KR100536884B1 - Zinc-calcium based coloring composition, preparation thereof and parkerizing process using the same - Google Patents

Zinc-calcium based coloring composition, preparation thereof and parkerizing process using the same Download PDF

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KR100536884B1
KR100536884B1 KR10-2002-0048135A KR20020048135A KR100536884B1 KR 100536884 B1 KR100536884 B1 KR 100536884B1 KR 20020048135 A KR20020048135 A KR 20020048135A KR 100536884 B1 KR100536884 B1 KR 100536884B1
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phosphate coating
zinc
same
colorant
calcium
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KR10-2002-0048135A
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KR20020089214A (en
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송길웅
장관섭
김시연
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김시연
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates

Abstract

본 발명은 아연칼슘계 인산염피막 착색제, 그 제조방법 및 이를 이용한 인산염피막 처리공정에 관한 것으로, 인산 100∼200 g/L, 질산 250∼350 g/L, 산화아연 10∼100 g/L, 탄산칼슘 100∼200 g/L, 구연산 10∼50 g/L, 질산니켈 1∼10 g/L 및 황산구리 0.05∼0.1 g/L를 포함하는 인산염피막 착색제, 이를 제조하는 방법 및 이를 이용한 개선된 인산염피막 처리공정을 제공한다.The present invention relates to a zinc calcium-based phosphate coating colorant, a method for preparing the same, and a phosphate coating treatment process using the same. Phosphate coating colorant comprising calcium 100-200 g / L, citric acid 10-50 g / L, nickel nitrate 1-10 g / L and copper sulfate 0.05-0.1 g / L, method for preparing the same and improved phosphate coating using the same Provide a treatment process.

본 발명의 아연칼슘계 인산염피막 착색제를 이용하면 종래의 착색공정 중 유해공정인 6가크롬 침적공정을 폐지할 수 있으므로 인체유해, 환경오염, 장비장애, 작업자의 근무기피 현상을 방지할 수 있다. 또한 6가크롬 침적공정의 생략으로 작업공정 및 작업시간이 대폭 축소되어 작업인원을 감축할 수 있고 폐수처리비, 인건비, 연료비 등을 절감할 수 있을 뿐만 아니라, 종래에 비하여 제조원가가 저렴하면서도 착색제품의 품질은 우수하다.By using the zinc calcium-based phosphate coating colorant of the present invention, it is possible to abolish the hexavalent chromium deposition process, which is a harmful process in the conventional coloring process, so that it is possible to prevent human harm, environmental pollution, equipment failure, and avoidance of workers. In addition, by eliminating the hexavalent chromium deposition process, the work process and working time can be greatly reduced, which can reduce the number of workers, reduce waste water treatment cost, labor cost, fuel cost, etc. The quality is excellent.

Description

아연칼슘계 인산염피막 착색제 조성물, 그 제조방법 및 이를 이용한 인산염피막 처리공정{Zinc-calcium based coloring composition, preparation thereof and parkerizing process using the same}Zinc-calcium-based phosphate coating colorant composition, preparation method thereof and phosphate coating treatment process using the same

본 발명은 아연칼슘계 인산염피막 착색제 조성물, 그 제조방법 및 이를 이용한 인산염피막 처리공정에 관한 것으로, 보다 상세하게는 종래의 착색공정 중 유해공정인 6가크롬 침적공정을 폐지할 수 있는 신규한 인산염피막 착색제 및 이를 통한 인산염피막공정의 개선에 관한 것이다.The present invention relates to a zinc calcium-based phosphate coating colorant composition, a method for preparing the same, and a phosphate coating treatment process using the same, and more particularly, a novel phosphate which can abolish a hexavalent chromium deposition process, which is a harmful process in a conventional coloring process. Coating colorant and the improvement of the phosphate coating process through the same.

금속표면에 화학적 변화(산화, 환원, 치환, 합금 등)를 일으켜 금속화합물의 층을 만드는 것을 화성피막처리라고 하며, 이 중 가장 대표적인 것이 인산염피막처리와 크로메이트처리이다.Chemical conversion (oxidation, reduction, substitution, alloying, etc.) on the metal surface to form a layer of a metal compound is called chemical conversion coating, the most representative of which is phosphate coating and chromate treatment.

