JPH10168596A - Surface treatment of copper foil - Google Patents
Surface treatment of copper foilInfo
- Publication number
- JPH10168596A JPH10168596A JP8329384A JP32938496A JPH10168596A JP H10168596 A JPH10168596 A JP H10168596A JP 8329384 A JP8329384 A JP 8329384A JP 32938496 A JP32938496 A JP 32938496A JP H10168596 A JPH10168596 A JP H10168596A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- copper foil
- copper
- bath
- electrolysis
- 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.)
- Granted
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
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Landscapes
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は銅箔の、特に粗面化
表面処理に関するものであり、特に詳しくはプリント配
線板用を代表とする導電体用途において、均一でかつ、
適用樹脂に対し接着性の高い表面処理を提供する方法に
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, particularly to a roughened surface treatment.
The present invention relates to a method for providing a surface treatment having high adhesiveness to an applied resin.
【０００２】[0002]
【従来の技術】銅箔は電子、電気材料用としては特にプ
リント配線板用途に多く使用されている。プリント配線
板は年々高性能化、高信頼性が進んでおり、そのため複
雑で且つ多様化してきている。このプリント配線板の構
成材料の一つとなっている銅箔についても同様に、厳し
い品質要求が課せられて来ている。2. Description of the Related Art Copper foils are widely used for electronic and electric materials, especially for printed wiring boards. The performance and reliability of printed wiring boards have been improving year by year, and as a result, they have become more complicated and diversified. Strict quality requirements have similarly been imposed on copper foil, which is one of the constituent materials of this printed wiring board.
【０００３】プリント配線板製造では、まず銅箔の粗面
側を合成樹脂含浸基材と合わせて積層し、プレスにより
加熱圧着して銅張積層板を得る。一般によく使用される
ガラスエポキシ基材では 160℃〜170 ℃で１〜２時間の
プレスで完了する。プリント配線板用銅箔としては片側
粗面、片側光沢面を持つ電解銅箔が圧倒的に多く使用さ
れており、通常、銅の電解液から電着装置により、銅を
電解析出させ、未処理銅箔と呼ばれる原箔を製造し、次
に処理装置により、一連の表面処理を行う。一般的に
は、粗面側（非光沢面側）を酸洗し、粗面化して樹脂と
の接着力を確保する処理を行い、さらにその接着性にお
ける耐熱、耐薬品などの特性やエッチング特性などを向
上、安定化させる処理を行い、完成される。これらの処
理についてはさまざまな技術が開発、提案され、高機能
性表面となっている。最近のプリント配線板の高密度
化、例えば薄物プリント配線板やビルドアップ工法のプ
リント配線板では絶縁層となる樹脂層が極めて薄く、銅
箔粗面が大きい場合、層間絶縁性に問題が生じる可能性
がある。In the production of printed wiring boards, first, the copper foil is laminated with the rough side of the copper foil together with a synthetic resin-impregnated base material, and heated and pressed by a press to obtain a copper-clad laminate. For a commonly used glass epoxy substrate, it is completed by pressing at 160 ° C. to 170 ° C. for 1 to 2 hours. As copper foil for printed wiring boards, electrolytic copper foil having a rough surface on one side and a glossy surface on one side is overwhelmingly used, and usually copper is electrolytically deposited from a copper electrolytic solution by an electrodeposition apparatus. An original foil called a treated copper foil is manufactured, and then a series of surface treatments are performed by a processing apparatus. Generally, the rough side (non-glossy side) is pickled and roughened to ensure adhesion to the resin. In addition, the adhesive properties such as heat resistance and chemical resistance, and etching properties The process is performed to improve and stabilize, etc., and it is completed. Various techniques have been developed and proposed for these treatments, resulting in highly functional surfaces. Recent densification of printed wiring boards, such as thin printed wiring boards and build-up printed wiring boards, where the resin layer serving as the insulating layer is extremely thin and the copper foil rough surface is large, may cause problems with interlayer insulation. There is.
【０００４】また、ファインライン化により、銅箔粗面
はなるべくその粗さが低い方が対応できるなど粗面側は
低プロファイル化が望まれてきている。しかし接着力が
十分でないと製造工程や製品となった後での銅箔回路の
剥がれや浮き等、デラミネーションの問題が生じてくる
ので、両者を満足する表面処理が最も好ましいが、互い
に相反する事であるので優れた方法が待たれていた。一
方反対側の面、光沢面側には粗面側とは異なる特性、す
なわち耐熱変色性、半田濡れ性、レジスト密着性、など
が要求されており、粗面側、光沢面側それぞれ別の処理
方法が必要である。但し多層プリント配線板用途には特
に内層用として適用する場合においては半田濡れ性の必
要はなく、また、光沢面側は従来粗面化処理を施す必要
はなかったが、ＤＴ箔（Double treatment) と称する銅
箔用途以外でもレジストの密着性、プリント板形成時の
内層処理の密着力上昇のため、軽い粗面化処理が要望さ
れてきている。[0004] In addition, it has been desired to reduce the profile on the roughened surface side, for example, by making the copper foil roughened surface as low as possible by forming a fine line. However, if the adhesive force is not sufficient, a problem of delamination, such as peeling or floating of the copper foil circuit after the production process or product, occurs, so a surface treatment that satisfies both is most preferable, but it is contradictory to each other Because of that, a better way was waiting. On the other hand, the opposite side, the glossy side, requires different properties from the rough side, that is, heat discoloration resistance, solder wettability, resist adhesion, etc. I need a way. However, there is no need for solder wettability especially in the case of application as an inner layer for multilayer printed wiring board applications, and the glossy side conventionally did not need to be roughened, but DT foil (Double treatment) In addition to the use of copper foil, which is referred to as "copper foil", a light surface roughening treatment has been demanded due to an increase in the adhesiveness of the resist and the adhesiveness of the inner layer treatment when forming a printed board.
【０００５】以上のように銅箔の両面において種々の要
望に答えるべく複雑な処理が開発されてきている。従来
の技術では粗化処理に関する技術としては種々提案され
ており、たとえば特公昭53-38700号にヒ素を含む酸性電
解浴中で 3段の電解処理を行う方法や、また、特公昭53
-39327号、特公昭54-38053号には砒素、アンチモン、ビ
スマス、セレン、テルルを含む酸性銅電解浴中で限界電
流密度前後で電解する方法、また特公昭62-56677号、特
公昭62-56678号にはモリブデン、バナジウム或いは両者
を添加した銅電解浴中による方法などが提案されてい
る。また、特公昭61-54592号、特開平4-202796号には交
流電解による表面処理粗化方法が提案されている。As described above, complicated treatments have been developed on both surfaces of a copper foil in order to meet various demands. In the prior art, various techniques relating to the roughening treatment have been proposed. For example, Japanese Patent Publication No. 53-38700 discloses a method in which a three-stage electrolytic treatment is performed in an acidic electrolytic bath containing arsenic.
