KR100370821B1 - Etching composition for copper or copper alloy and method for etching copper or copper alloy using the same - Google Patents
Etching composition for copper or copper alloy and method for etching copper or copper alloy using the same Download PDFInfo
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- KR100370821B1 KR100370821B1 KR10-2000-0011484A KR20000011484A KR100370821B1 KR 100370821 B1 KR100370821 B1 KR 100370821B1 KR 20000011484 A KR20000011484 A KR 20000011484A KR 100370821 B1 KR100370821 B1 KR 100370821B1
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- Prior art keywords
- copper
- etching
- copper alloy
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- composition
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- 238000005530 etching Methods 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 229940045803 cuprous chloride Drugs 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 동 또는 동합금용 에칭액 조성물 및 이를 이용하여 동 또는 동합금액의 에칭방법에 관한 것으로, 더욱 상세하게는 a) 동 또는 동합금을 산화시킬 수 있는 산화제 10.0∼30.0중량%, b) 물 30.0∼80.0중량%, c) 염산 0.1∼5.0 중량% 및 d) 무기염화합물 5.0∼20.0중량%로 구성되는 동 또는 동합금용 에칭액 조성물 및 이를 이용하여 40∼60℃의 에칭온도에서 동 또는 동합금을 에칭하는 방법에 관한 것이다. 본 발명의 에칭액은 특수한 산화제를 사용함으로써 염소가스를 거의 배출하지 않기 때문에 환경오염 및 각종 장비를 부식시키지 않을 뿐만 아니라, 에칭속도 및 에칭능력이 향상됨과 동시에 고농축된 에칭액은 폐액의 감소와 폐액 판매시 높은 부가가치가 있음으로써 생산원가를 줄일 수 있는 장점이 있다.The present invention relates to an etching solution composition for copper or copper alloy and a method for etching copper or copper alloy using the same, and more particularly, a) 10.0 to 30.0 wt% of an oxidizing agent capable of oxidizing copper or copper alloy, b) 30.0 to water 80.0% by weight, c) 0.1 to 5.0% by weight of hydrochloric acid and d) 5.0 to 20.0% by weight of an inorganic salt compound, and an etching solution composition for copper or copper alloy using the same to etch copper or copper alloy at an etching temperature of 40 to 60 ° C. It is about a method. Etching liquid of the present invention does not corrode environmental pollution and various equipments because it uses almost no chlorine gas by using a special oxidizing agent, and the etching concentration and etching ability are improved, and the highly concentrated etching liquid reduces waste and sells waste. The high added value has the advantage of reducing the cost of production.
Description
본 발명은 동 또는 동합금용 에칭액 조성물 및 이를 이용하여 동 또는 동합금액의 에칭방법에 관한 것으로, 더욱 상세하게는 인쇄회로기판(PCB) 또는 리드프레임 회로상의 불필요한 동 또는 동합금층을 에칭시켜 제거시키는 동 또는 동합금용 에칭액 조성물 및 이를 이용한 동 또는 동합금의 에칭방법에 관한 것이다.The present invention relates to an etching liquid composition for copper or copper alloy and a method for etching copper or copper alloy using the same, and more particularly, copper for removing unnecessary copper or copper alloy layers on a printed circuit board (PCB) or lead frame circuit by etching. Or it relates to an etching solution composition for copper alloy and a method of etching copper or copper alloy using the same.
일반적으로 금속층에 패턴을 형성하는 공정은 인쇄회로기판(PCB) 또는 리드프레임 반도체 소지상에 드라이필름층을 형성하고, 이 드라이필름 패턴을 마스크로 해서 불필요한 금속층(동 또는 동합금층)을 에칭하여 제거시키는 것이다.In general, a process of forming a pattern on a metal layer is performed by forming a dry film layer on a printed circuit board (PCB) or a lead frame semiconductor substrate, and removing unnecessary metal layers (copper or copper alloy layers) by using the dry film pattern as a mask. It is to let.
이와 관련된 선행기술로서, 대한민국 등록특허 제203419호에서는 구리 또는 구리합금을 기질로 하는 리드프레임의 제조공정에서 실시되는 산세, 즉 화학적 용해처리를 위한 용액을 개시하고 있다.As a related art, Korean Patent No. 203419 discloses a solution for pickling, ie, chemical dissolution treatment, performed in a manufacturing process of a lead frame based on copper or a copper alloy.
