KR101381849B1 - Corrosion inhibtor composition for picking solution - Google Patents

Corrosion inhibtor composition for picking solution Download PDF

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KR101381849B1
KR101381849B1 KR1020130101470A KR20130101470A KR101381849B1 KR 101381849 B1 KR101381849 B1 KR 101381849B1 KR 1020130101470 A KR1020130101470 A KR 1020130101470A KR 20130101470 A KR20130101470 A KR 20130101470A KR 101381849 B1 KR101381849 B1 KR 101381849B1
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metal
corrosion
corrosion inhibitor
acid
inhibitor composition
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김수원
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남동화학(주)
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2105/00—Erosion prevention

Abstract

The present invention relates to a metal corrosion inhibitor composition and a pickling solution using same, in which metal can obtain a beautiful surface because the metal is not partially melted or corroded when the surface of the metal is subject to a pickling process. The metal corrosion inhibitor composition according to the present invention includes heterocyclic aromatic nitrogen compounds, epichlorohydrin, and an organic compound expressed as RYX. In the RXY, R is C1-C12, Y is H2-H24, and X is a hydroxyl group. The bond between at least two carbons is one of a single bond, a double bond, and a triple bond. [Reference numerals] (AA,JJ) White color degree; (BB) Example 1; (CC) Example 2; (DD) Example 3; (EE) Example 4; (FF) Example 5; (GG) Comparative example 1; (HH) Comparative example 2; (II) Amount of corrosion; (KK) Amount of corrosion (mg/m^2)

Description

금속부식억제 조성물 및 이를 이용한 금속 산세용액{CORROSION INHIBTOR COMPOSITION FOR PICKING SOLUTION}Metal corrosion inhibitor composition and metal pickling solution using same {CORROSION INHIBTOR COMPOSITION FOR PICKING SOLUTION}

본 발명은 금속표면의 산세정시 사용되는 금속부식억제 조성물 및 이를 이용한 금속 산세용액에 관한 것으로, 보다 상세하게는 금속표면의 산세정시, 국부적으로 금속이 용해되거나 부식의 발생이 없어 미려한 표면을 얻을 수 있는 금속부식억제 조성물 및 이를 이용한 금속 산세용액에 관한 것이다.
The present invention relates to a metal corrosion inhibitor composition used in the pickling of the metal surface and a metal pickling solution using the same, and more particularly, when the metal surface is pickled, there is no locally dissolved metal or corrosion occurs to obtain a beautiful surface. It relates to a metal corrosion inhibitor composition and a metal pickling solution using the same.

일반적으로 열연강판과 같이 열처리를 실시한 금속재료의 표면에는 산화물 피막이 부착되어 있으며 후 공정인 냉연 및 도금공정 등에 공급하기 위하여 이러한 산화물 피막을 제거할 필요가 있다. 이들 금속의 표면에 부착된 산화물 피막의 제거에는 일반적으로 염산, 황산, 질산, 불화수소산, 설파믹산(sulfamic acid) 등의 무기산 또는 유기산을 포함하는 산 수용액이 사용된다.In general, the oxide film is attached to the surface of the heat-treated metal material, such as hot-rolled steel sheet, it is necessary to remove the oxide film in order to supply to the cold rolling and plating process, which is a post-process. In general, an acid aqueous solution containing inorganic or organic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and sulfamic acid is used to remove the oxide film attached to the surface of these metals.

이들 산 수용액에 의해 산화물 피막을 제거하는 경우 산화물 피막이나 스케일을 용해시키는 동시에 금속표면이 용해되거나 부식될 수 있어 이를 방지하기 위하여 부식억제제가 사용되고 있다. 그러나 모재보호를 위하여 사용하고 있는 부식억제제의 대부분은 금속의 산세정시에 산세속도를 느리게 하여 작업속도가 느려지는 단점이 있다. 따라서, 완전한 산세를 위해서는 더욱 긴 산세시간이 필요하며 금속의 부식 또한 진행하여 국부적인 과산세 현상이 발생하는 등의 품질 및 작업능률의 저하를 피할 수 없는 실정이다. 따라서, 산세속도에 큰 영향을 주지 않고 금속 모재의 부식을 억제시킬 수 있는 산세방법이 공업적으로 크게 요구되고 있다.When the oxide film is removed by these acid aqueous solutions, corrosion inhibitors are used to prevent the oxide film or scale from dissolving or corroding the metal surface. However, most of the corrosion inhibitors used for the protection of the base metal have a disadvantage of slowing down the pickling speed during metal pickling. Therefore, a longer pickling time is required for complete pickling, and the degradation of quality and work efficiency is inevitable, such as corrosion of the metal and local peroxidation. Therefore, there is a great industrial demand for a pickling method capable of suppressing corrosion of a metal base material without significantly affecting the pickling speed.

