KR20030015392A - Palladium removing solution and method for removing palladium - Google Patents

Palladium removing solution and method for removing palladium Download PDF

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KR20030015392A
KR20030015392A KR10-2003-7000582A KR20037000582A KR20030015392A KR 20030015392 A KR20030015392 A KR 20030015392A KR 20037000582 A KR20037000582 A KR 20037000582A KR 20030015392 A KR20030015392 A KR 20030015392A
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palladium
nitrate
ether
removal liquid
liquid
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KR100761608B1 (en
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곤도오사무
와타나베요시히로
이시하라후쿠사부로
이마이데루히코
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미츠비시 가스 가가쿠 가부시키가이샤
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    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/26—Cleaning or polishing of the conductive pattern
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/07—Electric details
    • H05K2201/0753—Insulation
    • H05K2201/0761—Insulation resistance, e.g. of the surface of the PCB between the conductors
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/121—Metallo-organic compounds
    • 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
    • H05K3/181—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 electroless plating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

본 발명의 팔라듐 제거액은 (a) 질산염, (b) 산화팔라듐을 수용화하기 위한 수용화제 및 (c) 물을 함유한다. 상기 팔라듐 제거액은 경우에 따라 (4) 습윤제 및/또는 (5) 킬레이트제를 추가로 포함한다. 상기 팔라듐 제거액은 구리선을 부식하지 않고 또한 절연성 기판의 표면을 거칠게 하지 않고, 이 표면에 잔류하는 팔라듐을 제거하므로써 회로패턴의 절연성을 향상시킨다.The palladium removal liquid of this invention contains (a) nitrate, (b) the water solubilizer for receiving palladium oxide, and (c) water. The palladium removal liquid optionally further comprises (4) wetting agent and / or (5) chelating agent. The palladium removal liquid does not corrode the copper wire and does not roughen the surface of the insulating substrate, thereby improving the insulation of the circuit pattern by removing palladium remaining on the surface.

Description

팔라듐 제거액 및 팔라듐 제거방법{PALLADIUM REMOVING SOLUTION AND METHOD FOR REMOVING PALLADIUM}Palladium removal solution and palladium removal method {PALLADIUM REMOVING SOLUTION AND METHOD FOR REMOVING PALLADIUM}

회로 패턴을 형성하는 한 방법으로 첨가제법이 사용되어 왔다. 이 방법에서, 팔라듐은 절연성 기판의 전체 표면에 부가된 후 팔라듐층상에서 무전해 도금법에 의해 구리도금층을 형성한다. 회로패턴을 형성하는 구리도금층의 회로패턴 부분은 에칭-방지 레지스트로 피복되며, 피복되지 않은 부분은 에칭제거된다. 그 후, 잔류 에칭-방지 레지스트를 제거함으로써 회로패턴이 형성된다.An additive method has been used as one method of forming a circuit pattern. In this method, palladium is added to the entire surface of the insulating substrate and then forms a copper plated layer by electroless plating on the palladium layer. The circuit pattern portion of the copper plating layer forming the circuit pattern is covered with an anti-etch resist, and the uncoated portion is etched away. Thereafter, a circuit pattern is formed by removing the residual etch-preventing resist.

이같은 통상의 방법에 의하면, 회로패턴의 형성 후 절연성 기판의 표면상에 팔라듐이 다시 잔류된다. 팔라듐은 무전해도금시 도금 촉매제 역할을 하며 전도층을 용이하게 형성하는데 효과적이다. 그러나, 팔라듐은 일반 에칭용액에 용해되기 어려우므로, 구리도금층의 에칭 후에도 제거되지 않은 상태로 잔류된다. 잔류 팔라듐은 회로 패턴의 절연성을 감소시킨다.According to such a conventional method, palladium again remains on the surface of the insulating substrate after the formation of the circuit pattern. Palladium acts as a plating catalyst in electroless plating and is effective in easily forming conductive layers. However, palladium is difficult to dissolve in a general etching solution, and thus remains unremoved even after etching of the copper plating layer. Residual palladium reduces the insulation of the circuit pattern.

회로패턴의 표면 전체 혹은 부품접합용 패드부는 표면처리로서 종종 무전해니켈도금, 무전해 금도금 등으로 처리된다. 그러나, 절연성 기판의 표면에 잔류하는 팔라듐은 도금 촉매제의 역할을 하므로 회로기판의 불필요한 부분에까지도 니켈 혹은 금을 부착시키므로 회로패턴의 절연성이 감소된다.The entire surface of the circuit pattern or the pad portion for joining parts is often treated with electroless nickel plating, electroless gold plating or the like as surface treatment. However, palladium remaining on the surface of the insulating substrate serves as a plating catalyst, and thus nickel or gold is deposited even on unnecessary portions of the circuit board, thereby reducing the insulation of the circuit pattern.

그러므로, 양질의 회로기판을 생산하기 위해 회로기판에 잔류되는 팔라듐을 제거하는 것이 매우 중요하다. 통상의 첨가방법에서는, 에칭-방지 레지스트를 벗겨낸 후, 기질표면상에 잔류하는 불필요한 팔라듐을 다음 방법으로 제거해왔다.Therefore, it is very important to remove palladium remaining in the circuit board in order to produce a good quality circuit board. In a conventional addition method, after removing the anti-etch resist, unnecessary palladium remaining on the substrate surface has been removed by the following method.

(1) 기판을 요오드/요오드화 암모늄 용액에 침지하여 팔라듐을 요오드/요오드화 암모늄 용액에 용해시키는 방법.(1) A method in which a substrate is immersed in an iodine / ammonium iodide solution to dissolve palladium in an iodine / ammonium iodide solution.