No.-39327, JP-B-54-38053, a method of electrolysis at around the limiting current density in an acidic copper electrolytic bath containing arsenic, antimony, bismuth, selenium, and tellurium, and JP-B-62-56677 and JP-B-62 No. 56678 proposes a method in a copper electrolytic bath to which molybdenum, vanadium or both are added. Japanese Patent Publication No. 61-54592 and Japanese Patent Application Laid-Open No. 4-202796 propose a surface treatment roughening method using alternating current electrolysis.
【０００６】しかし、上記のような従来の方法において
は、ヒ素、アンチモン、ビスマス、セレン、テルルのよ
うな人体に有害な物質を使用することは環境問題上使用
が極めて制限されてきている。プリント板再利用の点で
も有害成分の蓄積が懸念され、代替方法が強く要求され
ているものである。一方、モリブデン、バナジウムなど
の添加による方法は接着力、均一性、残銅などの点にお
いていまだ必ずしも十分とはいえず、要求されている高
度な信頼性を得ることができない。またさらに交流電解
のみの粗化処理では十分な接着力を得ることができず実
用的でない。However, in the above-mentioned conventional methods, the use of substances harmful to the human body such as arsenic, antimony, bismuth, selenium, and tellurium has been extremely limited due to environmental problems. There is also a concern about the accumulation of harmful components in the reuse of printed boards, and alternative methods are strongly required. On the other hand, the method based on the addition of molybdenum, vanadium or the like is not yet sufficient in terms of adhesive strength, uniformity, residual copper, and the like, and the required high reliability cannot be obtained. Further, a roughening treatment using only AC electrolysis cannot provide a sufficient adhesive force, and is not practical.
【０００７】[0007]
【発明が解決しようとする課題】本発明者らは前記の従
来技術の問題を種々研究し、ヒ素、セレン、テルルなど
毒性のある元素を使用せず容易な方法で均一にかつ接着
力が高く得られる粗面化処理方法を開発し、完成させ
た。SUMMARY OF THE INVENTION The present inventors have studied various problems of the prior art described above, and have found that uniform and high adhesion can be obtained by an easy method without using toxic elements such as arsenic, selenium and tellurium. The resulting surface roughening method was developed and completed.
【０００８】[0008]
【問題を解決するための手段】問題を解決するための手
段はすなわち、銅箔の少なくとも一方の面を、酸洗工程
の後、塩素イオン 1ppm 〜1000ppm 含む硫酸酸性浴中で
正負の交番パルス電解、又は交流電解をすることによる
活性化処理工程により活性化、微細粗化し、続いて、硫
酸、硫酸銅浴中で限界電流密度付近又はそれ以上で陰極
電解することにより銅の突起物粗化を行い、さらに、銅
めっきによる被覆層を形成させて銅箔の粗面化を行い、
次いで防錆処理を行うことを特徴とする銅箔の表面処理
方法であり、必要に応じて、酸洗工程と活性化処理工程
の中間に、硫黄を含有する有機化合物を0.001 〜 0.5モ
ル/l含む水溶液で銅箔を処理するか、又は酸洗工程の浴
が硫黄を含有する有機化合物を含んでもよい。さらにま
た、適宜、正負の交番パルス電解時間を１サイクルあた
り 0.2〜200ms とすることを特徴とし、また、粗面化
後、必要に応じて防錆処理がクロメ−ト処理及び／又は
有機物防錆を施すことを特徴とする銅箔の表面処理方法
である。[Means for Solving the Problem] Means for solving the problem are as follows: at least one surface of the copper foil is subjected to an alternating pulse electrolysis in a sulfuric acid acid bath containing 1 ppm to 1000 ppm of chloride ions after an acid washing step. Or by an activation treatment step by performing AC electrolysis, activation, fine roughening, and then, by sulfuric acid, cathodic electrolysis at or near the critical current density in a copper sulfate bath, roughening of copper protrusions. Perform, further, to form a coating layer by copper plating to roughen the copper foil,
Then, a surface treatment method for the copper foil characterized by performing a rust prevention treatment.If necessary, a sulfur-containing organic compound is added in an amount of 0.001 to 0.5 mol / l between the pickling step and the activation treatment step. The copper foil may be treated with an aqueous solution containing the acid, or the bath of the pickling step may contain an organic compound containing sulfur. Further, the positive and negative alternating pulse electrolysis time is appropriately set to 0.2 to 200 ms per cycle, and after the surface is roughened, the rust preventive treatment is carried out, if necessary, by chromate treatment and / or organic matter rust preventive treatment. Is a method for surface treating a copper foil.
【０００９】本発明の粗面化処理方法は基本的に３段階
からなる。第１段階は未処理銅箔を酸洗浄し、表面酸化
物や汚れを除去する酸洗工程である。酸洗浄としては硫
酸水溶液を使用するのが好ましい。硫酸濃度としては 1
0 〜 200g/l が適当である。処理時間は 2〜60秒、浴温
度は10〜50℃が良い。第２段階は、塩素イオンを 1〜10
00ppm 含む硫酸酸性浴中で正負の交番パルス電解又は交
流電解を行う活性化処理工程である。浴組成としては、
例えば硫酸100g/l, 塩化ナトリウム 10ppmである。硫酸
濃度は10〜200g/lが良い。塩素濃度は 1〜1000ppm が良
く、1ppm以下では活性化及び微細粗化の程度が低く、10
00 ppm以上では銅表面の腐食が激しくなり、銅突起物の
固着化や均一性が阻害される。なお通常工業的には水の
リサイクルをするため工業用水としてイオン交換水を使
用するので水に塩素は含まれないが、水道水を使用した
場合、水中に塩素が 10ppm近く含まれる。しかし、本発
明の交番パルス電解又は交流電解をすることによって塩
素は消費されるので、連続的又は間欠的に塩素を添加し
なければならない。塩素の添加法としては塩酸や塩化ナ
トリウム、塩化カリウムなどアルカリ金属、アルカリ土
類金属の塩化物等を使用する。The surface roughening method of the present invention basically includes three steps. The first stage is a pickling step of pickling the untreated copper foil to remove surface oxides and stains. It is preferable to use an aqueous sulfuric acid solution for the acid cleaning. 1 for sulfuric acid concentration
0 to 200 g / l is appropriate. The treatment time is 2-60 seconds, and the bath temperature is 10-50 ° C. In the second stage, chloride ions are
This is an activation process in which positive and negative alternating pulse electrolysis or alternating current electrolysis is performed in a sulfuric acid acid bath containing 00 ppm. As bath composition,
For example, 100 g / l sulfuric acid and 10 ppm sodium chloride. The sulfuric acid concentration is preferably between 10 and 200 g / l. The chlorine concentration is preferably 1 to 1000 ppm, and if it is 1 ppm or less, the degree of activation and coarsening is low.
If the content is more than 00 ppm, the corrosion of the copper surface becomes severe, and the fixation and uniformity of the copper projection are hindered. Normally, ion-exchanged water is used as industrial water to recycle water industrially, so water does not contain chlorine. However, when tap water is used, water contains nearly 10 ppm of chlorine. However, since the alternating pulse electrolysis or the alternating current electrolysis according to the present invention consumes chlorine, the chlorine must be continuously or intermittently added. As a method for adding chlorine, an alkali metal such as hydrochloric acid, sodium chloride, or potassium chloride, or a chloride of an alkaline earth metal is used.
