KR100915640B1 - The method for plating fiber using electroless plating liquid - Google Patents
The method for plating fiber using electroless plating liquidInfo
- Publication number
- KR100915640B1 KR100915640B1 KR1020080126564A KR20080126564A KR100915640B1 KR 100915640 B1 KR100915640 B1 KR 100915640B1 KR 1020080126564 A KR1020080126564 A KR 1020080126564A KR 20080126564 A KR20080126564 A KR 20080126564A KR 100915640 B1 KR100915640 B1 KR 100915640B1
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- Prior art keywords
- plating
- fiber
- ppm
- solution
- electroless
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
Abstract
본 발명은 무전해 동도금액을 이용한 섬유의 도금방법에 관한 것으로서, 상기 도금방법은 5 내지 50g/ℓ의 에틸렌디니트릴로-테트라-2-프로판올(EDTP)과, 10 내지 20g/ℓ의 황산구리(Ⅱ) 5수화물 (CuSO4·5H2O)과, 5 내지 15g/ℓ의 수산화나트륨(NaOH)과, 2.5 내지 10g/ℓ의 포름알데히드(HCHO)와, 안정제를 포함하며, 상기 안정제는, 1 내지 100ppm의 2-2' 디피리딜(2-2' Dipyridyl)과, 10 내지 1000ppm의 페로시안화 칼륨(Potassium ferrocyanide)과, 1 내지 100ppm의 2-머캅토 벤조치아졸(2-Mercapto benzo thiazole)과, 1 내지 100ppm의 (티오) 우레아(Thio urea)를 포함하는 무전해 동도금액에 섬유를 35~45℃의 온도조건에서 침지하는 것을 특징으로 한다. 상기 도금방법에 따르면, 전체적인 도금효율을 향상시킬 수 있다는 등의 효과가 있다.The present invention relates to a method for plating fibers using an electroless copper plating solution, wherein the plating method is 5 to 50 g / l ethylenedinitro-tetra-2-propanol (EDTP) and 10 to 20 g / l copper sulfate ( II) pentahydrate (CuSO 4 · 5H 2 O), 5-15 g / l sodium hydroxide (NaOH), 2.5-10 g / l formaldehyde (HCHO), and a stabilizer, wherein the stabilizer is 1 To 100 ppm of 2-2 'Dipyridyl, 10 to 1000 ppm of Potassium ferrocyanide, and 1 to 100 ppm of 2-Mercapto benzo thiazole And immersing the fiber in an electroless copper plating solution containing 1 to 100 ppm (thio) urea (Thio urea) at a temperature of 35 to 45 ° C. According to the plating method, there is an effect that the overall plating efficiency can be improved.
Description
본 발명은 전체적인 도금효율을 향상시킬 수 있는 섬유의 도금방법에 관한 것이다.The present invention relates to a method of plating fibers that can improve the overall plating efficiency.
일반적으로 섬유 상에 금속을 부착시키는 방법으로는 진공증착, 수지코팅 등의 방법이 알려져 있으나, 진공 증착법 또는 수지코팅 방법은 고가의 장치를 필요로 하므로 제조 단가가 높고, 대량생산이 어려울 뿐만 아니라, 금속이 부착된 섬유를 장기간 사용하면 마찰이나 세탁 등에 의하여 금속이 쉽게 탈락되는 문제점이 있다. 또 다른 방법으로는 전기 도금에 의하여 금속을 섬유에 코팅하는 방법이 알려져 있으나, 이와 같은 전기 도금 방법은 섬유가 비전도성인 경우에는 사용할 수 없다는 단점이 있다.Generally, a method of depositing a metal on a fiber is known as vacuum deposition or resin coating. However, the vacuum deposition method or resin coating method requires an expensive device, and thus the manufacturing cost is high and mass production is difficult. If the metal is attached to the fiber for a long time there is a problem that the metal is easily dropped by friction or washing. As another method, a method of coating a metal on a fiber by electroplating is known, but such an electroplating method has a disadvantage that it cannot be used when the fiber is non-conductive.
따라서, 고가의 설비를 필요로 하지 않을 뿐만 아니라, 비전도성 섬유에도 적용할 수 있는 무전해 금속 도금(Electroless metal plating)법을 섬유의 금속 코팅에 이용하려는 시도가 계속되고 있다. 무전해 도금은 금속 이온과 화학적 환원제의 상호 작용에 의하여 금속 필름층을 형성하는 방법이다.Therefore, attempts have been made to use an electroless metal plating method for metal coating of fibers, which not only requires expensive equipment but also can be applied to non-conductive fibers. Electroless plating is a method of forming a metal film layer by interaction of metal ions and a chemical reducing agent.
