JP4618466B2 - Copper surface treatment - Google Patents
Copper surface treatment Download PDFInfo
- Publication number
- JP4618466B2 JP4618466B2 JP2000311066A JP2000311066A JP4618466B2 JP 4618466 B2 JP4618466 B2 JP 4618466B2 JP 2000311066 A JP2000311066 A JP 2000311066A JP 2000311066 A JP2000311066 A JP 2000311066A JP 4618466 B2 JP4618466 B2 JP 4618466B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- aqueous solution
- treatment
- sodium hydroxide
- oxide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【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おける銅表面の処理に関するものである。
【0002】
【従来の技術】
一般に多層プリント配線板は、銅張積層板の銅箔を加工し配線回路を形成した後、このプリント配線板を過硫酸ナトリウム又は過硫酸アンモニウム又は硫酸と過酸化水素を含む溶液等で処理して、銅表面を粗化した後、亜塩素酸塩と水酸化ナトリウムを含む溶液又は過硫酸カリウムと水酸化ナトリウムを含む溶液等により、銅表面を処理し酸化銅皮膜を形成した後、このプリント配線板にプリプレグを介して外層用の銅箔又は銅張積層板を積層接着し、スルーホール穴明け、スルーホール銅めっき、外層回路加工等を行い製造している。
【0003】
【発明が解決しようとする課題】
この多層プリント配線板の製造方法には、次の問題点がある。
多層プリント配線板は、スルーホール穴明け後、ドリル穴明け時に内層銅の切削断面に付着する樹脂の除去工程で酸性処理液に浸漬される。また、スルーホール銅めっきのためにスルーホール壁面にめっき触媒の付与するための工程で、酸性処理液に浸漬される。更に無電解銅めっき液に浸漬処理される。この時これらの処理液が、酸化銅皮膜形成層と絶縁樹脂層の間にしみ込み、銅回路表面と絶縁樹脂間の接着性を低下させる。また、スルーホール周辺が変色するという問題があった。
【0004】
本発明は、上記問題を解決し、銅回路表面と絶縁樹脂間の耐薬品性、接着性に優れる銅の表面処理法を提供するものである。
【0005】
【課題を解決するための手段】
本発明の表面処理法は、銅表面に酸化剤を含む水溶液で処理し酸化皮膜を形成させ、次に硫酸を含む水溶液に浸漬処理し、更にホルムアルデヒドと水酸化ナトリウムからなる水溶液にて処理することを特徴とする。
【0006】
【発明の実施の形態】
本発明で銅表面に酸化銅皮膜を形成する方法とは、亜塩素酸ナトリウム、亜塩素酸カリウム、塩素酸ナトリウム、塩素酸カリウム、過硫酸カリウム、過塩素酸カリウム等の酸化剤と水酸化ナトリウムを含む水溶液で銅表面を処理する。この酸化処理組成の一例としては、亜塩素酸ナトリウム5〜100g/l、水酸化ナトリウム1〜50g/lの水溶液である。処理条件は、上記酸化銅処理液の温度が50〜95℃で、酸化銅処理液と銅表面との接触時間は15秒以上である。
次に、硫酸を含む処理液に浸漬処理する。硫酸処理液の流酸濃度は、0.01vol%以上である。処理時間は10秒以上である。
次に、ホルムアルデヒドと水酸化ナトリウムからなる水溶液にて浸漬して処理を行う。ホルムアルデヒドの供給源は、ホルムアルデイド、パラホルムアルデヒド、芳香族ホルムアルデヒド化合物である。ホルムアルデヒドの供給源の濃度は、0.01モル/l以上である。この水溶液の水酸化ナトリウム濃度は、0.02モル/l以上である。この水溶液の処理条件は、水溶液の温度が50〜95℃で1分間以上処理する。
【0007】
【実施例】
実施例1
銅回路を形成した銅張積層板を過硫酸アンモニウム水溶液で粗化処理した後、次の処理液、処理条件にて酸化銅皮膜を形成した。
・亜塩素酸ナトリウム …50g/l
・水酸化ナトリウム …20g/l
・処理温度 …90℃
・処理時間 …5分
酸化銅皮膜を形成した後、水洗を行った。
次に、硫酸濃度0.01vol%の水溶液に1分間浸漬した。
次に、ホルムアルデヒド濃度が0.05モル/l、水酸化ナトリウム濃度が0.05モル/lの水溶液に1分間浸漬した。この時ホルムアルデヒドと水酸化ナトリウムからなる水溶液の温度は、60℃とした。
次に水洗を行い、90℃で30分間乾燥した。
上記処理を行った銅回路板の両面をエポキシ樹脂プリプレグで挟み、更にその両側を銅箔で挟み、加圧、加熱(加圧30kg/cm2、温度170℃120分)を行い多層化接着し、内層銅回路入り銅張積層板を作成した。
評価は、耐塩酸試験、はんだ耐熱試験を行った。評価結果を表1に示す。また、評価方法は、下記の通りである。
耐塩酸試験は、上記方法で作成した内層銅回路入り銅張り積層板の外層銅を除去した後、直径0.3mmのドリルで穴明けを行い、18%塩酸に60分間浸漬し、穴周辺の塩酸のしみ込みを目視で観察した。塩酸がしみ込んだ部分は、酸化銅皮膜が溶解しピンク色に変色する。
はんだ耐熱試験は、上記耐塩酸試験の後、260℃のはんだに20秒間浸漬し、膨れ剥がれの有無を目視で観察した。
【0008】
実施例2
銅回路を形成した銅張積層板を過硫酸アンモニウム水溶液で粗化処理した後、次の処理液、処理条件にて酸化銅皮膜を形成した。
・亜塩素酸ナトリウム …50g/l
・水酸化ナトリウム …20g/l
・処理温度 …90℃
・処理時間 …5分
酸化銅皮膜を形成した後、水洗を行った。
