔の被接
着面に、シランカップリング剤及びポリシロキサンから
なる混合物被覆層を設けることにより、耐湿性に優れた
プリント配線板用銅箔が得られることを見出し、この知
見に基づいて本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a mixture coating layer comprising a silane coupling agent and a polysiloxane is provided on the surface to be bonded of a copper foil. It has been found that by providing the same, a copper foil for a printed wiring board excellent in moisture resistance can be obtained, and based on this finding, the present invention has been completed.
【００１２】すなわち、本発明は銅箔の被接着面に、シ
ランカップリング剤及びポリシロキサンからなる混合物
被覆層を有することを特徴とするプリント配線板用銅箔
を提供するものである。That is, the present invention provides a copper foil for a printed wiring board, which has a mixture coating layer comprising a silane coupling agent and a polysiloxane on the surface to be bonded of the copper foil.
【００１３】本発明のプリント配線板用銅箔は、例え
ば、銅箔の被接着面に、シランカップリング剤を０．３
〜１０ｇ／ｌ及びポリシロキサンを０．０２〜１．０ｇ
／ｌの濃度で含有する混合物水溶液を塗布し、加熱乾燥
することにより製造することができる。The copper foil for a printed wiring board according to the present invention is, for example, a method in which a silane coupling agent is applied to the surface to be bonded of the copper foil in an amount of 0.3%.
10 to 10 g / l and 0.02 to 1.0 g of polysiloxane
/ L of an aqueous solution containing the mixture at a concentration of 1 / l, and drying by heating.
【００１４】[0014]
【発明の実施の形態】本発明に用いられる銅箔は電解銅
箔、圧延銅箔のいずれであってもよく、プリント配線板
の銅回路に供するものであれば特に限定されるものでは
ない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil, and is not particularly limited as long as it is used for a copper circuit of a printed wiring board.
【００１５】また、本発明に用いられる銅箔としては、
その被接着面側（銅箔の片面又は両面）、すなわち樹脂
基材層と積層接着する側の面に、例えば酸性硫酸銅めっ
き浴を使用して小球状の銅を電着させた粗化処理層を設
けたもの、更にその上にクロメート層、亜鉛層、亜鉛−
クロム合金層、銅−亜鉛合金層、インジウム−亜鉛合金
層、ニッケル−モリブデン−コバルト合金層などの金属
を主体とした防錆層を少なくとも一層以上設けたもの、
特にニッケル−モリブデン−コバルト合金層、銅−亜鉛
合金層若しくはインジウム−亜鉛合金層とクロメート層
からなる防錆層を設けたものが好ましく用いられる。こ
れらの粗化処理層、防錆層は、樹脂基材と積層し銅張積
層板としたとき、銅箔と樹脂基材間の引き剥し強さを向
上させる。[0015] The copper foil used in the present invention includes:
Roughening treatment in which small spherical copper is electrodeposited on the surface to be bonded (one or both surfaces of the copper foil), that is, the surface to be laminated and bonded to the resin base material layer using, for example, an acidic copper sulfate plating bath. Provided with a layer, a chromate layer, a zinc layer, a zinc layer
Chromium alloy layer, copper-zinc alloy layer, indium-zinc alloy layer, nickel-molybdenum-cobalt alloy layer provided with at least one or more rust prevention layer mainly composed of metal,
In particular, a layer provided with a rust preventive layer composed of a nickel-molybdenum-cobalt alloy layer, a copper-zinc alloy layer or an indium-zinc alloy layer and a chromate layer is preferably used. The roughening layer and the rust-preventing layer improve the peeling strength between the copper foil and the resin substrate when laminated with the resin substrate to form a copper-clad laminate.
【００１６】銅箔の厚さは、特に限定されないが、通常
９〜７０μｍのものが用いられる。The thickness of the copper foil is not particularly limited, but is usually 9 to 70 μm.
