JPH10296942A - Manufacture of laminate - Google Patents
Manufacture of laminateInfo
- Publication number
- JPH10296942A JPH10296942A JP9105046A JP10504697A JPH10296942A JP H10296942 A JPH10296942 A JP H10296942A JP 9105046 A JP9105046 A JP 9105046A JP 10504697 A JP10504697 A JP 10504697A JP H10296942 A JPH10296942 A JP H10296942A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper oxide
- circuit
- oxide film
- laminate
- 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
- Laminated Bodies (AREA)
- 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、プリント配線板の
製造に用いられる、積層板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 method for manufacturing a laminated board used for manufacturing a printed wiring board.
【０００２】[0002]
【従来の技術】電気・電子機器等に使用される多層のプ
リント配線板は、例えば、内層用基板の表面の銅箔をエ
ッチングして銅回路を形成した後、その銅回路に接着強
度を高めるために表面処理を行い、次いでその内層用基
板と、熱硬化性樹脂をガラスクロスに含浸して製造した
プリプレグを積層し、更にその積層物の外側に銅箔を積
層した後、加熱・加圧成形して多層の積層板を作製す
る。次いで、この多層の積層板に穴あけをした後、メッ
キ処理を行ってこの穴に内層の銅回路及び外層の銅箔を
導通するスルホールメッキ皮膜を形成し、次いで、外層
の銅箔をエッチングして外層回路を形成した後、電子部
品と接続を予定する外層回路以外の部分の積層板表面
に、ハンダが付着しないようにソルダーレジスト皮膜を
形成することにより製造されている。2. Description of the Related Art A multilayer printed wiring board used for electric / electronic equipment is formed by, for example, forming a copper circuit by etching a copper foil on a surface of an inner layer substrate and then increasing the adhesive strength to the copper circuit. Surface treatment, then laminate the substrate for the inner layer and the prepreg manufactured by impregnating the glass cloth with the thermosetting resin, and further laminate copper foil on the outside of the laminate, then heat and press It is molded to produce a multilayer laminate. Next, after making a hole in this multilayer laminate, a plating process is performed to form a through-hole plating film for conducting the inner layer copper circuit and the outer layer copper foil in the hole, and then the outer layer copper foil is etched. After the outer layer circuit is formed, a solder resist film is formed on the surface of the laminated board other than the outer layer circuit to be connected to the electronic component so that solder does not adhere.
【０００３】上記表面処理は、黒化処理と呼ばれる化学
的酸化処理が一般に行われている。この黒化処理は、銅
回路を亜塩素酸ナトリウムを含有するアルカリ水溶液等
で酸化処理して表面に酸化銅の皮膜を形成し、接着性を
高める処理であり、この処理により銅回路表面に微細な
突起が形成されるため接着性を高めることができる処理
である。[0003] The surface treatment is generally performed by a chemical oxidation treatment called a blackening treatment. This blackening treatment is a treatment for oxidizing a copper circuit with an alkaline aqueous solution containing sodium chlorite to form a copper oxide film on the surface and enhance the adhesiveness. This is a process that can enhance the adhesiveness because of the formation of the projections.
【０００４】一方、上記プリプレグに用いられる熱硬化
性樹脂としては、電気特性や価格等のバランスよりエポ
キシ樹脂系の熱硬化性樹脂が多用されている。なお、こ
のエポキシ樹脂系の熱硬化性樹脂には、プリプレグの保
存安定性等のために、硬化剤としてジシアンジアミド等
のアミン系の硬化剤を使用することが一般的に行われて
いる。しかし、近年の実装密度の増大に伴い、従来以上
に耐熱性及び耐湿性が優れる積層板が求められるように
なっており、従来のアミン系の硬化剤より耐湿性や耐熱
性等に優れるフェノール系の硬化剤が検討されている。
（例えば、特開平３−７９６２１号）。On the other hand, as the thermosetting resin used for the prepreg, an epoxy resin-based thermosetting resin is frequently used in view of the balance between electric characteristics and price. In addition, for this epoxy resin-based thermosetting resin, an amine-based curing agent such as dicyandiamide is generally used as a curing agent for the storage stability of the prepreg and the like. However, with the recent increase in mounting density, laminates having better heat resistance and moisture resistance have been demanded more than before, and phenol-based phenols which are more excellent in moisture resistance and heat resistance than conventional amine-based curing agents are required. Are being studied.
(For example, JP-A-3-79621).
【０００５】しかし、このフェノール系の硬化剤を含有
するエポキシ樹脂系熱硬化性樹脂を使用したプリプレグ
を用いて製造した多層の積層板の場合、銅回路の表面に
形成した酸化銅皮膜と熱硬化性樹脂の硬化物の間の接着
強度が低い場合があり、プリント配線板の加工時に行わ
れる穴あけ等により、その部分で剥離等が発生する場合
があるという問題があった。そのため、銅回路の表面に
形成した酸化銅皮膜と熱硬化性樹脂の硬化物との間の接
着強度が優れた積層板が得られる製造方法が求められて
いる。However, in the case of a multilayer laminate manufactured using a prepreg using an epoxy resin-based thermosetting resin containing a phenol-based curing agent, a copper oxide film formed on the surface of a copper circuit and a thermoset There is a problem that the adhesive strength between the cured products of the conductive resin may be low, and peeling or the like may occur at a portion due to a hole or the like performed during processing of the printed wiring board. Therefore, there is a demand for a manufacturing method capable of obtaining a laminate having excellent adhesive strength between a copper oxide film formed on the surface of a copper circuit and a cured product of a thermosetting resin.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記問題点
を改善するために成されたもので、その目的とするとこ
ろは、基板の表面に形成された銅回路を酸化処理して、
その銅回路の表面に酸化銅皮膜を形成した後、その酸化
銅皮膜と、エポキシ樹脂及びフェノール系硬化剤を含有
する熱硬化性樹脂とを接着して製造する積層板の製造方
法であって、銅回路の表面に形成した酸化銅皮膜と熱硬
化性樹脂の硬化物との間の接着強度が優れた積層板が得
られる積層板の製造方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to oxidize a copper circuit formed on the surface of a substrate,
After forming a copper oxide film on the surface of the copper circuit, a method of manufacturing a laminate by bonding the copper oxide film and a thermosetting resin containing an epoxy resin and a phenolic curing agent, It is an object of the present invention to provide a method for manufacturing a laminate, which can provide a laminate having excellent adhesive strength between a copper oxide film formed on the surface of a copper circuit and a cured product of a thermosetting resin.
【０００７】[0007]
【課題を解決するための手段】本発明の請求項１に係る
積層板の製造方法は、基板の表面に形成された銅回路を
酸化処理して、その銅回路の表面に酸化銅皮膜を形成し
た後、その酸化銅皮膜と、エポキシ樹脂及びフェノール
系硬化剤を含有する熱硬化性樹脂と、を接着して製造す
る積層板の製造方法において、銅回路の表面に形成する
酸化銅皮膜の量が、１ｃｍ2当たり０．０３〜０．１５
ｍｇであることを特徴とする。According to a first aspect of the present invention, there is provided a method for manufacturing a laminated board, wherein a copper circuit formed on a surface of a substrate is oxidized to form a copper oxide film on the surface of the copper circuit. After that, in a method of manufacturing a laminated board by bonding the copper oxide film and a thermosetting resin containing an epoxy resin and a phenolic curing agent, the amount of the copper oxide film formed on the surface of the copper circuit But 0.03 to 0.15 per cm 2
mg.