【００１０】電流密度は5 〜100 A/dm2で、電気量とし
て20〜1000クーロン/dm2が適当である。温度は10〜50℃
が良い。正負の交番パルス電解の場合はその電流の正負
ともオンタイム 0.1〜 100ms、オフタイム 0〜100ms 、
かつ1 サイクルが 0.2〜 200msであって、それぞれ短過
ぎる場合、長過ぎる場合とも活性化、微細粗面化の効率
が低い。また、波形は矩形波、正弦波、など限定されな
い。但しパルス電気量の正負の比は等しいくらいすなわ
ち、0.7 〜 1.3 とした方が良く、この範囲をはずれる
と粗面の活性化が低下する。交流電解はその電流値の正
負の比は同じである。これに直流を重複して流してもよ
いが、正負の比をやはり交番パルス電解と同様に0.7〜
1.3とした方がよい。この第２段階の処理により銅箔の
表面が活性化し、また非常に微細な凹凸を形成すること
で、続く第３段階の粗化処理の均一性を向上させる。前
記の第２段階処理を行わない場合は、第３段階の該粗面
化処理によって得られる銅突起物からなる粗面形状が極
めて不均一でかつ粗大な樹枝状物として発生し、プレス
成型後、エッチング基板面において残銅を生じる。この
欠陥はプリント配線板としては致命的となる。第２段階
の処理をかけることで第３段階の粗面化処理が均一化
し、表面粗さは低下しかつ接着力は上昇する。The current density is 5 to 100 A / dm 2 , and a suitable electric quantity is 20 to 1000 coulombs / dm 2 . Temperature is 10-50 ℃
Is good. In the case of positive and negative alternating pulse electrolysis, both the on and off times of the current are 0.1 to 100 ms, the off time is 0 to 100 ms,
In addition, one cycle is 0.2 to 200 ms, and the efficiency of activation and fine surface roughening is low even if each cycle is too short or too long. Further, the waveform is not limited to a rectangular wave, a sine wave, or the like. However, it is preferable that the positive / negative ratio of the pulse electric quantity is equal, that is, 0.7 to 1.3. If the ratio is out of this range, the activation of the rough surface is reduced. In AC electrolysis, the positive / negative ratio of the current value is the same. Although a direct current may be overlapped with this, the positive / negative ratio is also set to 0.7 to 0.7 as in the alternating pulse electrolysis.
1.3 is better. The second stage treatment activates the surface of the copper foil and forms very fine irregularities, thereby improving the uniformity of the subsequent third stage roughening treatment. When the above-mentioned second stage treatment is not performed, the rough surface shape composed of copper projections obtained by the surface roughening treatment of the third stage occurs as a very uneven and coarse dendritic material. , Copper remains on the etched substrate surface. This defect is fatal for a printed wiring board. By applying the second-stage treatment, the third-stage surface-roughening treatment is made uniform, the surface roughness is reduced, and the adhesive strength is increased.
【００１１】なお、第２段階での微細粗化は、銅表面薄
層における銅の溶出及び析出の反復であり、陰極析出物
形態とは全く異なる。第３段階は公知の粗化方法により
表面処理を行う。すなわち例えば樹枝状又は粒状突起物
銅を析出させ、次いでその突起物の脱落防止のためその
上に銅めっきを施し、被覆銅を形成させて銅の粗面を作
る。 銅突起物の形成は CuSO4・5H2O 50 g/l H2SO4 100 g/l 常温、10A/dm2 の電流密度、12
秒間の陰極電解 次いで被覆銅めっき CuSO4・5H2O 250 g/l H2SO4 100 g/l 50℃、 5A/dm2 の電流密度、80
秒間の陰極電解 以上により、粗面が完成される。The micro-roughening in the second stage is a repetition of copper elution and deposition in a thin copper surface layer, which is completely different from the form of a cathode deposit. In the third step, surface treatment is performed by a known roughening method. That is, for example, dendritic or granular copper is deposited, and then copper plating is applied thereon to prevent the projections from falling off, thereby forming coated copper to form a rough copper surface. Formation of the copper protrusions is CuSO 4 · 5H 2 O 50 g / l H 2 SO 4 100 g / l room temperature, a current density of 10A / dm 2, 12
Seconds cathodic electrolysis then coated copper plating CuSO of 4 · 5H 2 O 250 g / l H 2 SO 4 100 g / l 50 ℃, current density of 5A / dm 2, 80
Cathodic electrolysis for seconds The rough surface is completed.
【００１２】次いで必要に応じて耐熱性付与、耐薬品性
付与の処理をするが、この時は特公平2-24037 や特公平
8-19550 などのCo-Mo,W やCu-Zn のバリヤー層を形成さ
せても良い。さらに防錆力を上げるためにクロメート処
理やベンズトリアゾ−ルを代表とする有機防錆処理、ま
た、シランカップリング剤処理などを行う。以上により
プリント配線板用銅箔が完成する。通常、銅箔の光沢面
側は多層板内層用として用いる両面処理銅箔(DT 箔) と
して以外では従来粗面化処理を施す必要はなかったが、
近年、プリント配線板製造においてレジストの密着性、
ソフトエッチング工程の省略や、内層処理の密着力上昇
のため、あらかじめ微細均一で軽度の粗面化処理を施し
たＤＴ箔が要望されてきている。Next, if necessary, treatments for imparting heat resistance and chemical resistance are performed.
A barrier layer of Co-Mo, W or Cu-Zn such as 8-19550 may be formed. In order to further increase the rust-preventing ability, a chromate treatment, an organic rust-prevention treatment typified by benzotriazole, and a silane coupling agent treatment are performed. Thus, a copper foil for a printed wiring board is completed. Normally, the glossy side of the copper foil was not required to be roughened except for the double-sided treated copper foil (DT foil) used for the inner layer of the multilayer board.
In recent years, in the manufacture of printed wiring boards,
In order to omit the soft etching step and to increase the adhesion force of the inner layer treatment, there is a demand for a DT foil which has been subjected to fine uniform and light roughening treatment in advance.