【００１７】本発明によれば、必要に応じ、粗化処理層
又は防錆層が形成された銅箔の被接着面にシランカップ
リング剤を０．３〜１０ｇ／ｌ及びポリシロキサンを
０．０２〜１．０ｇ／ｌの濃度で含有する混合物水溶液
を塗布し、加熱乾燥することにより混合物被覆層を形成
する。この混合物被覆層の厚さは、混合物水溶液に含ま
れる各薬剤濃度、塗布量により変動するが、１０〜１０
０オングストロームとすることが好ましい。混合物被覆
層の厚さがこの範囲外であると耐湿性が低下する傾向に
ある。According to the present invention, 0.3 to 10 g / l of a silane coupling agent and 0.1 to 0.1 g of a polysiloxane are added to the surface of the copper foil on which the roughening layer or the rust-preventive layer is formed, if necessary. A mixture aqueous solution containing a concentration of 02 to 1.0 g / l is applied, and heated and dried to form a mixture coating layer. The thickness of the mixture coating layer varies depending on the concentration and application amount of each drug contained in the mixture aqueous solution,
Preferably, the thickness is 0 Å. If the thickness of the mixture coating layer is out of this range, the moisture resistance tends to decrease.
【００１８】混合物水溶液に含有されるシランカップリ
ング剤としては、ビニルトリメトキシシラン、ビニルト
リエトキシシラン、ビニルトリス（β−メトキシエトキ
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、γ−グリシドキシプロピル
トリメトキシシラン、γ−グリシドキシプロピルメチル
ジエトキシシラン、γ−グリシドキシプロピルトリエト
キシシラン、γ−メタクリロキシプロピルメチルジメト
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、Ｎ−β−（アミノエチル）−γ−アミノプロピ
ルトリエトキシシラン、γ−アミノプロピルトリメトキ
シシラン、Ｎ−フェニル−γ−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−メルカプトプロピルトリメトキシシラン、γ−メル
カプトプロピルメチルジメトキシシランなどが挙げら
れ、これらの１種以上を混合して用いることができる。
これらのシランカップリング剤の中では分子中にエポキ
シ基を有するエポキシシランが好ましく用いられる。Examples of the silane coupling agent contained in the aqueous mixture include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and β- (3,4-epoxycyclohexyl).
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl Trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
Examples include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane, and one or more of these can be used as a mixture.
Among these silane coupling agents, an epoxy silane having an epoxy group in a molecule is preferably used.
【００１９】シランカップリング剤は引き剥し強さを向
上させる成分であり、特にＨＣｌ浸漬処理後の引き剥し
強さの劣化を防止する効果に優れる。この混合物水溶液
に含有されるシランカップリング剤の濃度範囲は０．３
〜１０ｇ／ｌである。混合物水溶液中のシランカップリ
ング剤の濃度が０．３ｇ／ｌ未満では効果が十分に発揮
されず、１０ｇ／ｌを超える場合はその効果は飽和域に
達し薬剤コストが増大し好ましくない。濃度は好ましく
は、０．５〜８ｇ／ｌ、更に好ましくは１〜５ｇ／ｌで
ある。The silane coupling agent is a component for improving the peel strength, and is particularly excellent in the effect of preventing the deterioration of the peel strength after the HCl immersion treatment. The concentration range of the silane coupling agent contained in this mixture aqueous solution is 0.3
〜１０10 g / l. If the concentration of the silane coupling agent in the aqueous solution of the mixture is less than 0.3 g / l, the effect is not sufficiently exhibited, and if it exceeds 10 g / l, the effect reaches a saturation region and the cost of the drug increases, which is not preferable. The concentration is preferably between 0.5 and 8 g / l, more preferably between 1 and 5 g / l.
【００２０】混合物水溶液に含有されるポリシロキサン
は、シロキサン結合を有する分子量数百〜数千程度のも
ので、有機基を有せず、置換基のＯＨのＨの一部がアル
カリ金属で置換されているものである。このものは水に
分散（粒子径０．２〜１ｍμ）して溶液としたときのｐ
Ｈが１０．５〜１１．２、特に１０．８〜１１．０であ
るものが好ましく用いられる。また、溶液中のアルカリ
金属とケイ素のモル比はＭｅ2Ｏ／ＳｉＯ2（Ｍｅ：アル
カリ金属）に換算して、好ましくは０．０１〜１．０、
更に好ましくは０．１５〜０．７０とすることが好まし
い。The polysiloxane contained in the mixture aqueous solution has a molecular weight of about several hundreds to several thousands having siloxane bonds, does not have an organic group, and has a part of H of OH of a substituent substituted with an alkali metal. Is what it is. This product is dispersed in water (particle size: 0.2 to 1 μm) to form a solution,
Those in which H is from 10.5 to 11.2, particularly from 10.8 to 11.0 are preferably used. Further, the molar ratio of alkali metal to silicon in the solution is preferably 0.01 to 1.0 in terms of Me 2 O / SiO 2 (Me: alkali metal).