次に、硫酸濃度50vol%の水溶液に10秒間浸漬した後、水洗した。
次に、ホルムアルデヒド濃度が0.05モル/l、水酸化ナトリウム濃度が0.05モル/lの水溶液に1分間浸漬した。この時ホルムアルデヒドと水酸化ナトリウムからなる水溶液の温度は、60℃とした。
次に水洗を行い、90℃で30分間乾燥した。
実施例1と同様の方法で内層銅回路入り銅張積層板を作成し、実施例1と同様の方法で評価を行った。
評価結果を表1に示す。
【0009】
比較例
銅回路を形成した銅張積層板を過硫酸アンモニウム水溶液で粗化処理した後、次の処理液、処理条件にて酸化銅皮膜を形成した。
・亜塩素酸ナトリウム …50g/l
・水酸化ナトリウム …20g/l
・処理温度 …90℃
・処理時間 …5分
酸化銅皮膜を形成した後、水洗を行った。
次に90℃で30分間乾燥した。
実施例1と同様の方法で内層銅回路入り銅張積層板を作成し、実施例1と同様の方法で評価を行った。
評価結果を表1に示す。
【0010】
【表1】
【0011】
【発明の効果】
以上に説明したように、本発明は、銅表面に酸化剤を含む水溶液で処理し酸化皮膜を形成させ、次に硫酸を含む水溶液に浸漬処理し、更にホルムアルデヒドと水酸化ナトリウムからなる水溶液にて処理することにより、銅回路表面と絶縁樹脂間の接着性、耐薬品性に優れる銅の表面処理法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the treatment of copper surfaces in the production of printed wiring boards.
[0002]
[Prior art]
In general, a multilayer printed wiring board is formed by processing a copper foil of a copper clad laminate to form a wiring circuit, and then treating the printed wiring board with a solution containing sodium persulfate or ammonium persulfate or sulfuric acid and hydrogen peroxide. After the copper surface is roughened, this printed wiring board is formed by treating the copper surface with a solution containing chlorite and sodium hydroxide or a solution containing potassium persulfate and sodium hydroxide to form a copper oxide film. The outer layer copper foil or copper clad laminate is laminated and bonded to the prepreg, and through hole drilling, through hole copper plating, outer layer circuit processing, etc. are performed.
[0003]
[Problems to be solved by the invention]
This method for producing a multilayer printed wiring board has the following problems.
The multilayer printed wiring board is immersed in the acid treatment liquid in the step of removing the resin adhering to the cut cross section of the inner layer copper after drilling the through hole after drilling the through hole. Moreover, it is immersed in an acidic treatment liquid at the process for providing a plating catalyst to a through-hole wall surface for through-hole copper plating. Further, it is immersed in an electroless copper plating solution. At this time, these treatment liquids penetrate between the copper oxide film-forming layer and the insulating resin layer, and lower the adhesion between the copper circuit surface and the insulating resin. Moreover, there was a problem that the periphery of the through hole was discolored.
[0004]
This invention solves the said problem and provides the surface treatment method of copper which is excellent in the chemical resistance and adhesiveness between a copper circuit surface and insulating resin.
