KR100606658B1 - A dyeing method for aluminum alloy - Google Patents
A dyeing method for aluminum alloy Download PDFInfo
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- KR100606658B1 KR100606658B1 KR1020040048985A KR20040048985A KR100606658B1 KR 100606658 B1 KR100606658 B1 KR 100606658B1 KR 1020040048985 A KR1020040048985 A KR 1020040048985A KR 20040048985 A KR20040048985 A KR 20040048985A KR 100606658 B1 KR100606658 B1 KR 100606658B1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/14—Producing integrally coloured layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
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Abstract
본 발명은 알루미늄함금을 원하는 색상으로 염색할 수 있으며, 동시에 내식성 등의 물성을 부여할 수 있는 새로운 방식의 알루미늄합금의 염색방법에 관한 것이다. The present invention relates to a method for dyeing an aluminum alloy of a new method that can dye aluminum alloy in a desired color and at the same time can impart physical properties such as corrosion resistance.
본 발명에 따르면, 알루미늄합금을 탈지하고 에칭하는 전처리과정과, 전처리된 알루미늄합금을 양극산화하는 과정과, 양극산화된 알루미늄합금을 승화성 염료와 오일을 혼합하여 제조된 처리용액의 증기에 노출시키는 과정을 포함하여 이루어진 것을 특징으로 하는 알루미늄합금의 염색방법이 제공된다.According to the present invention, a pretreatment process for degreasing and etching an aluminum alloy, anodizing the pretreated aluminum alloy, and exposing the anodized aluminum alloy to a vapor of a treatment solution prepared by mixing a sublimable dye and oil are performed. Provided is a method of dyeing an aluminum alloy, comprising the process.
Description
본 발명은 알루미늄합금의 염색방법에 관한 것으로서, 보다 상세하게는 알루미늄함금을 원하는 색상으로 염색할 수 있으며, 동시에 내식성 등의 물성을 부여할 수 있는 새로운 방식의 알루미늄합금의 염색방법에 관한 것이다.The present invention relates to a method of dyeing an aluminum alloy, and more particularly, to a method of dyeing an aluminum alloy of a new method capable of dyeing an aluminum alloy to a desired color, and at the same time giving physical properties such as corrosion resistance.
알루미늄합금 중에서도 ADC12와 같은 Al-Cu-Si계 합금은 다이캐스팅성 및 기계적 특성이 우수하여 다이캐스팅용 합금으로 주로 사용되는데, 자동차용 미션케이스, 크랭크 케이스, 산업기계부품, 가정용품 등 여러 분야에 걸쳐 폭 넓게 적용된다. Among the aluminum alloys, Al-Cu-Si-based alloys such as ADC12 are mainly used as die casting alloys because of their excellent die casting properties and mechanical properties, and are widely used in various fields such as automotive case cases, crank cases, industrial machinery parts, and household products. Widely applied.
그러나 Al-Cu-Si계 합금을 비롯하여 Al-Si계 합금이나, Al-Si-Mg계 합금과 같이 Si를 함유하는 합금제품의 표면부위에는 Si가 고밀도로 분포되어 있는 급랭조직이 존재하는데, 이 조직에 분포되어 있는 Si에 의해 양극산화 후에는 표면전체가 짙은 흑회색으로 발색된다. 그리고 이와 같이 양극산화 후에 짙은 흑회색을 가지는 경우에는, 기존의 산화알루미늄 염색방법으로는 흑색이 외의 색상으로는 염색이 불가능하다. 따라서 외관상 좋지 않으며, 사용상 여러 가지 제약을 받게 된다. However, there is a quenching structure in which Si is densely distributed on the surface of Al-Cu-Si alloys, Al-Si alloys, or alloy products containing Si such as Al-Si-Mg alloys. After anodization with Si distributed in the structure, the entire surface is colored dark black. In the case of having a deep black gray after anodization as described above, it is impossible to dye with a color other than black by the conventional aluminum oxide dyeing method. Therefore, the appearance is not good, and there are various restrictions on use.