【００１３】そこで、銅箔の両面を上記本発明法におい
て第１の酸洗工程に続いて第２段階の活性化処理工程、
すなわち、塩素イオン 1ppm 〜1000ppm を含む硫酸酸性
浴中で正負の交番パルス電解、又は交流電解をすること
により活性化、微細粗化し、粗面側には第３段階の処理
すなわち、硫酸、硫酸銅浴中で限界電流密度付近又はそ
れ以上で陰極電解することにより銅の微細突起物粗化を
行い、さらに、その粗面側に銅めっきをして被覆層を形
成させる処理を施す方法が両面処理銅箔の改良として提
案できる。なお、銅箔処理における粗面、光沢面を逆に
して上記の処理を行ってもよい。この場合は銅張積層板
作成時、未処理銅箔で光沢面側であった面を先に樹脂と
接着させる。このような方法は片面に何も処理を施さな
い場合よりも樹脂との成型後、樹脂と接着していない面
は、レジストとの密着性が高く、また、接着性が良いの
でプリント板製造業者における内層処理工程において、
その前処理であるソフトエッチングの工程が不要とな
る。しかも銅箔の製造者側では銅箔の表面処理工程が従
来の両面処理銅箔を製造することと比較して軽い処理で
済むので非常に容易にできることになる。Therefore, in the above-mentioned method of the present invention, both sides of the copper foil are subjected to the second pickling step, the second step of the activation step,
That is, activation and fine roughening are performed by alternating positive and negative pulse electrolysis or alternating current electrolysis in a sulfuric acid acid bath containing 1 ppm to 1000 ppm of chlorine ions. The method of roughening copper fine projections by performing cathodic electrolysis at or near the limit current density in a bath, and further performing a process of forming a coating layer by copper plating on the rough surface side is a double-sided treatment. It can be proposed as an improvement of copper foil. Note that the above treatment may be performed with the rough surface and the glossy surface reversed in the copper foil treatment. In this case, at the time of preparing the copper-clad laminate, the surface which was the untreated copper foil on the glossy side is first bonded to the resin. In such a method, after molding with resin, the surface that is not bonded to the resin has higher adhesion with the resist after molding with resin than on the case where no treatment is applied to one side, and the adhesion is good, so the printed board manufacturer In the inner layer processing step,
This eliminates the need for a soft etching step as a pretreatment. In addition, the copper foil surface treatment can be performed very easily on the copper foil manufacturer side, since the copper foil surface treatment process requires only a lighter treatment than the conventional method of producing a double-sided copper foil.
【００１４】次に上記方法に加えてさらに改良された方
法を記す。上記第１段階と第２段階処理の間に第１−２
段階として、硫黄を含む有機化合物の水溶液にて銅箔表
面を処理させる工程を入れる方法が上げられる。また、
第１−２段階を挿入せずに、第１段階の処理液自身に硫
黄を含む有機化合物を添加して処理してもよい。なお、
その硫黄を含む有機化合物水溶液による表面処理工程を
本発明に記載していない前工程である未処理銅箔の製造
の後部工程に付設し、その巻き取った銅箔を次に処理機
械に適用した場合も同様の効果を示すことは同業者間で
は容易に類推できる。硫黄を含有する有機化合物として
はチオ尿素、アリルチオ尿素、エチレンチオ尿素、アセ
チルチオ尿素、ベンゾチアゾールチオール、アミノベン
ゾチアゾール、アミノチアゾ−ル、メルカプトチアゾリ
ン、チオアセトアミド、メルカプトメチルイミダゾー
ル、チオジプロピオン酸、ジチオジプロピオン酸、ベン
ズイミダゾ−ルチオ−ル、チオジエタノ−ル、ジチオジ
エタノール、メルカプト酢酸など水溶液に可溶性又は溶
媒を介して水溶性となる化合物であればどのようなもの
でも良い。これら化合物の水溶液濃度は 0.001〜0.5mol
/lが適当であり、温度は10〜50℃、処理時間は1 〜20秒
程度が良い。処理方法としては、スプレ−噴霧やシャワ
−掛けによる方法又は水溶液中電解処理を行うが、樹脂
との最初の接着面側に処理したほうが良い。非接着面側
に処理を行うと、プリント配線板製造工程の内層処理で
ある黒化処理の接着性を低下させることがある。この化
合物水溶液処理後はその処理外観を均一化するため、水
洗を施した方が好ましい。また、その後の粗面化処理は
電気量として20〜60% 程度通常より多く処理しなければ
接着力は出にくくなる。吸着した硫黄化合物が銅の電着
を抑制し、均一化を促進するものと考えられる。Next, a further improved method in addition to the above method will be described. Between the first and second stage processes, 1-2
As a step, there is a method in which a step of treating the copper foil surface with an aqueous solution of an organic compound containing sulfur is used. Also,
An organic compound containing sulfur may be added to the treatment liquid of the first stage without adding the first and second stages. In addition,
The surface treatment step using the sulfur-containing organic compound aqueous solution was attached to a later step of manufacturing an untreated copper foil, which is a preceding step not described in the present invention, and the wound copper foil was then applied to a processing machine. In this case, the same effect can be easily understood by those skilled in the art. Examples of organic compounds containing sulfur include thiourea, allylthiourea, ethylenethiourea, acetylthiourea, benzothiazolethiol, aminobenzothiazole, aminothiazole, mercaptothiazoline, thioacetamide, mercaptomethylimidazole, thiodipropionic acid, and dithiodipropion. Any compound which is soluble in an aqueous solution or becomes water-soluble via a solvent such as an acid, benzimidazolethiol, thiodiethanol, dithiodiethanol, and mercaptoacetic acid may be used. The concentration of these compounds in aqueous solution is 0.001-0.5mol
/ l is appropriate, the temperature is preferably 10 to 50 ° C, and the processing time is preferably about 1 to 20 seconds. As a treatment method, a method by spraying or showering or an electrolytic treatment in an aqueous solution is performed, but it is better to treat the resin on the side of the first bonding surface with the resin. When the treatment is performed on the non-adhesive surface side, the adhesiveness of the blackening treatment, which is the inner layer treatment in the printed wiring board manufacturing process, may be reduced. After the treatment with the aqueous compound solution, it is preferable to wash with water in order to make the appearance of the treatment uniform. Further, if the subsequent surface roughening treatment is not carried out more than the normal amount of about 20 to 60% in terms of the amount of electricity, it becomes difficult to obtain an adhesive force. It is considered that the adsorbed sulfur compound suppresses the electrodeposition of copper and promotes homogenization.
【００１５】[0015]
【発明の実施の形態】本発明法は量産的には電解銅箔又
は圧延銅箔を処理機械により表面処理することによって
得られる。前述の通り酸洗工程の第１段処理、次いで交
番パルス電解又は交流電解を行う活性化処理工程の第２
段処理、次いで第３段処理として硫酸−硫酸銅液からな
る粗化処理を行い、続いて必要に応じて公知の方法によ
り耐熱、耐薬品処理、さらにクロメート処理及び／又は
有機防錆処理を施す。また、第１段、第２段の中間に硫
黄を含む有機化合物の水溶液で処理する工程を入れる
か、第１段処理の処理浴中にその硫黄を含む有機化合物
を添加してもよい。BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention can be mass-produced by subjecting an electrolytic copper foil or a rolled copper foil to a surface treatment with a processing machine. As described above, the first stage of the pickling process, and then the second stage of the activation process of performing alternating pulse electrolysis or alternating current electrolysis.
Step treatment, followed by a roughening treatment comprising a sulfuric acid-copper sulfate solution as a third step treatment, and then, if necessary, heat treatment, chemical resistance treatment, further chromate treatment and / or organic rust prevention treatment by a known method. . Further, a step of treating with an aqueous solution of an organic compound containing sulfur may be provided between the first and second stages, or the organic compound containing sulfur may be added to the treatment bath of the first stage treatment.