[0005]
[Means for Solving the Problems]
In the surface treatment method of the present invention, the copper surface is treated with an aqueous solution containing an oxidant to form an oxide film, then immersed in an aqueous solution containing sulfuric acid, and further treated with an aqueous solution comprising formaldehyde and sodium hydroxide. It is characterized by.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the method for forming a copper oxide film on the copper surface includes sodium chlorite, potassium chlorite, sodium chlorate, potassium chlorate, potassium persulfate, potassium perchlorate and the like, and sodium hydroxide The copper surface is treated with an aqueous solution containing. An example of this oxidation treatment composition is an aqueous solution of sodium chlorite 5 to 100 g / l and sodium hydroxide 1 to 50 g / l. The treatment conditions are such that the temperature of the copper oxide treatment liquid is 50 to 95 ° C., and the contact time between the copper oxide treatment liquid and the copper surface is 15 seconds or longer.
Next, it is immersed in a treatment solution containing sulfuric acid. The flowing acid concentration of the sulfuric acid treatment liquid is 0.01 vol% or more. The processing time is 10 seconds or more.
Next, the treatment is performed by dipping in an aqueous solution of formaldehyde and sodium hydroxide. Formaldehyde sources are formaldehyde, paraformaldehyde and aromatic formaldehyde compounds. The concentration of the formaldehyde source is 0.01 mol / l or more. The concentration of sodium hydroxide in this aqueous solution is 0.02 mol / l or more. The treatment condition of this aqueous solution is that the temperature of the aqueous solution is 50 to 95 ° C. for 1 minute or longer.
[0007]
【Example】
Example 1
After the copper clad laminate having the copper circuit formed thereon was roughened with an aqueous ammonium persulfate solution, a copper oxide film was formed using the following treatment liquid and treatment conditions.
・ Sodium chlorite: 50 g / l
・ Sodium hydroxide: 20 g / l
・ Processing temperature: 90 ℃
Treatment time: 5 minutes After forming a copper oxide film, washing was performed.
Next, it was immersed in an aqueous solution having a sulfuric acid concentration of 0.01 vol% for 1 minute.
Next, it was immersed in an aqueous solution having a formaldehyde concentration of 0.05 mol / l and a sodium hydroxide concentration of 0.05 mol / l for 1 minute. At this time, the temperature of the aqueous solution composed of formaldehyde and sodium hydroxide was 60 ° C.
Next, it was washed with water and dried at 90 ° C. for 30 minutes.
The copper circuit board after the above treatment is sandwiched between epoxy resin prepregs, and both sides are sandwiched between copper foils. Pressurization and heating (pressurization 30 kg / cm 2 , temperature 170 ° C for 120 minutes) are applied to form a multilayer adhesive. A copper clad laminate with an inner layer copper circuit was prepared.
The evaluation was conducted using a hydrochloric acid resistance test and a solder heat resistance test. The evaluation results are shown in Table 1. Moreover, the evaluation method is as follows.
In the hydrochloric acid resistance test, after removing the outer layer copper of the copper-clad laminate with the inner layer copper circuit prepared by the above method, a hole was drilled with a drill having a diameter of 0.3 mm, immersed in 18% hydrochloric acid for 60 minutes, The penetration of hydrochloric acid was visually observed. The portion in which the hydrochloric acid has soaked turns the pink color as the copper oxide film dissolves.
The solder heat resistance test was immersed in 260 ° C. solder for 20 seconds after the hydrochloric acid resistance test, and the presence or absence of swelling and peeling was visually observed.
[0008]
Example 2
After the copper clad laminate having the copper circuit formed thereon was roughened with an aqueous ammonium persulfate solution, a copper oxide film was formed using the following treatment liquid and treatment conditions.
・ Sodium chlorite: 50 g / l
・ Sodium hydroxide: 20 g / l
・ Processing temperature: 90 ℃
Treatment time: 5 minutes After forming a copper oxide film, washing was performed.
Next, it was immersed in an aqueous solution having a sulfuric acid concentration of 50 vol% for 10 seconds and then washed with water.
Next, it was immersed in an aqueous solution having a formaldehyde concentration of 0.05 mol / l and a sodium hydroxide concentration of 0.05 mol / l for 1 minute. At this time, the temperature of the aqueous solution composed of formaldehyde and sodium hydroxide was 60 ° C.
Next, it was washed with water and dried at 90 ° C. for 30 minutes.
A copper-clad laminate with an inner layer copper circuit was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.
[0009]
Comparative Example After a copper clad laminate having a copper circuit formed thereon was roughened with an aqueous ammonium persulfate solution, a copper oxide film was formed using the following treatment liquid and treatment conditions.
・ Sodium chlorite: 50 g / l
・ Sodium hydroxide: 20 g / l
・ Processing temperature: 90 ℃
Treatment time: 5 minutes After forming a copper oxide film, washing was performed.
Next, it was dried at 90 ° C. for 30 minutes.
A copper-clad laminate with an inner layer copper circuit was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.