인산염피막은 금속을 비금속성과 비전도성을 갖는 새로운 표면을 만드는 것이다. 즉 철강, 알루미늄, 아연, 카드뮴과 그 합금들의 금속상에 인산금속염의 무기결정체나 무정형의 피막을 만드는 것을 말하며, 일명 파카라이징 혹은 본데라이징(미국Amchem사의 상품명)이라고도 한다.Phosphate coatings create a new surface of a metal that is nonmetallic and nonconductive. In other words, the inorganic crystals or amorphous coating of metal phosphate salts on the metals of steel, aluminum, zinc, cadmium and their alloys, also referred to as parkarizing or bondraising (trade name of Amchem, USA).

처리방법이 간편하고 설비도 간단한 인산염피막처리는 생산비용도 저렴하여 경제적인 철강상의 도장전처리이다. 인산염피막처리의 용도는 미국과 일본에서 도장의 하지용으로 약 65% 이상 압도적으로 많고 독일에서는 금속냉간소성 변형가공용으로 많이 활용하고 있다. 그외에 전기절연용, 방식용, 내마모용, 방산제품 플라스틱 라미네이트하지와 금속용사의 전처리로 그 활용이 다양하다.Phosphate coating treatment with simple processing method and simple installation is economical steel pre-painting treatment with low production cost. Phosphate coating treatment is overwhelmingly used in the US and Japan for over 65% of the coating, and in Germany, it is widely used for cold metal deformation processing. In addition, it is widely used for electrical insulation, anticorrosion, abrasion resistance, anti-dispersion plastic laminate base and metal spray pretreatment.

인산염피막처리는 그 피막의 기능을 미세한 요철로 표면적을 넓게 하고 상대면적을 크게 하여 분자내 인력으로 밀착성을 향상시킨다. 그리고 오목부위의 지탱성 즉 앵커효과(Anchoring effect) 또는 기계적인 자물쇠 역할(mechanical lock)과 외부충격으로부터의 완충과 쿠션의 기능을 갖고 있다. 이 피막은 금속 자체의 물리적 성질인 경도, 항장력, 탄성, 자성 등의 변화없이 가소성, 다공성과 흡착성이 우수하다.Phosphate film treatment improves the adhesion of the film by increasing the surface area with fine unevenness and increasing the relative area by increasing the relative area. In addition, it has the function of supporting the concave part, that is, anchoring effect or mechanical lock, cushioning and cushioning from external shock. This film is excellent in plasticity, porosity and adsorption without changing the physical properties of the metal itself, such as hardness, tensile strength, elasticity, and magnetic properties.

그러나, 종래의 인산염피막공정은 6가크롬을 사용하는 낙후된 침적공정을 포함하므로 인체에 유해하고 환경오염을 유발하고 있다. 또한 유해약품 및 유해가스가 발생하여 작업자에게 유해하고 그로 인하여 근무회피 현상이 증폭되며, 폐수처리비용이 과다하게 소요되고 주변장비에 장애가 발생한다.However, since the conventional phosphate coating process includes an outdated deposition process using hexavalent chromium, it is harmful to the human body and causes environmental pollution. In addition, harmful chemicals and harmful gases are generated, which is harmful to workers, thereby amplifying work avoidance, excessive wastewater treatment costs, and disturbance of peripheral equipment.

따라서, 본 발명의 목적은 종래의 유해공정인 6가크롬 침적공정을 폐지할 수 있는 신규한 아연칼슘계 인산염피막 착색제를 제공하는 것이다.Accordingly, an object of the present invention is to provide a novel zinc calcium-based phosphate coating colorant capable of abolishing the hexavalent chromium deposition process which is a conventional harmful process.

본 발명의 다른 목적은 상기 착색제를 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing the colorant.

본 발명의 또 다른 목적은 상기 착색제를 이용한 개선된 인산염피막 처리공정을 제공하는 것이다.Another object of the present invention is to provide an improved phosphate coating process using the colorant.