【００１６】[0016]
【実施例】以下、本発明の実施例について述べる。 実施例(1) 35μm 厚さの未処理電解銅箔の両面を の浴中において10秒浸漬後、 の浴中において両面とも 1サイクル 10ms,オフタイム0
ms, 正負とも 20 A/dm2,各オンタイム 5msの矩形波を持
つ交番パルス電解を 10 秒間行った。 次いで粗面側のみを の浴中において、10 A ／dm2 、12秒間陰極電解し、水
洗後、粗面側のみを の浴中において、 5 A ／dm2 、80秒間陰極電解し、水
洗後、 の浴中において光沢面は浸漬状態にして、粗面側のみを
0.5A/dm2 、5 秒間陰極電解し、水洗後、乾燥させた。
この銅箔の粗面を被着面としてFR-4グレードのガラスエ
ポキシ樹脂含浸基材に積層し、40 kgf／cm2 の圧力、 1
70℃、60分間の条件でプレスし、成型した。その銅張積
層板の特性（接着力、銅残）を調べた結果を表1 に示
す。また、光沢面側をソフトエッチングを行なわずに通
常の黒化処理浴で処理し、ＦＲ−４グレードのガラスエ
ポキシ樹脂含浸基材に積層し、同様にプレス成型し、そ
の接着力を測定した。その結果は同様に表１に示す。Embodiments of the present invention will be described below. Example (1) Both sides of an untreated electrolytic copper foil having a thickness of 35 μm After immersion in a bath for 10 seconds, 1 cycle 10 ms on both sides in the bath
Alternating pulse electrolysis was performed for 10 s with a square wave of 20 A / dm 2 on both the positive and negative sides and 5 ms each on-time. Then only the rough side In a bath of 10 A / dm 2 , cathodic electrolysis is performed for 12 seconds, and after washing with water, only the rough side is removed. In a bath of 5 A / dm 2 , cathodic electrolysis for 80 seconds, washing with water, In the bath, the glossy surface is immersed and only the rough side is
Cathodic electrolysis was performed at 0.5 A / dm 2 for 5 seconds, washed with water, and dried.
The rough surface of this copper foil is laminated as a surface to be adhered to a FR-4 grade glass epoxy resin impregnated substrate, and a pressure of 40 kgf / cm 2 is applied.
It was pressed and molded at 70 ° C. for 60 minutes. Table 1 shows the results of examining the properties (adhesive strength, copper residue) of the copper-clad laminate. The glossy side was treated in a normal blackening bath without performing soft etching, laminated on a FR-4 grade glass epoxy resin-impregnated substrate, press-molded in the same manner, and the adhesive strength was measured. The results are also shown in Table 1.
【００１７】実施例 (2) 実施例(1) において、 (B)浴での処理を1 サイクル時間
30ms,オフタイム 0ms正負とも20A/dm2 、各オンタイム
15ms の矩形波を持つ交番パルス電解により10秒間処理
とすること以外は実施例(1) と同じ方法で処理し、同じ
方法で各特性試験を行った。その結果を表１に示す。Example (2) In Example (1), (B) the treatment in the bath was performed for one cycle time.
30ms, off-time 0ms positive and negative with 20A / dm 2, each on-time
The treatment was performed in the same manner as in Example (1) except that the treatment was performed for 10 seconds by alternating pulse electrolysis having a rectangular wave of 15 ms, and each characteristic test was performed in the same manner. Table 1 shows the results.
【００１８】実施例 (3) 実施例(1) において、 (B)浴での処理を1 サイクル時間
2ms, オフタイム 0ms正負とも15A/dm2 各オンタイム 1
msの矩形波を持つ交番パルス電解により20秒間処理とす
ること以外は実施例(1) と同じ方法で処理し、同じ方法
で各特性試験を行った。その結果を表１に示す。Example (3) In Example (1), the treatment in the bath (B) was carried out for one cycle time.
2ms, Off time 0ms Both positive and negative 15A / dm 2 On time 1
The treatment was performed in the same manner as in Example (1) except that the treatment was performed for 20 seconds by alternating pulse electrolysis having a rectangular wave of ms, and each characteristic test was performed in the same manner. Table 1 shows the results.
【００１９】実施例 (4) 実施例(1) において、 (B)浴での処理を電流密度 20A/d
m2,60Hz の交流電解により20秒間処理とすること以外は
実施例(1) と同じ方法で処理し、同じ方法で各特性試験
を行った。その結果を表１に示す。Example (4) In Example (1), the treatment in the bath (B) was carried out at a current density of 20 A / d.
The treatment was performed in the same manner as in Example (1), except that the treatment was performed by AC electrolysis at m 2 and 60 Hz for 20 seconds, and each characteristic test was performed in the same manner. Table 1 shows the results.
【００２０】実施例 (5) 実施例(1) において、 (A)浴と(B) 浴の処理の間にチオ
尿素 0.3g/l の水溶液で粗面を20℃10秒間のスプレー噴
霧処理して水洗したこと、さらに (C) 浴において電解
時間を18秒としたこと以外は全て実施例(1) と同じ方法
で行った。また、実施例(1) と同じ方法で各特性試験を
おこなった。その結果を表１に示す。Example (5) In the same manner as in Example (1), the rough surface was subjected to a spraying treatment at 20 ° C. for 10 seconds with an aqueous solution of thiourea 0.3 g / l between the treatments of the baths (A) and (B). All were carried out in the same manner as in Example (1) except that the bath was washed with water and that the electrolysis time in the bath (C) was 18 seconds. Each characteristic test was performed in the same manner as in Example (1). Table 1 shows the results.
【００２１】実施例 (6) 35μm 厚さの未処理電解銅箔の両面を の浴中において10秒浸漬し、同じく両面を の浴中において 1サイクル 10ms,オフタイム0 ms, 正負
とも 20 A／dm2 各オンタイム5ms の矩形波を持つパル
ス交番電解を10秒間行った。 次いで光沢面側のみを の浴中において、10 A ／dm2 、18秒間陰極電解し、水
洗後、光沢面側のみを の浴中において、 5 A ／dm2 、80秒間陰極電解し、水
洗後、 の浴中において粗面側は浸漬状態にして、光沢面のみを
0.5A/dm2 、5 秒間陰極電解し、水洗後、乾燥させた。
この銅箔の粗面を被着面としてＦＲ−４グレードのガラ
スエポキシ樹脂含浸基材に積層し、40 kgf ／cm2 の圧
力、 170℃、60分間の条件でプレスし、成型した。その
銅張積層板の特性（接着力、銅残）を調べた結果を表２
に示す。また、粗面側をソフトエッチングを行わずに通
常の黒化処理浴で処理し、ＦＲ−４グレードのガラスエ
ポキシ樹脂含浸基材に積層し、同様にプレス成型し、そ
の接着力を測定した。その結果は同様に表２に示す。Example (6) Both sides of an untreated electrolytic copper foil having a thickness of 35 μm Immersion for 10 seconds in the bath In the bath, pulse alternating electrolysis with a rectangular wave of 10 ms per cycle, off time 0 ms, positive and negative 20 A / dm 2 and on time 5 ms each was performed for 10 seconds. Then only the glossy side In a bath of 10 A / dm 2 , cathodic electrolysis at 18 A for 18 seconds. In a bath of 5 A / dm 2 , cathodic electrolysis for 80 seconds, washing with water, In the bath, leave the rough side immersed and remove only the glossy surface.