【０００８】本発明の請求項２に係る積層板の製造方法
は、請求項１記載の積層板の製造方法において、銅回路
の表面に酸化銅皮膜を形成する方法が、銅回路を酸化処
理して、銅回路の表面に酸化銅層を形成した後、その酸
化銅層を酸処理し、その酸化銅層より酸化銅の量が少な
い酸化銅皮膜に加工する方法であることを特徴とする。According to a second aspect of the present invention, in the method for manufacturing a laminate according to the first aspect, the method of forming a copper oxide film on the surface of the copper circuit comprises oxidizing the copper circuit. Then, after forming a copper oxide layer on the surface of the copper circuit, the copper oxide layer is subjected to an acid treatment and processed into a copper oxide film having a smaller amount of copper oxide than the copper oxide layer.
【０００９】本発明の請求項３に係る積層板の製造方法
は、請求項１記載の積層板の製造方法において、銅回路
の表面に酸化銅皮膜を形成する方法が、銅回路を酸化処
理して、銅回路の表面に酸化銅層を形成した後、その酸
化銅層を還元処理し、その酸化銅層より酸化銅の量が少
ない酸化銅皮膜に加工する方法であることを特徴とす
る。According to a third aspect of the present invention, in the method for manufacturing a laminate according to the first aspect, the method of forming a copper oxide film on a surface of a copper circuit comprises oxidizing the copper circuit. And forming a copper oxide layer on the surface of the copper circuit, reducing the copper oxide layer, and processing the copper oxide layer into a copper oxide film having a smaller amount of copper oxide than the copper oxide layer.
【００１０】本発明の請求項４に係る積層板の製造方法
は、請求項１から請求項３のいずれかに記載の積層板の
製造方法において、熱硬化性樹脂に含有するエポキシ樹
脂のエポキシ基とフェノール系硬化剤の水酸基の当量比
が、１：０．５〜２であることを特徴とする。[0010] According to a fourth aspect of the present invention, there is provided a method of manufacturing a laminate according to any one of the first to third aspects, wherein the epoxy group of the epoxy resin contained in the thermosetting resin is used. And the equivalent ratio of the hydroxyl group of the phenolic curing agent to the phenolic curing agent is 1: 0.5 to 2.
【００１１】本発明の請求項５に係る積層板の製造方法
は、請求項１から請求項４のいずれかに記載の積層板の
製造方法において、酸化銅皮膜と接着する熱硬化性樹脂
が、ガラスクロスに含浸した熱硬化性樹脂であることを
特徴とする。According to a fifth aspect of the present invention, in the method for producing a laminate according to any one of the first to fourth aspects, the thermosetting resin which adheres to the copper oxide film is: It is a thermosetting resin impregnated in glass cloth.
【００１２】本発明によると、銅回路の表面に形成する
酸化銅皮膜の量が、１ｃｍ2当たり０．０３〜０．１５
ｍｇであるため、エポキシ樹脂及びフェノール系硬化剤
を含有する熱硬化性樹脂と接着した場合であっても、銅
回路の表面に形成した酸化銅皮膜と熱硬化性樹脂の硬化
物との間の接着強度が優れた積層板を得ることが可能と
なる。According to the present invention, the amount of the copper oxide film formed on the surface of the copper circuit is 0.03 to 0.15 per cm 2 .
mg, even when adhered to a thermosetting resin containing an epoxy resin and a phenolic curing agent, between the copper oxide film formed on the surface of the copper circuit and the cured product of the thermosetting resin. It is possible to obtain a laminate having excellent adhesive strength.
【００１３】[0013]
【発明の実施の形態】本発明に係る積層板の製造方法
は、基板の表面に形成された銅回路を酸化処理して、そ
の銅回路の表面に酸化銅皮膜を形成した後、その酸化銅
皮膜と、エポキシ樹脂及びフェノール系硬化剤を含有す
る熱硬化性樹脂と、を接着して製造する積層板の製造方
法である。BEST MODE FOR CARRYING OUT THE INVENTION In the method for manufacturing a laminate according to the present invention, a copper circuit formed on a surface of a substrate is oxidized to form a copper oxide film on the surface of the copper circuit, and then the copper oxide is formed. This is a method for manufacturing a laminated board manufactured by bonding a film and a thermosetting resin containing an epoxy resin and a phenolic curing agent.
【００１４】なお、熱硬化性樹脂と接着しようとする銅
回路の表面に形成する酸化銅皮膜の量が、銅回路の面積
１ｃｍ2当たり０．０３〜０．１５ｍｇであることが重
要である。０．０３ｍｇ未満の場合や、０．１５ｍｇを
越える場合は、エポキシ樹脂及びフェノール系硬化剤を
含有する熱硬化性樹脂と接着して積層板を製造した場
合、その積層板の銅回路の表面に形成した酸化銅皮膜と
熱硬化性樹脂の硬化物との間の接着強度が低い場合があ
る。It is important that the amount of the copper oxide film formed on the surface of the copper circuit to be bonded to the thermosetting resin is 0.03 to 0.15 mg per 1 cm 2 of the area of the copper circuit. If the amount is less than 0.03 mg or exceeds 0.15 mg, a laminate is manufactured by bonding to a thermosetting resin containing an epoxy resin and a phenolic curing agent. The adhesive strength between the formed copper oxide film and the cured product of the thermosetting resin may be low.
【００１５】なお、本発明の酸化銅皮膜の量は、この酸
化銅皮膜を、濃度０．５モル／リットルの硫酸に溶解さ
せた後、その硫酸に溶解した酸化銅の濃度を、０．０２
５モル／リットルのＥＤＴＡ（エチレンジアミン四酢
酸）を用いて滴定することにより求められる値を表すも
のである。The amount of the copper oxide film of the present invention is determined by dissolving the copper oxide film in sulfuric acid having a concentration of 0.5 mol / liter and then increasing the concentration of the copper oxide dissolved in the sulfuric acid by 0.02.
It represents a value determined by titration with 5 mol / liter of EDTA (ethylenediaminetetraacetic acid).
【００１６】この酸化銅皮膜を形成する方法としては、
酸化銅皮膜を形成する量が上記範囲内になるように温度
及び液濃度等を制御した酸化処理液を用いて、更に、時
間を制御して酸化処理する方法や、酸化処理液を用いて
上記範囲を越える量の酸化銅層を形成した後、後処理し
て上記範囲内になるように加工する方法が挙げられる。
上記範囲を越える量の酸化銅層を形成した後、後処理し
て上記範囲内になるように加工する方法の場合、酸化銅
皮膜の量を上記範囲内に調整しやすく好ましい。The method of forming the copper oxide film is as follows.