상기 특허는 주성분으로 수용성 과산화모노황산염(MHSO5)을 함유하며, 보조성분으로 황산유도체, 플루오르화물, 유기용매 및 계면활성제를 함유하는 리드프레임의 화학적 용해처리를 위한 산세용액을 제공한다.The patent provides a pickling solution for the chemical dissolution treatment of a lead frame containing a water-soluble mono persulfate (MHSO 5 ) as a main component, and a sulfur derivative, a fluoride, an organic solvent and a surfactant as an auxiliary component.
상기 특허의 산세용액에 의해 리드프레임의 제조공정에서 화학적 용해처리시에 발생할 수 있는 부반응에 의한 오염물질을 생성시키지 아니하고, 구리 또는 구리함금에 생성되는 구리산화 피막을 용이하게 제거할 수 있고, 실리콘화합물 또는 금속 표면에 흡착되는 금속잔유물에 의한 검은 스멋을 제거함으로써 깨끗한 리드프레임의 표면을 얻을 수 있다고 언급하고 있다. 그러나, 상기 특허는 금속층(동 또는 동합금층)을 에칭시키는 용액이 아니고, 세정용액에 관한 것이다.The pickling solution of the patent makes it easy to remove the copper oxide film generated on copper or copper alloy without generating contaminants due to side reactions that may occur during chemical dissolution in the lead frame manufacturing process, and It is stated that a clean leadframe surface can be obtained by removing black spots caused by compounds or metal residues adsorbed on the metal surface. However, the patent is not a solution for etching a metal layer (copper or copper alloy layer) but pertains to a cleaning solution.
또다른 관련기술로서, 대한민국 특허출원 제97-002586호에서는 구리 또는 구리합금에 대한 마이크로에칭 조성물을 개시하고 있다.As another related art, Korean Patent Application No. 97-002586 discloses a microetching composition for copper or copper alloy.
상기 발명은 (a) 구리 또는 구리합금을 산화시킬 수 있는 산화제, (b) 폴리아민 사슬 또는 양이온기 또는 그 둘 다를 0.000001 내지 1.0중량%의 양으로 함유하는 중합체 화합물 및 (c) 물을 포함하는 구리 또는 구리합금의 마이크로에칭 조성물에 관한 것이다. 상기 조성물은 프리프레그 또는 레지스트와 같은 수지에 대한 접착력이 우수하고, 납땜성이 우수한 구리 또는 구리합금 표면을 제조할 수 있다.The invention relates to a polymer comprising (a) an oxidizing agent capable of oxidizing copper or a copper alloy, (b) a polymer compound containing polyamine chains or cationic groups or both in an amount of 0.000001 to 1.0% by weight and (c) copper comprising water Or to a microetching composition of a copper alloy. The composition can produce a copper or copper alloy surface that is excellent in adhesion to resins such as prepregs or resists and has excellent solderability.
또한, 상기 조성물은 고도로 집적된 미세 라인 패턴을 갖는 프린트-배선 기판을 제조하는데 이용될 수 있으나, 인쇄회로기판(PCB) 또는 리드프레임 반도체 소지상에 드라이필름층을 형성하고, 이 드라이필름 패턴을 마스크로 해서 불필요한금속층(동 또는 동합금층)을 에칭하기 위한 조성물로는 적합하지 않다.In addition, the composition may be used to produce a printed-wiring substrate having a highly integrated fine line pattern, but a dry film layer is formed on a printed circuit board (PCB) or a lead frame semiconductor substrate, and the dry film pattern is formed. It is not suitable as a composition for etching an unnecessary metal layer (copper or copper alloy layer) as a mask.
현재, 동 또는 동합금층을 에칭시키는 에칭액 조성물로는 과산화수소(H2O2)를 주성분으로 하는 동 또는 동합금 에칭액이 주로 이용되어 왔으나, 이러한 에칭액은 에칭속도가 늦을 뿐만 아니라, 에칭능력이 저하되고 염소가스가 과다 배출되어 인쇄회로기판(PCB) 또는 리드프레임 생산라인의 각종 장비를 부식시키는 동시에 환경오염을 유발시키는 현상이 문제시되어 이에 대응할 수 있는 에칭액 조성물이 요구되는 실정이다.Currently, copper or copper alloy etching liquids mainly composed of hydrogen peroxide (H 2 O 2 ) have been mainly used as etching liquid compositions for etching copper or copper alloy layers. As the gas is excessively discharged to corrode various equipment of a printed circuit board (PCB) or a lead frame production line and cause environmental pollution, an etching solution composition that can cope with this problem is required.
따라서, 동 또는 동합금층으로 이루어지는 인쇄회로기판(PCB) 또는 리드프레임에 대해서도 에칭속도 및 에칭능력을 효과적으로 상승시키고 환경오염을 방지할 수 있는 동 또는 동합금용 에칭액의 개발이 요구되고 있다.Accordingly, there is a demand for development of an etching solution for copper or copper alloy capable of effectively increasing the etching rate and the etching capability and preventing environmental pollution even on a printed circuit board (PCB) or lead frame made of copper or copper alloy layer.
이에 본 발명에서는 광범위한 연구를 수행한 결과, 산화제, 물, 염산, 무기염화합물을 특정의 비율로 배합한 동 또는 동합금용 에칭액을 이용함으로써 상술한 문제점을 해결할 수 있었고, 본 발명은 이에 기초하여 완성하였다.Accordingly, in the present invention, as a result of extensive research, the above-mentioned problems can be solved by using an etching solution for copper or copper alloy in which an oxidizing agent, water, hydrochloric acid and an inorganic salt compound are blended in a specific ratio. It was.
따라서, 본 발명의 목적은 에칭속도 및 에칭능력을 향상시키고 환경오염을 유발시키는 염소가스가 거의 배출되지 않는 우수한 에칭성을 갖는 동 또는 동합금용 에칭액 조성물을 제공하는데 있다.Accordingly, it is an object of the present invention to provide an etching solution composition for copper or copper alloy which has an excellent etching property in which chlorine gas, which improves the etching rate and etching ability and causes environmental pollution, is hardly discharged.
본 발명의 다른 목적은 상기 조성물을 이용하여 인쇄회로기판(PCB) 또는 리드프레임 회로상의 불필요한 동 또는 동합금층을 에칭시키는 방법을 제공하는데 있다.Another object of the present invention is to provide a method for etching unnecessary copper or copper alloy layers on a printed circuit board (PCB) or lead frame circuit using the composition.
상기 목적을 달성하기 위한 본 발명의 조성물은 a) 동 또는 동합금을 산화시킬 수 있는 산화제 10.0∼30.0중량%, b) 물 30.0∼80.0중량%, c) 염산 0.1∼5.0 중량% 및 d) 무기염화합물 5.0∼20.0중량%로 구성된다.The composition of the present invention for achieving the above object is a) 10.0 to 30.0% by weight oxidizing agent capable of oxidizing copper or copper alloy, b) 30.0 to 80.0% by weight water, c) 0.1 to 5.0% by weight hydrochloric acid and d) inorganic salt It consists of 5.0-20.0 weight% of compounds.
상기 다른 목적을 달성하기 위한 본 발명의 에칭방법은 금속층(동 또는 동합금)을 형성한 인쇄회로기판(PCB) 또는 리드프레임상에 드라이필름 패턴을 형성하고, 이 드라이필름 패턴을 마스크로 해서 불필요한 금속층을 에칭시켜 제거시키는 방법에 있어서, 상기 에칭액 조성물을 이용하여 40∼60℃의 에칭온도에서 침지법 또는 스프레이법으로 금속층을 에칭시키는 것으로 이루어진다.The etching method of the present invention for achieving the above another object is to form a dry film pattern on a printed circuit board (PCB) or lead frame on which a metal layer (copper or copper alloy) is formed, and the unnecessary metal layer using the dry film pattern as a mask In the method of etching and removing, it consists of etching a metal layer by the immersion method or the spray method using the said etching liquid composition at the etching temperature of 40-60 degreeC.
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
전술한 바와 같이, 본 발명의 동 또는 동합금용 에칭액 조성물은 a) 동 또는 동합금을 산화시킬 수 있는 산화제 10.0∼30.0중량%, b) 물 30.0∼80.0중량%, c) 염산 0.1∼5.0중량% 및 d) 무기염화합물 5.0∼20.0중량%로 구성된다.As described above, the etching liquid composition for copper or copper alloy of the present invention comprises a) 10.0 to 30.0% by weight of an oxidizing agent capable of oxidizing copper or copper alloy, b) 30.0 to 80.0% by weight of water, c) 0.1 to 5.0% by weight of hydrochloric acid, and d) 5.0 to 20.0% by weight of inorganic salt compound.
본 발명에서 a)성분인 동 또는 동합금을 산화시킬 수 있는 산화제로는 중크롬산나트륨, 과망간산나트륨, 과산화수소, 과염소산나트륨, 차아염소산나트륨, 염소산나트륨 및 염소산칼륨으로 이루어진 군으로부터 하나 또는 그 이상 선택되어이용될 수 있으며, 그 사용량은 10.0∼30.0중량%, 바람직하게는 20.0∼30.0중량%이다. 이때, 사용량이 10.0중량%미만이면 에칭속도가 현저하게 감소하고 에칭능력이 저하되며, 30중량%를 초과하면 염소가스가 배출될 수 있다.In the present invention, the oxidizing agent capable of oxidizing copper or copper alloy as a) is selected from one or more selected from the group consisting of sodium dichromate, sodium permanganate, hydrogen peroxide, sodium perchlorate, sodium hypochlorite, sodium chlorate and potassium chlorate. And the amount used is 10.0 to 30.0% by weight, preferably 20.0 to 30.0% by weight. At this time, when the amount of use is less than 10.0% by weight, the etching rate is significantly reduced and the etching ability is lowered. When the amount exceeds 30% by weight, chlorine gas may be discharged.
상기 b)성분인 물은 c)성분에 필수적으로 함유되어 있으나, 별도로 더욱 첨가하여 그 배합량을 조정할 수 있다. 그 사용량은 30.0∼80.0중량%, 바람직하게는 50∼75중량%이고, 30.0중량%미만이면 침전물이 생성될 수 있으며, 80중량%를 초과하면 에칭속도가 현저하게 감소하는 경향이 있다.The water b) is essentially contained in the c) component, but may be further added separately to adjust the blending amount. The amount used is 30.0 to 80.0% by weight, preferably 50 to 75% by weight, and less than 30.0% by weight may result in the formation of precipitates. When the amount exceeds 80% by weight, the etching rate tends to decrease significantly.
상기 c)성분인 염산의 사용량은 0.1∼5.0중량%, 바람직하게는 0.1∼1.0 중량 %이다. 이때 상기 사용량이 0.1중량%미만이면 에칭능력이 저하될 수 있으며, 5.0중량%를 초과하면 침전물이 생성될 수 있으며 염소가스가 배출될 수도 있다.The amount of hydrochloric acid as the component c) is 0.1 to 5.0% by weight, preferably 0.1 to 1.0% by weight. At this time, when the amount is less than 0.1% by weight, the etching ability may be lowered. If the amount exceeds 5.0% by weight, precipitates may be generated and chlorine gas may be discharged.
상기 d)성분인 무기염화합물로는 염화칼륨, 염화나트륨, 염화암모늄 및 염화동으로 이루어진 군으로부터 하나 또는 그 이상 선택되어 이용될 수 있으며, 그 사용량은 5.0∼20.0중량%, 바람직하게는 7.0∼10.0중량%이다. 이때 사용량이 5.0중량%미만이면 침전물이 생성될 수 있고 에칭능력이 저하될 수도 있으며, 20.0중량%를 초과하면 염소가스가 배출될 수 있다.As the inorganic salt compound as the d) component, one or more selected from the group consisting of potassium chloride, sodium chloride, ammonium chloride and copper chloride may be used, and the amount thereof is 5.0 to 20.0% by weight, preferably 7.0 to 10.0% by weight. to be. In this case, if the amount is less than 5.0% by weight, precipitates may be generated, and the etching ability may be lowered. If the amount is more than 20.0% by weight, chlorine gas may be emitted.
본 발명에 따르면, 상기 a)∼d)의 성분 배합비율은 매우 중요하고, 각 성분의 배합량을 상기 범위내에서 조절함으로써 동 및 동합금층을 효과적으로 에칭속도를 빠르게 할 수 있으며 에칭능력도 향상시킬 수 있다.According to the present invention, the component blending ratio of a) to d) is very important, and by controlling the blending amount of each component within the above range, the copper and copper alloy layers can be effectively etched and the etching ability can be improved. have.
특히 a)성분인 동 또는 동합금을 산화시킬 수 있는 산화제를 첨가하지 않을 경우 에칭속도 및 에칭능력이 현저하게 감소하는 경향이 있으며, 또한 d)성분인 무기염화합물을 첨가하지 않을 경우 염화동 재생의 완충작용이 일어나지 않을 뿐만아니라, 에칭속도 및 에칭능력이 현저하게 감소하게 된다.In particular, the etch rate and the etching ability tend to be remarkably decreased when an oxidizing agent capable of oxidizing copper or copper alloy, which is a), is significantly decreased, and buffering of copper chloride regeneration is not performed when the inorganic salt compound, d), is not added. Not only does the action take place, but also the etching rate and the etching ability are significantly reduced.
한편, 본 발명의 동 및 동합금 에칭방법은 금속소지상에 패턴을 형성하고 불필요한 부분을 에칭하는 상기 조성물을 이용한다. 예를 들어, 금속층을 형성한 인쇄회로기판(PCB) 또는 리드프레임상에 드라이필름 패턴을 형성하고 이 드라이필름 패턴을 마스크로 해서 불필요한 금속층(동 또는 동합금)을 에칭시켜 제거시키는 공정에 있어서 본 발명의 동 또는 동합금 에칭액 조성물을 이용하여 40∼60℃의 온도 범위내에서 금속층(동 또는 동합금)을 에칭시켜 제거시킨다.On the other hand, the copper and copper alloy etching method of the present invention uses the composition for forming a pattern on the metal substrate and etching the unnecessary portion. For example, in the process of forming a dry film pattern on a printed circuit board (PCB) or lead frame in which a metal layer is formed, and removing unnecessary metal layers (copper or copper alloy) by etching the dry film pattern as a mask. The metal layer (copper or copper alloy) is etched and removed in the temperature range of 40-60 degreeC using the copper or copper alloy etching liquid composition.
본 발명에 따르면, 상기 에칭 조성물은 자동적으로 용액의 흐름, 약품투입, 약품누수 등이 자동 검지되는 자동공급장치에 의해 소정의 용기(또는 탱크)에 공급되며, 에칭처리는 통상적으로 침적법 또는 스프레이법에 의하여 실시된다.According to the present invention, the etching composition is supplied to a predetermined container (or tank) by an automatic supply device which automatically detects a flow of a solution, a chemical injection, a chemical leak, and the like, and the etching treatment is usually performed by a deposition method or a spray. It is enforced by law.
이상적인 시스템에서는 에칭액의 산화-환원전위(OPR)가 연속적으로 모니터되어야 하고, 유효염소가 제일 부족한 시점에서 OPR을 올리기 위해 염소가 주입되어야 한다.In an ideal system, the oxidation-reduction potential (OPR) of the etchant should be continuously monitored, and chlorine should be injected to raise the OPR at the point of the lack of effective chlorine.
염산은 자동 적정기, 전도성 모니터 또는 수동 적정에 의해 조절될 수 있다. 물은 용액의 비중을 연속으로 측정하는 장치(보메조절기)에 의해 자동으로 첨가되고, 고정포인트 아래로 유지한다.Hydrochloric acid can be adjusted by automatic titrator, conductivity monitor or manual titration. Water is added automatically by a device (bome regulator) that continuously measures the specific gravity of the solution and keeps it below the fixed point.
이것은 염화제2동 함량을 포화점 아래에서 유지하므로 에칭액은 슬러지가 없는 상태로 남는다. 에칭탱크에서 넘친 과량의 에칭액은 나중에 판매하기 위해 저장소로 주입된다. 여기서 만들어진 염화제2동은 매우 순수하고, 경제성이 있다.This maintains the cupric chloride content below the saturation point so the etchant remains free of sludge. Excess etchant overflowed from the etch tank is poured into the reservoir for later sale. The cupric chloride produced here is very pure and economical.