따라서 흑회색 그대로 사용되거나 또는 굳이 다른 색상을 부여하기 위해서는 도장을 하여야 하는데, 도장을 하는 경우에는 도막이 박리되어 외관상 좋지 않을 뿐만 아니라 알루미늄 합금 자체의 재질감이 은폐되어 금속감을 느낄 수 없는 단점이 있다. Therefore, to be used as it is black or dare to give a different color, the coating should be applied, but when painting, the coating film is peeled off not only in appearance but also has the disadvantage that the texture of the aluminum alloy itself is concealed and do not feel the metallic feeling.
한편, 전술한 바와 같이 산업기계부품이나 자동차용 부품들은 상당히 높은 수준의 내식성 및 발수성, 발유성 등이 요구되므로, 요구되는 수준의 물성을 부여할 수 있도록 가공처리 되어야 한다. On the other hand, as described above, industrial machinery parts or automotive parts are required to have a fairly high level of corrosion resistance, water repellency, oil repellency, and the like, and thus should be processed to give a required level of physical properties.
본 발명은 상기의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 알루미늄합금을 양극산화한 후 원하는 색상으로 염색할 수 있으며, 동시에 내식성과 발수성, 발유성이 부여되고 별도의 봉공처리를 요하지 않으므로 저렴한 코스트로 고품질의 제품을 생산할 수 있는 새로운 방식의 알루미늄합금의 염색방법을 제공하는 것이다.
The present invention is to solve the above problems, the object of the present invention can be dyed in the desired color after anodizing the aluminum alloy, and at the same time it is inexpensive because it is given corrosion resistance and water repellency, oil repellency and does not require a separate sealing treatment It is to provide a new method of dyeing aluminum alloy to produce high quality products at low cost.
본 발명에 따르면, 알루미늄합금을 탈지하고 에칭하는 전처리과정과, 전처리된 알루미늄합금을 양극산화하는 과정과, 양극산화된 알루미늄합금을 승화성 염료 와 오일을 혼합하여 제조된 처리용액의 증기에 노출시키는 과정을 포함하여 이루어진 것을 특징으로 하는 알루미늄합금의 염색방법이 제공된다.According to the present invention, a pretreatment process for degreasing and etching an aluminum alloy, anodizing the pretreated aluminum alloy, and exposing the anodized aluminum alloy to a vapor of a treatment solution prepared by mixing a sublimable dye and oil are performed. Provided is a method of dyeing an aluminum alloy, comprising the process.
본 발명의 다른 특징에 따르면, 상기 오일은 실리콘오일, 불소오일 및 중유 중에서 선택되는 것을 특징으로 하는 알루미늄합금의 염색방법이 제공된다.According to another feature of the invention, the oil is provided a method of dyeing an aluminum alloy, characterized in that selected from silicon oil, fluorine oil and heavy oil.
이하, 본 발명을 실시예를 통해 구체적으로 설명하면 다음과 같다. 본 발명은 Al-Cu-Si계 합금으로 성형된 다이캐스팅 제품을 염색하는 방법에 관한 것으로 다음과 같이 이루어진다. Hereinafter, the present invention will be described in detail with reference to Examples. The present invention relates to a method for dyeing a die-casting product formed of an Al-Cu-Si-based alloy.
먼저, 전처리과정으로 피가공물을 탈지한 다음, 에칭한다. 알루미늄합금의 양극산화시 합금성분들이 산화되거나 전해액에 용해되지 않고 피막에 잔류하여 석출되며, 이에 따라 피막의 조도가 낮아지므로, 이를 방지하기 이해 알루미늄합금의 양극산화 전에 피가공물을 에칭하는 것이다. First, the workpiece is degreased by pretreatment and then etched. During anodization of the aluminum alloy, alloying components are oxidized or remain in the coating instead of being dissolved in the electrolyte, and thus, the roughness of the coating is lowered. Thus, the workpiece is etched before the anodization of the aluminum alloy.
에칭된 피가공물을 수세하여 건조시킨 다음, 통상의 일반적인 방법으로 양극산화한다. 이어서 양극산화된 피가공물을 염색하는데, 이때에는 승화성 염료와 오일을 혼합하여 제조된 처리용액의 증기에 피가공물을 노출시킨다. The etched workpiece is washed with water, dried, and then anodized in a conventional manner. The anodized workpiece is then dyed, wherein the workpiece is exposed to the vapor of the treatment solution prepared by mixing the sublimable dye with the oil.