Using an oxidizing treatment liquid whose temperature and solution concentration are controlled so that the amount of forming the copper oxide film is within the above range, further, a method of performing oxidizing treatment by controlling the time, and using the oxidizing treatment liquid After forming the copper oxide layer in an amount exceeding the range, there is a method of performing post-processing and processing to be within the above range.
In the case of a method in which a copper oxide layer having an amount exceeding the above range is formed and then post-processed and processed so as to be within the above range, the amount of the copper oxide film can be easily adjusted within the above range, which is preferable.
【００１７】この上記範囲を越える量の酸化銅層を形成
した後、後処理して上記範囲内になるように加工する方
法としては、銅回路を酸化処理液を用いて酸化処理し
て、銅回路の表面に上記範囲を越える量の酸化銅層を形
成した後、その酸化銅層を酸を用いて酸処理し、その酸
化銅層より酸化銅の量が少ない酸化銅皮膜に加工する方
法や、銅回路を酸化処理液を用いて酸化処理して、銅回
路の表面に上記範囲を越える量の酸化銅層を形成した
後、その酸化銅層を還元液を用いて還元処理し、その酸
化銅層より酸化銅の量が少ない酸化銅皮膜に加工する方
法が挙げられる。As a method of forming a copper oxide layer in an amount exceeding the above range and then performing post-processing so as to be within the above range, a copper circuit is oxidized using an oxidizing solution, and the copper circuit is oxidized. After forming a copper oxide layer in an amount exceeding the above range on the surface of the circuit, the copper oxide layer is subjected to an acid treatment using an acid, and a copper oxide film having a smaller amount of copper oxide than the copper oxide layer is processed. After the copper circuit is oxidized using an oxidizing solution to form a copper oxide layer in an amount exceeding the above range on the surface of the copper circuit, the copper oxide layer is reduced using a reducing solution, and the oxidation is performed. There is a method of processing a copper oxide film having a smaller amount of copper oxide than a copper layer.
【００１８】なお、酸化処理液としては、亜塩素酸ナト
リウム、過硫酸カリウム等の酸化剤と、水酸化ナトリウ
ム等のアルカリを含む水溶液が挙げられ、一般にはこの
水溶液を加熱して用いて酸化処理を行う。なお、この酸
化処理液で処理する前に、必要に応じて、銅回路の表面
を機械的な研磨を行なって粗面化処理してもよく、ま
た、硫酸及び過酸化水素を含有する硫酸銅水溶液や、塩
酸を含有する塩化銅水溶液等で、銅回路の表面を化学的
にマイクロエッチングを行なって粗面化処理してもよ
い。粗面化処理を行った後、酸化処理液で処理する場
合、銅回路の表面に形成される酸化銅の量の、基板内の
位置によるばらつきが小さくなり好ましい。Examples of the oxidizing solution include an aqueous solution containing an oxidizing agent such as sodium chlorite, potassium persulfate and the like and an alkali such as sodium hydroxide. I do. Before the treatment with the oxidizing solution, the surface of the copper circuit may be mechanically polished and roughened if necessary, or copper sulfate containing sulfuric acid and hydrogen peroxide may be used. The surface of the copper circuit may be chemically microetched with an aqueous solution, an aqueous solution of copper chloride containing hydrochloric acid, or the like to perform a roughening treatment. It is preferable to use an oxidizing solution after the surface roughening treatment because the variation in the amount of copper oxide formed on the surface of the copper circuit depending on the position in the substrate is small.
【００１９】また、酸を用いて酸処理する方法として
は、例えば、ギ酸や、酢酸等の、酸化銅を溶解すること
が可能な弱酸に浸漬する方法が挙げられる。なおこの酸
に銅のキレート剤を含有すると、酸処理の速度が安定し
好ましい。また、還元液を用いて還元処理する方法とし
ては、例えば、ジメチルアミンボラン等の有機性還元剤
水溶液に浸漬する方法や、亜鉛粉末をコーティングして
硫酸に浸漬することにより活性水素を発生させ処理する
方法等が挙げられる。As a method of acid treatment using an acid, for example, a method of dipping in a weak acid capable of dissolving copper oxide, such as formic acid or acetic acid, may be mentioned. It is preferable that the acid contains a chelating agent of copper because the rate of acid treatment is stable. Examples of a method of performing a reduction treatment using a reducing solution include, for example, a method of immersing in an aqueous solution of an organic reducing agent such as dimethylamine borane, or a method of generating active hydrogen by coating zinc powder and immersing in sulfuric acid. And the like.
【００２０】本発明に用いる基板としては、表面に銅回
路を有する板であれば特に限定するものではなく、例え
ば、エポキシ樹脂系、フェノール樹脂系、ポリイミド樹
脂系、不飽和ポリエステル樹脂系、ポリフェニレンエー
テル樹脂系等の熱硬化性樹脂や、これらの熱硬化性樹脂
に無機充填材等を配合したもののシートの片面又は両面
に銅箔が張られている板や、ガラス等の無機質繊維やポ
リエステル、ポリアミド、木綿等の有機質繊維のクロ
ス、ペーパー等の基材を、上記熱硬化性樹脂等で接着
し、片面又は両面に銅箔が張られている板等を用いて、
銅箔をエッチングして銅回路を表面に形成したもの、及
び、銅箔が張られていない上記板の表面に銅メッキを行
い、銅回路を表面に形成したもの等が挙げられる。な
お、この基板は、内部にも銅回路を有していてもよく、
その壁面に金属層を形成したスルホールや、その内部に
銀ペースト等の導電体を充填したスルホールを有してい
てもよい。なお、銅回路の厚みは、特に限定するもので
はないが、１８〜１００μｍ程度のものが一般的であ
る。The substrate used in the present invention is not particularly limited as long as it has a copper circuit on its surface. Examples thereof include epoxy resin, phenol resin, polyimide resin, unsaturated polyester resin, and polyphenylene ether. Thermosetting resins such as resin-based, or a plate in which one or both sides of a sheet of a sheet obtained by blending an inorganic filler or the like with these thermosetting resins, or inorganic fibers such as glass, polyester, or polyamide , A cloth of organic fibers such as cotton, a substrate such as paper, is adhered with the above thermosetting resin or the like, using a plate or the like having a copper foil on one or both sides,
A copper circuit is formed on the surface by etching a copper foil, and a copper circuit is formed on the surface of the above-mentioned plate on which the copper foil is not stretched by copper plating. This board may have a copper circuit inside,
A through hole having a metal layer formed on its wall surface or a through hole filled with a conductor such as silver paste may be provided therein. The thickness of the copper circuit is not particularly limited, but is generally about 18 to 100 μm.
【００２１】本発明で用いる熱硬化性樹脂は、少なくと
もエポキシ樹脂及びフェノール系硬化剤を含有する熱硬
化性樹脂であり、必要に応じて、硬化促進剤や、充填材
や、溶剤等を含有することができる。The thermosetting resin used in the present invention is a thermosetting resin containing at least an epoxy resin and a phenolic curing agent, and optionally contains a curing accelerator, a filler, a solvent, and the like. be able to.