본 발명의 특징은 종래의 유해공정인 6가크롬 침적공정을 폐지함으로써 환경오염 및 인체유해를 방지하면서 작업공정의 축소 및 경비의 절감을 달성하고, 착색제품의 품질을 향상시키는 것으로, 이를 위하여 인산 100∼200 g/L, 질산 150∼250 g/L, 산화아연 10∼100 g/L, 탄산칼슘 100∼200 g/L, 구연산 10∼50 g/L, 질산니켈 1∼10 g/L 및 황산구리 0.05∼0.1 g/L를 포함하는 아연칼슘계 인산염피막 착색제를 제공한다.A feature of the present invention is to abolish the hexavalent chromium deposition process, which is a conventional hazardous process, to achieve reduction of work process and cost reduction while preventing environmental pollution and human harm, and to improve the quality of colored products. 100-200 g / L, 150-250 g / L nitric acid, 10-100 g / L zinc oxide, 100-200 g / L calcium carbonate, 10-50 g / L citric acid, 1-10 g / L nickel nitrate and A zinc calcium-based phosphate coating colorant containing 0.05 to 0.1 g / L of copper sulfate is provided.

상기 착색제는 소정량의 물에 인산, 질산, 산화아연, 탄산칼슘, 구연산, 질산니켈 및 황산구리 순으로 각각 투입하여 용해시킨 후 물을 보충하여 각 성분의 농도가 상기한 농도가 되도록 제조한다.The colorant is prepared by adding and dissolving phosphoric acid, nitric acid, zinc oxide, calcium carbonate, citric acid, nickel nitrate, and copper sulfate in a predetermined amount of water, and then replenishing water to prepare the concentration of each component at the above-mentioned concentration.

상기한 아연칼슘계 인산염피막 착색제를 적용한 본 발명에 따른 인산염피막 처리공정은 탈지, 수세, 제청, 착색, 수세 및 방청하는 6단계로 구성되며, 6가크롬 침적공정이 포함된 종래의 공정에 비하여 적어도 1개 라인 및 2개 공정 이상을 축소할 수 있다.The phosphate coating treatment process according to the present invention to which the zinc calcium-based phosphate coating colorant is applied is composed of six steps of degreasing, washing, washing, coloring, washing and rusting, compared with a conventional process including a hexavalent chromium deposition process. At least one line and two or more processes can be reduced.

종래의 아연계 인산염피막공정은 탈지, 수세, 건조, 제청, 착색, 수세, 6가크롬 침적, 수세, 스팀 건조, 도유하는 10단계로 구성되어 있으며, 구체적으로 설명하면 다음과 같다.The conventional zinc-based phosphate coating process consists of 10 steps of degreasing, washing with water, drying, dehumidification, coloring, washing with water, hexavalent chromium deposition, washing with water, steam drying, and oiling.

철강제품과 같은 금속 피착물의 표면에는 녹 발생을 방지하기 위해서 광물성이나 식물성 등 여러 종류의 기름이 부착되어 있어서 이를 제거하기 위한 표면처리를 해야 하는데, 이러한 작업을 탈지라고 한다. 통상적으로 콤파운드를 사용하여 탈지하며, 80∼100℃에서 30∼40분간 실시한다.In order to prevent the occurrence of rust, various kinds of oils such as mineral or vegetable are attached to the surface of metal adherends such as steel products, and surface treatment to remove them is called degreasing. Usually, it is degreased using a compound, and it carries out for 30 to 40 minutes at 80-100 degreeC.

탈지가 끝나면 제거된 기름이나 부착물을 세척한다. 세척효율을 높이기 위하여 100℃의 온수를 사용하여 3분간 수세한다. 피착물을 수세한 후 건조한 후 착색을 원활하게 하기 위한 표면처리인 제청을 실시한다. 제청방법 중 샌딩이 가장 효과적이며, 샌딩은 일종의 연마공정으로 금속 표면의 평활성을 부여하는 작업이다. 통상적으로 금강사를 사용하여 50∼60 lb/in2의 압력하에서 실시한다.After degreasing, wash off any oil or attachments that have been removed. In order to increase the washing efficiency, wash with 100 ℃ hot water for 3 minutes. After washing the adherend with water, it is dried and then the surface treatment for smoothing the stain is performed. Sanding is the most effective of the methods of sanding, and sanding is a kind of polishing process that gives the smoothness of the metal surface. Usually, using a steel thread is carried out under a pressure of 50 to 60 lb / in 2 .