또한, 이때의 에칭온도는 통상적으로 약 40∼60℃에서 이루어지는데, 상기온도범위가 40℃미만이면 에칭속도가 감소하고, 60℃를 초과하면 에칭속도는 증가하나 환경오염을 유발할 수 있는 염소가스가 배출되는 경향이 있다.In addition, the etching temperature at this time is usually made at about 40 ~ 60 ℃, if the temperature range is less than 40 ℃ etch rate is reduced, if it exceeds 60 ℃ etch rate increases but chlorine gas that can cause environmental pollution Tends to be discharged.
또한, 에칭속도는 에칭되기에 충분한 속도이면 무방하며, 특별히 한정되어 있지는 않지만 종래의 산화제로 과산화수소를 사용할 경우보다 15∼20%정도 빠르다.Further, the etching rate may be any speed sufficient to be etched, and is not particularly limited, but is about 15 to 20% faster than using hydrogen peroxide as a conventional oxidant.
본 발명의 방법에 따르면, 인쇄회로기판(PCB) 또는 리드프레임을 상기 조성물에 침적시키면 상기 조성물중의 염산과 구리와 염소산소다가 반응하여 염화제2동(CuCl2)을 생성하고, 생성된 CuCl2는 다시 Cu와 반응하여 생성된 염화제1동(CuCl)과 염소가 반응하여 염화제2동(CuCl2)을 재형성하여 에칭액과 에칭속도를 안정하게 유지시킨다.According to the method of the present invention, when a printed circuit board (PCB) or a lead frame is deposited on the composition, the hydrochloric acid, copper, and sodium chloride in the composition react to form cupric chloride (CuCl 2 ), and the resulting CuCl 2 reacts with Cu again to form cuprous chloride (CuCl) and chlorine to reform cupric chloride (CuCl 2 ) to maintain stable etching rate and etching rate.
상기 용액의 산성도가 기준치 아래로 떨어지면, Cu(OH)2가 생성되고, 이는 HCl의 첨가로 보정된다. 산화제 존재하에서 HCl은 H와 Cl로 분리되고, H는 Cu(OH)2의 OH와 재결합해서 물을 형성하고, Cl은 CuCl이 되면 일부는 CuCl2가 되고, Cl은 염(salt), 예를 들어 Na와 결합하여 NaCl을 재형성한다.When the acidity of the solution falls below the baseline, Cu (OH) 2 is produced, which is corrected by the addition of HCl. In the presence of an oxidant, HCl is separated into H and Cl, H recombines with OH of Cu (OH) 2 to form water, and Cl becomes CuCl, some become CuCl 2 , and Cl is a salt, for example For example, it binds with Na to reform NaCl.
이는 에칭액에서 염의 촉매와 완충효과를 의미하는 것이다. 본 발명에서는 이러한 완충효과를 연속적으로 이용하는 것이다.This means the catalyst and buffering effect of the salt in the etchant. In the present invention, such a buffering effect is continuously used.
이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
금속층을 형성한 인쇄회로기판(PCB) 및 리드프레임 상에 드라이필름 패턴을 형성하고 불필요한 부분을 에칭하는 공정에 있어서, 하기 표 1에 기재된 성분과 양의 동 또는 동합금 에칭액 조성물에 약 50℃에서 침적처리하여 그 각각의 동 또는 동합금층을 에칭처리하였다.In the process of forming a dry film pattern on a printed circuit board (PCB) and a lead frame on which a metal layer is formed and etching an unnecessary portion, it is deposited at about 50 ° C. in a copper or copper alloy etching liquid composition having the amounts and components shown in Table 1 below. The respective copper or copper alloy layers were etched by treatment.
다음과 같은 상태를 관찰함으로써 에칭속도, 에칭능력 및 염소가스발생 여부를 평가하여 그 결과를 하기 표 1에 나타내었다.By observing the following conditions to evaluate the etching rate, etching ability and the occurrence of chlorine gas and the results are shown in Table 1 below.