승화성 염료는 분자량이 적을 수록 승화성이 좋으므로, 분자량이 적은 것이 사용되는데, 바람직하게는 분자량이 265~390이며, 승화온도가 140~250℃ 인 것이 사용된다. 그리고 오일로는 비교적 증기압은 낮고 인화점은 높은 것이 사용되는데, 바람직하게는 인화점이 250℃ 이상인 것이 사용된다. 사용되는 오일의 증기압이 낮을 수록 승화성이 좋으며, 인화점이 높을수록 가열시 위험성이 적기 때문이다. 특히 바람직하게는 내열성, 내한성, 내수성, 내화학성이 우수하며, 전기절연성과 이형성, 발수성. 윤활성 등이 우수한 실리콘오일, 불소오일, 중유가 사용하다. The lower the molecular weight is, the lower the molecular weight is, the better the sublimation. Therefore, a lower molecular weight is used, preferably a molecular weight of 265 to 390, and a sublimation temperature of 140 to 250 ° C. In addition, the oil has a relatively low vapor pressure and a high flash point, and preferably has a flash point of 250 ° C. or higher. The lower the vapor pressure of the oil used, the better the sublimation. The higher the flash point, the lower the risk of heating. Especially preferably, it is excellent in heat resistance, cold resistance, water resistance, chemical resistance, electrical insulation, release property, and water repellency. Silicone oil, fluorine oil and heavy oil with excellent lubricity and the like are used.
상기 처리용액은 이러한 승화성 염료와 오일을 혼합하여 제조되는데, 승화성 염료와 오일은 상호 반응하는 것이 아니므로 이들의 혼합비율은 한정되지 않으나, 경제성 등을 고려하여 할 때 승화성 염료는 오일에 대해 5~30부피% 정도로 혼합된다. The treatment solution is prepared by mixing such sublimable dyes and oils. Sublimable dyes and oils are not reacted with each other, so the mixing ratio thereof is not limited. About 5-30% by volume.
상기 염색과정을 좀 더 구체적으로 살펴보면, 전술한 바와 같이 제조된 처리용액을 도기 그릇에 담아 전기로에 넣고 피가공물도 전기로 내부에 거치시킨 다음, 전기로를 작동시킨다. 이때 전기로의 내부온도는 오일의 끓는점 정도의 온도로 가열하며, 처리시간은 승화성 염료의 혼합량에 따라 약 5~10분 정도로 조절된다. 이와 같이 하면, 처리액이 증발되면서 그 증기가 피가공물에 부착되어 피가공물이 염색되는데, 염료가 증기상으로 피가공물에 부착되므로 피가공물이 효과적으로 염색된다. 또한, 오일의 증기가 피가공물에 부착됨에 따라 양극산화피막에 내식성과 발수성, 발유성이 동시에 부여되며, 별도의 봉공처리를 하지 않아도 봉공효과를 얻을 수 있다. Looking at the dyeing process in more detail, the treatment solution prepared as described above is placed in an electric furnace in a ceramic bowl and the workpiece is also placed inside the electric furnace, and then operate the electric furnace. At this time, the internal temperature of the electric furnace is heated to the temperature of the boiling point of the oil, the treatment time is adjusted to about 5 ~ 10 minutes depending on the amount of the sublimable dye mixture. In this way, as the treatment liquid is evaporated, the vapor is attached to the workpiece and the workpiece is dyed. The dye is attached to the workpiece in vapor form, so that the workpiece is dyed effectively. In addition, as the vapor of oil adheres to the workpiece, corrosion resistance, water repellency, and oil repellency are simultaneously provided to the anodized film, and a sealing effect can be obtained without a separate sealing treatment.