(2) 기판을 과망간산칼륨 용액에 침지하여 팔라듐을 과망간산칼륨 용액에 용해시키는 방법.(2) A method in which a substrate is immersed in a potassium permanganate solution to dissolve palladium in a potassium permanganate solution.

(3) 반응성 이온 에칭법(RIE)에 사용된 진공배출장치를 이용하여 기판표면에서 팔라듐을 제거하는 방법 등이 있다.(3) Palladium is removed from the surface of the substrate by using a vacuum discharge device used in reactive ion etching (RIE).

그러나, 상기 통상의 팔라듐 제거방법은 다음과 같은 문제점이 있다.However, the conventional palladium removal method has the following problems.

(1) 요오드/요오드화 암모늄 용액에 침수시키는 단계에서, 이 용액에 팔라듐뿐만 아니라 구리도 용해되어, 배선이 얇아지게 되거나 또는 선이 파열된다.(1) In the step of immersion in the iodide / ammonium iodide solution, not only palladium but also copper is dissolved in this solution, resulting in thinner wires or broken lines.

(2) 과망간산칼륨 용액에 침지하는 방법에서, 수지 기판의 표면이 산화되어 미세한 요철형상으로 된다. 이같은 수지의 산화는 팔라듐의 용해보다 빠르게 진행된다. 이에 따라, 팔라듐 제거액은 산화된 수지표면의 홈(recess)에 잔류된 팔라듐과 반응할 수 없어, 부분적으로 제거되지 않은 팔라듐이 남아있게 된다.(2) In the method of immersing in the potassium permanganate solution, the surface of the resin substrate is oxidized to a fine concavo-convex shape. Oxidation of such resins proceeds faster than dissolution of palladium. As a result, the palladium removal liquid cannot react with the palladium remaining in the recesses of the oxidized resin surface, leaving palladium partially removed.

(3) 진공배출장치를 사용하는 방법은 상기 습식방법과 비교하여 비용이 비싸다. 또한, 이 방법은 처리용량 측면 즉 한회분의 처리시, 기판수가 제한되기 쉽다. 이것은 배선판 제조비용을 증가시킨다.(3) The method of using the vacuum discharge device is expensive compared with the wet method. In addition, this method tends to limit the number of substrates in terms of processing capacity, i.e., one batch. This increases the wiring board manufacturing cost.

최근, 일본특허 3-254179 및 4-179191는 기판을 과망간산칼륨 용액에 침지하며 경우에 따라 기판을 초음파-세정하고, 기판을 방향족 니트로화합물, 아민화합물, 아미노카르복실산, 수산화나트륨, 황산 히드록시 암모늄을 함유하는 용액에 침지하는 단계를 포함하는 팔라듐 제거방법을 공지한다. 상기 공지된 제거액은 기판상에서 산화된 수지층과 팔라듐을 동시에 제거한다. 이에 따라, 과망간산칼륨 용액은 기판표면을 거칠게할 뿐만 아니라 구리 회로패턴 및 기판 사이의 인터페이스를 부식시킨다.Recently, Japanese Patent Nos. 3-254179 and 4-179191 immerse a substrate in a potassium permanganate solution and ultrasonically clean the substrate in some cases, and the substrate is aromatic nitro compound, amine compound, aminocarboxylic acid, sodium hydroxide, hydroxy sulfate. Known methods for removing palladium comprising immersing in a solution containing ammonium. The known removal liquid simultaneously removes the oxidized resin layer and palladium on the substrate. Accordingly, the potassium permanganate solution not only roughens the substrate surface but also corrodes the interface between the copper circuit pattern and the substrate.

본 발명은 팔라듐 제거액 및 이를 이용한 팔라듐 제거방법에 관한 것으로, 보다 상세하게는 처리될 기판의 표면상에 잔류하는 팔라듐을 이 기판에 손상을 가하지 않고 제거하는 제거액 및 팔라듐 제거방법에 관한 것이다.The present invention relates to a palladium removal liquid and a palladium removal method using the same, and more particularly, to a removal liquid and a palladium removal method for removing palladium remaining on the surface of a substrate to be treated without damaging the substrate.

도 1a 내지 도 1d는 프린트배선기판의 제조시 본 발명의 팔라듐 제거액으로 처리하는 회로패턴 형성 기판의 제조단계를 나타내는 개략도.1A to 1D are schematic diagrams illustrating a manufacturing step of a circuit pattern forming substrate treated with a palladium removing liquid of the present invention in the manufacture of a printed wiring board.

본 발명의 목적은 상기 문제점들을 해소하고, 기판의 표면상에 잔류하는 팔라듐을 기판에 손상을 입히지 않고서 제거하는 팔라듐 제거액 및 이 팔라듐 제거액을 이용한 팔라듐 제거방법을 제공하는 것이다. 특히, 본 발명의 목적은 회로기판의 제조시 회로패턴 형성 후 배선 재료 및 절연성 기판상에서 부식을 일으키지 않으면서도 이 절연성 기판의 표면상에 잔류하는 팔라듐을 용이하게 제거하는 팔라듐 제거액을 제공하며, 이 팔라듐 제거액을 이용하여 팔라듐을 제거하는 방법을 제공하는 것이다.It is an object of the present invention to solve the above problems and to provide a palladium removal liquid for removing palladium remaining on the surface of the substrate without damaging the substrate and a palladium removal method using the palladium removal liquid. In particular, an object of the present invention is to provide a palladium removal liquid which easily removes palladium remaining on the surface of the insulating substrate without causing corrosion on the wiring material and the insulating substrate after forming the circuit pattern in the manufacture of the circuit board. It is to provide a method for removing palladium using a removal liquid.