【００２２】本発明で用いるエポキシ樹脂としては、１
分子中にエポキシ基を２個以上有するエポキシ樹脂であ
ればどのようなものでもよく、例えば、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
フェノールノボラック型エポキシ樹脂、ビスフェノール
Ａノボラック型エポキシ樹脂、クレゾールノボラック型
エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹
脂及びこれらのエポキシ樹脂構造体中の水素原子の一部
をハロゲン化することにより難燃化したエポキシ樹脂等
の単独、変性物、混合物が挙げられる。The epoxy resin used in the present invention includes 1
Any epoxy resin having two or more epoxy groups in the molecule may be used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin,
Phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, diaminodiphenylmethane type epoxy resin, and epoxy resin flame-retarded by halogenating some hydrogen atoms in these epoxy resin structures And the like, alone, modified products and mixtures.
【００２３】なお、エポキシ樹脂中のエポキシ基の数の
上限は、あまり多いと熱硬化性樹脂の粘度が高くなっ
て、基材へ含浸しようとした場合に含浸性が低下するた
め、３０個以下のものを使用すると好ましい。なお、分
子内にエポキシ基を１個有するエポキシ樹脂を併用する
こともできる。It should be noted that the upper limit of the number of epoxy groups in the epoxy resin is too small, since the viscosity of the thermosetting resin becomes too high to impregnate the base material when impregnation is attempted. It is preferred to use Note that an epoxy resin having one epoxy group in the molecule can be used in combination.
【００２４】なお、エポキシ樹脂が、ビスフェノールＡ
型エポキシ樹脂、テトラブロモビスフェノールＡ型エポ
キシ樹脂、フェノールノボラック型エポキシ樹脂、クレ
ゾールノボラック型エポキシ樹脂、ビスフェノールＡノ
ボラック型エポキシ樹脂からなる群の中から選ばれた少
なくとも１種のエポキシ樹脂であると、優れた電気特性
と物理特性をもち、かつ、両者のバランスが取れた積層
板を得ることができ好ましい。The epoxy resin is bisphenol A
Epoxy resin, tetrabromobisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin It is preferable to obtain a laminate having good electrical and physical properties and a good balance between the two.
【００２５】本発明で用いるフェノール系硬化剤は、フ
ェノール性水酸基を２個以上有するフェノール系硬化剤
であり、フェノールノボラック樹脂、クレゾールノボラ
ック樹脂、ｐ−キシレン−ノボラック樹脂等が例示で
き、これらは単独で用いてもよく、２種類以上併用して
もよい。なお、フェノール系硬化剤中のフェノール性水
酸基の数の上限は、特に限定するものではないが、分子
内に３０個以下のものが一般に用いられる。The phenolic curing agent used in the present invention is a phenolic curing agent having two or more phenolic hydroxyl groups, and examples thereof include a phenol novolak resin, a cresol novolak resin, and a p-xylene-novolak resin. Or two or more of them may be used in combination. The upper limit of the number of phenolic hydroxyl groups in the phenolic curing agent is not particularly limited, but one having 30 or less in the molecule is generally used.
【００２６】フェノール系硬化剤の配合量は、エポキシ
樹脂のエポキシ基とフェノール系硬化剤の水酸基の当量
比が、１：０．５〜２となるように配合することが望ま
しい。０．５未満の場合や、２を越える場合は、得られ
る積層板の耐熱性が低下する場合がある。The amount of the phenolic curing agent is preferably such that the equivalent ratio of the epoxy group of the epoxy resin to the hydroxyl group of the phenolic curing agent is 1: 0.5 to 2. If it is less than 0.5 or more than 2, the heat resistance of the obtained laminate may decrease.
【００２７】本発明で用いることができる硬化促進剤と
しては、特に限定するものではないが、２−メチルイミ
ダゾール、２−エチル−４−メチルイミダゾール、２−
フェニルイミダゾール等のイミダゾール類、１，８−ジ
アザ−ビシクロ［５．４．０］ウンデセン−７、トリエ
チレンジアミン、ベンジルジメチルアミン等の三級アミ
ン類、トリブチルホスフィン、トリフェニルホスフィン
等の有機ホスフィン類、テトラフェニルホスホニウムテ
トラフェニルボレート、トリフェニルホスフィンテトラ
フェニルボレート等のテトラフェニルボロン塩等が例示
でき、これらは単独で用いてもよく、２種類以上併用し
てもよい。通常、硬化促進剤の含有量は、エポキシ樹脂
組成物の固形分１００重量部に対して１重量部以下程度
が好ましい。The curing accelerator that can be used in the present invention is not particularly limited, but includes 2-methylimidazole, 2-ethyl-4-methylimidazole,
Imidazoles such as phenylimidazole, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine and benzyldimethylamine, organic phosphines such as tributylphosphine and triphenylphosphine; Examples thereof include tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate. These may be used alone or in combination of two or more. Usually, the content of the curing accelerator is preferably about 1 part by weight or less based on 100 parts by weight of the solid content of the epoxy resin composition.
【００２８】また、本発明で用いることができる溶剤と
しては、均一な溶液の熱硬化性樹脂を得ることが可能な
溶剤であれば、特に限定するものではないが、アセト
ン、メチルエチルケトン等のケトン類、エチレングリコ
ールモノメチルエーテル等のエーテル類、ベンゼン、ト
ルエン等の芳香族炭化水素類、メトキシプロパノール等
が例示できる。The solvent that can be used in the present invention is not particularly limited as long as it can obtain a thermosetting resin in a uniform solution. Ketones such as acetone and methyl ethyl ketone can be used. And ethers such as ethylene glycol monomethyl ether, aromatic hydrocarbons such as benzene and toluene, and methoxypropanol.
【００２９】なお、熱硬化性樹脂が、ガラスクロス等の
基材に熱硬化性樹脂を含浸して製造した、一般にプリプ
レグと呼ばれる基材に含浸された熱硬化性樹脂の場合、
得られる積層板の絶縁層の厚みを確実に確保可能なた
め、絶縁信頼性が優れ好ましいが、本発明の熱硬化性樹
脂は、プリプレグに用いられた熱硬化性樹脂のみに限定
するものではなく、内層用の基板の表面に、熱硬化性樹
脂単独の絶縁層と、金属箔とを、交互に積み上げて接着
しながら製造する、一般にビルドアップ基板と呼ばれる
積層板を製造する場合に用いられる熱硬化性樹脂でもよ
い。In the case where the thermosetting resin is a thermosetting resin impregnated into a substrate generally called a prepreg, which is produced by impregnating a substrate such as glass cloth with the thermosetting resin,
Because the thickness of the insulating layer of the obtained laminate can be reliably ensured, the insulation reliability is excellent and preferable, but the thermosetting resin of the present invention is not limited to only the thermosetting resin used for the prepreg. Insulating layers of a thermosetting resin alone and metal foil are alternately stacked and bonded on the surface of the substrate for the inner layer, which is used for manufacturing a laminated board generally called a build-up board. Curable resin may be used.