Cathodic electrolysis was performed at 0.5 A / dm 2 for 5 seconds, washed with water, and dried.
The rough surface of the copper foil was laminated on an FR-4 grade glass epoxy resin-impregnated base material as an adhered surface, and pressed and molded at 40 kgf / cm 2 at 170 ° C. for 60 minutes. Table 2 shows the results of examining the characteristics (adhesive strength and copper residue) of the copper-clad laminate.
Shown in Further, the rough surface side was treated in a normal blackening treatment bath without performing soft etching, laminated on an FR-4 grade glass epoxy resin impregnated base material, press-molded in the same manner, and the adhesive strength was measured. The results are also shown in Table 2.
【００２２】実施例 (7) 実施例(6) において、 (B)浴での処理を電流密度 15A/d
m2,60Hz の交流電解により10秒間処理とすること以外は
実施例(6) と同じ方法で処理し、同じ方法で各特性試験
を行った。その結果を表２に示す。Example (7) In Example (6), the treatment in the bath (B) was carried out at a current density of 15 A / d.
The treatment was performed in the same manner as in Example (6), except that the treatment was performed for 10 seconds by AC electrolysis at m 2 and 60 Hz, and each characteristic test was performed in the same manner. Table 2 shows the results.
【００２３】実施例 (8) 実施例(1) において、(A)浴中にエチレンチオ尿素を0.5
g/l添加したこと、(B)浴による処理を電流密度 20/dm2,
60Hz の交流電解により10秒間処理したこと、また(C)
浴での処理の電解時間を18秒としたこと以外は実施例
(1) と同じ方法で処理し、同じ方法で各特性試験を行っ
た。その結果を表１に示す。Example (8) In Example (1), 0.5% of ethylene thiourea was added to the bath (A).
g / l was added, and the treatment with the bath (B) was performed at a current density of 20 / dm 2 ,
10 seconds treatment with 60Hz AC electrolysis, and (C)
Example except that the electrolysis time of the treatment in the bath was set to 18 seconds
Processing was performed in the same manner as in (1), and each property test was performed in the same manner. Table 1 shows the results.
【００２４】実施例 (9) 実施例(1) において、(A) 浴処理の後、水洗し、銅箔粗
面側にエチレンチオ尿素1g/l水溶液で20℃10秒間のスプ
レ−噴霧処理し、水洗した後、(B) 浴による処理に続く
ことと、(C)浴での処理の電解時間を18秒間としたこと
以外は実施例(1)と同じ方法で処理し、同じ方法で各特
性試験を行った。その結果を表１に示す。Example (9) In the same manner as in Example (1), after the bath treatment (A), the copper foil was washed with water, and the copper foil rough side was spray-sprayed with a 1 g / l aqueous solution of ethylene thiourea at 20 ° C. for 10 seconds. After washing with water, the treatment was performed in the same manner as in Example (1) except that the treatment in the bath (B) was continued, and the electrolysis time in the treatment in the bath (C) was set to 18 seconds. The test was performed. Table 1 shows the results.
【００２５】実施例 (10) 実施例(1) において、(A) 浴処理の後、水洗し、銅箔粗
面側にエチレンチオ尿素 1g/l水溶液、20℃10秒間のス
プレ−噴霧処理を行い、水洗した後、(B) 浴で両面を電
流密度 15A/dm2、60Hzの交流電解により10秒間処理し、
また(C) 浴での処理の電解時間を18秒間としたこと以外
同じ方法で処理し、同じ方法で各特性試験を行った。そ
の結果を表１に示す。Example (10) In Example (1), after the bath treatment (A), the copper foil was washed with water, and sprayed at 20 ° C. for 10 seconds with a 1 g / l aqueous solution of ethylene thiourea on the copper foil rough side. After washing with water, (B) Both sides were treated in a bath with a current density of 15 A / dm 2 and 60 Hz AC electrolysis for 10 seconds,
(C) The treatment was performed in the same manner except that the electrolysis time in the bath was set to 18 seconds, and each characteristic test was performed in the same manner. Table 1 shows the results.
【００２６】実施例 (11) 実施例(6) において、(A) 浴にアミノチアゾール1.0g/l
を添加したこと、また(B) 浴でのKCl 濃度が100ppmであ
ること以外は実施例(6) と同じ方法で処理し、同じ方法
で各特性試験を行った。その結果を表２に示す。Example (11) In Example (6), 1.0 g / l of aminothiazole was added to the bath (A).
Was treated in the same manner as in Example (6), except that (B) the KCl concentration in the bath was 100 ppm, and each property test was conducted in the same manner. Table 2 shows the results.
【００２７】実施例 (12) 実施例(6) において、(A) 浴処理の後、水洗し、銅箔光
沢面側をチオ尿素 0.2g/l 水溶液、20℃10秒間のスプレ
−噴霧処理を行い、水洗した後、(B) 浴において処理電
流密度 10A/dm2、電解時間を18秒間としたこと以外は実
施例(6) と同じ方法で処理し、同じ方法で各特性試験を
行った。その結果を表２に示す。Example (12) In Example (6), after the bath treatment (A), the copper foil was washed with water, and the glossy side of the copper foil was sprayed with a 0.2 g / l aqueous solution of thiourea at 20 ° C. for 10 seconds. Then, after washing with water, the treatment was performed in the same manner as in Example (6) except that the treatment current density was 10 A / dm 2 in the bath (B) and the electrolysis time was 18 seconds, and each characteristic test was performed in the same manner. . Table 2 shows the results.
【００２８】表１、２において 「均一性」は電子顕微鏡により約500 倍の倍率で観察
し、良好なものから◎、○、△、×と評価を行った。
「接着力」はその基材からの引きはがし強度を示し、 J
IS-C-6481-1986 5.7項の方法に準じた。「エッチング
基板残留銅」は塩化第二銅エッチングにより、銅をエッ
チング除去後、２０倍の倍率の実体顕微鏡観察を行っ
た。 残銅が全く無いもの ○ 残銅が認められるもの × で評価した。黒化処理条件は NaClO2 50g/l,Na3PO4・12H
2O 10g/l, NaOH 8g/l, 92 ℃ 2分で行った。In Tables 1 and 2, "uniformity" was observed by an electron microscope at a magnification of about 500 times, and evaluated as 、, ○, Δ, and × from good.
"Adhesive strength" indicates the peel strength from the base material, J
IS-C-6481-1986 According to the method described in 5.7. The “residual copper on the etched substrate” was removed by etching cupric chloride, and then observed with a stereoscopic microscope at a magnification of 20 times. Those with no residual copper ○ Those with residual copper were evaluated as ×. The blackening treatment conditions are NaClO 2 50g / l, Na 3 PO 4・ 12H
The reaction was performed at 2 g of 10 g / l, 8 g / l of NaOH, and 92 ° C. for 2 minutes.