〈에칭속도 평가〉<Etching Speed Evaluation>
에칭액 조성물을 1ℓ비이커에 넣고 마그네틱 교반자를 사용하여 교반하면서 약 50℃에서 드라이필름 패턴이 형성된 금속소지(약 1온스/m2)를 침적하여 완전히 제거되는 시간을 측정하여 평가하였다.The etching liquid composition was placed in a 1 L beaker and the metal body (about 1 oz / m 2 ) on which the dry film pattern was formed was deposited at about 50 ° C. while stirring using a magnetic stirrer to evaluate the time for complete removal.
〈에칭력 평가〉<Etching force evaluation>
에칭액 조성물을 1ℓ비이커에 넣고 마그네틱 교반자를 사용하여 교반하면서 50℃에서 드라이필름 패턴이 형성된 금속소지(약 1온스/m2)를 계속 침적하여 더 이상 에칭이 안될 때까지 에칭처리하여 평가하였다.The etchant composition was placed in a 1 l beaker and continuously agitated using a magnetic stirrer to continuously deposit the metal body (about 1 oz / m 2 ) having a dry film pattern at 50 ° C. until the etching was no longer possible.
〈염소가스발생 평가〉<Chlorine gas generation evaluation>
에칭액 조성물을 1ℓ비이커에 넣고 마그네틱 교반자를 사용하여 교반하면서 50℃에서 드라이필름 패턴이 형성된 금속소지(약 1온스/m2)를 침적하여 에칭시키면서 발생되는 가스상태를 관찰하여 평가하였다.The etching liquid composition was placed in a 1 L beaker and the metal body (about 1 oz / m 2 ) on which the dry film pattern was formed was deposited at 50 ° C. while stirring using a magnetic stirrer to evaluate the gas state generated while etching.
주) SC:염소산나트륨, SPC:과염소산나트륨, HP:과산화수소, SHC:차아염소산나트륨, HC:염산, FC:염화제이철, SCR:염화나트륨, KC:염화칼륨, AC:염화암모늄Note: SC: sodium chloride, SPC: sodium perchlorate, HP: hydrogen peroxide, SHC: sodium hypochlorite, HC: hydrochloric acid, FC: ferric chloride, SCR: sodium chloride, KC: potassium chloride, AC: ammonium chloride
- 염소가스 발생 평가-Chlorine gas generation evaluation
◎: 거의 발생 안함, Ｏ: 약간 발생함, △: 심하게 발생함.(Double-circle): It hardly arises, O: Slightly generate | occur | produces and (triangle | delta): Severe occurrence.
상기 표 1의 결과에서 알 수 있듯이, 실시예 1∼5의 어떠한 동 또는 동합금용 에칭액 조성물도 과산화수소와 과량의 염산을 사용한 비교예들과 비교하여 에칭속도 및 에칭력이 우수하다는 것을 알 수 있다.As can be seen from the results of Table 1, it can be seen that the etching solution composition for any copper or copper alloy of Examples 1 to 5 is superior in the etching rate and the etching power as compared to the comparative examples using hydrogen peroxide and excess hydrochloric acid.
이중에서도 실시예 2의 동 또는 동합금용 에칭액 조성물이 가장 우수한 효과를 나타내었다.Among them, the etching liquid composition for copper or copper alloy of Example 2 showed the most excellent effect.
이와 같이, 본 발명에 따른 동 또는 동합금용 에칭액 조성물 및 에칭방법은 인쇄회로기판(PCB) 또는 리드프레임의 양자에 대해서도 일정한 에칭속도 및 에칭력이 우수하고 염소가스가 거의 발생하지 않는 효과가 있다.As described above, the etching liquid composition and the etching method for copper or copper alloy according to the present invention are excellent in constant etching rate and etching power and hardly generate chlorine gas for both a printed circuit board (PCB) or a lead frame.
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| KR10-2000-0011484A KR100370821B1 (en) | 2000-03-08 | 2000-03-08 | Etching composition for copper or copper alloy and method for etching copper or copper alloy using the same |
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| KR20040107546A (en) * | 2003-06-13 | 2004-12-21 | 이승희 | an etching solution |
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