More preferably, it is preferably 0.15 to 0.70.
【００２１】ポリシロキサンはシランカップリング剤の
存在下で耐湿性を向上させる成分であり、特にＰＣＴ
（プレッシャークッカーテスト）後の引き剥し強さの劣
化を防止する効果に優れる。この混合物水溶液に含有さ
れるポリシロキサンの濃度範囲は０．０２〜１．０ｇ／
ｌである。混合物水溶液中のポリシロキサンの濃度が
０．０２ｇ／ｌ未満では効果が十分に発揮されず、１．
０ｇ／ｌを超える場合は混合物水溶液中に沈殿を生ずる
ことがあり、作業効率に悪影響を及ぼすことがある。濃
度は好ましくは、０．０２〜０．８ｇ／ｌ、更に好まし
くは０．０４〜０．５ｇ／ｌである。Polysiloxane is a component for improving moisture resistance in the presence of a silane coupling agent,
Excellent in preventing peel strength deterioration after (pressure cooker test). The concentration range of the polysiloxane contained in the aqueous mixture solution is 0.02 to 1.0 g /
l. If the concentration of the polysiloxane in the aqueous mixture solution is less than 0.02 g / l, the effect is not sufficiently exhibited.
If it exceeds 0 g / l, precipitation may occur in the aqueous solution of the mixture, which may adversely affect the working efficiency. The concentration is preferably between 0.02 and 0.8 g / l, more preferably between 0.04 and 0.5 g / l.
【００２２】本発明で用いられる混合物水溶液は、混合
物水溶液中の各薬剤の濃度を前記範囲内にとどめるよう
に管理し、十分に混合して使用することが好ましい。ま
た混合物水溶液はｐＨ８〜１２となるようなアルカリ域
に調整して使用することが好ましい。また混合物水溶液
は好ましくは１０〜５０℃、更に好ましくは２０〜３０
℃の温度で銅箔の被接着面側に塗布することが好まし
い。The aqueous mixture solution used in the present invention is preferably used in such a manner that the concentration of each drug in the aqueous mixture solution is controlled so as to be within the above range, and that the mixture is sufficiently mixed. Further, it is preferable to use the mixture aqueous solution after adjusting it to an alkaline range so as to have a pH of 8 to 12. The aqueous mixture solution is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.
It is preferable to apply to the surface of the copper foil to be bonded at a temperature of ° C.
【００２３】本発明においては、銅箔の被接着面側にシ
ランカップリング剤とポリシロキサンの混合物層被覆層
を設けたことを特徴とし、銅箔の被接着面側にシランカ
ップリング剤からなる被覆層とポリシロキサンからなる
被覆層との２層を設けても、また、シランカップリング
剤からなる被覆層又はポリシロキサンからなる被覆層の
いずれか１層のみを設けても、いずれの場合も耐湿性の
向上は認められない。The present invention is characterized in that a mixture layer coating layer of a silane coupling agent and a polysiloxane is provided on the side of the copper foil to be bonded, and the silane coupling agent is formed on the side of the copper foil to be bonded. Even if two layers of a coating layer and a coating layer made of polysiloxane are provided, or only one of a coating layer made of a silane coupling agent and a coating layer made of polysiloxane is provided, No improvement in moisture resistance is observed.
【００２４】本発明においては、シランカップリング剤
とポリシロキサンを含有する混合物水溶液を銅箔の被接
着面（最表層）に塗布、乾燥する。In the present invention, an aqueous solution of a mixture containing a silane coupling agent and a polysiloxane is applied to the surface to be bonded (the outermost layer) of the copper foil and dried.
【００２５】混合物水溶液を塗布する方法については特
に制限されないが、スプレー法、浸漬法などの方法によ
り簡便に行うことができる。塗布量は好ましくは１０〜
１００ｇ／ｍ2であり、塗布処理時間は通常３０秒以
内、好ましくは１〜１５秒で銅箔の被接着面に塗布す
る。The method for applying the mixture aqueous solution is not particularly limited, but it can be easily carried out by a method such as a spray method or a dipping method. The coating amount is preferably 10
It is 100 g / m 2 , and the application time is usually within 30 seconds, preferably 1 to 15 seconds.