[0010]
[Table 1]
[0011]
【The invention's effect】
As described above, the present invention treats the copper surface with an aqueous solution containing an oxidant to form an oxide film, and then immerses in an aqueous solution containing sulfuric acid, and further with an aqueous solution comprising formaldehyde and sodium hydroxide. By performing the treatment, it is possible to provide a copper surface treatment method having excellent adhesion between the copper circuit surface and the insulating resin and chemical resistance.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000311066A JP4618466B2 (en) | 2000-10-11 | 2000-10-11 | Copper surface treatment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000311066A JP4618466B2 (en) | 2000-10-11 | 2000-10-11 | Copper surface treatment |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002115078A JP2002115078A (en) | 2002-04-19 |
JP4618466B2 true JP4618466B2 (en) | 2011-01-26 |
Family
ID=18790896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000311066A Expired - Lifetime JP4618466B2 (en) | 2000-10-11 | 2000-10-11 | Copper surface treatment |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4618466B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009084652A (en) * | 2007-10-01 | 2009-04-23 | Hitachi Chem Co Ltd | Oxidation treatment method and oxidation treatment liquid for metal |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63190179A (en) * | 1987-01-31 | 1988-08-05 | Hitachi Chem Co Ltd | Surface treatment of copper |
JPH01156479A (en) * | 1987-12-14 | 1989-06-20 | Hitachi Chem Co Ltd | Surface treatment of copper |
JPH0897559A (en) * | 1994-09-26 | 1996-04-12 | Okuno Chem Ind Co Ltd | Method and solution for treating copper foil of circuit board for inner layer of multilayer printed wiring board |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56153797A (en) * | 1980-04-28 | 1981-11-27 | Hitachi Chemical Co Ltd | Method of manufacturing multilayer printed circuit board substrate |
JPS62185884A (en) * | 1986-02-12 | 1987-08-14 | Hitachi Chem Co Ltd | Production of laminate of metal and resin layer |
JPH0719957B2 (en) * | 1988-06-09 | 1995-03-06 | 日立化成工業株式会社 | Copper surface treatment method |
-
2000
- 2000-10-11 JP JP2000311066A patent/JP4618466B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63190179A (en) * | 1987-01-31 | 1988-08-05 | Hitachi Chem Co Ltd | Surface treatment of copper |
JPH01156479A (en) * | 1987-12-14 | 1989-06-20 | Hitachi Chem Co Ltd | Surface treatment of copper |
JPH0897559A (en) * | 1994-09-26 | 1996-04-12 | Okuno Chem Ind Co Ltd | Method and solution for treating copper foil of circuit board for inner layer of multilayer printed wiring board |
Also Published As
Publication number | Publication date |
---|---|
JP2002115078A (en) | 2002-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0713304B2 (en) | Copper surface treatment method | |
EP0245305A1 (en) | Copper oxide treatment in printed circuit board | |
JP4618466B2 (en) | Copper surface treatment | |
JPH07123181B2 (en) | Manufacturing method of printed wiring board | |
JP2009097034A (en) | Copper surface treatment method | |
JPS63190179A (en) | Surface treatment of copper | |
JPH02230794A (en) | Processing method for copper circuit of circuit board for inner layer | |
JPH09321443A (en) | Manufacture of multilayer board | |
JPH05308191A (en) | Surface treatment method of inner-layer circuit board for multilayer printed wiring board | |
JP2000216536A (en) | Manufacture of laminate board with inner layer circuits | |
JPH05167248A (en) | Method of manufacturing printed wiring board | |
JPH01297883A (en) | Manufacture of printed wiring board | |
JPH0380595A (en) | Manufacture of multilayer printed-wiring board | |
JP2768122B2 (en) | Method for manufacturing multilayer wiring board | |
JPH0637452A (en) | Manufacture of multilayer printed wiring board | |
JPH0496292A (en) | Manufacture of board for multilayer printed circuit | |
JPH10173340A (en) | Method of manufacturing multilayer printed-wiring board | |
JP2768123B2 (en) | Method for manufacturing multilayer wiring board | |
JPH0719957B2 (en) | Copper surface treatment method | |
JPS62218124A (en) | Manufacture of laminate of metal and resin layer | |
JPS61241329A (en) | Method of bonding copper and resin | |
JPH0774465A (en) | Treatment method of copper circuit of inner layer wiring board | |
JPH07162148A (en) | Multilayer printed wiring board and inner board used therefor | |
JPH03268389A (en) | Manufacture of multilayer printed-circuit board | |
JPH045754B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070919 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100518 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100520 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100930 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101013 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131105 Year of fee payment: 3 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4618466 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131105 Year of fee payment: 3 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131105 Year of fee payment: 3 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |