KR20090012872A - Electrolytic copper plating additives for flexible printed circuit board - Google Patents

Electrolytic copper plating additives for flexible printed circuit board Download PDF

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KR20090012872A
KR20090012872A KR1020070077062A KR20070077062A KR20090012872A KR 20090012872 A KR20090012872 A KR 20090012872A KR 1020070077062 A KR1020070077062 A KR 1020070077062A KR 20070077062 A KR20070077062 A KR 20070077062A KR 20090012872 A KR20090012872 A KR 20090012872A
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copper plating
additive
electrolytic copper
flexible pcb
copper
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KR1020070077062A
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KR100910877B1 (en
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강석환
김희산
박현규
김문한
한희덕
김종수
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(주) 유니플라텍
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

A copper plating additive for flexible PCB is provided to be possible for evenly plating by restraining growth of a protrusion by using Janus green B as a leveler. A copper plating additive for flexible PCB for flexible PCB comprises chlorine ion; polyethylene glycol of a polyethylene system as surfactant; 3-N,N- dimethylaminodithiocarbamoyl -1- prophansulfon acid which is a sulfur-containing compound as a brightener; and Janus green B which is a nitrogen-contained compound as a leveler.

Description

연성 ＰＣＢ용 전해 동 도금 첨가제{Electrolytic copper plating additives for flexible printed circuit board}Electrolytic copper plating additives for flexible printed circuit boards

본 발명은 연성 PCB용 전해 동 도금 첨가제에 관한 것으로서, 보다 상세하게는 전해 동 도금막을 유연성이 요구되는 FPCB용 원판에 형성할 경우 저 응력을 유지하면서 낮은 표면조도를 만족시킬 수 있는 전해액에 첨가되는 첨가제에 관한 것이다.The present invention relates to an electrolytic copper plating additive for a flexible PCB, and more particularly, when the electrolytic copper plating film is formed on an FPCB disc requiring flexibility, it is added to an electrolyte solution that can satisfy low surface roughness while maintaining low stress. It relates to an additive.

동 도금으로 제조된 FPCB 원판은 절연층으로 폴리이미드가 주로 사용되며, 니켈과 크롬을 이온 주입하여 씨앗층을 만들고 그 위에 동을 스퍼터링 한 후 전해 동 도금으로 FPCB 원판을 제조하게 된다. 연성 PCB는 유연성, 굴곡성이 필요한 주로 복잡한 기구나 반복적으로 움직이는 부위, 주로 카메라, 프린터 헤드부위, 액정 디스플레이 등의 박형 전자 부품의 회로 기판으로 사용된다.Polyimide is mainly used as an insulating layer for FPCB discs made of copper plating, and a seed layer is formed by ion implanting nickel and chromium, and then sputtered copper is used to manufacture FPCB discs by electrolytic copper plating. Flexible PCBs are often used as circuit boards for thin electronic components such as complex devices or repetitive moving parts, mainly cameras, printer heads, and liquid crystal displays, which require flexibility and flexibility.

연성 PCB에 사용되는 원판의 요구 조건으로서는 배선의 단락이나 박리를 유발하는 휨이 없어야 한다. FPCB 원판의 휨은 전해 동 도금 시 도금 조건에 의해 필 연적으로 발생하는 잔류응력이 그 원인이다. 또한, FPCB 원판에 에칭을 통하여 극 미세 배선을 형성하게 되는데, 배선이 미세해질수록 FPCB 원판의 표면조도는 낮아야 한다. As a requirement for the originals used in flexible PCBs, there should be no warpage that causes short circuits or delamination of the wiring. The deflection of FPCB discs is caused by residual stress inevitably caused by plating conditions in electrolytic copper plating. In addition, an extremely fine wiring is formed on the FPCB disc through etching. As the wiring becomes finer, the surface roughness of the FPCB disc should be lower.

연성 PCB용 전해 동 도금 시 사용되는 첨가제는 잔류응력을 크게 낮추어야 하기 때문에 기존의 경성 PCB용 전해 동 도금 첨가제를 그대로 사용할 수 없다. Additives used in electrolytic copper plating for flexible PCBs must significantly reduce residual stress, so existing electrolytic copper plating additives for rigid PCBs cannot be used as they are.

종래에는 첨가제 성분 중에서 잔류응력을 유발시키는 레벨러 성분을 적게 넣거나 또는 포함시키지 않은 경성 PCB용 전기 동 도금 첨가제를 FPCB 원판 제조를 위한 전해 동 도금 첨가제로 사용해왔다. In the past, electrolytic copper plating additives for hard PCBs containing little or no leveler components that cause residual stress in additive components have been used as electrolytic copper plating additives for manufacturing FPCB discs.

그러나, 레벨러 성분이 배제된 전해 동 도금 첨가제를 사용하여 얻어진 도금막은 잔류응력은 최소화되어지나, 레벨러 성분이 없기 때문에 표면조도는 높은 값을 가지게 된다. However, the plated film obtained by using the electrolytic copper plating additive excluding the leveler component minimizes the residual stress, but the surface roughness has a high value because there is no leveler component.

따라서, 낮은 표면조도를 가지면서 잔류응력도 최소화된 동 도금막을 형성하기 어려운 실정이다.Therefore, it is difficult to form a copper plated film having low surface roughness and minimizing residual stress.

본 발명은 상기 문제점을 해결하기 위한 것으로서, 본 발명은 저 응력, 저 조도, 저 결함이 요구되는 연성 PCB 원판의 전해 동 도금 시, 잔류응력을 최소화시키면서 낮은 표면조도를 가지는 전기 구리 도금막을 형성시킬 수 있도록 전해액에 첨가되는 연성 PCB용 전해 동 도금 첨가제를 제공하는 것을 목적으로 한다.The present invention is to solve the above problems, the present invention is to provide an electro-copper plating film having a low surface roughness while minimizing the residual stress during electrolytic copper plating of a flexible PCB disc that requires low stress, low roughness, low defects An object of the present invention is to provide an electrolytic copper plating additive for a flexible PCB that is added to the electrolyte.

본 발명은 연성 PCB 원판에 동 도금막을 형성하기 위한 전기 동 도금에 있어서의 첨가제의 성분 및 조성을 제공하는 것이다.The present invention provides a component and composition of an additive in electrocopper plating for forming a copper plating film on a flexible PCB original plate.

상기 목적을 달성하기 위해, 본 발명은 양극은 함인동을 사용하고, 음극은 동이 스퍼터링된 폴리이미드 필름을 사용하며, 전해액은 황산구리 용액을 사용하여 동 이온을 음극면에서 전기 분해함으로써 동 도금막을 연성 PCB 원판에 형성할 경우, 상기 전해액에 첨가되는 첨가제에 있어서;In order to achieve the above object, the present invention is a positive electrode using a copper-containing copper, the cathode is a copper sputtered polyimide film, the electrolytic solution using a copper sulfate solution to soften the copper plated film by electrolyzing copper ions at the cathode surface In the case of forming in the PCB disc, the additive added to the electrolyte;

상기 첨가제는 염소 이온과, 계면활성제로서 폴리에틸렌 계열의 폴리에틸렌 글리콜과, 광택제로서 유황 함유 화합물인 3-N,N-디메틸아미노디티오카바모일-1-프로판술폰산과, 레벨러로서 질소 함유 화합물인 야누스그린B를 함유하는 것을 특징으로 하는 연성 ＰＣＢ용 전해 동 도금 첨가제를 제공한다.The additives include chlorine ions, polyethylene-based polyethylene glycol as a surfactant, 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a sulfur-containing compound as a polishing agent, and Janus green as a nitrogen-containing compound as a leveler. It provides the electrolytic copper plating additive for flexible PCs which contain B.

또한, 상기 첨가제는 0.01g/L 내지 0.1g/L의 염소 이온과, 계면활성제로서 폴리에틸렌 계열의 폴리에틸렌 글리콜 0.1g/L 내지 1g/L와, 광택제로서 유황 함유 화합물인 3-N,N-디메틸아미노디티오카바모일-1-프로판술폰산 0.001g/L 내지 0.1g/L와, 레벨러로서 질소 함유 화합물인 야누스그린B 0.001g/L 내지 0.1g/L를 함유하는 것이 바람직하다.In addition, the additive is 0.01 g / L to 0.1 g / L of chlorine ions, polyethylene-based polyethylene glycol 0.1 g / L to 1 g / L as a surfactant, and 3-N, N-dimethyl which is a sulfur-containing compound as a brightening agent It is preferable to contain 0.001 g / L to 0.1 g / L of aminodithiocarbamoyl-1-propanesulfonic acid, and 0.001 g / L to 0.1 g / L of Janusgreen B which is a nitrogen containing compound as a leveler.

연성 PCB 원판 제조를 위한 전기 동 도금은 폴리이미드 필름 위에 니켈과 크롬을 이온 주입하여 씨앗층을 만들고 그 위에 동을 스퍼터링 한 필름을 음극으로 사용하며, 함인동 볼을 양극으로 사용한다. 양극과 음극 사이에 공급되는 전해액으로서는 황산구리용액으로 액조성은 다음과 같다. Electrolytic copper plating for flexible PCB disc manufacturing uses seed film by ion implanting nickel and chromium on polyimide film, using sputtered copper film as cathode, and using copper phosphorus ball as anode. The electrolyte solution supplied between the positive electrode and the negative electrode is a copper sulfate solution, and the liquid composition is as follows.

황산구리5수화물의 농도는 30g/L 내지 100g/L이며 바람직하게는 60g/L 내지 80g/L, 황산 농도는 50g/L 내지 200g/L이며 바람직하게는 160g/L 내지 190g/L로 하고, 전해액의 온도는 20℃ 내지 30℃로 한다. 전류밀도는 20mA/cm2 내지 80mA/cm2이며 바람직하게는 30mA/cm2 내지 40mA/cm2으로 한다.The concentration of copper sulfate pentahydrate is 30 g / L to 100 g / L, preferably 60 g / L to 80 g / L, sulfuric acid concentration of 50 g / L to 200 g / L, preferably 160 g / L to 190 g / L, and the electrolyte solution. The temperature of is set at 20 ° C to 30 ° C. The current density is 20 mA / cm 2 to 80 mA / cm 2 and preferably 30 mA / cm 2 to 40 mA / cm 2 .

상기 전해액의 첨가제로서, 계면활성제로는 폴리에틸렌 계열의 폴리에틸렌 글리콜 0.1g/L 내지 1g/L, 광택제로는 유황 함유 화합물로 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산 0.001g/L 내지 0.1g/L, 레벨러로는 질소 함유 화합물로 야누스그린B 0.001g/L 내지 0.1g/L, 및 0.01g/L 내지 0.1g/L의 염소이온을 함유한다.As an additive of the electrolyte, 0.1 g / L to 1 g / L polyethylene glycol as a surfactant, and 0.001 g of 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a sulfur-containing compound as a brightener. / L to 0.1 g / L, the leveler contains a nitrogenous compound containing Janusgreen B 0.001 g / L to 0.1 g / L, and 0.01 g / L to 0.1 g / L of chlorine ion.

본 발명에 있어서 상기 첨가제들의 역할은 대단히 중요하다. 본 발명에 따른 첨가제들 중 계면활성제로 사용한 폴리에틸렌 글리콜은 동 도금층 표면에 균일성을 부여하여 표면 조도를 낮추고, 미세한 결정립을 만드는 역할을 한다. The role of the additives in the present invention is very important. Polyethylene glycol used as a surfactant among the additives according to the present invention provides uniformity to the surface of the copper plating layer to lower the surface roughness and serve to make fine grains.

광택제로 사용된 유황 함유 화합물인 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산은 결정립을 미세하게 하며, 골부분의 도금속도를 증가시켜 평평하고 광택있는 도금층을 만들게 한다. Sulfur-containing compounds used as polishes, 3-N and N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid, make grains fine and increase the plating speed of bones to make flat and glossy plating layers.

레벨러로 사용된 야누스그린B는 용액 내에서 확산의 영향을 크게 받아 주로 음극 표면의 돌출부나 모서리에 흡착하여 돌출부의 성장을 억제함으로써 평활한 도금이 이루어지게 한다. Janus Green B, which is used as a leveler, is greatly influenced by diffusion in the solution, and is mainly adsorbed to the protrusions or corners of the cathode surface to suppress the growth of the protrusions, thereby making smooth plating.

상기한 바와 같이, 이들 첨가제는 연성 PCB 원판 제조에 있어서 반드시 필요하다. 이들 첨가제들은 도금층의 잔류응력에 영향을 미치게 된다. 계면활성제와 레벨러는 인장 잔류응력을 유발하며, 광택제는 압축 잔류응력을 유발시킨다. 따라서, 잔류응력이 낮으면서도 표면조도가 낮은 연성 PCB 원판을 전기 동 도금하기 위해서는 본 발명에 따른 연성 PCB용 전해 동 도금 첨가제가 반드시 필요하게 된다.As mentioned above, these additives are necessary for the manufacture of flexible PCB discs. These additives affect the residual stress of the plating layer. Surfactants and levelers cause tensile residual stress, and polishers cause compressive residual stress. Therefore, electrolytic copper plating additive for flexible PCB according to the present invention is necessary to electroplate the flexible PCB disc with low residual stress and low surface roughness.

본 발명에 의하면, 저 응력, 저 조도, 저 결함이 요구되는 연성 PCB 원판의 전해 동 도금 시, 본 발명에 따른 연성 PCB용 전해 동 도금 첨가제를 전해액에 첨가함으로써 잔류응력을 최소화시키면서 낮은 표면조도를 가지는 전기 구리 도금막을 형성시킬 수 있다.According to the present invention, when electrolytic copper plating of a flexible PCB disc requiring low stress, low roughness, and low defects, by adding an electrolytic copper plating additive for a flexible PCB according to the present invention to the electrolyte, low surface roughness is minimized while minimizing residual stress. The branch can form an electrocopper plating film.

이하, 실시예와 비교예를 참조하여 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

표 1에 도시된 바와 같이, 실시예와 비교예의 첨가제 조성을 갖는 전해액이 준비된다. 상기 전해액의 황산구리5수화물의 농도는 70g/L, 황산농도는 180g/L이며, 염소 이온은 30mg/L이다. 전해액의 온도는 25±1℃이며, 전류밀도는 30mA/cm2로 하였으며 용액은 순환시켜 교반하였다.As shown in Table 1, an electrolyte solution having an additive composition of Examples and Comparative Examples is prepared. The concentration of copper sulfate pentahydrate in the electrolyte solution is 70 g / L, sulfuric acid concentration is 180 g / L, and chlorine ion is 30 mg / L. The temperature of the electrolyte was 25 ± 1 ℃, the current density was 30mA / cm 2 and the solution was circulated and stirred.

첨가제additive 액 조성Liquid composition PEG (ppm)PEG (ppm) DPS (ppm)DPS (ppm) JGB (ppm)JGB (ppm) SPS (ppm)SPS (ppm) Com.I (mL/L)Com.I (mL / L) Com.II (mL/L)Com.II (mL / L) 황산구리5수화물 (g/L)Copper sulfate pentahydrate (g / L) 황산 (g/L)Sulfuric acid (g / L) 실시예1Example 1 300300 55 1010 -- -- -- 70    70 180    180 실시예2Example 2 300300 4040 1010 -- -- -- 실시예3Example 3 300300 7070 1010 -- -- -- 실시예4Example 4 300300 4040 00 -- -- -- 실시예5Example 5 300300 4040 1One -- -- -- 비교예1Comparative Example 1 300300 -- 1010 4040 -- -- 비교예2Comparative Example 2 -- -- -- -- 첨가adding -- 비교예3Comparative Example 3 -- -- -- -- -- 첨가adding

Cl-: 30mg/L, 온도: 25±1℃, 전류밀도: 30mA/cm2 Cl-: 30mg / L, Temperature: 25 ± 1 ℃, Current Density: 30mA / cm 2

실시예 1의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산(DPS) 5mg/L, 야누스그린B(JGB) 10mg/L이 사용되었다. For Example 1, 300 mg / L polyethylene glycol (PEG), 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid (DPS) 5 mg / L, Janus Green B (JGB) 10 mg / L are used It became.

실시예 2의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산(DPS) 40mg/L, 야누스그린B(JGB) 10mg/L이 사용되었다. For Example 2, 300 mg / L polyethylene glycol (PEG), 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid (DPS) 40 mg / L, Janus Green B (JGB) 10 mg / L are used It became.

실시예 3의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산(DPS) 70mg/L, 야누스그린B(JGB) 10mg/L이 사용되었다. For Example 3, 300 mg / L polyethylene glycol (PEG), 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid (DPS) 70 mg / L, Janus Green B (JGB) 10 mg / L are used It became.

실시예 4의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산(DPS) 40mg/L이 사용되었다.For Example 4, 300 mg / L polyethylene glycol (PEG), 40 mg / L, 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid (DPS) was used.

실시예 5의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 3-N, N-디메틸아미노디티오카바모일-1-프로판술폰산(DPS) 40mg/L, 야누스그린B(JGB) 1mg/L이 사용되었다. For Example 5, 300 mg / L polyethylene glycol (PEG), 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid (DPS) 40 mg / L, Janus Green B (JGB) 1 mg / L are used It became.

비교예 1의 경우, 폴리에틸렌 글리콜(PEG) 300mg/L, 비스-(3-술포프로필)-디설파이드, 디소디움솔트)(SPS) 40mg/L, 야누스그린B(JGB) 1mg/L이 사용되었다. For Comparative Example 1, 300 mg / L polyethylene glycol (PEG), bis- (3-sulfopropyl) -disulfide, disodium salt) (SPS) 40 mg / L, Janusgreen B (JGB) 1 mg / L were used.

비교예 2의 경우, 현재 시판중인 연성 PCB용 전기 동 도금 첨가제 com.I가 사용되었다. For Comparative Example 2, a commercially available electroplating additive com.I for flexible PCBs was used.

비교예 3의 경우, 현재 시판중인 연성 PCB용 전기 동 도금 첨가제 com.II가 사용되었다. For Comparative Example 3, a commercially available electroplating additive com.II for flexible PCBs was used.

또한, 상기 첨가제 조건별로 얻어진 FPCB용 원판의 표면조도(Ra, Rz)와 잔류응력을 측정한 결과를 표2에 도시하였다.In addition, Table 2 shows the results of measuring the surface roughness (Ra, Rz) and the residual stress of the FPCB disc obtained by the additive conditions.

표면조도(nm) Surface Roughness (nm) 잔류응력(MPa)  Residual stress (MPa) Ra Ra Rz Rz 실시예 1Example 1 13 13 49 49 2.5 2.5 실시예 2Example 2 10 10 40 40 ~ 0 To 0 실시예 3Example 3 55 55 580 580 -5.5 -5.5 실시예 4Example 4 30 30 96 96 -2 -2 실시예 5Example 5 29 29 80 80 -1 -One 비교예 1Comparative Example 1 22 22 60 60 8.5 8.5 비교예 2Comparative Example 2 45 45 120 120 ~ 0 To 0 비교예 3Comparative Example 3 50 50 200 200 ~ 0 To 0

상기한 바와 같이 준비된 전해액과 표 1에 도시된 바와 같은 첨가제 조건 하에서 FPCB 원판의 도금층을 각각 형성한 결과, 유황 함유 화합물 DPS의 40mg/L까지는 도금층의 표면조도가 감소하였으나 초과하는 범위에서는 표면 조도가 상승하였으며, DPS의 농도범위가 증가할수록 도금층의 인장 잔류응력은 점점 감소하여 최소화되었다. As a result of forming the plating layer of the FPCB disc under the electrolyte prepared as described above and the additive conditions as shown in Table 1, the surface roughness of the plating layer was decreased up to 40 mg / L of the sulfur-containing compound DPS, but the surface roughness was exceeded. As the concentration range of DPS increased, the tensile residual stress of the plated layer gradually decreased and minimized.

또한, 유황 함유 화합물 DPS 대신 비교예 1과 같이 SPS가 40mg/L사용된 경우 도금층의 표면조도는 감소하였으나 도금층의 인장 잔류응력은 존재하였다. 질소 함유 화합물 JGB의 농도가 증가한 경우 도금층의 표면조도가 감소하였다.In addition, when SPS was used 40 mg / L as in Comparative Example 1 instead of the sulfur-containing compound DPS, the surface roughness of the plating layer was reduced, but the tensile residual stress of the plating layer was present. When the concentration of the nitrogen-containing compound JGB was increased, the surface roughness of the plating layer was decreased.