【００２６】混合物水溶液を塗布した銅箔はただちに、
好ましくは５０〜１２０℃の熱風乾燥機内で、好ましく
は１〜５分間十分に乾燥することにより、本発明にかか
る銅箔の被接着面に混合物被覆層を有するプリント配線
板用銅箔が得られる。The copper foil coated with the mixture aqueous solution immediately
The copper foil for a printed wiring board having a mixture coating layer on the surface to be adhered of the copper foil according to the present invention is obtained by sufficiently drying the film in a hot air dryer at preferably 50 to 120 ° C., preferably for 1 to 5 minutes. .
【００２７】本発明により得られた銅箔は各種の銅張積
層板の製造においてプリント配線板用銅箔として樹脂基
材と積層されるが、適用可能な樹脂基材の樹脂としては
エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹
脂、ケイ素樹脂などの熱硬化性樹脂、ポリエチレン、飽
和ポリエステル、ポリエーテルサルフォンなどの熱可塑
性樹脂が挙げられ、基材としては紙、ガラス、ガラス
布、ガラス織布などが挙げられ、またポリイミドフィル
ム、ポリエステルフィルム、あるいはアルミニウム、鉄
等の金属板をベースとした樹脂基材も挙げられる。The copper foil obtained according to the present invention is laminated with a resin substrate as a copper foil for a printed wiring board in the production of various copper-clad laminates. Examples include thermosetting resins such as phenolic resins, unsaturated polyester resins, and silicon resins, and thermoplastic resins such as polyethylene, saturated polyester, and polyethersulfone. The base material is paper, glass, glass cloth, glass woven cloth, and the like. And a resin substrate based on a polyimide film, a polyester film, or a metal plate such as aluminum or iron.
【００２８】[0028]
【実施例】以下、本発明の実施例及びその比較例によっ
て本発明を更に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。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.
【００２９】実施例１ 厚さ１８μｍの電解銅箔の粗面側に硫酸銅めっき液を使
用して小球状の銅電着物による粗化処理層を厚さ１μｍ
に形成した。これを水洗した後、重クロム酸ナトリウム
２水和物５ｇ／ｌ水溶液に銅箔を浸漬し、電流密度０．
５Ａ／ｄｍ2、電解時間５秒の条件で粗化処理層上にク
ロメート層（防錆層）を形成した。これを水洗した後、
このクロメート層上に、γ−グリシドキシプロピルトリ
メトキシシラン １ｇ／ｌ、ポリシロキサン溶液（商品
名；ストロンＪコート、日本表面化学（株）製、固形分
６重量％、比重１．０６）３ｇ／ｌを含有するｐＨ９．
３、温度２５℃の混合物水溶液（ポリシロキサン０．１
８ｇ／ｌ）１０ｇ／ｍ2をスプレー法により５秒間塗布
処理した。処理後直ちに温度１００℃に設定された熱風
乾燥機中に導き５分間乾燥し、銅箔の被接着面側（最表
層）に本発明による混合物被覆層（厚さ２５オングスト
ローム）を形成した。Example 1 A roughened layer made of a small spherical copper electrodeposit using a copper sulfate plating solution to a thickness of 1 μm was formed on the rough side of an electrolytic copper foil having a thickness of 18 μm.
Formed. After washing with water, the copper foil was immersed in a 5 g / l aqueous solution of sodium dichromate dihydrate, and the current density was adjusted to 0.
A chromate layer (rust prevention layer) was formed on the roughened layer under the conditions of 5 A / dm 2 and an electrolysis time of 5 seconds. After washing this with water,
On this chromate layer, 1 g / l of γ-glycidoxypropyltrimethoxysilane, 3 g of a polysiloxane solution (trade name: Stron J coat, manufactured by Nippon Surface Chemical Co., Ltd., solid content 6% by weight, specific gravity 1.06) PH 9.
3. A mixture aqueous solution at a temperature of 25 ° C (polysiloxane 0.1
(8 g / l) 10 g / m 2 was applied by a spray method for 5 seconds. Immediately after the treatment, the mixture was introduced into a hot-air dryer set at a temperature of 100 ° C. and dried for 5 minutes to form a mixture coating layer (thickness: 25 Å) according to the present invention on the surface to be bonded (top layer) of the copper foil.
【００３０】得られた銅箔の被接着面側をエポキシ樹脂
含浸ガラス布基材（ＡＮＳＩグレードＦＲ−４）と重ね
て合わせて、温度１６８℃、圧力３０ｋｇｆ／ｃｍ2で
６０分間加熱加圧処理し、縦２５ｃｍ、横２５ｃｍ、厚
さ１．６ｍｍの銅張積層板を作製した。The obtained copper foil is bonded to an epoxy resin-impregnated glass cloth substrate (ANSI grade FR-4) by heating and pressing at a temperature of 168 ° C. and a pressure of 30 kgf / cm 2 for 60 minutes. Then, a copper-clad laminate having a length of 25 cm, a width of 25 cm and a thickness of 1.6 mm was produced.
【００３１】この銅張積層板を下記試験に供し、その結
果を一括して表１に示した。 １．引き剥がし強さ試験（引き剥し巾１ｍｍ、ＪＩＳ−
Ｃ−６４８１に準拠） （１）常態引き剥し試験：積層後の引き剥し強さ（Ａ、
単位ｋｇｆ／ｃｍ）を測定 （２）耐湿性（ＰＣＴ後劣化率）：温度１２１℃、圧力
１．２ｋｇｆ／ｃｍ2、湿度１００％の条件で３時間保
持後の引き剥し強さ（Ｂ、単位ｋｇｆ／ｃｍ）を測定
し、劣化率（％）＝［（Ａ−Ｂ）／Ａ］×１００で示し
た。The copper-clad laminate was subjected to the following tests, and the results are shown in Table 1 collectively. 1. Peel strength test (peel width 1 mm, JIS-
(Based on C-6481) (1) Peeling test in normal condition: Peeling strength after lamination (A,
(2) Moisture resistance (deterioration rate after PCT): Peeling strength (B, unit) after holding for 3 hours under conditions of a temperature of 121 ° C., a pressure of 1.2 kgf / cm 2 and a humidity of 100%. kgf / cm), and the deterioration rate (%) = [(AB) / A] × 100.
【００３２】実施例２〜４ 実施例１と同様の銅箔を使用して、実施例１と同様の粗
化処理層及び防錆層（クロメート層）を形成し、水洗し
た後、表１に示す混合物水溶液を使用して混合物被覆層
（最表層）を形成し、乾燥を施した。得られた銅箔を実
施例１と同様に銅張積層板とし、実施例１と同様に試験
片を作製し、実施例１と同様の特性試験を実施した。そ
の評価結果を表１に示した。Examples 2 to 4 Using the same copper foil as in Example 1, a roughening layer and a rust-preventive layer (chromate layer) were formed in the same manner as in Example 1. A mixture coating layer (outermost layer) was formed using the mixture aqueous solution shown, and dried. The obtained copper foil was used as a copper-clad laminate in the same manner as in Example 1, a test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed. Table 1 shows the evaluation results.
【００３３】実施例５ 実施例１と同様の銅箔を使用して、防錆層形成を下記に
示す浴組成、電解条件に変え、ニッケル−モリブデン−
コバルト合金層とクロメート層からなる層に変えた以外
は実施例１と同様に表１に示す混合物水溶液を使用して
混合物被覆層（最表層）を形成し、乾燥を施した。得ら
れた銅箔を実施例１と同様に銅張積層板とし、実施例１
と同様に試験片を作製し、実施例１と同様の特性試験を
実施した。その評価結果を表１に示した。 浴組成（１） クエン酸三ナトリウム・２水和物 ３０ｇ／ｌ 硫酸ニッケル・６水和物 ８ｇ／ｌ モリブデン酸ナトリウム・２水和物 ３ｇ／ｌ 硫酸コバルト・７水和物 ２８ｇ／ｌ ｐＨ ６．２ 浴温 ３０℃ 電解条件（１） 電流密度 ３Ａ／ｄｍ2 電解時間 ４秒 浴組成（２） 重クロム酸ナトリウム・２水和物 ５ｇ／ｌ ｐＨ ４．７ 浴温 ２５℃ 電解条件（２） 電流密度 ０．５Ａ／ｄｍ2 電解条件 ５秒 実施例６ 実施例１と同様の銅箔を使用して、防錆層形成を下記に
示す浴組成、電解条件に変え、インジウム−亜鉛合金層
とクロメート層に変えた以外は実施例１と同様に表１に
示す混合物水溶液を使用して混合物被覆層（最表層）を
形成し、乾燥を施した。得られた銅箔を実施例１と同様
に銅張積層板とし、実施例１と同様に試験片を作製し、
実施例１と同様の特性試験を実施した。その評価結果を
表１に示した。 浴組成（１） 硫酸インジウム ０．５ｇ／ｌ 硫酸亜鉛・７水和物 ５．０ｇ／ｌ ｐＨ ３．０ 浴温 ３０℃ 電解条件（１） 電流密度 ０．３Ａ／ｄｍ2 電解時間 ３秒 浴組成（２） 重クロム酸ナトリウム・２水和物 ５ｇ／ｌ ｐＨ ４．７ 浴温 ３０℃ 電解条件（２） 電流密度 ０．５Ａ／ｄｍ2 電解時間 ５秒 実施例７ 実施例１と同様の銅箔を使用して、防錆層形成を下記に
示す浴組成、電解条件に変え、銅−亜鉛合金層とクロメ
ート層に変えた以外は実施例１と同様に表１に示す混合
物水溶液を使用して混合物被覆層（最表層）を形成し、
乾燥を施した。得られた銅箔を実施例１と同様に銅張積
層板とし、実施例１と同様に試験片を作製し、実施例１
と同様の特性試験を実施した。その評価結果を表１に示
した。 浴組成（１） グルコヘプトン酸ナトリウム ５０ｇ／ｌ 蓚酸カリウム・２水和物 １５ｇ／ｌ チオシアン酸カリウム １５ｇ／ｌ 硫酸銅・５水和物 １６ｇ／ｌ 硫酸亜鉛・７水和物 ８ｇ／ｌ ｐＨ １１ 浴温 ４０℃ 電解条件（１） 電流密度 ５Ａ／ｄｍ2 電解時間 ２２秒 浴組成（２） 重クロム酸ナトリウム・２水和物 ５ｇ／ｌ ｐＨ ４．７ 浴温 ３０℃ 電解条件（２） 電流密度 ０．５Ａ／ｄｍ2 電解時間 ５秒 比較例１ 実施例１と同様の銅箔を使用して実施例１と同様の粗化