본 발명자들이 상기 목적을 달성하기 위해 예의검토를 거듭한 결과, 추가방법으로 회로패턴을 형성한 후 절연성 기판상에 잔류하는 팔라듐이 (a) 질산염, (b) 산화팔라듐을 수용화하기 위한 수용화제, (c) 물, 경우에 따라 (d) 습윤제 및/또는킬레이트제를 함유하는 액체 조성물에 의해 단기에 용이하게 제거된다는 것에 근거하여, 회로패턴의 절연성 향상 및 고신뢰성의 인쇄회로기판을 제조할 수 있음을 발견함으로써 본 발명을 완성하게 되었다.As a result of the inventors' thorough review to achieve the above object, the palladium remaining on the insulating substrate after forming the circuit pattern by an additional method is a solubilizing agent for accommodating (a) nitrate and (b) palladium oxide. on the basis of being easily removed in the short term by a liquid composition containing water, and optionally (d) wetting and / or chelating agents, to improve the insulation of the circuit pattern and to produce a highly reliable printed circuit board. The present invention has been completed by discovering that it can.

이에 따라, 본 발명의 한 측면은 (a) 질산염, (b) 산화팔라듐을 수용화하기 위한 수용화제 및 (c) 물을 함유하는 팔라듐 제거액을 제공한다. 상기 팔라듐 제거액은 경우에 따라 습윤제 및/또는 킬레이트제를 함유하는 것이 좋다.Accordingly, one aspect of the present invention provides a palladium removal liquid containing (a) nitrate, (b) a solubilizer for solubilizing palladium oxide, and (c) water. The palladium removing liquid may optionally contain a humectant and / or a chelating agent.

본 발명의 두번째 측면에서, 절연성 기판의 표면상에 팔라듐층을 형성하는 단계; 이 팔라듐층 상에 구리도금층을 형성하는 단계; 이 구리도금층의 표면에 레지스트를 도포한 후 구리도금층을 에칭하여 회로패턴을 형성하는 단계; 레지스트를 박리한 후 기판 표면에 잔류하는 팔라듐을 제거하는 단계를 포함하는 팔라듐 제거방법을 제공한다.In a second aspect of the invention, there is provided a method of forming a palladium layer on a surface of an insulating substrate; Forming a copper plating layer on the palladium layer; Applying a resist to the surface of the copper plating layer and then etching the copper plating layer to form a circuit pattern; It provides a palladium removal method comprising the step of removing the palladium remaining on the surface of the substrate after peeling the resist.

질산염(a)으로는 질산암모늄, 질산리튬, 질산아연, 질산망간, 질산니켈, 질산코발트, 질산나트륨, 질산암모늄을 갖는 질산칼륨이 특히 바람직하다. 질산염은 팔라듐상에서 산화반응을 한다. 팔라듐 제거액 내 질산염의 농도는 0.001 내지 40중량%이며, 바람직하게는 0.005 내지 30중량%이다.As the nitrate (a), potassium nitrate having ammonium nitrate, lithium nitrate, zinc nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, sodium nitrate and ammonium nitrate is particularly preferable. Nitrate oxidizes on palladium. The concentration of nitrate in the palladium removal liquid is 0.001 to 40% by weight, preferably 0.005 to 30% by weight.

산화팔라듐을 수용화 하기 위한 수용화제(b)는 무기산 또는 무기산염이며,바람직하게는 염산, 질산, 황산, 염화암모늄 및 염화알루미늄과 같은 염산염, 황산암모늄 및 황산알루미늄과 같은 황산염이다. 팔라듐 제거액 내 수용화제의 농도는 0.01 내지 50중량%이며, 바람직하게는 0.05 내지 30중량%이다.The solubilizer (b) for solubilizing palladium oxide is an inorganic acid or an inorganic acid salt, preferably hydrochloric acid, nitric acid, sulfuric acid, hydrochlorides such as ammonium chloride and aluminum chloride, sulfates such as ammonium sulfate and aluminum sulfate. The concentration of the solubilizer in the palladium removal liquid is 0.01 to 50% by weight, preferably 0.05 to 30% by weight.

본 발명의 효과에 손상을 주지 않는 범위 내에서, 산화력을 고양하거나 혹은 기타 팔라듐 산화성 물질을 혼합하거나 팔라듐상에서 산화반응을 갖는 기타의 팔라듐 산화물을 수용화 시킬 물질을 혼합해도 좋다.As long as it does not impair the effects of the present invention, it is also possible to mix materials which enhance the oxidizing power, or mix other palladium oxidizing materials or other palladium oxides having an oxidation reaction on the palladium.

상기 팔라듐 제거액은 성분 (a) 내지 (c)에 추가로 습윤제(d)를 함유한다. 이 습윤제(d)는 계면활성제, 알콜 또는 에테르이다. 이 계면활성제는 또한 양이온계, 비이온계 혹은 음이온계이다. 알콜의 예로는 에틸알콜, 이소프로필알콜, 부탄올, 에틸렌 글리콜, 디에틸렌 글리콜, 프로필렌 글리콜, 디프로필렌 글리콜이 있다. 에테르의 예로는 에틸렌 글리콜 모노에틸 에테르, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 모노메틸 에테르, 디에틸렌 글리콜 모노에틸 에테르, 디에틸렌 글리콜 모노부틸 에테르, 프로필렌 글리콜 모노메틸 에테르, 프로필렌 글리콜 모노에틸 에테르, 프로필렌 글리콜 모노부틸 에테르, 디프로필렌 글리콜 모노메틸 에테르, 디프로필렌 글리콜 모노에틸 에테르, 디프로필렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 디메틸 에테르, 디프로필렌 글리콜 디메틸 에테르, 폴리옥시에틸렌 메틸 페닐 에테르, 폴리옥시에틸렌 에틸 페닐 에테르, 폴리옥시에틸렌 옥틸 페닐 에테르, 폴리옥시에틸렌 노닐 페닐 에테르가 있다.The palladium removal liquid further contains a humectant (d) in addition to the components (a) to (c). This humectant (d) is a surfactant, alcohol or ether. This surfactant is also cationic, nonionic or anionic. Examples of alcohols are ethyl alcohol, isopropyl alcohol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol. Examples of ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene ethyl phenyl Ethers, polyoxyethylene octyl phenyl ethers, polyoxyethylene nonyl phenyl ethers.