【００２９】[0029]
比較例(1) 実施例(1) において (A)浴と同じ浴で10秒浸漬し水洗
後、(B) 浴を省いて(C)浴、(D) 浴、(E) 浴の処理を実
施例(1) と同様に行った。また、この銅箔を実施例(1)
と同じ方法で各特性試験を行った。その結果を表１に示
す。Comparative Example (1) In Example (1), immerse in the same bath as the bath (A) for 10 seconds and wash with water, then omit the bath (B), and perform the treatment of the baths (C), (D) and (E). This was performed in the same manner as in Example (1). In addition, this copper foil was used in Example (1)
Each characteristic test was performed in the same manner as described above. Table 1 shows the results.
【００３０】比較例(2) 比較例(1) において(C) 浴で電解時間を18秒としたこと
以外は同じ処理を行った。また、この銅箔を実施例(1)
と同じ方法で各特性試験を行った。その結果を表１に示
す。Comparative Example (2) The same treatment as in Comparative Example (1) was carried out except that the electrolysis time in the bath (C) was changed to 18 seconds. In addition, this copper foil was used in Example (1)
Each characteristic test was performed in the same manner as described above. Table 1 shows the results.
【００３１】比較例(3) 35μm 厚さの未処理電解銅箔の粗面を実施例(4) の(A)
浴と同じ浴に１０秒間浸漬し、水洗後、HCl 無添加の
(B) 浴中で電流密度 20A/dm2,60Hz の交流電解により30
秒間処理し、(C) 浴、(D) 浴の処理を省き、(E) 浴で実
施例(1) と同じ処理を行った。また、この銅箔を実施例
(1) と同じ方法で各特性試験を行った。その結果を表１
に示す。Comparative Example (3) The rough surface of an untreated electrolytic copper foil having a thickness of 35 μm was prepared by using (A) of Example (4).
Immerse in the same bath for 10 seconds, wash with water and add no HCl
(B) Current density 20 A / dm 2
The treatment was carried out for 2 seconds, the treatment of bath (C) and bath (D) was omitted, and the same treatment as in Example (1) was carried out in bath (E). In addition, this copper foil
Each characteristic test was performed in the same manner as (1). Table 1 shows the results.
Shown in
【００３２】比較例(4) 35μm 厚さの未処理電解銅箔の粗面を実施例(1) におい
て、(A) 浴と同じ浴で10秒浸漬し水洗後、(B) 浴の処理
を省き、(C) 浴、(E) 浴と処理を行い、(D) 浴の処理を
省いた処理を行った。また、この銅箔を実施例(1) と同
じ方法で各特性試験を行った。その結果を表１に示す。Comparative Example (4) The rough surface of the untreated electrolytic copper foil having a thickness of 35 μm was immersed in the same bath as the bath (A) for 10 seconds in Example (1), washed with water, and treated in the bath (B). The treatment was performed with the bath (C) and the bath (E) omitted, and the treatment without the bath (D) was performed. The copper foil was subjected to each property test in the same manner as in Example (1). Table 1 shows the results.
【００３３】比較例(5) 実施例(1) において、(B) 浴による処理を省き、(C) 浴
が五酸化バナジウムを50ppm含むこと以外は実施例(1)
と同様に行った。また、この銅箔を実施例(1)と同じ方
法で各特性試験を行った。その結果を表１に示す。Comparative Example (5) In Example (1), except that the treatment with the bath (B) was omitted and that the bath (C) contained 50 ppm of vanadium pentoxide.
The same was done. Each characteristic test was performed on the copper foil in the same manner as in Example (1). Table 1 shows the results.
【００３４】比較例(6) 実施例(6) において、(B) 浴による処理を省いたこと以
外は実施例(6) と同様に行った。また、この銅箔を実施
例(6) と同じ方法で各特性試験を行った。その結果を表
２に示す。Comparative Example (6) The procedure of Example (6) was repeated except that the treatment with the bath (B) was omitted. Each characteristic test was performed on this copper foil in the same manner as in Example (6). Table 2 shows the results.
【００３５】比較例(7) 比較例(1) で得られた銅箔を使用して、その銅箔光沢面
をソフトエッチング液(組成 H2SO4 100g/l, 35% H2O2水
50ml/l, CuSO4・5H2O 1g/l)により 40 ℃ 1分間ソフト
エッチングを行い、次いで実施例(1) と同じ黒化処理を
行った。これを同様にＦＲ−４グレードのガラスエポキ
シ樹脂含浸基材に積層し、プレス成型し、その接着力を
測定したが、1.46kg/cm を得た。この結果から本発明法
による銅箔はソフトエッチングを適用したものと同等の
接着力向上が得られることがわかる。Comparative Example (7) Using the copper foil obtained in Comparative Example (1), the glossy surface of the copper foil was etched with a soft etching solution (composition H 2 SO 4 100 g / l, 35% H 2 O 2 water).
Soft etching was performed at 40 ° C. for 1 minute with 50 ml / l, CuSO 4 .5H 2 O 1 g / l), and then the same blackening treatment as in Example (1) was performed. This was similarly laminated on an FR-4 grade glass epoxy resin-impregnated substrate, press-molded, and the adhesive strength was measured to obtain 1.46 kg / cm 2. From these results, it can be seen that the copper foil according to the method of the present invention can achieve the same improvement in adhesive strength as that obtained by applying soft etching.
【００３６】実施例及び比較例の結果から、本発明方法
は従来方法よりも表面状態の均一性が高く、樹脂との接
着力に優れ、表面粗さを低減させる効果を持っており、
さらに黒化処理を施した面は通常の処理しない銅箔に比
較して接着力が高く、ソフトエッチング工程を導入して
粗化する必要がなく、優れた表面処理銅箔となっている
ことがわかる。From the results of the Examples and Comparative Examples, the method of the present invention has higher uniformity of the surface state than the conventional method, has excellent adhesion to resin, and has the effect of reducing the surface roughness.
Furthermore, the surface that has been subjected to the blackening treatment has a higher adhesive strength than the copper foil that is not normally treated, does not need to be roughened by introducing a soft etching process, and has an excellent surface-treated copper foil. Recognize.
【００３７】[0037]
【発明の効果】本発明により、以下のような効果があ
る。 (1) 従来のような砒素、セレン、テルルなど毒性のあ
る元素を使用せずに粗面化する方法であり、環境及び人
体への悪影響が無い。 (2) 均一かつ接着力の高い表面処理銅箔が得られ、高
密度のプリント配線板に適合する。 (3) 改良された両面処理により、樹脂との接着性が高
いため、多層プリント配線板製造の銅箔内層処理工程に
おけるソフトエッチング工程等を省略することができ、
プリント配線板製造のコスト低減に貢献することができ
る。 (4) この表面処理方法は実工程において導入が容易で
あり、量産製造が可能である。According to the present invention, the following effects can be obtained. (1) This is a method of roughening without using toxic elements such as arsenic, selenium and tellurium as in the past, and has no adverse effect on the environment and the human body. (2) A uniform and high-adhesion surface-treated copper foil can be obtained, which is suitable for high-density printed wiring boards. (3) Due to the improved double-sided treatment, the adhesiveness with the resin is high, so that the soft etching step and the like in the copper foil inner layer processing step of the multilayer printed wiring board manufacturing can be omitted,
This can contribute to cost reduction in manufacturing a printed wiring board. (4) This surface treatment method is easy to introduce in an actual process, and mass production is possible.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【図１】本発明の交番パルス電解の波形の例である。FIG. 1 is an example of a waveform of alternating pulse electrolysis according to the present invention.
【図２】本発明の交番パルス電解の波形の例である。FIG. 2 is an example of a waveform of alternating pulse electrolysis according to the present invention.
【図３】交流電解の波形の例である。FIG. 3 is an example of a waveform of AC electrolysis.
Claims (5)
の後、塩素イオン 1ppm 〜1000ppm 含む硫酸酸性浴中で
正負の交番パルス電解、又は交流電解をする活性化処理
工程により活性化、微細粗化し、続いて、硫酸、硫酸銅
浴中で限界電流密度付近又はそれ以上で陰極電解するこ
とにより銅の突起物粗化を行い、さらに、銅めっきによ
る被覆層を形成させる銅箔の粗面化を行い、次いで防錆
処理を行うことを特徴とする銅箔の表面処理方法。At least one surface of a copper foil is activated by a positive / negative alternating pulse electrolysis or an activation process of performing an alternating current electrolysis in a sulfuric acid acid bath containing 1 ppm to 1000 ppm of chloride ions after the pickling step. Fine roughening, followed by roughening of copper projections by performing cathodic electrolysis near or above the limiting current density in sulfuric acid and copper sulfate baths, and further roughening of copper foil to form a coating layer by copper plating. A surface treatment method for a copper foil, comprising performing surface treatment and then performing rust prevention treatment.
黄を含有する有機化合物を0.001 〜 0.5モル/l含む水溶
液で銅箔を処理させることを特徴とする請求項１に記載
の銅箔の表面処理方法。2. The copper foil according to claim 1, wherein the copper foil is treated with an aqueous solution containing 0.001 to 0.5 mol / l of an organic compound containing sulfur between the pickling step and the activation treatment step. Surface treatment method for foil.
物を0.001 〜0.5 モル/l含む水溶液であることを特徴と
する請求項１に記載の銅箔の表面処理方法。3. The method according to claim 1, wherein the bath in the pickling step is an aqueous solution containing 0.001 to 0.5 mol / l of an organic compound containing sulfur.
あたり 0.2〜200msであることを特徴とする請求項１に
記載の銅箔の表面処理方法。4. The method according to claim 1, wherein the positive and negative alternating pulse electrolysis time is 0.2 to 200 ms per cycle.
有機物防錆を施すことを特徴とする請求項１に記載の銅
箔の表面処理方法。5. The copper foil surface treatment method according to claim 1, wherein the rust prevention treatment is performed by chromate treatment and / or organic matter rust prevention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32938496A JP3623621B2 (en) | 1996-12-10 | 1996-12-10 | Copper foil surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32938496A JP3623621B2 (en) | 1996-12-10 | 1996-12-10 | Copper foil surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10168596A true JPH10168596A (en) | 1998-06-23 |
| JP3623621B2 JP3623621B2 (en) | 2005-02-23 |
Family
ID=18220846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32938496A Expired - Fee Related JP3623621B2 (en) | 1996-12-10 | 1996-12-10 | Copper foil surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3623621B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048272A1 (en) * | 1999-12-28 | 2001-07-05 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil |
| JP2008144232A (en) * | 2006-12-11 | 2008-06-26 | Fukuda Metal Foil & Powder Co Ltd | Method for roughening surface of copper foil |
| JP2010047842A (en) * | 2009-10-01 | 2010-03-04 | Nippon Mining & Metals Co Ltd | Electrolytic copper foil and method for electropolishing glossy surface of electrolytic copper foil |
| JP2010059547A (en) * | 2009-10-01 | 2010-03-18 | Nippon Mining & Metals Co Ltd | Electrolytic copper foil and method of electropolishing glossy surface of the electrolytic copper foil |
| JP2011084801A (en) * | 2009-10-19 | 2011-04-28 | Furukawa Electric Co Ltd:The | Method and apparatus for manufacturing surface roughened copper plate |
| JP2011162860A (en) * | 2010-02-12 | 2011-08-25 | Furukawa Electric Co Ltd:The | Surface-roughened copper foil, method of producing the same and copper-clad laminate plate |
| WO2011108467A1 (en) | 2010-03-01 | 2011-09-09 | 古河電気工業株式会社 | Surface treatment method for copper foil, surface treated copper foil and copper foil for negative electrode collector of lithium ion secondary battery |
| WO2018004152A1 (en) * | 2016-06-30 | 2018-01-04 | 일진머티리얼즈 주식회사 | Surface-treated copper foil having excellent etching property after post-processing thereof and method for manufacturing same |
| CN112921371A (en) * | 2021-01-21 | 2021-06-08 | 江苏铭丰电子材料科技有限公司 | Surface roughening and curing treatment method of RTF copper foil for high-frequency copper-clad plate |
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-
1996
- 1996-12-10 JP JP32938496A patent/JP3623621B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048272A1 (en) * | 1999-12-28 | 2001-07-05 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil |
| US6544663B1 (en) * | 1999-12-28 | 2003-04-08 | Mitsui Mining & Smelting Co., Ltd. | Electrodeposited copper foil |
| JP2008144232A (en) * | 2006-12-11 | 2008-06-26 | Fukuda Metal Foil & Powder Co Ltd | Method for roughening surface of copper foil |
| JP2010047842A (en) * | 2009-10-01 | 2010-03-04 | Nippon Mining & Metals Co Ltd | Electrolytic copper foil and method for electropolishing glossy surface of electrolytic copper foil |
| JP2010059547A (en) * | 2009-10-01 | 2010-03-18 | Nippon Mining & Metals Co Ltd | Electrolytic copper foil and method of electropolishing glossy surface of the electrolytic copper foil |
| JP2011084801A (en) * | 2009-10-19 | 2011-04-28 | Furukawa Electric Co Ltd:The | Method and apparatus for manufacturing surface roughened copper plate |
| JP2011162860A (en) * | 2010-02-12 | 2011-08-25 | Furukawa Electric Co Ltd:The | Surface-roughened copper foil, method of producing the same and copper-clad laminate plate |
| WO2011108467A1 (en) | 2010-03-01 | 2011-09-09 | 古河電気工業株式会社 | Surface treatment method for copper foil, surface treated copper foil and copper foil for negative electrode collector of lithium ion secondary battery |
| WO2018004152A1 (en) * | 2016-06-30 | 2018-01-04 | 일진머티리얼즈 주식회사 | Surface-treated copper foil having excellent etching property after post-processing thereof and method for manufacturing same |
| CN113795615A (en) * | 2019-06-07 | 2021-12-14 | 古河电气工业株式会社 | Surface-treated copper foil, copper-clad laminate, and printed wiring board |
| CN113795615B (en) * | 2019-06-07 | 2024-08-02 | 古河电气工业株式会社 | Surface-treated copper foil, copper-clad laminate, and printed circuit board |
| CN112921371A (en) * | 2021-01-21 | 2021-06-08 | 江苏铭丰电子材料科技有限公司 | Surface roughening and curing treatment method of RTF copper foil for high-frequency copper-clad plate |
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