処理層、防錆層（クロメート層）を形成し、混合物被覆
層を形成しなかった以外は実施例１と同様に銅張積層板
を得、実施例１と同様に試験片を作製し、実施例１と同
様の特性試験を実施した。その評価結果を表２に示し
た。Example 5 Using the same copper foil as in Example 1, the formation of the rust-preventive layer was changed to the bath composition and electrolysis conditions shown below, and nickel-molybdenum-
A mixture coating layer (outermost layer) was formed using the aqueous mixture solution shown in Table 1 in the same manner as in Example 1 except that the layer was changed to a layer composed of a cobalt alloy layer and a chromate layer, and dried. The obtained copper foil was used as a copper-clad laminate in the same manner as in Example 1, and
A test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed. Table 1 shows the evaluation results. Bath composition (1) Trisodium citrate dihydrate 30 g / l Nickel sulfate hexahydrate 8 g / l Sodium molybdate dihydrate 3 g / l Cobalt sulfate heptahydrate 28 g / l pH 6 .2 Bath temperature 30 ° C Electrolysis conditions (1) Current density 3A / dm 2 Electrolysis time 4 seconds Bath composition (2) Sodium dichromate dihydrate 5g / l pH 4.7 Bath temperature 25 ° C Electrolysis conditions (2 Current density 0.5 A / dm 2 Electrolysis condition 5 seconds Example 6 Using the same copper foil as in Example 1, changing the rust-preventive layer to the bath composition and electrolysis conditions shown below, and changing the indium-zinc alloy layer A mixture coating layer (outermost layer) was formed using the mixture aqueous solution shown in Table 1 in the same manner as in Example 1 except that the composition was changed to a chromate layer and dried. The obtained copper foil was used as a copper-clad laminate in the same manner as in Example 1, and a test piece was prepared in the same manner as in Example 1.
The same property test as in Example 1 was performed. Table 1 shows the evaluation results. Bath composition (1) Indium sulfate 0.5 g / l Zinc sulfate heptahydrate 5.0 g / l pH 3.0 Bath temperature 30 ° C. Electrolysis conditions (1) Current density 0.3 A / dm 2 Electrolysis time 3 seconds Bath Composition (2) Sodium dichromate dihydrate 5 g / l pH 4.7 Bath temperature 30 ° C. Electrolysis condition (2) Current density 0.5 A / dm 2 Electrolysis time 5 seconds Example 7 Same as Example 1 Using a copper foil, the aqueous solution of the mixture shown in Table 1 was used in the same manner as in Example 1 except that the formation of the rust preventive layer was changed to the bath composition and electrolysis conditions shown below, and the copper-zinc alloy layer and the chromate layer were changed. To form a mixture coating layer (outermost layer)
Drying was applied. The obtained copper foil was used as a copper-clad laminate in the same manner as in Example 1, and a test piece was prepared in the same manner as in Example 1.