제청이 끝나면 냉수로 수세한 후 착색한다. 아연계 인산염피막 착색제는 인산아연(Zn(H2PO4)2), 인산철(Fe(H2PO4)2 ), 인산(H3PO4), 초산아연(Zn(NO3)2) 등으로 구성된다. 80∼90℃에서 30∼40분간 착색하면 회색 내지 진회색의 피막의 형성된다.After finishing the washing, wash with cold water and color. Zinc-based phosphate coating colorant is zinc phosphate (Zn (H 2 PO 4 ) 2 ), iron phosphate (Fe (H 2 PO 4 ) 2 ), phosphoric acid (H 3 PO 4 ), zinc acetate (Zn (NO 3 ) 2 ) And the like. When it is colored for 30 to 40 minutes at 80 to 90 ° C, a gray to dark gray film is formed.

착색이 끝나면 6가크롬 침적공정을 실시한다. 침적공정은 착색단계에서 형성된 피막을 연마, 실링하는 피막조정 공정이며, 내식성의 향상과 건조를 촉진한다. CrO3, CrO3+H3PO4, 중크롬산, 크롬산염과 같은 6가크롬 약제를 사용하여 70∼80℃에서 30초∼1분간 실시한다.After coloring, hexavalent chromium deposition process is performed. The deposition step is a film adjustment step of polishing and sealing the film formed in the coloring step, and promotes improvement of corrosion resistance and drying. Carried CrO 3, CrO 3 + H 3 PO 4, dichromate, 6, such as a chromate of 30 sec at 70~80 ℃ using chromium medicament to 1 minute.

침적공정이 끝나면 온수로 다시 수세하고 70∼80℃에서 40∼50분간 건조한 후 최종적으로 녹 방지를 위해 방청유를 도유하는 방청공정을 실시한다.After the immersion process, rinse again with hot water, dry for 40 to 50 minutes at 70 to 80 ℃, and finally perform an rust prevention process to oil the rust preventive oil to prevent rust.

상기와 같은 종래의 공정은 6가크롬 침적공정을 포함하여 인체에 유해하며, 환경오염을 유발한다. 6가크롬은 널리 알려진 바와 같이 유독물질로서, 흡입하거나 접촉하게 되면 알레르기반응, 폐이상, 신장이상, 비중격천공 등이 발생하며, 발암위험 등이 있다.Such a conventional process is harmful to the human body, including the hexavalent chromium deposition process, causing environmental pollution. Hexavalent chromium is a toxic substance, as it is widely known, and when inhaled or contacted, allergic reactions, lung abnormalities, kidney abnormalities, nasal septum perforation, and carcinogenic risks.

본 발명은 이처럼 유해한 6가크롬을 사용하는 종래의 공정을 개선하기 위한 것으로, 6가크롬 침적공정을 필요로 하지 않는 새로운 착색제를 제공한다.The present invention is to improve the conventional process using such hexavalent chromium, and provides a new colorant that does not require a hexavalent chromium deposition process.

본 발명의 신규한 아연칼슘계 인산염피막 착색제는 인산 100∼200 g/L, 질산 150∼250 g/L, 산화아연 10∼100 g/L, 탄산칼슘 100∼200 g/L, 구연산 10∼50 g/L, 질산니켈 1∼10 g/L 및 황산구리 0.05∼0.1 g/L를 포함한다.The novel zinc calcium-based phosphate coating colorant of the present invention is 100-200 g / L phosphoric acid, 150-250 g / L nitric acid, 10-100 g / L zinc oxide, 100-200 g / L calcium carbonate, 10-50 citric acid g / L, nickel nitrate 1-10 g / L and copper sulfate 0.05-0.1 g / L.

인산과 질산은 산화제, 산화아연은 무기안료, 탄산칼슘과 구연산 및 황산구리는 피막보조제로서 작용하며, 니켈은 촉진제로서 인산아연피막시 결정을 미세하게 만드는 역할을 한다. 본 발명의 착색제는 착색뿐만 아니라 6가크롬 침적공정의 피막조정 역할까지 수행하므로 상기 침적공정이 필요하지 않다. 상기 조성비는 수차례의 실험을 통하여 최적의 농도를 결정한 것이다. 착색시의 주반응은 다음 반응식 1과 같다.Phosphoric acid and silver nitrate are oxidizing agents, zinc oxide is an inorganic pigment, calcium carbonate, citric acid and copper sulfate serve as film aids, and nickel serves as an accelerator to make fine crystals in zinc phosphate coatings. The colorant of the present invention does not need the deposition process because it performs not only the coloring but also the film adjusting role of the hexavalent chromium deposition process. The composition ratio is to determine the optimum concentration through several experiments. The main reaction at the time of coloring is shown in Scheme 1 below.