상기 습윤제는 단독으로 또는 두가지 이상의 복합물로 사용될 수도 있다. 팔라듐 제거액 내의 습윤제의 농도는 0.001 내지 10중량%이며, 바람직하게는 0.005내지 5중량%, 보다 바람직하게는 0.005 내지 1중량%이다.The wetting agents may be used alone or in combination of two or more. The concentration of the humectant in the palladium removal liquid is 0.001 to 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.005 to 1% by weight.

성분 (a) 내지 (c) 또는 성분 (a) 내지 (d)에서, 팔라듐 제거액은 킬레이트제(e)를 추가로 함유한다. 킬레이트제는 팔라듐을 함유한 착화물을 형성할 수 있는 화합물이며, 디메틸글리옥심, 티오우레아, 티옥신(8-메르캅토퀴놀린), 디티존, 2-니트로소-1-나프톨 및 p-니트로소디메틸아닐린을 들 수 있다. 디메틸글리옥심 및 티오우레아가 특히 바람직하다.In components (a) to (c) or (a) to (d), the palladium removal liquid further contains a chelating agent (e). Chelating agents are compounds capable of forming complexes containing palladium and include dimethylglyoxime, thiourea, thioxin (8-mercaptoquinoline), ditizone, 2-nitroso-1-naphthol and p-nitroso Dimethyl aniline is mentioned. Dimethylglyoxime and thiourea are particularly preferred.

킬레이트제(e)는 팔라듐 산화물의 수용화제로서 작용하는 것만이 아니라 또한 절연성 기판의 거친 표면의 홈에 소량으로 잔류된 팔라듐과 함께 착화물을 형성한다. 회로패턴 형성후, 팔라듐은 무전해 니켈도금 및 무전해 금도금에 대해 비활성화하며 따라서, 니켈 및 금이 절연성 기판의 부적절한 부분에 부착되어 회로패턴의 절연성이 나빠지는 것을 방지한다.The chelating agent (e) not only acts as an acceptor of the palladium oxide, but also forms a complex with palladium remaining in small amounts in the grooves of the rough surface of the insulating substrate. After formation of the circuit pattern, palladium is deactivated for electroless nickel plating and electroless gold plating, thus preventing nickel and gold from adhering to inappropriate portions of the insulating substrate, thereby degrading the insulation of the circuit pattern.

팔라듐 제거액 내의 킬레이트제 농도는 0.01 내지 5중량%이며, 바람직하게는 0.01 내지 2중량%, 보다 바람직하게는 0.05 내지 2중량%이다.The chelating agent concentration in the palladium removal liquid is 0.01 to 5% by weight, preferably 0.01 to 2% by weight, more preferably 0.05 to 2% by weight.

본 발명의 팔라듐 제거액은 질산염, 수용화제, 경우에 따라 습윤제 및/또는 킬레이트제 및 나머지로서 물을 포함하는 수성액이다. 상기 수성액은 분산 또는 현탁액일 수도 있으나 일반적으로는 수용액이다.The palladium removal liquid of the present invention is an aqueous solution comprising nitrate, water soluble agent, optionally a humectant and / or chelating agent and water as the remainder. The aqueous solution may be a dispersion or a suspension but is generally an aqueous solution.

본 발명에 따른 팔라듐 제거방법은 처리할 기판을 실온 내지 80℃에서 팔라듐 제거액에 침지시키므로써 시행된다. 팔라듐 제거액의 pH는 통상 0 내지 5이며, 성분(b)으로서 사용되는 무기산의 첨가양을 변경하므로써 pH값을 조정한다. 팔라듐 제거액은 처리대상 기판으로부터 팔라듐을 효율적으로 제거하기에 충분한 양으로사용되며, 당업자가 적절한 실험을 통해 그 양을 용이하게 결정할 수 있다. 본 발명의 팔라듐 제거방법에 따라, 회로패턴 형성 후 기판상에 잔류하는 팔라듐을 실질적으로 완전히 제거할 수 있다 (회로기판에 대한 잔류팔라듐 농도가 5ppm 이하).The palladium removal method according to the present invention is carried out by immersing the substrate to be treated in a palladium removal liquid at room temperature to 80 ℃. The pH of a palladium removal liquid is 0-5 normally, and pH value is adjusted by changing the addition amount of the inorganic acid used as component (b). The palladium removal liquid is used in an amount sufficient to efficiently remove palladium from the substrate to be treated, and those skilled in the art can easily determine the amount through appropriate experiments. According to the palladium removal method of the present invention, palladium remaining on the substrate after the circuit pattern formation can be substantially completely removed (residual palladium concentration of 5 ppm or less on the circuit board).

본 발명은 다음 실시예 및 비교예를 참조하여 보다 상세히 설명한다. 그러나, 이 실시예 및 비교예들은 예시를 위한 것이며 본 발명의 범위를 한정하기 위한 것은 아니다.The invention is described in more detail with reference to the following examples and comparative examples. However, these examples and comparative examples are for illustration only and are not intended to limit the scope of the invention.

도 1은 회로기판의 제조시 회로형성에 따른 공정을 나타내는 개략도이다. 도 1a에 도시된 바와 같이, 팔라듐 촉매층(2)을 절연성 기판(1)상에 형성했다. 팔라듐은 일반적으로 절연성 기판에 흡착되어 매우 얇은 층을 형성하며, 무전해도금에 대한 촉매제 역할을 한다. 구리도금층으로 만들어진 전도층(3)은 상기 절연성 기판상의 팔라듐 촉매층(2)상에서 도 1b에 도시된 바와 같이 무전해 도금에 의해 형성된다. 전도층은 전기도금에 의해 무전해도금 표면상에 형성되어도 좋다.1 is a schematic diagram showing a process according to circuit formation in the manufacture of a circuit board. As shown in FIG. 1A, a palladium catalyst layer 2 was formed on the insulating substrate 1. Palladium is generally adsorbed on an insulating substrate to form a very thin layer and serves as a catalyst for electroless plating. A conductive layer 3 made of a copper plated layer is formed by electroless plating on the palladium catalyst layer 2 on the insulating substrate as shown in FIG. 1B. The conductive layer may be formed on the surface of the electroless plating by electroplating.

이어서, 도 1c와 같이, 전도층의 일부분(3)은 회로가 포토레지스트층(4)으로 피복되는 구조인 것이며 비-피복 구리도금층(3)을 에칭용액으로 용해제거한다. 상기 포토레지스트층은 예를들어 포토레지스트층이 건식 포토필름, 포토레지스트 잉크, 또는 스크린 프린팅 레지스트에 의해 형성된다. 에칭용액의 예로는 황산과 과산화수소의 혼합액, 염화제2동 함유액, 염화제2철 함유용액이 있다.Subsequently, as shown in FIG. 1C, the portion 3 of the conductive layer has a structure in which the circuit is covered with the photoresist layer 4, and the non-coated copper plating layer 3 is dissolved and removed with an etching solution. The photoresist layer is formed by, for example, a dry photo film, a photoresist ink, or a screen printing resist. Examples of the etching solution include a mixed solution of sulfuric acid and hydrogen peroxide, a cupric chloride containing solution, and a ferric chloride containing solution.

에칭후, 포토레지스트를 제거함으로써 도 1d와 같이 절연성 기판(1)의 표면상에 전도체 회로(3a)가 형성된다. 구리도금층의 비-마스크 부분을 에칭한 후, 절연성 기판(1)의 표면에 부착된 팔라듐(2a)는 제거되지 않고 절연성 수지에 흡착된상태로서 그대로 잔류한다.After etching, the conductor circuit 3a is formed on the surface of the insulating substrate 1 by removing the photoresist. After etching the non-mask portion of the copper plating layer, the palladium 2a adhered to the surface of the insulating substrate 1 is not removed but remains as it is adsorbed to the insulating resin.

실시예 1 ∼ 7Examples 1-7

상기의 팔라듐 잔류의 회로기판을 표 1의 조성으로 된 각 팔라듐 제거액에 소정의 조건에서 침지하고, 정수로 세정한 후 건조했다. 그 다음, 20-μm의 간격을 갖는 회로 부분들 사이의 절연저항을 측정하고, 절연성 기판 표면에 대한 형광 X-선 분석법 및 X-선 마이크로 분석기를 이용하여 팔라듐 잔존량을 측정, 회로패턴부에 대해 무전해 니켈도금을 시행하고, 절연성 기판상에서 니켈의 석출이 일어나는지의 유무, 또한 회로패턴부에 있어서 동의 부식성 유무를 관찰했다. 이 측정 및 관찰 결과는 다음을 기준으로 평가했고 평가결과를 표 1에 나타내었다.The palladium residual circuit board was immersed in each palladium removal liquid having the composition shown in Table 1 under predetermined conditions, washed with purified water, and dried. Then, the insulation resistance between the circuit portions having a spacing of 20-μm is measured, and the residual amount of palladium is measured by using a fluorescent X-ray analysis method and an X-ray micro analyzer on the surface of the insulating substrate. Electroless nickel plating was carried out on the substrate, and the presence or absence of precipitation of nickel on the insulating substrate and the presence of copper corrosion on the circuit pattern portion were observed. The measurement and observation results were evaluated based on the following criteria, and the evaluation results are shown in Table 1.

1. 절연성1. Insulation

A:처리전의 절연저항치: 수MΩ-> 처리후의 절연저항치: 무한대A: Insulation resistance value before treatment: Several MΩ-> Insulation resistance value after treatment: Infinite

C:처리전의 절연저항치: 수MΩ-> 처리후의 절연저항치: 수MΩC: Insulation resistance value before treatment: several MΩ-> Insulation resistance value after treatment: several MΩ

2. 팔라듐 제거성2. Palladium removal

A:완전 제거됨A: completely removed

B:부분 잔존함B: partial remaining

C:상당한 부분 잔존함C: Significant portion remaining

3. 니켈 석출성3. Nickel precipitation

A+:석출이 전혀 확인되지 않음A + : Precipitation not confirmed at all

A:석출이 실질적으로 확인되지 않음A: Precipitation has not been substantially confirmed

B:일부 석출이 확인됨B: Some precipitation confirmed

C:석출이 확인됨C: Precipitation confirmed

4. 구리 부식성4. Copper corrosive

A:부식이 확인되지 않음A: Corrosion not confirmed

B:일부 부식이 확인됨B: Some corrosion is identified

C:전면에 걸쳐 부식이 확인됨C: Corrosion confirmed throughout

표 1Table 1

팔라듐 제거액의 조성Composition of palladium removal liquid 질산염nitrate 수용화제Solubilizer 습윤제Humectant 물water 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 농도(wt%)Concentration (wt%) 실시예 1Example 1 질산암모늄Ammonium Nitrate 22 염산Hydrochloric acid 55 -- -- 나머지Remainder 실시예 2Example 2 질산암모늄Ammonium Nitrate 55 염산Hydrochloric acid 55 -- -- 나머지Remainder 실시예 3Example 3 질산암모늄Ammonium Nitrate 0.50.5 염산Hydrochloric acid 55 -- -- 나머지Remainder 실시예 4Example 4 질산암모늄Ammonium Nitrate 22 염산Hydrochloric acid 1One a* a * 33 나머지Remainder 실시예 5Example 5 질산암모늄Ammonium Nitrate 22 염산Hydrochloric acid 1One b* b * 0.10.1 나머지Remainder 실시예 6Example 6 질산암모늄Ammonium Nitrate 22 황산Sulfuric acid 33 -- -- 나머지Remainder 실시예 7Example 7 질산암모늄Ammonium Nitrate 22 질산nitric acid 55 -- -- 나머지Remainder

a*:이소프로필 알콜a * : isopropyl alcohol

b*:폴리옥시에틸렌 노닐 페닐에테르b * : polyoxyethylene nonyl phenyl ether

표 1(계속)Table 1 (continued)

제거 조건Removal condition 평가 결과Evaluation results 온도(℃)Temperature (℃) 시간(분)Minutes 절연성Insulation Pd 제거Pd removal Ni 석출Ni precipitation Cu 부식Cu corrosion 실시예 1Example 1 6060 55 AA AA AA AA 실시예 2Example 2 6060 55 AA AA AA AA 실시예 3Example 3 7070 55 AA AA AA AA 실시예 4Example 4 5050 33 AA AA AA AA 실시예 5Example 5 5050 33 AA AA AA AA 실시예 6Example 6 6060 55 AA AA AA AA 실시예 7Example 7 6060 55 AA AA AA AA

비교예 1 ∼ 8Comparative Examples 1 to 8

표 2와 같은 조성물을 각각 갖는 팔라듐 제거액을 이용하여 실시예 1 내지 7를 반복했다. 그 결과는 표 2에 도시했다.Examples 1 to 7 were repeated using palladium removal liquids each having a composition as in Table 2. The results are shown in Table 2.

표 2TABLE 2

팔라듐 제거액의 조성Composition of palladium removal liquid 질산염nitrate 수용화제Solubilizer 습윤제Humectant 물water 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 농도(wt%)Concentration (wt%) 비교예 1Comparative Example 1 질산암모늄Ammonium Nitrate 55 -- -- -- -- 나머지Remainder 비교예 2Comparative Example 2 -- -- 염산Hydrochloric acid 55 -- -- 나머지Remainder 비교예 3Comparative Example 3 -- -- 황산Sulfuric acid 33 -- -- 나머지Remainder 비교예 4Comparative Example 4 -- -- 염화암모늄Ammonium chloride 55 -- -- 나머지Remainder 비교예 5Comparative Example 5 질산암모늄Ammonium Nitrate 55 -- -- a* a * 33 나머지Remainder 비교예 6Comparative Example 6 질산암모늄Ammonium Nitrate 55 -- -- b* b * 0.10.1 나머지Remainder 비교예 7Comparative Example 7 -- -- 염산Hydrochloric acid 55 a* a * 33 나머지Remainder 비교예 8Comparative Example 8 -- -- 염화암모늄Ammonium chloride 55 a* a * 33 나머지Remainder

a*:이소프로필 알콜a * : isopropyl alcohol

b*:폴리옥시에틸렌 노닐 페닐에테르b * : polyoxyethylene nonyl phenyl ether

표 2(계속)Table 2 (continued)

제거 조건Removal condition 평가 결과Evaluation results 온도(℃)Temperature (℃) 시간(분)Minutes 절연성Insulation Pd 제거Pd removal Ni 석출Ni precipitation Cu 부식Cu corrosion 비교예 1Comparative Example 1 6060 55 CC CC CC AA 비교예 2Comparative Example 2 6060 55 BB BB CC AA 비교예 3Comparative Example 3 6060 55 CC CC CC AA 비교예 4Comparative Example 4 6060 55 CC CC CC AA 비교예 5Comparative Example 5 6060 55 CC CC CC AA 비교예 6Comparative Example 6 6060 55 CC CC CC AA 비교예 7Comparative Example 7 6060 55 BB BB CC AA 비교예 8Comparative Example 8 6060 55 CC CC CC AA

실시예 8 ∼ 9Examples 8-9

킬레이트제를 함유하는 팔라듐 제거액을 이용하여 실시예 1 내지 7를 반복했다. 그 결과는 표 3에 도시했다.Examples 1-7 were repeated using the palladium removal liquid containing a chelating agent. The results are shown in Table 3.

표 3TABLE 3

팔라듐 제거액의 조성Composition of palladium removal liquid 질산염nitrate 수용화제Solubilizer 습윤제Humectant 물water 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 종류Kinds 농도(wt%)Concentration (wt%) 농도(wt%)Concentration (wt%) 실시예 8Example 8 질산암모늄Ammonium Nitrate 22 염산Hydrochloric acid 1One c* c * 0.10.1 나머지Remainder 실시예 9Example 9 질산암모늄Ammonium Nitrate 22 염산Hydrochloric acid 1One d* d * 0.10.1 나머지Remainder

c*:디메틸글리옥심c * : dimethylglyoxime

d*:티오우레아d * : thiourea

표 3(계속)Table 3 (continued)

제거 조건Removal condition 평가 결과Evaluation results 온도(℃)Temperature (℃) 시간(분)Minutes 절연성Insulation Pd 제거Pd removal Ni 석출Ni precipitation Cu 부식Cu corrosion 실시예 8Example 8 5050 33 AA AA A+ A + AA 실시예 9Example 9 5050 33 AA AA A+ A + AA

본 발명의 팔라듐 제거액에 침지함으로써 회로기판의 표면에 존재하는 팔라듐을 제거하는 것이 가능하다. 본 발명의 팔라듐 제거액은 특히, 절연성 기판의 표면에 잔류하는 팔라듐을 제거하는 것이 적절하고, 구리배선을 침식하는 일이 없고 또한 절연성 기판 표면을 거칠게 만들지 않기 때문에 회로패턴의 절연성을 향상시킬 수 있다.It is possible to remove palladium existing on the surface of a circuit board by immersing in the palladium removal liquid of this invention. The palladium removal liquid of the present invention is particularly suitable for removing palladium remaining on the surface of the insulating substrate, and does not corrode copper wiring and does not roughen the surface of the insulating substrate, thereby improving the insulation of the circuit pattern.

또한, 회로패턴에 대해 무전해 니켈도금 또는 무전해 금도금 등을 시행하는 경우, 표면의 팔라듐이 제거되었으므로 절연성 기판 표면에 대한 도금처리에 의한 절연성 저하를 미연에 방지할 수 있게 된다.In addition, when electroless nickel plating or electroless gold plating is performed on the circuit pattern, palladium on the surface is removed, and thus the deterioration in insulation due to the plating treatment on the surface of the insulating substrate can be prevented.

Claims (15)

(a) 질산염, (b) 팔라듐 산화물을 수용화할 수용화제 및 (c) 물을 포함하는 것을 특징으로 하는 팔라듐 제거액.A palladium removal liquid comprising (a) a nitrate, (b) a solubilizer to solubilize the palladium oxide, and (c) water. 제 1항에 있어서,The method of claim 1, 0.001∼40중량%의 질산염, 0.01∼50중량%의 수용화제 및 나머지로서 물을 포함하는 것을 특징으로 하는 팔라듐 제거액.A palladium removal liquid comprising 0.001 to 40% by weight of nitrate, 0.01 to 50% by weight of a solubilizer and water as the remainder. 제 1항 또는 제 2항에 있어서,The method according to claim 1 or 2, 상기 질산염은 질산암모늄, 질산리튬, 질산아연, 질산망간, 질산니켈, 질산코발트, 질산나트륨, 및 질산칼륨으로 구성된 군에서 선택된 적어도 하나의 화합물인 것을 특징으로 하는 팔라듐 제거액.The nitrate is at least one compound selected from the group consisting of ammonium nitrate, lithium nitrate, zinc nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, sodium nitrate, and potassium nitrate. 제 1항 내지 제 3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 상기 수용화제는 염산, 질산, 황산, 염화암모늄, 염화알루미늄, 황산암모늄, 및 황산알루미늄으로 구성된 군에서 선택된 적어도 하나의 화합물인 것을 특징으로 하는 팔라듐 제거액.The water solubilizer is at least one compound selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, ammonium chloride, aluminum chloride, ammonium sulfate, and aluminum sulfate. 제 1항 내지 제 4항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 4, (d) 습윤제를 추가로 포함하는 것을 특징으로 하는 팔라듐 제거액.(d) A palladium removal liquid, further comprising a humectant. 제 5항에 있어서,The method of claim 5, 0.001∼10중량%의 습윤제를 함유하는 것을 특징으로 하는 팔라듐 제거액.A palladium removing liquid, comprising 0.001 to 10% by weight of a humectant. 제 5항 또는 제 6항에 있어서,The method according to claim 5 or 6, 상기 습윤제가 계면활성제, 알콜 또는 에테르인 것을 특징으로 하는 팔라듐 제거액.The palladium removing liquid, characterized in that the wetting agent is a surfactant, alcohol or ether. 제 7항에 있어서,The method of claim 7, wherein 상기 계면활성제가 양이온, 비이온 또는 음이온인 것을 특징으로 하는 팔라듐 제거액.The palladium removing liquid, characterized in that the surfactant is a cation, a nonionic or an anion. 제 7항에 있어서The method of claim 7, 상기 알콜은 에틸알콜, 이소프로필알콜, 부탄올, 에틸렌 글리콜, 디에틸렌 글리콜, 프로필렌 글리콜, 및 디프로필렌 글리콜로 구성된 군에서 선택된 적어도 하나의 화합물인 것을 특징으로 하는 팔라듐 제거액.The alcohol is palladium removing liquid, characterized in that at least one compound selected from the group consisting of ethyl alcohol, isopropyl alcohol, butanol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. 제 7항에 있어서,The method of claim 7, wherein 상기 에테르는 에틸렌 글리콜 모노에틸 에테르, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 모노메틸 에테르, 디에틸렌 글리콜 모노에틸 에테르, 디에틸렌 글리콜 모노부틸 에테르, 프로필렌 글리콜 모노메틸 에테르, 프로필렌 글리콜 모노에틸 에테르, 프로필렌 글리콜 모노부틸 에테르, 디프로필렌 글리콜 모노메틸 에테르, 디프로필렌 글리콜 모노에틸 에테르, 디프로필렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 디메틸 에테르, 디프로필렌 글리콜 디메틸 에테르, 폴리옥시에틸렌 메틸 페닐에테르, 폴리옥시에틸렌 에틸 페닐에테르, 폴리옥시에틸렌 옥틸 페닐에테르, 및 폴리옥시에틸렌 노닐 페닐에테르로 구성된 군에서 선택된 적어도 하나의 화합물인 것을 특징으로 하는 팔라듐 제거액.The ethers are ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene ethyl phenyl ether At least one compound selected from the group consisting of polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether. 제 1항 내지 제 10항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 10, (e) 킬레이트제를 추가로 포함하는 것을 특징으로 하는 팔라듐 제거액.(e) A palladium removing liquid, further comprising a chelating agent. 제 11항에 있어서,The method of claim 11, 0.01∼5중량%의 킬레이트제를 함유하는 것을 특징으로 하는 팔라듐 제거액.A palladium removal liquid containing 0.01 to 5% by weight of a chelating agent. 제 11항 또는 제 12항에 있어서,The method of claim 11 or 12, 상기 킬레이트제는 디메틸글리옥심, 티오우레아, 티옥신(8-메르캅토퀴놀린), 디티존, 2-니트로소-1-나프톨, 및 p-니트로소디메틸아닐린으로 구성된 군에서 선택된 적어도 하나의 화합물인 것을 특징으로 하는 팔라듐 제거액.The chelating agent is at least one compound selected from the group consisting of dimethylglyoxime, thiourea, thioxin (8-mercaptoquinoline), ditizone, 2-nitroso-1-naphthol, and p-nitrosodimethylaniline Palladium removal liquid, characterized in that. 제 1항 내지 제 13항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 13, 절연성 기판 표면상에 형성된 구리도금층에 의해 회로패턴이 형성되는 첨가제법에 의해 회로기판 제조에 사용되는 것을 특징으로 하는 팔라듐 제거액.A palladium removing liquid, characterized in that it is used for the manufacture of a circuit board by an additive method in which a circuit pattern is formed by a copper plating layer formed on an insulating substrate surface. 절연성 기판의 표면상에 팔라듐을 부착하여 팔라듐층을 형성하는 단계;Attaching palladium on the surface of the insulating substrate to form a palladium layer; 상기 팔라듐층 상에 구리도금층을 형성하는 단계;Forming a copper plating layer on the palladium layer; 상기 구리도금층의 표면에 레지스트를 도포한 후 구리도금층을 에칭하는 단계; 및Etching the copper plating layer after applying a resist to the surface of the copper plating layer; And 레지스트를 박리하여 회로패턴을 형성한 후 절연성 기판 표면에 잔류하는 팔라듐을 제 1항 내지 제 13항에 기재된 팔라듐 제거액을 사용하여 제거하는 단계를 포함하는 것을 특징으로 하는 팔라듐 제거방법.A method of removing palladium, comprising removing the resist to form a circuit pattern, and then removing the palladium remaining on the surface of the insulating substrate using the palladium removing liquid according to claim 1.
KR1020037000582A 2000-07-26 2001-07-23 Palladium removing solution and method for removing palladium KR100761608B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011019189A2 (en) * 2009-08-11 2011-02-17 동우 화인켐 주식회사 Resist stripping solution composition, and method for stripping resist by using same

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100674315B1 (en) * 2002-02-08 2007-01-24 에스케이 주식회사 Cleaning agent and method for cleaning heater tubes
AU2003902423A0 (en) * 2003-05-19 2003-06-05 Intellirad Solutions Pty. Ltd Apparatus and method
JP2008106354A (en) * 2006-09-25 2008-05-08 Mec Kk Metal removing solution and metal removing method using the same
JP5304637B2 (en) * 2007-03-12 2013-10-02 三菱化学株式会社 Etching solution and etching method
CN102191501B (en) * 2010-03-10 2013-01-30 比亚迪股份有限公司 Palladium remover and preparation method thereof, and plastic surface activation method
JP5195858B2 (en) * 2010-09-22 2013-05-15 日立金属株式会社 Silicon nitride substrate
CN103945654A (en) * 2013-01-18 2014-07-23 北大方正集团有限公司 Method for leaving palladium ions in non-metallized holes of passivation circuit board and circuit board manufactured through same
CN103249254A (en) * 2013-04-22 2013-08-14 胜宏科技（惠州）股份有限公司 Method of removing palladium in NPTHs of PCB
KR20170008309A (en) 2014-07-10 2017-01-23 오꾸노 케미칼 인더스트리즈 컴파니,리미티드 Resin plating method
CN114945246A (en) * 2022-05-11 2022-08-26 深圳市松柏实业发展有限公司 Palladium removal process of circuit board, palladium passivator with non-metal holes and preparation method of palladium passivator

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5112582B1 (en) * 1970-10-17 1976-04-20
SE426178B (en) * 1981-05-21 1982-12-13 Ericsson Telefon Ab L M SET FOR CHEMICAL Peel-off layers containing PALLADIUM AND ATMINSTONE ONE OF THE METALS COPPER AND NICKEL
JPS6421020A (en) * 1987-07-15 1989-01-24 Fuji Electric Co Ltd Etching recovery method for palladium
US6030520A (en) * 1997-04-23 2000-02-29 The Regents Of The University Of California Nitrate reduction

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011019189A2 (en) * 2009-08-11 2011-02-17 동우 화인켐 주식회사 Resist stripping solution composition, and method for stripping resist by using same
WO2011019189A3 (en) * 2009-08-11 2011-06-23 동우 화인켐 주식회사 Resist stripping solution composition, and method for stripping resist by using same
US9081291B2 (en) 2009-08-11 2015-07-14 Dongwoo Fine-Chem Co., Ltd. Resist stripping solution composition, and method for stripping resist by using same

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