【００３０】熱硬化性樹脂を含浸する基材としては、特
には限定しないが、ガラス繊維、アラミド繊維、ポリエ
ステル繊維、ナイロン繊維等の繊維を使用したクロスも
しくは不織布、又はクラフト紙、リンター紙等の紙など
を使用することができる。なお、ガラスクロス等の無機
質繊維が耐熱性、耐湿性に優れており好ましい。The substrate to be impregnated with the thermosetting resin is not particularly limited, but may be cloth or nonwoven fabric using fibers such as glass fiber, aramid fiber, polyester fiber, nylon fiber, etc., or kraft paper, linter paper or the like. Paper or the like can be used. In addition, inorganic fibers such as glass cloth are preferable because they have excellent heat resistance and moisture resistance.
【００３１】基材に熱硬化性樹脂を含浸する場合の樹脂
量は、基材及び熱硬化性樹脂の合計１００重量部に対
し、４０〜８０重量部であることが好ましい。４０重量
部未満の場合には、そのプリプレグを用いて製造した積
層板中に気泡が残留する場合がある。また、８０重量部
を越えた場合には板厚不良が発生する場合がある。When the base material is impregnated with the thermosetting resin, the amount of the resin is preferably 40 to 80 parts by weight based on 100 parts by weight of the total of the base material and the thermosetting resin. If the amount is less than 40 parts by weight, air bubbles may remain in a laminate manufactured using the prepreg. On the other hand, when the amount exceeds 80 parts by weight, a sheet thickness defect may occur.
【００３２】積層板は、上記範囲の酸化銅皮膜を形成し
た銅回路を表面に有する基板の、その両側又は片側に上
記で得られたプリプレグを配したり、熱硬化性樹脂を塗
布し、更にその外側に金属箔を配して積層し、次いで加
熱加圧して成形を行う方法等により製造される。このよ
うにして得られた積層板は、銅回路の表面に形成した酸
化銅皮膜と、熱硬化性樹脂の硬化物との間の接着強度が
優れた積層板となる。なお、このとき用いる基板は、表
面に銅回路を形成している板であれば特に限定するもの
ではなく、上記熱硬化性樹脂を用いた板でもよく、他の
熱硬化性樹脂を用いた板でもよい。The laminated board is provided with a prepreg obtained as described above or coated with a thermosetting resin on both sides or one side of a substrate having a copper circuit formed with a copper oxide film in the above-described range on the surface thereof. It is manufactured by a method in which a metal foil is arranged on the outside, laminated, and then heated and pressed to perform molding. The laminate thus obtained is a laminate having excellent adhesive strength between the copper oxide film formed on the surface of the copper circuit and the cured product of the thermosetting resin. The substrate used at this time is not particularly limited as long as it is a plate on which a copper circuit is formed, and may be a plate using the above-described thermosetting resin, or a plate using another thermosetting resin. May be.
【００３３】[0033]
（実施例１）大きさ５０×５０ｃｍ、銅箔を除く厚み
０．５ｍｍの両面ガラス基材エポキシ樹脂銅張り積層板
［松下電工株式会社製、商品名Ｒ−１７６６］の銅箔
（厚み３５μｍ）をエッチングして、銅回路を一方の面
に有する基板を得た。(Example 1) Copper foil (35 μm thick) of a 50 × 50 cm, double-sided glass substrate epoxy resin copper-clad laminate (trade name: R-1766, manufactured by Matsushita Electric Works, Ltd.) having a thickness of 0.5 mm excluding copper foil Was etched to obtain a substrate having a copper circuit on one surface.
【００３４】また、熱硬化性樹脂として、下記の２種類
のエポキシ樹脂、フェノール系硬化剤及び硬化促進剤を
配合して混合した後、溶剤（メチルエチルケトン）で粘
度調整した熱硬化性樹脂を用いて、この熱硬化性樹脂
を、厚み０．１ｍｍのガラスクロス［旭シュエーベル株
式会社製、品番２１６Ｌ］に含浸し、次いで１５０℃で
乾燥して、樹脂量５０重量％のプリプレグを作製した。As the thermosetting resin, the following two types of epoxy resins, a phenolic curing agent and a curing accelerator are blended and mixed, and then a thermosetting resin whose viscosity is adjusted with a solvent (methyl ethyl ketone) is used. The thermosetting resin was impregnated into a glass cloth [manufactured by Asahi Schwebel Co., Ltd., product number 216L] having a thickness of 0.1 mm, and then dried at 150 ° C. to prepare a prepreg having a resin amount of 50% by weight.
【００３５】熱硬化性樹脂の原料としては、エポキシ樹
脂として、エポキシ当量が５００であるテトラブロモビ
スフェノールＡ型エポキシ樹脂［ダウケミカル株式会社
製、商品名ＤＥＲ５１１］を５３．７重量部と、エポキ
シ当量が２００であるクレゾールノボラック型エポキシ
樹脂［東都化成株式会社製、商品名ＹＤＣＮ７０２］を
２３重量部、フェノール系硬化剤として、フェノール性
水酸基当量１０５のフェノールノボラック樹脂［荒川化
学工業株式会社製、商品名タマノール７５２］を２３．
３重量部、硬化促進剤として、２−エチル−４−メチル
イミダゾール［四国化成工業株式会社製］を０．１重量
部用いた。As a raw material of the thermosetting resin, as an epoxy resin, 53.7 parts by weight of a tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 500 [DER511, manufactured by Dow Chemical Co., Ltd.] Novolak type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name YDCN702] with a phenolic curing agent of 23 parts by weight and a phenolic novolak resin having a phenolic hydroxyl equivalent of 105 [Arakawa Chemical Industry Co., Ltd., trade name Tamanol 752].
3 parts by weight and 0.1 part by weight of 2-ethyl-4-methylimidazole [manufactured by Shikoku Chemical Industry Co., Ltd.] were used as a curing accelerator.
【００３６】次いで、上記銅回路を表面に有する基板
に、下記のアルカリ処理、マイクロエッチング、酸洗
浄、酸化処理及び乾燥の各工程の処理を行って、銅回路
の表面に酸化銅皮膜を形成した。Next, the substrate having the copper circuit on its surface was subjected to the following alkali treatment, microetching, acid washing, oxidation treatment and drying to form a copper oxide film on the surface of the copper circuit. .
【００３７】アルカリ処理は、濃度６０ｇ／リットル
（以下、Ｌと記す）、温度６０℃のアルカリ処理液［日
本マクダーミッド株式会社製、商品名Ｍｅｔｅｘ Ｓ−
１７０７］で５分間処理した後、４０℃の温水で３分間
と、室温の水で３分間洗浄した。In the alkali treatment, an alkali treatment solution having a concentration of 60 g / liter (hereinafter referred to as “L”) and a temperature of 60 ° C. (trade name Metex S- manufactured by MacDermid Japan Co., Ltd.)
1707] for 5 minutes, followed by washing with 40 ° C. warm water for 3 minutes and room temperature water for 3 minutes.