A characteristic test similar to that described above was performed. Table 1 shows the evaluation results. Bath composition (1) Sodium glucoheptonate 50 g / l Potassium oxalate dihydrate 15 g / l Potassium thiocyanate 15 g / l Copper sulfate pentahydrate 16 g / l Zinc sulfate heptahydrate 8 g / l pH 11 Temperature 40 ° C Electrolysis conditions (1) Current density 5 A / dm 2 Electrolysis time 22 seconds Bath composition (2) Sodium dichromate dihydrate 5 g / l pH 4.7 Bath temperature 30 ° C Electrolysis conditions (2) Current density 0.5 A / dm 2 electrolysis time 5 seconds Comparative Example 1 Using the same copper foil as in Example 1, a roughening layer and a rust-preventive layer (chromate layer) were formed as in Example 1, and a mixture coating layer was formed. A copper-clad laminate was obtained in the same manner as in Example 1 except that no was formed, a test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed. Table 2 shows the evaluation results.
【００３４】比較例２〜３ 実施例１と同様の銅箔を使用して実施例１と同様の粗化
処理層、防錆層（クロメート層）を形成し、単独物水溶
液として表２に示すものを用い、混合物被覆層に変え
て、シランカップリング剤層（比較例２）及びポリシロ
キサン層（比較例３）のみの単独物被覆層とした以外は
実施例１と同様に銅張積層板を得、実施例１と同様に試
験片を作製し、実施例１と同様の特性試験を実施した。
その評価結果を表２に示した。Comparative Examples 2-3 Using the same copper foil as in Example 1, a roughened layer and a rust-proof layer (chromate layer) were formed in the same manner as in Example 1 and shown in Table 2 as an aqueous solution of a single substance. A copper-clad laminate was prepared in the same manner as in Example 1 except that a single-layered coating layer was used instead of the mixture coating layer and only the silane coupling agent layer (Comparative Example 2) and the polysiloxane layer (Comparative Example 3) Was obtained, a test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed.
Table 2 shows the evaluation results.
【００３５】比較例４ 実施例１と同様の銅箔を使用して実施例１と同様の粗化
処理層、防錆層（クロメート層）を形成し、単独物水溶
液として表２に示すものを用い、混合物被覆層に変え
て、ポリシロキサン層及びシランカップリング剤層のみ
の単独物被覆層を乾燥工程を介して順次形成した以外は
実施例１と同様に銅張積層板を得、実施例１と同様に試
験片を作製し、実施例１と同様の特性試験を実施した。
その評価結果を表２に示した。Comparative Example 4 Using the same copper foil as in Example 1, a roughened layer and a rust-preventive layer (chromate layer) were formed in the same manner as in Example 1. A copper-clad laminate was obtained in the same manner as in Example 1 except that a single product coating layer comprising only a polysiloxane layer and a silane coupling agent layer was sequentially formed through a drying step in place of the mixture coating layer. A test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed.
Table 2 shows the evaluation results.
【００３６】比較例５〜６ 実施例１と同様の銅箔を使用して実施例１と同様の粗化
処理層、防錆層（クロメート層）を形成し、混合物水溶
液として表２に示すものを用い、混合物被覆層を形成し
た以外は実施例１と同様に銅張積層板を得、実施例１と
同様に試験片を作製し、実施例１と同様の特性試験を実
施した。その評価結果を表２に示した。Comparative Examples 5 to 6 Using the same copper foil as in Example 1, a roughened layer and a rust-preventive layer (chromate layer) were formed in the same manner as in Example 1. , A copper-clad laminate was obtained in the same manner as in Example 1 except that a mixture coating layer was formed, a test piece was prepared in the same manner as in Example 1, and the same characteristic test as in Example 1 was performed. Table 2 shows the evaluation results.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 ＊ 単独物水溶液 ＊＊沈澱物あり高濃度の場合白だく沈澱する[Table 2] * Aqueous solution of a single substance ** White precipitates at high concentration with precipitate
【００３９】[0039]
【発明の効果】本発明により得られたプリント配線板用
銅箔は銅箔の被接着面に樹脂基材を積層し、銅張積層板
としたとき、銅箔と樹脂基材間の引き剥し強さを高く保
持すると共に、耐湿性に優れプリント配線板の製造にお
いてその工業的価値は極めて大である。The copper foil for printed wiring boards obtained according to the present invention is obtained by laminating a resin base material on the surface to be bonded of the copper foil to form a copper-clad laminate, and peeling off the copper foil and the resin base material. While maintaining high strength, it has excellent moisture resistance, and its industrial value is extremely large in the production of printed wiring boards.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 H05K 3/38 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) B32B 15/08 H05K 3/38
Claims (6)
剤及びポリシロキサンからなる混合物被覆層を有するこ
とを特徴とするプリント配線板用銅箔。1. A copper foil for a printed wiring board, comprising a mixture coating layer comprising a silane coupling agent and polysiloxane on a surface to be bonded of the copper foil.