2H3PO4 + Fe → Fe(H2PO4)2 + H2 2H 3 PO 4 + Fe → Fe (H 2 PO 4 ) 2 + H 2

상기 착색제의 제조방법은 다음과 같다. 첫째, 소정량의 물에 인산을 용해시킨다. 둘째, 상기 용액에 질산을 넣고 용해시킨다. 인산 및 질산은 통상 용액형태의 시약을 사용한다. 셋째, 산화아연을 투입하여 용해시킨다. 넷째, 탄산칼슘을 투입하여 용해시킨다. 탄산칼슘을 급격히 용해시키면 자체 발열하면서 용액이 범람할 수 있으므로 서서히 용해시킨다. 다섯째, 물을 보충하고 구연산을 투입하여 용해시킨다. 여섯째, 질산니켈을 투입하여 용해시킨다. 마직막으로 황산구리을 투입하여 용해시킨 후 물을 보충하여 일정량의 농축액을 제조한다.The manufacturing method of the said coloring agent is as follows. First, phosphoric acid is dissolved in a predetermined amount of water. Second, nitric acid is dissolved in the solution. Phosphoric acid and nitric acid usually use reagents in solution. Third, zinc oxide is added and dissolved. Fourth, calcium carbonate is added to dissolve. Rapid dissolution of calcium carbonate may cause the solution to overflow while self-heating, so dissolve slowly. Fifth, add water and dissolve by adding citric acid. Sixth, nickel nitrate is added to dissolve it. Finally, copper sulfate is added to dissolve and then replenished with water to prepare a certain amount of concentrate.

본 발명에 따른 아연칼슘계 인산염피막 처리공정은 탈지, 수세, 제청, 착색, 수세 및 방청하는 단계를 포함하며, 착색코팅단계에서 상기 신규한 착색제를 사용하여 85∼90℃에서 5∼10분간 착색하며, 제청시에는 금강사 대신 염산용액을 사용할 수 있다. 이와 같은 본 발명의 피막공정은 6개의 주요 공정으로 구성되며, 종래의 인산염 피막공정과 비교하면 4개의 공정이 축소되었다.The zinc calcium-based phosphate coating process according to the present invention includes the steps of degreasing, washing, washing, coloring, washing and rusting, and coloring for 5 to 10 minutes at 85 to 90 ° C. using the novel coloring agent in the coloring coating step. In case of suggestion, hydrochloric acid solution can be used instead of Geumgangsa. Such a coating process of the present invention is composed of six main processes, compared with the conventional phosphate coating process, four processes are reduced.

이하, 본 발명의 바람직한 실시예를 들어 본 발명을 상세히 설명하지만, 본 발명의 권리범위가 하기 실시예에 대해서만 한정되지는 않는다.Hereinafter, the present invention will be described in detail with reference to preferred examples of the present invention, but the scope of the present invention is not limited only to the following examples.