종래의 무전해 금속 도금법을 이용한 섬유도금방법이 대한민국 공개특허 공개번호 제2002-0088842호인 "섬유원단에 금속을 차등 도금하는 방법"이 개시되어 있다. 상기의 공보에 따르면, 아세트산제2구리 10 중량부, 안트라퀴논-2,6-이슬폰산-이나트륨염 2 중량부, 글리세린 1중량부를 물 100중량부에 용해시켜 금속핵 형성용 용액을 제조하고, 세정처리를 거친 섬유원단을 금속핵 형성용 용액이 담겨있는 도금조에 침지하여 130℃에서 20분간 처리하여 금속핵이 직물의 내부에 형성된 섬유원단을 얻는다. 상기의 방법에 의하여 얻어진 금속핵이 형성되어 있는 섬유원단의 일면에 황산구리5수화물(CuSO4 ㆍ5H2 O) 0.04몰%, EDTA-4Na 염 0.12몰%, 포름알데히드 0.2 몰%, 황산나트륨 0.14몰%, 개미산나트륨 0.3몰% 및 폴리에틸렌글리콜 0.033몰%가 되도록 용해시키고 수산화 나트륨용액을 이용하여 pH가 12가 되도록 조제된 무전해 도금액을 도포하고 상온에서 16시간 동안 방치하여 일면에 육안으로 확인될 수 있을 정도의 구리의 도금층이 형성된 직물원단을 얻는다.Disclosed is a method for differentially plating a metal on a fiber fabric, which is disclosed in Korean Patent Laid-Open Publication No. 2002-0088842, which uses a conventional electroless metal plating method. According to the above publication, 10 parts by weight of cupric acetate, 2 parts by weight of anthraquinone-2,6-isosulfonic acid-disodium salt, and 1 part by weight of glycerin are dissolved in 100 parts by weight of water to prepare a solution for forming metal cores. The fiber fabric after washing is immersed in a plating bath containing a solution for forming metal nuclei and treated at 130 ° C. for 20 minutes to obtain a fiber fabric in which metal nuclei are formed inside the fabric. Copper sulfate pentahydrate (CuSO4-5H2O) 0.04 mol%, ED2-4Na salt 0.12 mol%, formaldehyde 0.2 mol%, sodium sulfate 0.14 mol%, formic acid Dissolve to 0.3 mol% sodium and 0.033 mol% polyethylene glycol, apply an electroless plating solution prepared at a pH of 12 using sodium hydroxide solution, and leave it at room temperature for 16 hours to visually identify the surface. A fabric fabric having a copper plating layer formed thereon is obtained.
[문헌 1] 대한민국 공개특허 2002-0088842호[Document 1] Republic of Korea Patent Publication No. 2002-0088842
종래 섬유도금방법은 무전해 도금액에 섬유를 침지하는 침지시간의 경과에 따라 도금속도가 느리고, 도금에 대한 저항이 커져 도금효율이 낮다는 문제점이 있다.The conventional fiber plating method has a problem in that the plating speed is slow as the immersion time for immersing the fiber in the electroless plating solution and the plating efficiency is low because the resistance to plating is increased.
또한, 상기 무전해 도금액이 불안정하여 시간이 경과함에 따라 도금조 바닥에 구리가 석출되어 도금조 청소로 인하여 작업시간이 늘어나고, 비효율적이다는 문제점이 있다.In addition, the electroless plating solution is unstable, and as time elapses, copper precipitates on the bottom of the plating bath, which increases the working time due to the cleaning of the plating bath, which is inefficient.
따라서, 본 발명은 상기한 문제점을 해결하기 위하여 안출된 것으로, 도금속도가 빠르고, 도금에 대한 저항을 감소시킬 수 있어 전체적인 도금효율을 향상시킬 수 있는, 무전해 동도금액을 이용한 섬유도금방법을 제공하고자 한다.Accordingly, the present invention has been made in order to solve the above problems, and provides a fiber plating method using an electroless copper plating solution, which can improve the plating efficiency because the plating speed is fast and the resistance to plating can be reduced. I would like to.