剤を０．３〜１０ｇ／ｌ及びポリシロキサンを０．０２
〜１．０ｇ／ｌの濃度で含有する混合物水溶液を塗布
し、加熱乾燥することを特徴とするプリント配線板用銅
箔の製造方法。2. A silane coupling agent of 0.3 to 10 g / l and a polysiloxane of 0.02 on a surface to be adhered of a copper foil.
A method for producing a copper foil for a printed wiring board, comprising applying a mixture aqueous solution containing the mixture at a concentration of 1.0 to 1.0 g / l, and drying by heating.
である請求項２記載のプリント配線板用銅箔の製造方
法。3. The method according to claim 2, wherein the silane coupling agent is epoxy silane.
が設けられた銅箔である請求項２又は３記載のプリント
配線板用銅箔の製造方法。4. The method for producing a copper foil for a printed wiring board according to claim 2, wherein the copper foil is a copper foil having a surface to be bonded provided with a roughening layer and a rust-preventive layer.
請求項４記載のプリント配線板用銅箔の製造方法。5. The method for producing a copper foil for a printed wiring board according to claim 4, wherein the rust preventive layer is a layer composed of a chromate layer.
ト合金層、インジウム−亜鉛合金層若しくは銅−亜鉛合
金層とクロメート層からなる層である請求項４記載のプ
リント配線板用銅箔の製造方法。6. The method for producing a copper foil for a printed wiring board according to claim 4, wherein the rust preventive layer is a layer comprising a nickel-molybdenum-cobalt alloy layer, an indium-zinc alloy layer or a copper-zinc alloy layer and a chromate layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9029364A JP3067672B2 (en) | 1997-02-13 | 1997-02-13 | Copper foil for printed wiring board and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9029364A JP3067672B2 (en) | 1997-02-13 | 1997-02-13 | Copper foil for printed wiring board and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10226009A JPH10226009A (en) | 1998-08-25 |
| JP3067672B2 true JP3067672B2 (en) | 2000-07-17 |
Family
ID=12274131
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9029364A Expired - Fee Related JP3067672B2 (en) | 1997-02-13 | 1997-02-13 | Copper foil for printed wiring board and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3067672B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005340382A (en) * | 2004-05-25 | 2005-12-08 | Mitsui Mining & Smelting Co Ltd | Flexible printed wiring board and method for manufacturing same |
| JP2008111188A (en) * | 2007-09-25 | 2008-05-15 | Hitachi Chem Co Ltd | Copper foil for printed circuit board |
| JP5136768B2 (en) * | 2008-01-21 | 2013-02-06 | 日立電線株式会社 | Copper foil for circuit boards |
| KR20140034698A (en) * | 2012-09-12 | 2014-03-20 | 주식회사 두산 | Surface treatment method of a copper foil and the copper foil surface-treated by the method |
| JP6570430B2 (en) * | 2015-11-12 | 2019-09-04 | Ｊｘ金属株式会社 | Method for producing copper foil with carrier, method for producing printed wiring board, and method for producing electronic device |
| CN108264882A (en) * | 2017-01-03 | 2018-07-10 | 台虹科技股份有限公司 | Adhesive composition and flexible laminate structure |
| JP7057689B2 (en) | 2018-03-16 | 2022-04-20 | 日本ピラー工業株式会社 | Laminated board |
-
1997
- 1997-02-13 JP JP9029364A patent/JP3067672B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10226009A (en) | 1998-08-25 |
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