실시예 1Example 1

85% 인산용액 60 kg을 소정량의 물에 넣고 용해시킨 후, 상기 용액에 68% 질산용액 112 kg, 산화아연(ZnO) 20 kg, 탄산칼슘(CaCO3) 52 kg, 구연산(C6H8O7, 99.5% 이상) 7.2 kg, 질산니켈(Ni(NO3)2·6H2O) 2 kg 및 황산구리(Cu2SO4) 30 g을 차례로 투입하면서 용해시킨 후 물을 보충하여 400 L의 착색제 농축액을 제조하였다. 상기 실시예를 물 1L당 투입량(g/L)으로 환산해 보면 다음과 같다. 투입량(kg) 농도 물을 제외한 성분 실제투입량(kg) 물1L당 투입량(g/L) 인산용액 60 85% 인산 51 127.5 질산용액 112 68% 질산 76.16 190.4 산화아연 20 100% 산화아연 20 50 탄산칼슘 52 100% 탄산칼슘 52 130 구연산 7.2 100% 구연산 7.2 18 질산니켈 2 100% 질산니켈 2 5 황산구리 0.03 100% 황산구리 0.03 0.075 * 물을 제외한 성분 인산의 계산 예 : 60 * 0.85 = 51kg* 물1L당 투입량 (g/L) 인산의 계산 예 : 51kg/400L = 127.5 g/LAfter dissolving 60 kg of 85% phosphoric acid solution in a predetermined amount of water, the solution was dissolved in 112 kg of 68% nitric acid solution, 20 kg of zinc oxide (ZnO), 52 kg of calcium carbonate (CaCO 3 ), and citric acid (C 6 H 8). O 7 , 99.5% or more) 7.2 kg, nickel nitrate (Ni (NO 3 ) 2 · 6H 2 O) 2 kg, and copper sulfate (Cu 2 SO 4 ) were added in succession to dissolve it, followed by supplementing with water. Colorant concentrates were prepared. Looking at the above embodiment in terms of the input amount (g / L) per 1L of water is as follows. Input (kg) density Ingredients other than water Actual input amount (kg) Input amount per 1L of water (g / L) Phosphate solution 60 85% Phosphoric Acid 51 127.5 Nitric acid solution 112 68% nitric acid 76.16 190.4 Zinc oxide 20 100% Zinc oxide 20 50 Calcium carbonate 52 100% Calcium carbonate 52 130 Citric acid 7.2 100% Citric acid 7.2 18 Nickel Nitrate 2 100% Nickel Nitrate 2 5 Copper sulfate 0.03 100% Copper sulfate 0.03 0.075 * Example of Calculation of Phosphoric Acid without Water: 60 * 0.85 = 51kg * Calculation of Phosphoric Acid (g / L) per 1L of Water

이와 같이 제조한 착색제를 물과의 혼합비 9:1∼10:1로 희석하여 상술한 탈지, 수세, 제청과정을 거쳐서 착색, 수세 및 방청을 실시하여 탄소강 제품에 인산염피막을 코팅하였고, 착색코팅은 85℃에서 10분간 수행하였다.The colorant thus prepared was diluted in a mixing ratio of 9: 1 to 10: 1 with water and subjected to the above-described degreasing, washing, and dehumidification to perform coloring, washing, and rusting to coat the phosphate coating on the carbon steel product. 10 minutes was performed at 85 degreeC.

실시예 2Example 2

상기 실시예 1에서 제조한 본 발명의 아연칼슘계 인산염피막 착색제와 종래의 약품을 비교하면 다음 표 1과 같다.Comparing the zinc calcium-based phosphate coating colorant of the present invention prepared in Example 1 and the conventional medicine is shown in Table 1 below.

구분division 종래약품Conventional drugs 본발명 착색제Invention colorant 규격standard 내마모성(모래낙하마모시험)Abrasion Resistance (Sand Falling Wear Test) 0.17 kg/㎛0.17 kg / μm 0.59 kg/㎛0.59 kg / μm ASTM D 968∼1993ASTM D 968 ~ 1993 내식성(염수분무시험,24시간 적녹발생유무)Corrosion resistance (salt spray test, red rust occurrence for 24 hours) 이상 있음Has abnormal 이상 없음clear KS D 9502∼1992KS D 9502-1992

상기 시험은 한국화학시험연구원 금속재료센터에 의뢰한 결과이며, 본 발명의 인산염피막 착색제는 종래의 약품에 비하여 내마모성이 3배 이상 높았고, 24시간 염수분무 결과 적녹이 발생하지 않았다.The test was a result of requesting to the Korea Center for Chemical Testing, and the phosphate coating colorant of the present invention was three times higher in wear resistance than conventional chemicals, and red rust did not occur as a result of 24 hours of salt spraying.

구분division 종래공정Conventional Process 본발명공정Invention process 비고Remarks 착색약품 제조비용Production cost of coloring chemicals 9,865,032원9,865,032 KRW 3,200,000원3,200,000 KRW 6,665,032원 절감KRW 6,665,032 폐수처리비용Wastewater Treatment Cost 10,395,000원10,395,000 won 1,160,000원1,160,000KRW 9,235,000원 절감Save 9,235,000 won 연료비용Fuel cost 35,773,782원KRW 35,773,782 20,418,655원KRW 20,418,655 15,355,127원 절감Save 15,355,127 won 계(년간)(Year) 56,033,814원KRW 56,033,814 24,778,655원$ 24,778,655 31,255,159원 절감KRW 31,255,159 작업인시(년간)Work Initiation (Year) 42,029인시(61명)42,029 person (61) 25,217인시(37명)25,217 person (37) 16,812인시(24명) 절감Reduction of 16,812 Persons (24) 내구성durability 미흡Inadequate 우수Great 내구성 4배 향상4 times more durability 작업공정/작업시간Work process / work time 10개 공정/2시간10 processes / 2 hours 6개 공정/1.5시간6 processes / 1.5 hours 4개 공정 축소/25% 단축4 processes reduced / 25% shorter 인체유해도Human body 치명적Fatal 경미Minor 작업환경 개선Work environment improvement 환경오염Pollution 심각serious 경미Minor 환경보호Environmental protection

표 2과 같이 본 발명의 인산염피막공정의 경우 종래의 피막공정에 비하여 약품비, 폐수처리비 및 연료비가 모두 절반 이상 절감되었으며, 또한 작업인시도 24명이나 대폭 절감되었다. 작업공정은 10개에서 6개로 4개 공정이 축소되고, 작업시간은 25% 단축되었으며, 내구성은 4배나 향상되었다. 인체유해도 및 환경오염도 경미하여 작업환경이 개선되었고 환경보호적이다.As shown in Table 2, in the case of the phosphate coating process of the present invention, the chemical cost, wastewater treatment cost, and fuel cost were all reduced by more than half compared to the conventional coating process, and the operation recognition was greatly reduced by 24 people. Work processes have been reduced from 10 to 6, with 4 processes reduced, 25% less time and 4 times more durable. Human injuries and environmental pollution are also mild, improving the working environment and protecting the environment.

이상 설명한 바와 같이, 본 발명의 아연칼슘계 인산염피막 착색제를 이용하면 종래의 유해공정인 6가크롬 침적공정을 폐지할 수 있으므로 인체유해, 환경오염, 장비장애, 작업자의 근무기피 현상을 방지할 수 있다. 또한 6가크롬 침적공정의 생략으로 작업공정 및 작업시간이 대폭 축소되어 작업인원을 감축할 수 있고 폐수처리비, 인건비, 연료비 등을 절감할 수 있다. 또한 본 발명의 인산염피막 착색제는 종래에 비하여 제조원가가 저렴하면서도 착색제품의 품질은 우수하다.As described above, the use of the zinc-calcium phosphate coating colorant of the present invention can abolish the hexavalent chromium deposition process, which is a conventional harmful process, and thus can prevent human health, environmental pollution, equipment failure, and worker's avoidance. have. In addition, by eliminating the hexavalent chromium deposition process, the working process and working time can be greatly reduced, thereby reducing the number of workers and reducing waste water treatment cost, labor cost, and fuel cost. In addition, the phosphate coating colorant of the present invention is cheaper than the conventional manufacturing cost, but the quality of the colored product is excellent.

Claims (3)

인산 100∼200 g/L, 질산 150∼250 g/L, 산화아연 10∼100 g/L, 탄산칼슘 100∼200 g/L, 구연산 10∼50 g/L, 질산니켈 1∼10 g/L 및 황산구리 0.05∼0.1 g/L를 포함하는 아연칼슘계 인산염피막 착색제.100-200 g / L phosphoric acid, 150-250 g / L nitric acid, 10-100 g / L zinc oxide, 100-200 g / L calcium carbonate, 10-50 g / L citric acid, 1-10 g / L nickel nitrate And a zinc calcium-based phosphate coating colorant containing 0.05 to 0.1 g / L of copper sulfate. 삭제delete 탈지, 수세, 제청, 착색, 수세 및 방청하는 단계를 포함하며, 상기 착색단계에서 제 1항의 아연칼슘계 인산염피막 착색제를 사용하는 것을 특징으로 하는 인산염피막 처리방법.Degreasing, rinsing, dehumidifying, coloring, rinsing and rust prevention step, the phosphate coating treatment method characterized by using the zinc calcium-based phosphate coating colorant of claim 1 in the coloring step.
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KR101523546B1 (en) 2015-02-16 2015-05-28 한영선재(주) Method for manufacturing non phosphate coated metal material for cold heading plastic working
CN104630867A (en) * 2015-02-17 2015-05-20 蚌埠市钰诚新材料科技有限公司 High-efficiency electrolytic phosphating solution

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