종래에는 금속방제의 유효성분으로 유기아민계 화합물을 사용하고 있다. 예를 들어, 일본 특허공개공보 2012-036431호에는 산세정액의 금속부식억제제와 세정방법을 개시하고 있으며, 금속부식억제제에는 제1아민기 및 제2아민기를 가지는 폴리알킬렌 폴리아민의 C3-C5 아실화 유도체를 함유하고 있다.Conventionally, an organic amine compound is used as an active ingredient of metal control. For example, Japanese Patent Laid-Open No. 2012-036431 discloses a metal corrosion inhibitor and a cleaning method of an acid wash liquid, and the metal corrosion inhibitor has a C3-C5 subtype of a polyalkylene polyamine having a first amine group and a second amine group. Contains misfired derivatives.

또한, 미국특허 8,278,258에는 폴리아미노-알데히드 레진과 아세틸레닉 알코올과 에톡시화 지방산 아민, 에톡시화 지방산 아민 염에서 선택된 어느 하나를 포함하는 부식억제제가 개시되어 있다.In addition, US Pat. No. 8,278,258 discloses a corrosion inhibitor comprising any one selected from polyamino-aldehyde resins, acetylenic alcohols, ethoxylated fatty acid amines, and ethoxylated fatty acid amine salts.

이러한 종래의 부식억제제는 금속표면이 부분적으로 용해되거나 부식이 발생되어 금속표면이 거칠게 되어 미세한 요철이 생성될 수 있는 문제점이 있다. 특히, 전기아연도금 강판의 제조시 산세 후에 플래쉬 전기도금 처리를 하여야만 전기도금강판의 표면을 미려하게 제조하는 것이 가능하다.
Such a conventional corrosion inhibitor has a problem in that the metal surface is partially dissolved or corrosion is generated so that the metal surface is coarse to produce fine irregularities. Particularly, the surface of the electroplated steel sheet can be beautifully produced only by performing a flash electroplating treatment after pickling in the production of the galvanized steel sheet.

일본 특허공개공보 제2012-036431호Japanese Patent Laid-Open No. 2012-036431 미국 특허 제8,278,258호U.S. Patent 8,278,258

본 발명은 이러한 문제점을 해결하기 위해 안출된 것으로, 본 발명의 목적은 산세공정에서 금속표면의 국부적인 부식을 방지하여 표면의 요철을 최대한 감소시킬 수 있는 금속부식억제 조성물 및 이를 이용한 금속 산세용액을 제공하는 데 있다.
The present invention has been made to solve this problem, an object of the present invention is to prevent the local corrosion of the metal surface in the pickling process metal corrosion inhibitor composition and metal pickling solution using the same that can reduce the unevenness of the surface as much as possible To provide.

위 목적을 달성하기 위하여 본 발명의 일 실시예에 따른 금속부식억제 조성물은 헤테로 고리 방향족 화합물, 에피크로로히드린 및 RYX로 표현되는 유기 화합물을 포함하며, 상기 RYX에서 R은 C1~C12, Y는 H2~H24, X는 하이드록실기이고, 상기 2이상의 탄소간의 결합은 단일, 2중 및 3중 결합 중 어느 하나인 것을 특징으로 한다.In order to achieve the above object, the metal corrosion inhibitor composition according to an embodiment of the present invention includes a heterocyclic aromatic compound, epichlorohydrin and an organic compound represented by RYX, in which RYX is C1 to C12, Y Is H2 to H24, X is a hydroxyl group, and the bond between two or more carbons is one of single, double and triple bonds.

상기 헤테로 고리 방향족 화합물은 피롤, 이미다졸, 피라졸, 티아졸 및 헥사메틸렌테트라아민 중에서 적어도 어느 하나 이상을 포함할 수 있다. The heterocyclic aromatic compound may include at least one or more of pyrrole, imidazole, pyrazole, thiazole, and hexamethylenetetraamine.

상기 RYX로 표현되는 유기 화합물은 알코올일 수 있다.The organic compound represented by RYX may be an alcohol.

상기 헤테로 고리 방향족 화합물 1몰당 상기 에피크로로히드린은 0.5 몰, 상기 RYX로 표현되는 유기화합물은 0.5~1.4 몰을 포함할 수 있다.0.5 mole of the epichlorohydrin per mole of the heterocyclic aromatic compound, the organic compound represented by the RYX may include 0.5 to 1.4 moles.