【００３８】マイクロエッチングは、９８％硫酸［試
薬］を８体積％と、３５％過酸化水素［試薬］を４．５
体積％と、硫酸銅（５水和物）［試薬］を２５ｇ／Ｌ
と、マイクロエッチング添加液［日本マクダーミッド株
式会社製、商品名ＭｅｔｅｘＧ−６Ｓ］を７体積％と、
を含有する、温度３５℃の水溶液で２分間処理した後、
室温の水で１分間洗浄した。In the microetching, 8% by volume of 98% sulfuric acid [reagent] and 4.5% of 35% hydrogen peroxide [reagent] are used.
Volume% and copper sulfate (pentahydrate) [reagent] at 25 g / L
And 7% by volume of a micro-etching additive solution (trade name Metex G-6S, manufactured by MacDermid Japan Co., Ltd.)
After treatment with an aqueous solution at a temperature of 35 ° C. for 2 minutes containing
Washed with room temperature water for 1 minute.
【００３９】酸洗浄は、９８％硫酸［試薬］を１０体積
％含有する、室温の水溶液で１分間処理した後、室温の
水で１分間洗浄した。The acid washing was carried out for 1 minute with an aqueous solution at room temperature containing 10% by volume of 98% sulfuric acid [reagent], and then washed with water at room temperature for 1 minute.
【００４０】酸化処理は、酸化処理液Ａ［日本マクダー
ミッド株式会社製、商品名Ｏｍｎｉ Ｂｏｎｄ ９２
４９］を７．５体積％含有する温度４０℃の水溶液で２
分間、前処理した後、上記酸化処理液Ａを７．５体積％
と、酸化処理液Ｂ［日本マクダーミッド株式会社製、商
品名Ｏｍｎｉ Ｂｏｎｄ ９２５１］を５０体積％含
有する、アルカリ濃度０．２規定、温度５０℃の水溶液
で４分間処理し、次いで、室温の水で４分間と、４０℃
の純水で３分間洗浄した。乾燥は、１５０℃で２０分間
行った。The oxidation treatment was carried out using an oxidation treatment solution A [trade name: Omni Bond 92, manufactured by MacDermid Japan Co., Ltd.]
49] in an aqueous solution containing 7.5 vol.
After pre-treatment for 7.5 minutes, the above-mentioned oxidation treatment solution A was 7.5% by volume.
And 50% by volume of an oxidation treatment solution B [manufactured by MacDermid Japan Co., Ltd., trade name: Omni Bond 9251], treated with an aqueous solution having an alkali concentration of 0.2 N and a temperature of 50 ° C. for 4 minutes, and then with water at room temperature. 4 minutes and 40 ° C
Of pure water for 3 minutes. Drying was performed at 150 ° C. for 20 minutes.
【００４１】次いで、銅回路の表面に形成した酸化銅皮
膜の量を測定したところ、１ｃｍ 2当たり０．０５ｍｇ
であった。なお、測定方法は、約３×３ｃｍに切断した
試料を、濃度０．５モル／Ｌの硫酸２５ｍＬに浸漬した
後、３分間振動させて酸化銅皮膜を溶解させ、次いで濃
度１モル／Ｌの水酸化ナトリウムを２３ｍＬ添加してｐ
Ｈ調整した後、０．０２５モル／ＬのＥＤＴＡを用いて
滴定し、要したＥＤＴＡの量と、試料の大きさより計算
して求めた。Next, the copper oxide skin formed on the surface of the copper circuit
When the amount of the film was measured, 1 cm Two0.05mg per
Met. In addition, the measuring method cut | disconnected about 3x3cm.
The sample was immersed in 25 mL of sulfuric acid having a concentration of 0.5 mol / L.
Then, vibrate for 3 minutes to dissolve the copper oxide film, and then
Add 23 mL of 1 mol / L sodium hydroxide
After adjusting H, using 0.025 mol / L EDTA
Titrated, calculated from the amount of EDTA required and the sample size
I asked.
【００４２】次いで、この銅回路の表面に酸化銅皮膜を
形成した基板の両面に、上記プリプレグを２枚づつ重ね
て積層し、さらにその積層物の両外層に厚み１８μｍの
銅箔を積層し、この積層物を温度１７０℃、圧力３．９
ＭＰａの条件で９０分成形して多層の積層板を得た。Next, two prepregs were stacked and laminated on both sides of a substrate having a copper oxide film formed on the surface of the copper circuit, and a copper foil having a thickness of 18 μm was laminated on both outer layers of the laminate. This laminate was subjected to a temperature of 170 ° C. and a pressure of 3.9.
Molding was performed for 90 minutes under the conditions of MPa to obtain a multilayer laminate.
【００４３】（実施例２）酸化処理として、上記酸化処
理液Ａを７．５体積％含有する温度４０℃の水溶液で２
分間、前処理した後、上記酸化処理液Ａを１５体積％
と、上記酸化処理液Ｂを５０体積％含有する、アルカリ
濃度０．４規定、温度５０℃の水溶液で４分間処理し、
次いで、室温の水で４分間と、４０℃の純水で３分間洗
浄したこと以外は、実施例１と同様にして多層の積層板
を得た。なお、実施例１と同様にして銅回路の表面に形
成した酸化銅皮膜の量を測定したところ、１ｃｍ2当た
り０．１０ｍｇであった。Example 2 As an oxidation treatment, an aqueous solution containing 7.5% by volume of the oxidation treatment solution A and having a temperature of 40 ° C. was used.
After the pre-treatment for 15 minutes, the oxidation treatment solution A was added to 15% by volume.
And treated with an aqueous solution containing 50% by volume of the oxidizing solution B and having an alkali concentration of 0.4N and a temperature of 50 ° C. for 4 minutes.
Next, a multilayer laminate was obtained in the same manner as in Example 1 except that the laminate was washed with water at room temperature for 4 minutes and pure water at 40 ° C. for 3 minutes. When the amount of the copper oxide film formed on the surface of the copper circuit was measured in the same manner as in Example 1, it was 0.10 mg / cm 2 .
【００４４】（実施例３）酸化処理として、上記酸化処
理液Ａを７．５体積％含有する温度４０℃の水溶液で２
分間、前処理した後、上記酸化処理液Ａを３０体積％
と、上記酸化処理液Ｂを５０体積％含有する、アルカリ
濃度０．７規定、温度６５℃の水溶液で４分間処理し、
次いで、室温の水で４分間と、４０℃の純水で３分間洗
浄して酸化銅層を形成したこと、及び下記方法で、その
酸化銅層を酸処理し、その酸化銅層より酸化銅の量が少
ない酸化銅皮膜に加工した後、プリプレグを重ねたこと
以外は、実施例１と同様にして多層の積層板を得た。な
お、実施例１と同様にして銅回路の表面に形成した酸化
銅皮膜の量を測定したところ、１ｃｍ2当たり０．０４
ｍｇであった。Example 3 As the oxidation treatment, an aqueous solution containing 7.5% by volume of the above-mentioned oxidation treatment solution A and having a temperature of 40 ° C. was used.
