KR100293532B1 - Metal plating method of plastic polymer surface - Google Patents
Metal plating method of plastic polymer surface Download PDFInfo
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- KR100293532B1 KR100293532B1 KR1019980023549A KR19980023549A KR100293532B1 KR 100293532 B1 KR100293532 B1 KR 100293532B1 KR 1019980023549 A KR1019980023549 A KR 1019980023549A KR 19980023549 A KR19980023549 A KR 19980023549A KR 100293532 B1 KR100293532 B1 KR 100293532B1
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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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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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
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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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
Abstract
본 발명은 플라스틱 고분자 표면의 금속 도금방법 및 이들 도금된 고분자의 이용에 관한 것이다. 좀 더 구체적으로, 본 발명은 플라스틱 고분자 표면을 식각하여 촉매를 흡착시키고 금속을 도금하는 단계를 포함하는 플라스틱 고분자 표면의 금속 도금방법 및 전기 방법에 의해 도금된 플라스틱 고분자를 이용하여 제조된 자동차용 연료탱크에 관한 것이다. 이러한 본 발명의 플라스틱 고분자 표면의 금속 도금방법에 따르면, 수득한 플라스틱 고분자는 사용하는 식각용액내 산화크롬의 농도가 진할수록, 또한 식각용액의 온도가 높을수록 식각효과가 우수하여, 플라스틱 고분자와 도금층 사이의 접착력이 1000 N/㎠ 이상까지인 매우 우수한 플라스틱 고분자를 얻을 수 있으며, 또한 이러한 플라스틱 고분자를 이용하여 가스누출 차폐효과가 우수한 자동차용 연료탱크 등을 제조할 수 있다.The present invention relates to metal plating methods for plastic polymer surfaces and the use of these plated polymers. More specifically, the present invention relates to a fuel for automobiles manufactured by using a plastic polymer plated by a metal plating method and an electrical method on the surface of a plastic polymer, including etching a surface of the plastic polymer to adsorb a catalyst and plating a metal. It's about tanks. According to the metal plating method of the surface of the plastic polymer of the present invention, the obtained plastic polymer has an excellent etching effect as the concentration of chromium oxide in the etching solution used is higher, and the temperature of the etching solution is higher, and thus, between the plastic polymer and the plating layer. It is possible to obtain a very good plastic polymer having an adhesive strength of up to 1000 N / ㎠ or more, and can also produce a fuel tank for automobiles having excellent gas leakage shielding effect using this plastic polymer.
Description
본 발명은 플라스틱 고분자 표면의 금속 도금방법 및 이들 도금된 고분자의 이용에 관한 것이다. 좀 더 구체적으로, 본 발명은 플라스틱 고분자 표면을 식각하여 촉매를 흡착시키고 금속을 도금하는 단계를 포함하는 플라스틱 고분자 표면의 금속 도금방법 및 전기 방법에 의해 도금된 플라스틱 고분자를 이용하여 제조한 자동차용 연료탱크에 관한 것이다.The present invention relates to metal plating methods for plastic polymer surfaces and the use of these plated polymers. More specifically, the present invention provides a fuel for automobiles manufactured by using a plastic polymer plated by a metal plating method and an electric method on the surface of the plastic polymer including etching a surface of the plastic polymer to adsorb a catalyst and plating a metal. It's about tanks.
일반적으로, 플라스틱 고분자를 이용하여 자동차용 연료탱크를 제조하는 경우, 전기 플라스틱 고분자로는 고밀도 폴리에틸렌을 이용하여 제조하는 것이 알려져 있다. 그러나, 이러한 고밀도 폴리에틸렌 자체만으로 자동차용 연료탱크를 제조하는 경우, 고밀도 폴리에틸렌 자체의 물리적 특성으로 인해 물질전달속도가 높고, 그로 인해 자동차 연료 중 탄화수소와 같은 기체가 외부로 누출되는 문제점이 있어 왔다. 따라서, 종래기술의 이러한 문제점을 해결하기 위하여, 자동차용 연료탱크를 구성하고 있는 고밀도 폴리에틸렌을 개질시키기 위한 많은 연구가 있어 왔다.In general, when manufacturing a fuel tank for automobiles using a plastic polymer, it is known to manufacture using high density polyethylene as the electric plastic polymer. However, when manufacturing a fuel tank for automobiles using only the high-density polyethylene itself, there is a problem that the material transfer rate is high due to the physical properties of the high-density polyethylene itself, and therefore gas such as hydrocarbons in the vehicle fuel leaks to the outside. Therefore, in order to solve this problem of the prior art, there have been many studies for modifying the high density polyethylene constituting the fuel tank for automobiles.
이러한 고밀도 폴리에틸렌의 개질방법으로는 가령, 플루오르화 반응, 술폰화 반응, 라미나 블랜드 배리어(laminar blend barrier), 공분출(coextrusion) 방법 등이 알려져 있다[참조: J.H. Schut Plastics Technology, May 1992, pp 52 ∼ 57]. 그러나, 이들 중 우선 고밀도 폴리에틸렌을 플루오르화시키는 반응의 경우 플루오르화 이후 독성을 나타내는 플루오르 기체를 처리해야 하는 문제점을 지니고 있으며, 술폰화시키는 경우 역시 술폰화 이후 독성 기체인 이산화황을 처리하여야 하는 문제점이 있어 바람직하지 않았다. 또한, 고밀도 폴리에틸렌에 라미나 블랜드 배리어를 구비시키는 방법은 특수한 혼합스크류를 필요로 하는 문제점을 지니고 있으며, 공분출 방법은 고도의 기계가공기술과 정밀한 가공기계를 필요로 하는 문제점을 지니고 있었다.As a method of modifying such a high density polyethylene, for example, a fluorination reaction, a sulfonation reaction, a laminar blend barrier, a coextrusion method, and the like are known [J.H. Schut Plastics Technology, May 1992, pp 52-57. However, among these reactions, fluorination of high-density polyethylene has a problem of treating toxic fluorine gas after fluorination, and in the case of sulfonation, sulfur dioxide, which is a toxic gas after sulfonation, is also undesirable. Did. In addition, the method of providing a lamina blend barrier in the high density polyethylene has a problem that requires a special mixing screw, the co-injection method has a problem that requires a high degree of machining technology and a precision processing machine.
따라서, 상기와 같은 문제점을 개선하기 위하여 무전해 도금기술을 이용하여 고밀도 폴리에틸렌과 같은 플라스틱 고분자 표면을 개질시키는 방법이 제안되었다[참조: B.S. Chiou, J.H. Chang and J.G. Dhh, Plat. and Surf. Fin., 80, 65, June(1990)]. 그러나, 이러한 무전해 도금기술을 고밀도 폴리에틸렌와 같은 자동차 연료탱크용 플라스틱 고분자에 적용한 예는 없었으며, 또한 이 도금기술을 자동차 연료탱크용 플라스틱 고분자에 적용하는 경우, 여전히 플라스틱 고분자와 도금층간의 접착력에 문제가 있고, 따라서 탄화수소의 누출을 막을 수 없어 물질전달의 차폐에 문제가 발생하여 이에 대한 개선의 필요성이 절실히 대두되고 있던 실정이었다.Therefore, in order to improve the above problems, a method of modifying a plastic polymer surface such as high density polyethylene by using an electroless plating technique has been proposed [B.S. Chiou, J.H. Chang and J.G. Dhh, Plat. and Surf. Fin., 80, 65, June (1990)]. However, none of these electroless plating techniques have been applied to plastic polymers for automotive fuel tanks such as high density polyethylene, and when this plating technique is applied to plastic polymers for automotive fuel tanks, there is still a problem in adhesion between the plastic polymer and the plating layer. Therefore, the leakage of hydrocarbons cannot be prevented, causing problems in the shielding of material transfer, and the necessity for improvement thereof has been urgently raised.
이에, 본 발명의 발명자들은 선행기술에 있어서 플라스틱 고분자와 도금층간의 접착력 및 이들 도금층의 물질전달의 차폐가 불량한 문제점을 해결하기 위하여 예의 연구노력한 결과, 식각용액의 농도 및 온도를 조절하여 플라스틱 고분자를 식각시키고, 촉매를 흡착시킨 다음, 니켈 및 인이 함유된 무전해 도금용액에 도입하여 도금함으로써 해결할 수 있음을 확인하고, 본 발명을 완성하게 되었다.Therefore, the inventors of the present invention intensively researched in order to solve the problem that the adhesion between the plastic polymer and the plating layer and the shielding of material transfer of these plating layers in the prior art is poor, by controlling the concentration and temperature of the etching solution to etch the plastic polymer. After adsorbing the catalyst, it was confirmed that the present invention could be solved by introducing and plating the electroless plating solution containing nickel and phosphorus, thereby completing the present invention.
결국, 본 발명의 목적은 플라스틱 고분자 표면을 식각하여 촉매를 흡착시키고 금속을 도금하는 단계를 포함하는 플라스틱 고분자 표면의 금속 도금방법을 제공하는 것이다.After all, it is an object of the present invention to provide a metal plating method of a surface of a plastic polymer comprising etching a surface of the plastic polymer to adsorb a catalyst and plating a metal.
또한, 본 발명의 다른 목적은 무전해 전기도금 방법에 의해 도금된 플라스틱 고분자를 이용하여 제조한 자동차용 연료탱크를 제공하는 것이다.In addition, another object of the present invention is to provide a fuel tank for an automobile manufactured using a plastic polymer plated by an electroless electroplating method.
도 1은 본 발명에 따른 무전해 금속 도금방법을 개략적으로 도시한 그림이다.1 is a view schematically showing an electroless metal plating method according to the present invention.
도 2는 본 발명의 식각용액내 온도변화에 따른 도금층의 접착력 차이를 나타낸 그래프이다.2 is a graph showing the difference in adhesion between the plating layer according to the temperature change in the etching solution of the present invention.
도 3은 본 발명의 식각용액내 산화크롬의 농도변화에 따른 도금층의 접착력 차이를 나타낸 그래프이다.3 is a graph showing the difference in the adhesion of the plating layer according to the change in the concentration of chromium oxide in the etching solution of the present invention.
도 4는 본 발명의 도금층 두께 변화에 따른 탄화수소의 누출속도를 나타낸 그래프이다.Figure 4 is a graph showing the leak rate of the hydrocarbon according to the thickness change of the plating layer of the present invention.
본 발명의 플라스틱 고분자 표면의 금속 도금방법은 플라스틱 고분자 표면의 식각공정, 촉매의 흡착공정 및 도금공정을 포함한다. 이러한 본 발명의 플라스틱 고분자 표면의 금속 도금방법은 플라스틱 고분자로서 자동차의 연료탱크로 주로 사용되는 고밀도 폴리에틸렌을 비롯하여, 기타 폴리프로필렌 또는 폴리비닐클로라이드 등에도 적용할 수 있다.The metal plating method of the surface of the plastic polymer of the present invention includes the etching process of the surface of the plastic polymer, the adsorption process of the catalyst and the plating process. The metal plating method of the surface of the plastic polymer of the present invention can be applied to high-density polyethylene, which is mainly used as a fuel tank of automobiles as plastic polymers, and other polypropylene or polyvinyl chloride.
이하, 본 발명의 플라스틱 고분자 표면의 금속 도금방법을 각 단계별로 더욱 상세히 살펴보면 다음과 같다(참조: 도 1).Hereinafter, the metal plating method of the surface of the plastic polymer of the present invention will be described in more detail in each step (see FIG. 1).
제 1단계: 플라스틱 고분자의 식각 Step 1 : Etching the Plastic Polymer
먼저, 플라스틱 고분자 표면상에 존재하는 유기물을 제거하지 않은 채 다음 공정을 수행하는 경우 식각이 불량해지는 것은 물론, 도금처리후 접착력도 약하게 되는 문제점이 있게 되기 때문에, 도금처리하고자 하는 플라스틱 고분자의 표면에 존재하는 유기물을 초음파세척기 등을 이용하여 제거한 플라스틱 고분자를 준비한다.First, if the following process is performed without removing the organic material present on the surface of the plastic polymer, the etching is not only poor, but also the adhesive strength after the plating treatment is weak, so that the surface of the plastic polymer to be plated Prepare the plastic polymer from which the organic substance is removed by using an ultrasonic cleaner.
본 플라스틱 고분자 표면을 식각하는 공정은 최종 도금결과 플라스틱 고분자와 도금층내 금속과의 사이에 접착력을 결정하는 데 매우 중요하다. 이 단계는 식각용액의 농도 및 온도를 적절히 선택할 필요성이 있어 식각용액으로서 50 (g/ℓ) 내지 360 (g/ℓ), 보다 바람직하게는 200 (g/ℓ) 내지 360 (g/ℓ)의 산화크롬(CrO3)을 함유하는 진한 황산용액에 플라스틱 고분자를 도입하여 식각한다. 이때, 황산용액내 산화크롬의 농도가 50 (g/ℓ) 미만이면 접착력이 약해지는 문제가 발생하여 바람직하지 않을 뿐만 아니라, 360 (g/ℓ)를 초과하는 경우도 식각은 잘 되지만, 포화용액에 가까워져 점도가 너무 강하게 되고, 결국 고밀도 폴리에틸렌을 식각시키는데 문제가 발생하여 역시 바람직하지 않게 된다. 또한, 상기와 같은 식각용액의 식각 공정시 식각용액의 온도는 높을수록 그 효과가 비례하여 나타나나, 바람직하게는 20℃ 내지 90℃, 보다 바람직하게는 60℃ 내지 90℃, 또한, 가장 바람직하게는 80℃ 내지 90℃ 범위로 유지시키는 것이다.The process of etching the surface of the plastic polymer is very important for determining the adhesion between the plastic polymer and the metal in the plating layer. In this step, it is necessary to appropriately select the concentration and temperature of the etching solution, so that the etching solution is 50 (g / L) to 360 (g / L), more preferably 200 (g / L) to 360 (g / L). Plastic polymer is introduced into a concentrated sulfuric acid solution containing chromium oxide (CrO 3 ) and etched. At this time, if the concentration of chromium oxide in the sulfuric acid solution is less than 50 (g / l), the problem of weakening of the adhesive force occurs, which is not preferable, and in the case of more than 360 (g / l), the etching is good, but saturated solution The viscosity becomes too strong and eventually causes problems in etching high density polyethylene, which is also undesirable. In addition, the higher the temperature of the etching solution in the etching process of the etching solution as described above, the effect is proportional, preferably 20 ℃ to 90 ℃, more preferably 60 ℃ to 90 ℃, and most preferably Is maintained in the range of 80 ° C to 90 ° C.
제 2단계: 촉매의 흡착 Second step : adsorption of catalyst
상기 식각공정에서 수득한 플라스틱 고분자 표면에 촉매인 팔라듐(Pd) 원소가 고분자 표면에 용이하게 흡착되도록 개시제로서 염화주석(SnCl2)을 처리한다. 그런 다음, 순차적으로 상기 고분자 표면에 염화팔라듐(PdCl2)을 처리하여 팔라듐(Pd) 원소를 흡착시킨다. 여기서, 이들 촉매는 다음 공정에서 니켈(Ni) 금속과 인(P) 성분이 고분자 표면에 흡착하는 반응을 유도하는 중요한 성분으로, 본 발명에서 목적으로 하는 플라스틱 고분자와 도금층의 금속과의 접착력을 양호하도록 한다.Tin chloride (SnCl 2 ) is treated as an initiator to readily adsorb palladium (Pd) element as a catalyst on the surface of the plastic polymer obtained in the etching process. Then, palladium chloride (PdCl 2 ) is sequentially treated on the surface of the polymer to adsorb palladium (Pd) elements. Here, these catalysts are important components inducing a reaction in which the nickel (Ni) metal and the phosphorus (P) component are adsorbed on the surface of the polymer in the next step, and the adhesion between the plastic polymer and the metal of the plating layer, which is the object of the present invention, is good. Do it.
제 3단계: 금속의 도금 Step 3 : Plating the Metal
상기 단계에서 수득한 촉매가 흡착된 플라스틱 고분자를 무전해 도금용액에 도입한다. 이때, 무전해 도금용액으로는 황산니켈, 아인산나트륨(NaPH2O2) 및 아세트산나트륨을 포함하는 용액; 황산니켈, 아인산나트륨(NaPH2O2) 및 소듐하이드록시아세테이트(sodium hydroxyacetate)를 포함하는 용액; 황산니켈, 아인산나트륨(NaPH2O2), 소듐시트레이트(sodium citrate) 및 염화암모늄를 포함하는 용액; 황산니켈, 아인산나트륨(NaPH2O2) 및 소듐피로포스페이트(sodium pyrophosphate)를 포함하는 용액; 또는, 염화니켈, 디메틸아민 보란(dimethylamine borane) 및 말론산(malonic acid)을 포함하는 용액을 사용한다. 이러한 무전해 도금용액내에 상기 플라스틱 고분자를 도입하면 팔라듐 촉매에 의하여 환원반응이 활성화되게 되고, 그 결과 플라스틱 고분자 표면에 니켈-인 금속이 접착되어 도금 처리되게 된다. 이때, 도금되는 금속의 두께는 5 ㎛ 내지 50 ㎛가 바람직한데, 도금층의 두께가 5 ㎛ 미만으로 너무 얇은 경우 단위면적당 물질전달량이 규제치를 만족하지 못하고, 또한 50 ㎛를 초과하여 과대한 경우 단위면적당 물질전달량의 누출이 없지만 도금시간이 오래 걸리고 비용도 많이 들어가기 때문에 바람직하지 않다. 이와 같이 하여 수득된 플라스틱 고분자는 우수한 접착력 뿐만 아니라, 도금두께에 따른 물질전달 특성을 나타내게 된다.The polymer obtained by adsorbing the catalyst obtained in the above step is introduced into an electroless plating solution. In this case, the electroless plating solution is a solution containing nickel sulfate, sodium phosphite (NaPH 2 O 2 ) and sodium acetate; A solution comprising nickel sulfate, sodium phosphite (NaPH 2 O 2 ), and sodium hydroxyacetate; A solution comprising nickel sulfate, sodium phosphite (NaPH 2 O 2 ), sodium citrate, and ammonium chloride; A solution comprising nickel sulfate, sodium phosphite (NaPH 2 O 2 ), and sodium pyrophosphate; Alternatively, a solution containing nickel chloride, dimethylamine borane and malonic acid is used. When the plastic polymer is introduced into the electroless plating solution, the reduction reaction is activated by the palladium catalyst, and as a result, nickel-phosphorus metal is adhered to the surface of the plastic polymer to be plated. At this time, the thickness of the metal to be plated is preferably 5 ㎛ to 50 ㎛, if the thickness of the plating layer is too thin, less than 5 ㎛ the mass transfer amount per unit area does not meet the regulation value, and if the excess exceeds 50 ㎛ per unit area Although there is no leakage of mass transfer amount, it is not preferable because plating takes a long time and costs are high. The plastic polymer thus obtained shows not only excellent adhesion but also material transfer characteristics depending on the plating thickness.
본 발명은 상술한 도금방법에 의해 금속도금된 플라스틱 고분자는 전자파 장해의 차폐(EMI shielding), 자동차 부품, 컴퓨터 부품 등의 여러 분야에 응용될 수 있으나, 특히, 철 또는 알루미늄를 이용하는 통상의 연료탱크를 대체하여 자동차용 연료탱크의 제조에 이용될 수 있다. 즉, 고밀도 폴리에틸렌, 폴리프로필렌 또는 폴리비닐클로라이드 등의 고분자 플라스틱을 이용하여 자동차용 연료탱크를 사출하여 제조하고, 무전해 도금용액에 도입하여 도금을 수행한다. 이렇게 하여 제조한 자동차용 연료탱크는 종래와 같은 탄화수소 기체의 누설을 방지할 수 있는 등의 매우 우수한 물성을 나타낸다.The present invention can be applied to various fields such as electromagnetic shielding (EMI shielding), automobile parts, computer parts, etc., the plastic polymer metal plated by the above-described plating method, in particular, a conventional fuel tank using iron or aluminum Alternatively it can be used in the manufacture of fuel tanks for automobiles. That is, by injection molding the fuel tank for automobiles using high-molecular plastic such as high-density polyethylene, polypropylene or polyvinyl chloride, and is introduced into the electroless plating solution to perform plating. The fuel tank for automobiles manufactured in this way exhibits very excellent physical properties such as preventing leakage of hydrocarbon gas as in the prior art.
이하, 본 발명을 실시예에 의거 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 국한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples according to the gist of the present invention.
실시예 1: 식각용액내 온도에 따른 도금층의 접착력 비교 Example 1 Comparison of Adhesion of Plating Layer According to Etching Solution Temperature
초음파 세척기를 이용하여 표면에 존재하는 유기물을 제거한 1.7 ㎜ 두께의 고밀도 폴리에틸렌 시편을 농도 360 g/ℓ의 산화크롬(CrO3)을 함유하는 진한 황산으로 이루어진 45℃ 내지 90℃로 유지되는 식각용액 1000 ㎖에 도입하여 60분간 고분자 표면을 식각처리하였다. 그런 다음, 식각처리된 고밀도 폴리에틸렌 표면에 각각 10 g/ℓ SnCl2용액과 0.25 g/ℓ PdCl2용액을 순차적으로 처리하여 촉매를 흡착시켰다. 이어, 팔라듐이 흡착된 고밀도 폴리에틸렌을 황산니켈, 아세트산나트륨, 아인산나트륨(NaPH2O2)을 각각 35 g/ℓ, 10 g/ℓ, 10 g/ℓ씩을 함유하는 무전해 도금용액에 도입하여 평균 20 ㎛ 두께로 도금시켰다. 이와 같이 도금된 고밀도 폴리에틸렌 시편을 ASTM C-633-79 방법에 의하여 도금층의 접착력을 식각용액의 온도를 달리하며 7회에 걸쳐 반복하여 측정하였으며, 그 결과를 도 2에 요약하여 나타내었다. 도 2에서 보듯이, 도금층의 접착력은 온도 증가에 따라 누승적으로 증가하는 것을 알 수 있었으며, 특히 1000 N/㎠ 이상의 바람직한 접착력을 나타내기 위해서는, 식각용액의 농도가 360 g/ℓ인 경우 80℃ 이상인 것이 바람직한 것을 알 수 있었다.Etch solution 1000 maintained at 45 ° C. to 90 ° C., consisting of concentrated sulfuric acid containing a concentration of 360 g / l chromium oxide (CrO 3 ), on a 1.7 mm-thick polyethylene specimen from which organic matter was removed from the surface using an ultrasonic cleaner. The surface of the polymer was etched for 60 minutes by introducing into ml. Then, the catalyst was adsorbed by sequentially treating the etched high-density polyethylene surface with 10 g / l SnCl 2 solution and 0.25 g / l PdCl 2 solution, respectively. Then, the high density polyethylene adsorbed with palladium was introduced into an electroless plating solution containing 35 g / l, 10 g / l and 10 g / l of nickel sulfate, sodium acetate, and sodium phosphite (NaPH 2 O 2 ), respectively. Plated to 20 μm thickness. The plated high-density polyethylene specimens were measured repeatedly by seven times, varying the temperature of the etching solution, by the ASTM C-633-79 method, and the results are summarized in FIG. 2. As shown in Figure 2, the adhesion of the plated layer was found to increase gradually with increasing temperature, in particular, in order to exhibit a desirable adhesion of more than 1000 N / ㎠, 80 ℃ when the concentration of the etching solution is 360 g / ℓ It turned out that the above is preferable.
실시예 2: 식각용액내 산화크롬의 농도 변화에 따른 접착력의 비교 Example 2 Comparison of Adhesion at Different Concentrations of Chromium Oxide in Etch Solution
25℃의 식각용액 1000 ㎖에 산화크롬의 농도를 50 g/ℓ 내지 350 g/ℓ로 조절한 점을 제외하고는, 상기 실시예 1에서와 동일한 조건 및 방법을 이용하여 금속 도금처리된 고밀도 폴리에틸렌 시편을 제조하였다. 그런 다음, 도금층의 접착력을 ASTM C-633-79 방법에 의하여 3회 반복측정하였고, 그 결과를 도 3에 요약하여 나타내었다. 도 3에서 보듯이, 일정 온도의 식각용액내 산화크롬의 농도가 증가함에 따라 도금층의 접착력은 역시 누승적으로 증가하는 것을 알 수 있었다.High density polyethylene metal-plated using the same conditions and methods as in Example 1, except that the concentration of chromium oxide was adjusted to 50 g / l to 350 g / l in 1000 ml of an etching solution at 25 ° C. Specimen was prepared. Then, the adhesion of the plated layer was repeated three times by ASTM C-633-79 method, the results are summarized in FIG. As shown in Figure 3, as the concentration of the chromium oxide in the etching solution at a constant temperature it was found that the adhesion of the plating layer also increases progressively.
결론적으로, 상기 실시예 1의 경우와 함께 비교하여 볼 때, 도금층의 접착력은 식각용액의 온도 및 식각용액내 산화크롬의 농도에 누승적으로 비례함을 알 수 있다. 그러나, 식각용액의 농도가 350 g/ℓ을 초과하는 경우 용액내의 점도가 높아져 효율적인 식각이 일어나지 않는다.In conclusion, when compared with the case of Example 1, it can be seen that the adhesion of the plating layer is a power proportional to the temperature of the etching solution and the concentration of chromium oxide in the etching solution. However, when the concentration of the etching solution exceeds 350 g / l, the viscosity in the solution is high, the efficient etching does not occur.
실시예 3: 도금층 두께에 따른 탄화수소 누출량 비교 Example 3 Comparison of Hydrocarbon Leakage According to Plating Layer Thickness
도금두께를 평균 5 ㎛ 내지 20 ㎛로 조절한 점을 제외하고는, 상기 실시예 1에서와 동일한 조건 및 방법을 이용하여 금속 도금처리된 1.7 ㎜ 두께의 고밀도 폴리에틸렌 시편을 제조하였다. 이들 시편 각각에 대하여 탄화수소인 펜탄 가스의 누출속도를 측정하였고, 그 결과를 도 4에 요약하여 나타내었다. 도 4에서 보듯이, 도금두께가 18 ㎛ 이상인 경우 0.0002 g/day·㎠ 이하의 가스누출속도를 나타내는 등 우수한 물성을 나타냄을 알 수 있었다.A 1.7 mm thick high density polyethylene specimen was prepared using the same conditions and methods as in Example 1 except that the plating thickness was adjusted to an average of 5 μm to 20 μm. For each of these specimens, the leakage rate of pentane gas, which is a hydrocarbon, was measured, and the results are summarized in FIG. 4. As shown in Figure 4, when the plating thickness is more than 18 ㎛ it can be seen that exhibiting excellent physical properties such as showing a gas leakage rate of 0.0002 g / day · cm 2 or less.
이상에서 상세히 설명하고 입증하였듯이, 본 발명은 플라스틱 고분자 표면의 금속 도금방법 및 상기에서 도금된 플라스틱 고분자를 이용한 자동차용 연료탱크에 관한 것이다. 이러한 본 발명의 플라스틱 고분자 표면의 금속 도금방법에 따르면, 수득한 플라스틱 고분자는 사용하는 식각용액내 산화크롬의 농도가 진할수록, 또한 식각용액의 온도가 높을수록 식각효과가 우수하여, 플라스틱 고분자와 도금층 사이의 접착력이 1000 N/㎠ 이상까지인 매우 우수한 플라스틱 고분자를 얻을 수 있으며, 또한 이러한 플라스틱 고분자를 이용하여 가스누출 차폐효과가 우수한 자동차용 연료탱크 등을 제조할 수 있다.As described and demonstrated in detail above, the present invention relates to a metal plating method of the surface of the plastic polymer and a fuel tank for automobiles using the plastic polymer plated above. According to the metal plating method of the surface of the plastic polymer of the present invention, the obtained plastic polymer has an excellent etching effect as the concentration of chromium oxide in the etching solution used is higher, and the temperature of the etching solution is higher, and thus, between the plastic polymer and the plating layer. It is possible to obtain a very good plastic polymer having an adhesive strength of up to 1000 N / ㎠ or more, and can also produce a fuel tank for automobiles having excellent gas leakage shielding effect using this plastic polymer.
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| KR100960681B1 (en) | 2009-09-08 | 2010-05-31 | 씨앤지머트리얼즈(주) | Preparation method of polypropylene shaped body with plating layer and the shaped body |
| KR102154861B1 (en) | 2020-06-01 | 2020-09-11 | 지원석 | Method and apparatus for continuous plating process based on hood device control |
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| KR100960681B1 (en) | 2009-09-08 | 2010-05-31 | 씨앤지머트리얼즈(주) | Preparation method of polypropylene shaped body with plating layer and the shaped body |
| KR102154861B1 (en) | 2020-06-01 | 2020-09-11 | 지원석 | Method and apparatus for continuous plating process based on hood device control |
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