상기한 바와 같이, 본 발명에 따른 저 조도, 저 응력의 연성 PCB용 원판의 전기 동 도금층의 제조에 있어서 각 실시예별로 언급된 첨가제의 양은 단지 일 실시예에 불과하며, 본 발명의 상세한 설명에 기재된 첨가범위로부터 다른 다양한 실시예를 구현할 수 있음은 자명함으로, 본 발명은 상기한 실시예에 한정되는 것이 아니라 당업자에 의해 다양한 변형과 변경이 가능하고, 이는 첨부된 청구항의 취지와 범위에 모두 포함되는 것이다. As described above, in the manufacture of the electroplated layer of the low roughness, low stress flexible PCB original plate according to the present invention, the amount of the additives mentioned in each embodiment is just one embodiment, and is described in the detailed description of the present invention. It is apparent that various other embodiments can be implemented from the described ranges, and thus, the present invention is not limited to the above-described embodiments, but various modifications and changes can be made by those skilled in the art, which are included in both the spirit and scope of the appended claims. Will be.

도1은 실시예 2에 따라 제조된 전해 동 도금층의 전자현미경(SEM) 촬영 사진도이다. 1 is an electron micrograph (SEM) photographic photograph of an electrolytic copper plating layer prepared according to Example 2. FIG.

도2는 비교예 1에 따라 제조된 전해 동 도금층의 전자현미경(SEM) 촬영 사진도이다. 2 is an electron micrograph (SEM) photograph of the electrolytic copper plating layer prepared according to Comparative Example 1.

도3은 비교예 2에 따라 제조된 전해 동 도금층의 전자현미경(SEM) 촬영 사진도이다. 3 is an electron micrograph (SEM) photograph of the electrolytic copper plating layer prepared according to Comparative Example 2.

Claims (2)

양극은 함인동을 사용하고, 음극은 동이 스퍼터링된 폴리이미드 필름을 사용하며, 전해액은 황산구리 용액을 사용하여 동 이온을 음극면에서 전기 분해함으로써 동 도금막을 연성 PCB 원판에 형성할 경우, 상기 전해액에 첨가되는 첨가제에 있어서;The positive electrode uses phosphorus-containing copper, the negative electrode uses a copper sputtered polyimide film, and the electrolytic solution uses a copper sulfate solution to electrolyze copper ions on the negative electrode surface to form a copper plated film on the flexible PCB disc. In the additive to be added; 상기 첨가제는 염소 이온과, 계면활성제로서 폴리에틸렌 계열의 폴리에틸렌 글리콜과, 광택제로서 유황 함유 화합물인 3-N,N-디메틸아미노디티오카바모일-1-프로판술폰산과, 레벨러로서 질소 함유 화합물인 야누스그린B를 함유하는 것을 특징으로 하는 연성 PCB용 전해 동 도금 첨가제.The additives include chlorine ions, polyethylene-based polyethylene glycol as a surfactant, 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a sulfur-containing compound as a brightening agent, and Janusgreen as a nitrogen-containing compound as a leveler. Electrolytic copper plating additive for flexible PCB containing B. 제 1 항에 있어서,The method of claim 1, 상기 첨가제는 0.01g/L 내지 0.1g/L의 염소 이온과, 계면활성제로서 폴리에틸렌 계열의 폴리에틸렌 글리콜 0.1g/L 내지 1g/L와, 광택제로서 유황 함유 화합물인 3-N,N-디메틸아미노디티오카바모일-1-프로판술폰산 0.001g/L 내지 0.1g/L와, 레벨러로서 질소 함유 화합물인 야누스그린B 0.001g/L 내지 0.1g/L를 함유하는 것을 특징으로 하는 연성 PCB용 전해 동 도금 첨가제.The additive includes 0.01 g / L to 0.1 g / L of chlorine ions, 0.1 g / L to 1 g / L polyethylene glycol as a surfactant, and 3-N, N-dimethylaminodithi as a sulfur-containing compound as a brightening agent. Electrolytic copper plating for flexible PCB, which contains 0.001 g / L to 0.1 g / L of okabamoyl-1-propanesulfonic acid and Janusgreen B, a nitrogen-containing compound, as a leveler, 0.001 g / L to 0.1 g / L additive.
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KR101234589B1 (en) * 2010-05-24 2013-02-19 한국생산기술연구원 Copper plated layer for forming pattern of printed circuit board and method of manufacturing the same
CN105540948A (en) * 2015-12-21 2016-05-04 北京国环清华环境工程设计研究院有限公司 Gradient functional anodic electrolysis based treatment method for high-copper circuit board wastewater
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