실시예 1Example 1
ADC12 다이캐스팅 제품을 중성 탈지제로 탈지한 후에 68% 질산 600㏄와 55% 불화수소산 250㏄의 혼합용액에서 상온으로 60초간 침지시켜 표면을 에칭하였다. 이어서 피가공물을 황산수용액 15중량% 용액에 직류 1A/dm2로 30분간 양극산화한 다음 수세 건조 후에, 전기로에서 염색처리하였다. 이때에는 상품명 KT-96H(제조사 : shin- ETSU) 실리콘오일 100㏄에 C. I. Disperse yellow 30g을 혼합한 용액을 전기로에 넣고 온도 200℃에서 10분간 처리하여 피가공물을 혼합액의 증기에 노출시켰다. 이와 같이 하여 제조된 시편은 파스텔톤의 엘로우로 염색되었으며, 시편의 내식성 및 발수용, 발유성을 측정한 결과는 표 1 및 2와 같다.The ADC12 diecasting product was degreased with a neutral degreasing agent and then etched at room temperature for 60 seconds in a mixed solution of 600% of 68% nitric acid and 250% of 55% hydrofluoric acid. Subsequently, the workpiece was anodized in a 15 wt% solution of aqueous sulfuric acid solution at 1 A / dm 2 for 30 minutes, washed with water, and then dyed in an electric furnace. At this time, 100 g of a brand name KT-96H (manufacturer: shin-ETSU) silicone oil was mixed with 30 g of CI Disperse yellow in an electric furnace and treated at a temperature of 200 ° C. for 10 minutes to expose the workpiece to steam of the mixed solution. The specimens thus prepared were dyed in pastel yellow, and the results of measuring the corrosion resistance, water repellency, and oil repellency of the specimens are shown in Tables 1 and 2.
실시예 2Example 2
ADC12 다이캐스팅 제품을 중성 탈지제로 탈지한 후에 68% 질산 600㏄와 55% 불화수소산 200㏄의 혼합용액에서 상온으로 60초간 침지시켜 표면을 에칭하였다. 이어서 피가공물을 황산수용액 15중량% 용액에 직류 1A/dm2로 30분간 양극산화한 다음 수세 건조 후에, 전기로에서 염색처리하였다. 이때에는 상품명 FLONLUBE-FE-600(제조사:ASAHI GLASS) 불소오일 100㏄에 C.I.Disperse red 20g을 혼합한 용액을 전기로에 넣고 온도 250℃에서 20분간 처리하여 피가공물을 혼합액의 증기에 노출시켰다. 이와 같이 하여 제조된 시편은 파스텔톤의 레드로 염색되었으며, 시편의 내식성 및 발수용, 발유성을 측정한 결과는 표 1 및 2와 같다.The ADC12 diecasting product was degreased with a neutral degreasing agent and then etched at room temperature for 60 seconds in a mixed solution of 600% of 600% nitric acid and 200% of 55% hydrofluoric acid. Subsequently, the workpiece was anodized in a 15 wt% solution of aqueous sulfuric acid solution at 1 A / dm 2 for 30 minutes, washed with water, and then dyed in an electric furnace. At this time, a solution obtained by mixing CIDisperse red 20g with 100 mL of FLONLUBE-FE-600 (manufacturer: ASAHI GLASS) fluorine oil was placed in an electric furnace and treated at a temperature of 250 ° C. for 20 minutes to expose the workpiece to the vapor of the mixed solution. The specimens thus prepared were dyed in pastel red, and the results of measuring the corrosion resistance, water repellency, and oil repellency of the specimens are shown in Tables 1 and 2.
실시예 3Example 3
ADC12 다이캐스팅 제품을 중성 탈지제로 탈지한 후에 68% 질산 600㏄와 55% 불화수소산 200㏄의 혼합용액에서 상온으로 60초간 침지시켜 표면을 에칭하였다. 이어서 피가공물을 황산수용액 15중량% 용액에 직류 1A/dm2로 30분간 양극산화한 다음 수세 건조 후에, 전기로에서 염색처리하였다. 이때에는 중유 180㏄에 상품명 BLACK MG-FS-20(제조사:DYSTAR)을 20g을 혼합한 용액을 전기로에 넣고 온도 250℃에서 20분간 처리하여 피가공물을 혼합액의 증기에 노출시켰다. 이와 같이 하여 제조된 시편은 진한 흑색으로 염색되었으며, 시편의 내식성 및 발수용, 발유성을 측정한 결과는 표 1 및 2와 같다.The ADC12 diecasting product was degreased with a neutral degreasing agent and then etched at room temperature for 60 seconds in a mixed solution of 600% of 600% nitric acid and 200% of 55% hydrofluoric acid. Subsequently, the workpiece was anodized in a 15 wt% solution of aqueous sulfuric acid solution at 1 A / dm 2 for 30 minutes, washed with water, and then dyed in an electric furnace. At this time, a solution obtained by mixing 20 g of a brand name BLACK MG-FS-20 (manufacturer: DYSTAR) in 180 중 of heavy oil was placed in an electric furnace, and treated at a temperature of 250 ° C. for 20 minutes to expose the workpiece to steam of the mixed solution. The specimens thus prepared were dyed dark black, and the results of measuring the corrosion resistance, water repellency, and oil repellency of the specimens are shown in Tables 1 and 2.
비교예 1 Comparative Example 1
ADC12 다이캐스팅 제품을 중성 탈지제로 탈지한 후에 황산수용액 15중량% 용액에 직류 1A/dm2로 30분간 양극산화한 다음 저온 봉공하였다. 이와 같이 하여 제조된 시편의 내식성 및 발수용, 발유성을 측정한 결과는 표 1 및 표 2와 같다.The ADC12 diecasting product was degreased with a neutral degreasing agent, and then anodized for 30 minutes at 1 A / dm 2 in a 15% by weight aqueous solution of sulfuric acid, followed by cold sealing. The results of measuring the corrosion resistance, water repellency, and oil repellency of the specimens thus prepared are shown in Table 1 and Table 2.
<표 1> 내식성Table 1 Corrosion Resistance
* 내식성은 10%수산화나트륨수용액을 시편에 적하시켜 산화피막이 용해되어 제거되는 시간을 측정하였다. * Corrosion resistance was measured by dropping 10% sodium hydroxide solution onto the specimen and removing the oxide film.
<표 2> 발수성 및 발유성<Table 2> Water and Oil Repellency
* 발수성과 발유성의 척도로 발수접촉각과 발유접촉각을 측정하였다.* Water repellent contact angle and oil repellent contact angle were measured by measures of water repellency and oil repellency.
◎ - 표면에 수적 또는 유적이 전혀 부착되지 않음 ◎-No water drops or remains on the surface
○ - 표면에 수적 또는 유적이 일부 부착됨 ○-Some water droplets or remains are attached to the surface
×- 표면에 수적 또는 유적이 다량 부착됨 ×-large amount of water droplets or remains on the surface
표 1 및 2를 통해 알 수 있는 바와 같이, 본 발명에 의해 처리된 시편은 내식성이 우수하며, 발수성, 발유성도 상당히 우수함을 알 수 있다.As can be seen from Table 1 and 2, the specimen treated by the present invention is excellent in corrosion resistance, it can be seen that the water and oil repellency is also very good.
이상에서와 같이 본 발명에 의하면, 양극산화 처리된 알루미늄합금을 다양한 색상으로 염색하면서 동시에 내식성과 발수성, 발유성을 부여할 수 있으므로, 간단한 공정으로 외관이 미려하며 기타 물성도 우수한 고품질의 제품을 생산할 수 있는 새로운 방식의 알루미늄합금의 염색방법이 제공된다. 또한, 본 발명에 의해 표면처리하는 경우에는 염색과정에서 봉공효과도 얻을 수 있으므로, 별도의 봉공처리를 하지 않아도 되므로 상당히 경제적이다. As described above, according to the present invention, since the anodized aluminum alloy can be dyed in various colors, and at the same time, it can provide corrosion resistance, water repellency, and oil repellency, it is possible to produce a high quality product having a beautiful appearance and other physical properties with a simple process. A new method of dyeing aluminum alloys is provided. In addition, when the surface treatment according to the present invention can also obtain a sealing effect during the dyeing process, it is quite economical because it does not need to perform a separate sealing treatment.
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| JPH0499892A (en) * | 1990-08-13 | 1992-03-31 | Asahi Tec Corp | Production of aluminum product having anodized aluminum film |
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| JPH0499892A (en) * | 1990-08-13 | 1992-03-31 | Asahi Tec Corp | Production of aluminum product having anodized aluminum film |
| JPH05221154A (en) * | 1992-02-12 | 1993-08-31 | Kenichi Furukawa | Sublimating printing method |
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