After pre-treatment for 30 minutes, the oxidation treatment solution A was added to 30% by volume.
And treated with an aqueous solution containing 50% by volume of the oxidizing solution B and having an alkali concentration of 0.7 N and a temperature of 65 ° C. for 4 minutes,
Next, the copper oxide layer was formed by washing with water at room temperature for 4 minutes and pure water at 40 ° C. for 3 minutes, and the copper oxide layer was subjected to an acid treatment by the following method. Was processed in the same manner as in Example 1 except that a prepreg was laminated after processing into a copper oxide film having a small amount of the same. Incidentally, the measured amount of the copper oxide film formed on the surface of the copper circuit in the same manner as in Example 1, 1 cm 2 per 0.04
mg.
【００４５】酸処理は、酸処理液１［日本マクダーミッ
ド株式会社製、商品名ＢＯ−２２０Ａ］を２０体積％
と、酸処理液２［日本マクダーミッド株式会社製、商品
名ＢＯ−２２０Ｂ］を５体積％含有する、ｐＨ４．３、
温度５５℃の水溶液で６分間処理し、次いで、室温の水
で４分間と、４０℃の純水で３分間洗浄した。In the acid treatment, the acid treatment solution 1 [manufactured by Nippon MacDermid Co., Ltd., trade name: BO-220A] is 20% by volume.
And acid treatment liquid 2 [manufactured by Nippon MacDermid Co., Ltd., trade name BO-220B] containing 5% by volume, pH 4.3,
The substrate was treated with an aqueous solution at a temperature of 55 ° C. for 6 minutes, and then washed with water at room temperature for 4 minutes and pure water at 40 ° C. for 3 minutes.
【００４６】（比較例１）酸化処理として、上記酸化処
理液Ａを７．５体積％含有する温度４０℃の水溶液で２
分間、前処理した後、上記酸化処理液Ａを３０体積％
と、上記酸化処理液Ｂを５０体積％含有する、アルカリ
濃度０．７規定、温度６５℃の水溶液で４分間処理し、
次いで、室温の水で４分間と、４０℃の純水で３分間洗
浄したこと以外は、実施例１と同様にして多層の積層板
を得た。なお、実施例１と同様にして銅回路の表面に形
成した酸化銅皮膜の量を測定したところ、１ｃｍ2当た
り０．２７ｍｇであった。(Comparative Example 1) As the oxidation treatment, an aqueous solution containing 7.5% by volume of the oxidation treatment solution A and having a temperature of 40 ° C was used.
After pre-treatment for 30 minutes, the oxidation treatment solution A was added to 30% by volume.
And treated with an aqueous solution containing 50% by volume of the oxidizing solution B and having an alkali concentration of 0.7 N and a temperature of 65 ° C. for 4 minutes,
Next, a multilayer laminate was obtained in the same manner as in Example 1 except that the laminate was washed with water at room temperature for 4 minutes and pure water at 40 ° C. for 3 minutes. When the amount of the copper oxide film formed on the surface of the copper circuit was measured in the same manner as in Example 1, it was 0.27 mg / cm 2 .
【００４７】（比較例２）酸処理として、上記酸処理液
１を２０体積％と、上記酸処理液２を５．４体積％含有
する、ｐＨ３．５、温度５５℃の水溶液で６分間処理
し、次いで、室温の水で４分間と、４０℃の純水で３分
間洗浄したこと以外は、実施例３と同様にして多層の積
層板を得た。なお、実施例１と同様にして銅回路の表面
に形成した酸化銅皮膜の量を測定したところ、１ｃｍ2
当たり０．０１ｍｇであった。(Comparative Example 2) As an acid treatment, treatment with an aqueous solution containing 20% by volume of the above-mentioned acid treatment solution 1 and 5.4% by volume of the above acid treatment solution 2 and having a pH of 3.5 and a temperature of 55 ° C. was performed for 6 minutes. Then, a multilayer laminate was obtained in the same manner as in Example 3, except that the substrate was washed with water at room temperature for 4 minutes and pure water at 40 ° C. for 3 minutes. Incidentally, the measured amount of the copper oxide film formed on the surface of the copper circuit in the same manner as in Example 1, 1 cm 2
Was 0.01 mg per.
【００４８】（比較例３）アルカリ処理から酸化処理ま
での各工程の処理を行わないこと以外は、実施例１と同
様にして多層の積層板を得た。(Comparative Example 3) A multilayer laminate was obtained in the same manner as in Example 1, except that the treatment in each step from the alkali treatment to the oxidation treatment was not performed.
【００４９】（評価、結果）各実施例及び各比較例で得
られた多層の積層板について、内層銅箔接着強度、ガラ
ス転移温度及び吸湿率を測定した。(Evaluation and Results) The adhesive strength of the inner layer copper foil, the glass transition temperature, and the moisture absorption were measured for the multilayer laminates obtained in each of the examples and comparative examples.
【００５０】内層銅箔接着強度は、銅回路の表面に形成
した酸化銅皮膜と熱硬化性樹脂の硬化物との間の接着強
度を測定したものであり、測定方法としては、得られた
多層の積層板の、酸化処理をしていないマット面を露出
させた銅回路に１０ｍｍ幅のラインを形成し、そのライ
ンの９０度方向の引き剥がし強さを５０ｍｍ／分の引き
剥がし速度で測定した。The inner layer copper foil adhesive strength is a value obtained by measuring the adhesive strength between a copper oxide film formed on the surface of a copper circuit and a cured product of a thermosetting resin. A line having a width of 10 mm was formed on the copper circuit of the laminate having the mat surface that had not been subjected to the oxidation treatment, and the peeling strength of the line in the 90-degree direction was measured at a peeling speed of 50 mm / min. .
【００５１】ガラス転移温度は、得られた多層の積層板
の外層銅箔を全面エッチングした後、ＪＩＳ規格Ｃ６４
８１のＤＳＣ法に基づき求めた。The glass transition temperature is determined by etching the entire outer layer copper foil of the obtained multilayer laminate, and then measuring the JIS standard C64.
81 based on the DSC method.
【００５２】吸湿率は、得られた多層の積層板の外層銅
箔を全面エッチングした後、８５℃、８５％の恒温恒湿
槽で７日間吸湿処理し、試験片の重量を測定して、吸湿
処理前の試験片の重量からの増加重量より算出した。The moisture absorption rate was determined by etching the outer layer copper foil of the obtained multilayer laminate over the entire surface and then subjecting it to a moisture absorption treatment in a constant temperature and humidity chamber of 85 ° C. and 85% for 7 days. It was calculated from the weight increase from the weight of the test piece before the moisture absorption treatment.
【００５３】その結果は表１に示した通り、各実施例は
各比較例と比べて、内層銅箔接着強度が優れ、ガラス転
移温度及び吸湿率は同等以上であることが確認された。The results are shown in Table 1. As shown in Table 1, it was confirmed that each of the examples was superior to each of the comparative examples in the adhesive strength of the inner layer copper foil, and the glass transition temperature and the moisture absorption were equal or higher.
【００５４】[0054]
【表１】 [Table 1]
【００５５】[0055]
【発明の効果】本発明に係る積層板の製造方法を用いる
と、フェノール系の硬化剤を含有するエポキシ樹脂系熱
硬化性樹脂を使用した場合であっても、銅回路の表面に
形成した酸化銅皮膜と熱硬化性樹脂の硬化物との間の接
着強度が優れた積層板を得ることができる。According to the method of manufacturing a laminate according to the present invention, even when an epoxy resin-based thermosetting resin containing a phenol-based curing agent is used, the oxidation formed on the surface of the copper circuit can be improved. A laminate having excellent adhesive strength between the copper film and the cured product of the thermosetting resin can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０５Ｋ 1/03 ６３０ Ｈ０５Ｋ 1/03 ６３０Ｈ 3/38 3/38 Ｂ // Ｈ０５Ｋ 3/46 3/46 Ｇ (72)発明者 北川 修次 大阪府門真市大字門真1048番地松下電工株 式会社内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI H05K 1/03 630 H05K 1/03 630H 3/38 3/38 B // H05K 3/46 3/46 G (72) Inventor Shuji Kitagawa 1048 Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Works, Ltd.
Claims (5)
理して、その銅回路の表面に酸化銅皮膜を形成した後、
その酸化銅皮膜と、エポキシ樹脂及びフェノール系硬化
剤を含有する熱硬化性樹脂と、を接着して製造する積層
板の製造方法において、銅回路の表面に形成する酸化銅
皮膜の量が、１ｃｍ2当たり０．０３〜０．１５ｍｇで
あることを特徴とする積層板の製造方法。Claims: 1. A copper circuit formed on a surface of a substrate is oxidized to form a copper oxide film on the surface of the copper circuit.
In a method for manufacturing a laminate, wherein the copper oxide film is bonded to a thermosetting resin containing an epoxy resin and a phenolic curing agent, the amount of the copper oxide film formed on the surface of the copper circuit is 1 cm. 2. A method for producing a laminate, wherein the amount per 2 is 0.03 to 0.15 mg.
法が、銅回路を酸化処理して、銅回路の表面に酸化銅層
を形成した後、その酸化銅層を酸処理し、その酸化銅層
より酸化銅の量が少ない酸化銅皮膜に加工する方法であ
ることを特徴とする請求項１記載の積層板の製造方法。2. A method of forming a copper oxide film on a surface of a copper circuit, wherein the copper circuit is oxidized to form a copper oxide layer on the surface of the copper circuit, and then the copper oxide layer is acid-treated. The method for producing a laminate according to claim 1, wherein the method is a method of processing a copper oxide film having a smaller amount of copper oxide than a copper oxide layer.
法が、銅回路を酸化処理して、銅回路の表面に酸化銅層
を形成した後、その酸化銅層を還元処理し、その酸化銅
層より酸化銅の量が少ない酸化銅皮膜に加工する方法で
あることを特徴とする請求項１記載の積層板の製造方
法。3. A method of forming a copper oxide film on the surface of a copper circuit comprises oxidizing the copper circuit to form a copper oxide layer on the surface of the copper circuit, and then reducing the copper oxide layer. The method for producing a laminate according to claim 1, wherein the method is a method of processing a copper oxide film having a smaller amount of copper oxide than a copper oxide layer.
エポキシ基とフェノール系硬化剤の水酸基の当量比が、
１：０．５〜２であることを特徴とする請求項１から請
求項３のいずれかに記載の積層板の製造方法。4. An equivalent ratio of an epoxy group of an epoxy resin contained in a thermosetting resin to a hydroxyl group of a phenolic curing agent,
The method for producing a laminate according to any one of claims 1 to 3, wherein the ratio is 1: 0.5 to 2.
ガラスクロスに含浸した熱硬化性樹脂であることを特徴
とする請求項１から請求項４のいずれかに記載の積層板
の製造方法。5. A thermosetting resin which adheres to a copper oxide film,
The method for producing a laminate according to any one of claims 1 to 4, wherein the resin is a thermosetting resin impregnated in a glass cloth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9105046A JPH10296942A (en) | 1997-04-23 | 1997-04-23 | Manufacture of laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9105046A JPH10296942A (en) | 1997-04-23 | 1997-04-23 | Manufacture of laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10296942A true JPH10296942A (en) | 1998-11-10 |
Family
ID=14397065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9105046A Pending JPH10296942A (en) | 1997-04-23 | 1997-04-23 | Manufacture of laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10296942A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7651778B2 (en) | 2006-08-31 | 2010-01-26 | Fuji Xerox, Ltd. | Laminated body and producing method thereof, fixing belt, fixing device and image forming device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6022012B2 (en) * | 1982-03-29 | 1985-05-30 | 日東電工株式会社 | prepreg sheet |
| JPH0258898A (en) * | 1988-08-25 | 1990-02-28 | Toshiba Chem Corp | Manufacture of multilayer printed wiring board |
| JPH0379621A (en) * | 1989-05-12 | 1991-04-04 | Mitsubishi Electric Corp | Resin composition for laminate |
| JPH0462047A (en) * | 1990-07-02 | 1992-02-27 | Compeq Mfg Co Ltd | Method for bonding copper and resin |
| JPH05259611A (en) * | 1992-03-12 | 1993-10-08 | Hitachi Chem Co Ltd | Production of printed wiring board |
| JPH0636470B2 (en) * | 1989-03-03 | 1994-05-11 | 松下電工株式会社 | Method for treating copper circuit of circuit board for inner layer |
| JPH06262722A (en) * | 1993-01-14 | 1994-09-20 | Matsushita Electric Works Ltd | Preparation of composite body of metal copper and resin |
-
1997
- 1997-04-23 JP JP9105046A patent/JPH10296942A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6022012B2 (en) * | 1982-03-29 | 1985-05-30 | 日東電工株式会社 | prepreg sheet |
| JPH0258898A (en) * | 1988-08-25 | 1990-02-28 | Toshiba Chem Corp | Manufacture of multilayer printed wiring board |
| JPH0636470B2 (en) * | 1989-03-03 | 1994-05-11 | 松下電工株式会社 | Method for treating copper circuit of circuit board for inner layer |
| JPH0379621A (en) * | 1989-05-12 | 1991-04-04 | Mitsubishi Electric Corp | Resin composition for laminate |
| JPH0462047A (en) * | 1990-07-02 | 1992-02-27 | Compeq Mfg Co Ltd | Method for bonding copper and resin |
| JPH05259611A (en) * | 1992-03-12 | 1993-10-08 | Hitachi Chem Co Ltd | Production of printed wiring board |
| JPH06262722A (en) * | 1993-01-14 | 1994-09-20 | Matsushita Electric Works Ltd | Preparation of composite body of metal copper and resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7651778B2 (en) | 2006-08-31 | 2010-01-26 | Fuji Xerox, Ltd. | Laminated body and producing method thereof, fixing belt, fixing device and image forming device |
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