본 발명은 전술한 문제점을 해결하기 위하여 안출된 것으로, 5 내지 50g/ℓ의 에틸렌디니트릴로-테트라-2-프로판올(EDTP)과, 10 내지 20g/ℓ의 황산구리(Ⅱ) 5수화물 (CuSO4·5H2O)과, 5 내지 15g/ℓ의 수산화나트륨(NaOH)과, 2.5 내지 10g/ℓ의 포름알데히드(HCHO)와, 안정제를 포함하며, 상기 안정제는, 1 내지 100ppm의 2-2' 디피리딜(2-2' Dipyridyl)과, 10 내지 1000ppm의 페로시안화 칼륨(Potassium ferrocyanide)과, 1 내지 100ppm의 2-머캅토 벤조치아졸(2-Mercapto benzo thiazole)과, 1 내지 100ppm의 (티오) 우레아(Thio urea)를 포함하는 무전해 동도금액에 섬유를 35~45℃의 온도조건에서 침지하는 것을 특징으로 하는 섬유도금방법이 제공된다.The present invention has been made to solve the above-mentioned problems, 5 to 50g / L ethylenedinitro-tetra-2-propanol (EDTP) and 10 to 20g / L copper sulfate (II) pentahydrate (CuSO 4 5H 2 O), 5-15 g / l sodium hydroxide (NaOH), 2.5-10 g / l formaldehyde (HCHO), and a stabilizer, wherein the stabilizer is 1 to 100 ppm of 2-2 '. Dipyridyl (2-2 'Dipyridyl), 10 to 1000 ppm of potassium ferrocyanide, 1 to 100 ppm of 2-mercapto benzothiazole, and 1 to 100 ppm of ( The present invention provides a fiber plating method comprising immersing a fiber in an electroless copper plating solution containing thio) urea at a temperature of 35 to 45 ° C.
본 발명의 섬유도금방법에 따르면, 다음과 같은 효과가 있다.According to the fiber plating method of the present invention, the following effects are obtained.
첫째, 도금속도가 빠르고, 도금에 대한 저항을 감소시킬 수 있어 전체적인 도금효율을 향상시킬 수 있다.First, the plating speed is fast, and the resistance to plating can be reduced, thereby improving the overall plating efficiency.
둘째, 무전해 동도금액의 안정성이 뛰어나므로 도금조 바닥에 구리가 석출되는 것을 감소시킬 수 있어 도금 작업조 청소로 인한 낭비시간을 줄일 수 있고, 전체적인 작업효율을 향상시킬 수 있다.Second, because the stability of the electroless copper plating solution is excellent, it is possible to reduce the precipitation of copper on the bottom of the plating bath can reduce the waste time due to the cleaning of the plating work tank, it is possible to improve the overall work efficiency.
셋째, 무전해 동도금액에 황산구리(Ⅱ) 5수화물을 사용함으로써, 섬유에 전착되는 결정의 크기가 작으며, 도금된 섬유의 경사, 위사에 따른 저항의 차이가 작다. 또한, 저항이 일정하여 균일한 도금효과를 얻을 수 있으며, 연성이 뛰어나 외부충격에 균일이 없다.Third, by using copper (II) sulfate pentahydrate in the electroless copper plating solution, the size of crystals electrodeposited on the fiber is small, and the difference in resistance according to the warp and weft of the plated fiber is small. In addition, since the resistance is constant, a uniform plating effect can be obtained. The ductility is excellent and there is no uniformity in external impact.
도 1은 본 발명의 바람직한 실시예에 따른 섬유 동도금방법을 순차적으로 도시한 순서도.1 is a flow chart sequentially showing a fiber copper plating method according to a preferred embodiment of the present invention.
도 2는 도 1의 단계에서 섬유를 무전해 동도금액에 침지하는 방법의 일예를 도시한 개념도.2 is a conceptual diagram illustrating an example of a method of immersing a fiber in an electroless copper plating solution in the step of FIG.
<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>
10 : 도금조 20 : 가이드롤10: plating bath 20: guide roll
F : 섬유 L : 무전해 동도금액F: Fiber L: Electroless Copper
도 1을 참조하여 설명하면, 본 실시예의 섬유 동도금방법은 다음과 같은 단계로 이루어진다.Referring to Figure 1, the fiber copper plating method of the present embodiment consists of the following steps.
섬유를 에칭 용액에 침지하여 섬유의 표면을 에칭(Etching)한 다음, 섬유를 물로 세척(수세)한다.The surface of the fiber is etched by immersing the fiber in an etching solution, and then the fiber is washed (washed) with water.
이 단계에서 바람직하게는, 섬유를 100g/ℓ의 수산화나트륨(NaOH) 수용액에 70 내지 80℃의 온도에서 1 내지 2분 동안 침지하여 수행할 수 있다. 수산화나트륨의 농도가 100g/ℓ미만일 경우 섬유 표면의 에칭이 불충분하게 이루어지고, 수산화나트륨의 100g/ℓ를 초과하는 경우에는 섬유 표면이 훼손되어 섬유의 강도가 저하될 염려가 있다.In this step, preferably, the fibers may be immersed in 100 g / L sodium hydroxide (NaOH) aqueous solution at a temperature of 70 to 80 ° C. for 1 to 2 minutes. When the concentration of sodium hydroxide is less than 100 g / l, the surface of the fiber is insufficiently etched, and when the concentration of the sodium hydroxide exceeds 100 g / l, the surface of the fiber is damaged and the strength of the fiber may be lowered.
다음으로, 섬유를 제 1 산 용액에 침지한 후 섬유를 물로 세척(수세)한다. (b 단계) 제1 산 용액은 염산(HCl) 수용액 또는 황산(H2SO4) 수용액이 될 수 있다.Next, after immersing the fiber in the first acid solution, the fiber is washed with water (washing). (b step) The first acid solution may be an aqueous solution of hydrochloric acid (HCl) or an aqueous solution of sulfuric acid (H 2 SO 4 ).
이 단계에서 바람직하게는, 섬유를 10부피%의 염산(HCl) 수용액에 15 내지 25℃의 온도에서 1 내지 2분 동안 침지할 수 있다.In this step, preferably, the fibers can be immersed in a 10% by volume aqueous hydrochloric acid (HCl) solution for 1 to 2 minutes at a temperature of 15 to 25 ℃.
다음으로, 섬유를 반응속도를 가속화하기 위한 촉매 용액에 침지한 후 섬유를 물로 세척(수세)한다. (c 단계) Next, the fibers are immersed in a catalyst solution to accelerate the reaction rate and the fibers are washed with water (washing). (step c)
상기에서, 촉매 용액은 염화팔라듐(PdCl2), 황산팔라듐(PdSO4), 염화니켈(NiCl2), 염화아연(ZnCl2), 염화은(AgCl), 염화구리(CuCl2), 염화철(FeCl2), 염화주석(SnCl2), 염화안티몬(SbCl3) 및 염화인듐(InCl3)으로 이루어진 군에서 선택된 적어도 하나의 금속물질을 염산, 황산 등의 수용액인 산 용액에 용해시킨 것이 바람직하다.In the above, the catalyst solution is palladium chloride (PdCl 2 ), palladium sulfate (PdSO 4 ), nickel chloride (NiCl 2 ), zinc chloride (ZnCl 2 ), silver chloride (AgCl), copper chloride (CuCl 2 ), iron chloride (FeCl 2) ), Tin chloride (SnCl 2 ), antimony chloride (SbCl 3 ), and indium chloride (InCl 3 ) are preferably dissolved in an acid solution which is an aqueous solution of hydrochloric acid or sulfuric acid.
이 단계에서 일실시예로, 섬유를 20부피%의 염산(HCl)에 100 내지 200ppm의 염화팔라듐(PdCl2)을 용해시킨 촉매 용액에 20 내지 30℃의 온도에서 1 내지 2분 동안 침지하여 수행할 수 있다.In this step, as an example, the fibers were immersed in a catalyst solution in which 100 to 200 ppm of palladium chloride (PdCl 2 ) was dissolved in 20% by volume of hydrochloric acid (HCl) at a temperature of 20 to 30 ° C. for 1 to 2 minutes. can do.
다음으로, 섬유를 제 2 산 용액에 침지하여 섬유 표면에 부착된 팔라듐(Pd)이온을 제외한 불필요한 이온을 제거한 다음 섬유를 물로 세척(수세)한다. (d 단계) 제 2 산 용액은 제 1 산 용액과 마찬가지로 염산(HCl) 수용액 또는 황산(H2SO4) 수용액이 될 수 있다.Next, the fibers are immersed in a second acid solution to remove unnecessary ions except for palladium (Pd) ions attached to the fiber surface, and the fibers are washed with water (washing). (Step d) The second acid solution may be an aqueous solution of hydrochloric acid (HCl) or an aqueous solution of sulfuric acid (H 2 SO 4 ) similar to the first acid solution.
이 단계에서 바람직하게는, 섬유를 10부피%의 황산(H2SO4) 수용액에 50 내지 60℃의 온도에서 1 내지 2분 동안 침지하여 섬유 표면에 부착된 주석(Sn) 이온을 제거한다.In this step, preferably, the fibers are immersed in 10% by volume aqueous sulfuric acid (H 2 SO 4 ) solution for 1 to 2 minutes at a temperature of 50 to 60 ℃ to remove the tin (Sn) ions attached to the fiber surface.
다음으로, 섬유를 무전해 니켈(Ni) 도금하여 섬유에 니켈 도금층이 형성되도록 한다. 이 단계에서, 니켈 도금층의 두께가 0.1 내지 0.4㎛가 되도록 니켈 도금하고, 표면저항은 20 내지 100Ω으로 하는 것이 바람직하다.Next, electroless nickel (Ni) plating the fibers to form a nickel plating layer on the fibers. In this step, nickel plating is performed so that the thickness of the nickel plating layer is 0.1 to 0.4 mu m, and the surface resistance is preferably 20 to 100?.
니켈 도금을 실시하는 이유는 유연성과 가공성이 뛰어난 섬유 원단에 도금할 경우 섬유 원단과 금속의 밀착력이 중요한데, 이 단계에서와 같이 무전해 동도금 전에 니켈 도금을 실시할 경우 밀착력을 높일 수 있기 때문이다.The reason for performing nickel plating is that the adhesion between the fiber fabric and the metal is important when plating on a fabric fabric having excellent flexibility and processability, since the adhesion may be increased when the nickel plating is performed before electroless copper plating as in this step.
즉, 이 단계의 목적은 밀착력이 우수한 니켈을 섬유에 우선 도금한 다음 니켈보다 환원력이 강한 동도금을 실시하여 니켈과 동이 치환되도록 치환 도금하기 위함이다.That is, the purpose of this step is to plate the nickel with excellent adhesion to the fiber first, and then copper plating with a stronger reducing power than nickel to substitute plating nickel and copper to be substituted.
다음으로, 섬유를 무전해 동도금액에 침지하여 섬유의 표면에 금속층을 형성시킨 다음 섬유를 물로 세척(수세)한다. (e 단계)Next, the fiber is immersed in an electroless copper plating solution to form a metal layer on the surface of the fiber, and then the fiber is washed with water (washing). (step e)
무전해 동도금액은 5 내지 50g/ℓ의 에틸렌디니트릴로-테트라-2-프로판올(EDTP)과, 10 내지 20g/ℓ의 황산구리(Ⅱ) 5수화물 (CuSO4·5H2O)과, 5 내지 15g/ℓ의 수산화나트륨(NaOH)과, 2.5 내지 10g/ℓ의 포름알데히드(HCHO) 안정제를 포함하는 것이 바람직하다.The electroless copper plating solution is 5 to 50 g / l of ethylenedinitrilo-tetra-2-propanol (EDTP), 10 to 20 g / l of copper (II) sulfate pentahydrate (CuSO 4 · 5H 2 O), and 5 to It is preferred to include 15 g / l sodium hydroxide (NaOH) and 2.5 to 10 g / l formaldehyde (HCHO) stabilizer.
상기 무전해 동도금액에서, 상기 무전해 동도금액에 포함된 EDTP의 양을 줄이면서, 줄인 EDTP의 양만큼 에틸렌디아민-테트라-아세트산(EDTA)을 추가하는 것이 석출된 동의 연성을 증가시키고 제조원가를 15% 이상 낮출 수 있다는 측면에서 바람직하다. 여기에서, EDTA의 양은 1 내지 50g/ℓ의 범위 이내인 것이 바람직하다.In the electroless copper plating solution, adding ethylenediamine-tetra-acetic acid (EDTA) by the amount of EDTP reduced while reducing the amount of EDTP contained in the electroless copper plating solution increases the ductility of precipitated copper and increases the manufacturing cost. It is preferable at the point which can lower more than%. Herein, the amount of EDTA is preferably in the range of 1 to 50 g / l.
상기에서, 안정제는 1 내지 100ppm의 2-2' 디피리딜(2-2' Dipyridyl)과, 10 내지 1000ppm의 페로시안화 칼륨(Potassium ferrocyanide)과, 1 내지 100ppm의 2-머캅토 벤조치아졸(2-Mercapto benzo thiazole)과, 1 내지 100ppm의 (티오) 우레아(Thio urea)를 포함하는 것이 바람직하다.In the above, the stabilizer is 1 to 100 ppm of 2-2 'Dipyridyl, 10 to 1000 ppm of Potassium ferrocyanide, and 1 to 100 ppm of 2-mercapto benzothiazole ( It is preferable to include 2-Mercapto benzo thiazole) and 1 to 100 ppm of (thio) urea.
이 단계의 일실시예로, 섬유를 무전해 동도금액에 35 내지 45℃의 온도에서 2 내지 10분 동안 침지하여 수행할 수 있다.In one embodiment of this step, the fibers may be immersed in an electroless copper plating solution for 2 to 10 minutes at a temperature of 35 to 45 ℃.
섬유를 무전해 동도금액에 침지하는 방법의 일례로, 도 2에 도시한 바와 같이, 도금조(10) 내에는 무전해 동도금액(L)이 수용되어 있고, 도금조(10) 내,외부에 다수의 가이드롤(20)이 설치되어 있다. 이에 의해, 섬유(F)는 가이드롤(20)의 안내를 받으며 도금조(10) 내의 무전해 동도금액(L)에 침지되어 도금이 연속적으로 이루어진다.As an example of a method of immersing a fiber in an electroless copper plating solution, as shown in FIG. 2, an electroless copper plating solution L is accommodated in the plating bath 10, and the plating bath 10 is disposed inside or outside. A plurality of guide rolls 20 are provided. Thereby, the fiber F is guided by the guide roll 20, and is immersed in the electroless copper plating liquid L in the plating tank 10, and plating is performed continuously.
다음으로, 동도금이 실시된 섬유에 최종적으로 무전해 니켈 도금을 실시한 다음 섬유를 물로 세척(수세)한다. 이 단계는 실시예에 따라 니켈 도금후 금, 은 도금을 다시 실시할 수 있으며, 이 단계를 생략할 수도 있음은 물론이다.Next, the electroplated fibers are finally electroless nickel plated, and the fibers are then washed with water (washed). This step may be performed again gold and silver plating after nickel plating according to the embodiment, of course, this step may be omitted.
마지막으로, 금속층이 형성된 섬유를 건조(Dry)한다. (f 단계)Finally, the fiber on which the metal layer is formed is dried. (step f)
다음은 본 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 본 발명의 이해를 돕기 위한 것이며, 본 발명을 이에 한정하는 것은 아니다.The following presents preferred embodiments to aid the understanding of the present invention. However, the following examples are provided to aid the understanding of the present invention, and the present invention is not limited thereto.
[실시예 1]Example 1
섬유를 100g/ℓ의 수산화나트륨(NaOH) 수용액에 75℃의 온도에서 2분간 침지하여 에칭한 후 물로 세척하였다. 다음으로 섬유를 10부피%의 염산(HCl) 수용액에 20℃의 온도에서 2분간 침지한 후 20부피%의 염산(HCl)에 100ppm의 염화팔라듐(PdCl2)을 용해시킨 촉매 용액에 25℃의 온도에서 2분간 접촉시킨 후 물로 세척하였다. 다음으로 섬유를 10부피%의 황산(H2SO4) 수용액에 55℃의 온도에서 2분간 침지한 후 물로 세척하였다.The fibers were immersed in 100 g / L aqueous sodium hydroxide (NaOH) solution for 2 minutes at a temperature of 75 ° C. and then washed with water. Next, the fibers were immersed in an aqueous 10% by volume hydrochloric acid (HCl) solution at a temperature of 20 ° C. for 2 minutes and then dissolved in 100 ppm of palladium chloride (PdCl 2 ) in 20% by volume hydrochloric acid (HCl) at 25 ° C. It was contacted for 2 minutes at the temperature and washed with water. Next, the fibers were immersed in a 10% by volume aqueous sulfuric acid (H 2 SO 4 ) solution for 2 minutes at a temperature of 55 ℃ and washed with water.
다음으로 섬유를 30g/ℓ의 에틸렌디니트릴로-테트라-2-프로판올(EDTP)과, 15g/ℓ의 황산구리(Ⅱ) 5수화물 (CuSO4·5H2O)과, 10g/ℓ의 수산화나트륨(NaOH)과, 6g/ℓ의 포름알데히드(HCHO)와, 30ppm의 페로시안화 칼륨(Potassium ferrocyanide)과, 30ppm의 2-머캅토 벤조치아졸(2-Mercapto benzo thiazole)과, 30ppm의 (티오) 우레아(Thio urea)를 포함하는 무전해 동도금액에 40℃의 온도에서 10분간 침지하여 섬유의 표면에 금속을 도금한 후 물로 세척한 다음 열풍 건조기로 2분간 건조하여 도금 섬유를 제조하였다.The fibers were then 30 g / l ethylenedinitro-tetra-2-propanol (EDTP), 15 g / l copper sulfate (II) pentahydrate (CuSO 4 · 5H 2 O), and 10 g / l sodium hydroxide ( NaOH), 6 g / l formaldehyde (HCHO), 30 ppm potassium ferrocyanide, 30 ppm 2-mercapto benzothiazole, 30 ppm (thio) urea The electroless copper plating solution containing (Thio urea) was immersed for 10 minutes at a temperature of 40 ℃ to plate the metal on the surface of the fiber, washed with water and dried for 2 minutes in a hot air dryer to prepare a plated fiber.
[실시예 2]Example 2
실시예 1과 동일한 조건에서 무전해 동도금액의 성분 중 EDTP의 양을 10g/ℓ 줄이고, 줄인 EDTP의 양 만큼 EDTA·4Na를 추가하였다. Under the same conditions as in Example 1, the amount of EDTP in the components of the electroless copper plating solution was reduced by 10 g / L, and EDTA.4Na was added by the amount of EDTP reduced.
즉, 20g/ℓ의 EDTP와, 10g/ℓ의 EDTA·4Na와, 15g/ℓ의 황산구리(Ⅱ) 5수화물과, 10g/ℓ의 수산화나트륨과, 6g/ℓ의 포름알데히드와, 30ppm의 페로시안화 칼륨과, 30ppm의 2-머캅토 벤조치아졸과, 30ppm의 (티오) 우레아를 포함하는 무전해 동도금액을 사용하여 무전해 동도금을 실시하였다.That is, 20 g / l EDTP, 10 g / l EDTA.4Na, 15 g / l copper sulfate (II) pentahydrate, 10 g / l sodium hydroxide, 6 g / l formaldehyde, and 30 ppm ferrocyanide. Electroless copper plating was performed using an electroless copper plating solution containing potassium, 30 ppm 2-mercapto benzothiazol, and 30 ppm (thio) urea.
[실시예 3]Example 3
실시예 1과 동일한 조건에서 섬유를 무전해 동도금액에 침지하기 전에 무전해 니켈 도금을 실시하였다.Under the same conditions as in Example 1, electroless nickel plating was performed before the fibers were immersed in the electroless copper plating solution.
[비교예 1]Comparative Example 1
실시예 1,2와의 비교를 위하여 실시예 1과 동일한 조건에서 무전해 동도금액의 성분 중 EDTP 대신 20g/ℓ의 EDTA·4Na를 사용하였다.For comparison with Examples 1 and 2, 20 g / L of EDTA.4Na was used instead of EDTP under the same conditions as in Example 1.
[비교예 2]Comparative Example 2
실시예 1과의 비교를 위하여 실시예 1과 동일한 조건에서 30g/ℓ의 에틸렌디니트릴로-테트라-2-프로판올(EDTP)과, 15g/ℓ의 황산구리(Ⅱ) 5수화물 (CuSO4·5H2O)과, 10g/ℓ의 수산화나트륨(NaOH)과, 6g/ℓ의 포름알데히드(HCHO)로 구성된 무전해 동도금액을 사용하였다.For comparison with Example 1, 30 g / L of ethylenedinitrilo-tetra-2-propanol (EDTP) and 15 g / L of copper sulfate (II) pentahydrate (CuSO 4 · 5H 2 ) under the same conditions as in Example 1 O), 10 g / l sodium hydroxide (NaOH), and 6 g / l formaldehyde (HCHO) were used for the electroless copper plating solution.
1. 2-2' 디피리딜 양에 따른 연성 변화 및 인장강도 변화1. Change in Ductility and Tensile Strength According to 2-2 'Dipyridyl Amount
실시예 1,2 및 비교예 1의 무전해 동도금액에 포함되는 2-2' 디피리딜의 양을 10 내지 35ppm의 범위 내에서 조절하여 2-2' 디피리딜의 양에 따른 연성 변화 및 인장강도 변화를 측정하고, 그 결과를 그래프 1 및 그래프 2에 각각 나타내었다.The change in ductility according to the amount of 2-2 'dipyridyl by adjusting the amount of 2-2' dipyridyl contained in the electroless copper plating solution of Examples 1,2 and Comparative Example 1 within the range of 10 to 35ppm and The change in tensile strength was measured, and the results are shown in Graph 1 and Graph 2, respectively.
[그래프 1][Graph 1]
[그래프 2][Graph 2]
상기 그래프 1 및 그래프 2에서 알 수 있듯이, 디피리딜의 양에 따라 연성은 증가하고, 인장강도는 큰 변화가 없으며, 실시예1,2가 비교예 1보다 연성은 작고, 인장강도는 큼을 알 수 있다.As can be seen in the graphs 1 and 2, the ductility increases with the amount of dipyridyl, and the tensile strength does not change significantly, and Examples 1 and 2 are less ductile than Comparative Example 1, and the tensile strength is large. Can be.
2. 작업턴수에 따른 무전해 도금액 안정성 테스트2. Test of stability of electroless plating solution according to work turn
실시예 1과 비교예 2에 사용된 무전해 동도금액의 작업 턴수에 따른 안정성을 측정하여 그 결과를 그래프 3에 나타내었다.The stability according to the number of working turns of the electroless copper plating solution used in Example 1 and Comparative Example 2 was measured and the results are shown in Graph 3.
도금액 안정성이란, 도금액 내 구리 농도의 변화를 기준으로 하여, 12시간 상온 방치시 초기의 구리 농도 대비 구리 농도의 변화를 %로 나타낸 것이다.Plating solution stability shows the change of copper concentration with respect to the copper concentration at the time of initial stage at room temperature for 12 hours on the basis of the change of copper concentration in plating liquid in%.
또한, 도금액 작업 턴(Turn)수란, 초기 건욕량 대비 작업에 의한 황산구리(Ⅱ) 5수화물의 보충 투입량을 말하는 것이다.In addition, the plating solution working turn water means the supplemental input amount of copper sulfate (II) pentahydrate by the work compared with the initial dry bath amount.
[그래프 3][Graph 3]
상기의 그래프 3에서 알 수 있듯이, 도금액 작업턴수가 증가함에 따라 안정성이 감소하며, 비교예 2 보다 실시예 1의 도금액 안정성이 약 25% 이상 뛰어남을 알 수 있다.As can be seen from the graph 3, the stability of the plating solution decreases as the number of working solution turns, and the plating solution stability of Example 1 is superior to that of Comparative Example 2 by about 25% or more.
3. 니켈 도금층의 두께에 따른 동 도금층의 두께 변화3. Thickness change of copper plating layer according to thickness of nickel plating layer
실시예 3에서 무전해 니켈 도금시에 니켈 도금층의 두께를 0.1 내지 0.6㎛ 범위 내에서 조절하여 니켈 도금층의 두께에 따른 동 도금층의 두께 변화를 측정하고, 그 결과를 그래프 4에 나타내었다.The thickness change of the copper plating layer according to the thickness of the nickel plating layer was measured by adjusting the thickness of the nickel plating layer in the range of 0.1 to 0.6 μm during electroless nickel plating in Example 3, and the results are shown in Graph 4.
[그래프 4][Graph 4]
상기의 그래프 4에서도 알 수 있듯이, 니켈 도금층의 두께를 0.1 ~ 0.3㎛로 할 경우에 니켈 도금층의 두께에 비례하여 동 도금층의 두께가 상승하지만, 니켈 도금층의 두께를 0.3㎛ 이상으로 할 경우 동 도금층의 두께는 거의 상승하지 않으므로 제조원가 측면에서 볼 때 불필요하게 니켈 도금층의 두께를 크게 할 필요가 없음을 알 수 있다. 따라서, 니켈 도금층의 두께는 0.1 ~ 0.3㎛로 하는 것이 가장 바람직하다.As can be seen from the above graph 4, when the thickness of the nickel plated layer is 0.1 to 0.3 μm, the thickness of the copper plated layer increases in proportion to the thickness of the nickel plated layer, but when the thickness of the nickel plated layer is 0.3 μm or more, the copper plated layer Since the thickness of is hardly increased, it can be seen that it is not necessary to increase the thickness of the nickel plating layer unnecessarily in terms of manufacturing cost. Therefore, the thickness of the nickel plating layer is most preferably 0.1 to 0.3 m.
상기에서 살펴본 바와 같이, 본 발명에 의한 섬유 동도금방법에 따르면, 도금속도가 빠르고, 도금에 대한 저항을 감소시킬 수 있어 전체적인 도금효율을 향상시킬 수 있다.As described above, according to the fiber copper plating method of the present invention, the plating speed is fast, and the resistance to plating can be reduced, thereby improving the overall plating efficiency.
또한, 무전해 동도금액의 안정성이 뛰어나므로 도금조 바닥에 구리가 석출되는 것을 감소시킬 수 있어 도금 작업조 청소로 인한 낭비시간을 줄일 수 있고, 전체적인 작업효율을 향상시킬 수 있다.In addition, since the stability of the electroless copper plating solution is excellent, it is possible to reduce the precipitation of copper on the bottom of the plating bath, thereby reducing waste time due to the cleaning of the plating work tank, and improving the overall working efficiency.
나아가, 무전해 동도금액에 황산구리(Ⅱ) 5수화물을 사용함으로써, 섬유에 전착되는 결정의 크기가 작으며, 도금된 섬유의 경사, 위사에 따른 저항의 차이가 작다. 또한, 저항이 일정하여 균일한 도금효과를 얻을 수 있으며, 연성이 뛰어나 외부충격에 균일이 없다.Furthermore, by using copper (II) sulfate pentahydrate in the electroless copper plating solution, the size of crystals electrodeposited on the fiber is small, and the difference in resistance according to the warp and weft of the plated fiber is small. In addition, since the resistance is constant, a uniform plating effect can be obtained. The ductility is excellent and there is no uniformity in external impact.
본 발명에서 사용한 g/ℓ는 물 1ℓ당 용해한 물질의 g수를 나타낸다.G / l used in the present invention represents the number of g of substance dissolved per liter of water.
본 발명에 따른 도금을 수행할 수 있는 섬유는 폴리에스테르, 아크릴계섬유, 나일론, 부직포 등의 섬유뿐만 아니라, 폴리우레탄, 폴리에틸렌테레프탈레이트(PET), 폴리올레핀 등의 고분자 합성수지 또는 합성고무시트, 폴리이미드(P.I)필름 등이 될 수 있다.Fiber capable of plating according to the present invention is not only fibers such as polyester, acrylic fiber, nylon, nonwoven fabric, but also polymer synthetic resin or synthetic rubber sheet such as polyurethane, polyethylene terephthalate (PET), polyolefin, polyimide ( PI) film and the like.
상술한 바와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당기술분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 또는 변형하여 실시할 수 있다.As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art various modifications of the present invention without departing from the spirit and scope of the invention described in the claims below. Or it may be modified.
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| KR20060069508A (en) * | 2003-10-17 | 2006-06-21 | 닛코킨조쿠 가부시키가이샤 | Electroless copper plating solution and method for electroless copper plating |
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| KR20060069508A (en) * | 2003-10-17 | 2006-06-21 | 닛코킨조쿠 가부시키가이샤 | Electroless copper plating solution and method for electroless copper plating |
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