또한, 본 발명의 일 실시예에 따른 금속산세용액은 무기산 또는 유기산의 산 수용액에 헤테로 고리 방향족 화합물, 에피크로로히드린 및 RYX로 표현되는 유기 화합물(R은 C1~C12, Y는 H2~H24, X는 하이드록실기)을 포함하는 금속부식억제 조성물을 첨가하여 형성될 수 있다.In addition, the metal pickling solution according to an embodiment of the present invention is an organic compound represented by a heterocyclic aromatic compound, epichlorohydrin and RYX in an aqueous acid solution of an inorganic acid or an organic acid (R is C1 to C12, Y is H2 to H24). , X may be formed by adding a metal corrosion inhibitor composition containing a hydroxyl group).

상기 금속부식억제 조성물의 첨가량은 산 수용액 1리터 당 0.1 ~ 50000mg일 수 있다.
The amount of the metal corrosion inhibitor composition may be 0.1 to 50000 mg per liter of the aqueous acid solution.

본 발명에 의한 금속부식억제 조성물 및 이를 사용한 금속 산세용액에 따르면 다음과 같은 효과가 있다.According to the metal corrosion inhibitor composition and the metal pickling solution using the same according to the present invention has the following effects.

금속, 특히 열연강판의 산세공정 중에 산세시간을 증가시키지 않으면서도 금속 모재의 부식을 방지할 수 있다.Corrosion of the metal base material can be prevented without increasing the pickling time during the pickling process of metal, especially hot rolled steel sheet.

또한, 금속 모재의 표면의 국부적인 부식을 방지하여 표면이 미려한 금속 모재를 얻을 수 있으며, 특히 아연도금강판의 산세과정에서 사용하는 경우에 산세후의 표면이 미려하여 아연도금 전에 플래쉬도금과정을 거치지 않고서도 백색도가 향상된 아연도금강판을 제조할 수 있다.
In addition, it is possible to obtain a metal base material with a beautiful surface by preventing local corrosion of the surface of the metal base material, especially when used in the pickling process of galvanized steel sheet, the surface after pickling is beautiful, without undergoing the flash plating process before galvanizing It is also possible to manufacture a galvanized steel sheet with improved whiteness.

도1은 본 발명에 따른 부식억제제에 대한 부식량 및 백색도 측정결과를 나타낸 그래프이다.1 is a graph showing the results of measurement of corrosion and whiteness of a corrosion inhibitor according to the present invention.

여기서 사용되는 전문용어는 단지 특정 실시예를 언급하기 위한 것이며, 본 발명을 한정하는 것을 의도하지 않는다. 여기서 사용되는 단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다. 명세서에서 사용되는 "포함하는"의 의미는 특정 특성, 영역, 정수, 단계, 동작, 요소 및/또는 성분을 구체화하며, 다른 특정 특성, 영역, 정수, 단계, 동작, 요소, 성분 및/또는 군의 존재나 부가를 제외시키는 것은 아니다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

다르게 정의하지는 않았지만, 여기에 사용되는 기술용어 및 과학용어를 포함하는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 일반적으로 이해하는 의미와 동일한 의미를 가진다. 보통 사용되는 사전에 정의된 용어들은 관련기술문헌과 현재 개시된 내용에 부합하는 의미를 가지는 것으로 추가 해석되고, 정의되지 않는 한 이상적이거나 매우 공식적인 의미로 해석되지 않는다.
Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예에 의한 에 대하여 설명하기로 한다.Hereinafter, with reference to the accompanying drawings will be described with respect to preferred embodiments of the present invention.

본 발명에 따른 금속부식억제 조성물은 헤테로 고리 방향족 화합물(hetero cyclic compound), 에피크로로히드린 및 RYX로 표현되는 유기 화합물을 포함하며, 상기 RYX에서 R은 C1~C12, Y는 H2~H24, X는 하이드록실기이고, 상기 2이상의 탄소간의 결합은 단일, 2중 및 3중 결합 중 어느 하나인 것을 특징으로 한다.The metal corrosion inhibitor composition according to the present invention includes a heterocyclic aromatic compound, an organic compound represented by epichlorohydrin and RYX, in which R is C1 to C12, Y is H2 to H24, X is a hydroxyl group, and the bond between two or more carbons is one of single, double and triple bonds.

상기 헤테로 고리 방향족 화합물(hetero cyclic compound)는 방향족 화합물에 질소가 치환된 형태이며, 예를 들면, 피롤(pyrrole), 이미다졸(imidazole), 피라졸(pyrazole), 티아졸(thiazole), 헥사메틸렌테트라민(hexamethylenetetramine) 등이 사용될 수 있다. 또한, 이들 화합물 중에 선택된 적어도 어느 하나이상이 포함될 수 있다.The heterocyclic aromatic compound (hetero cyclic compound) is a form substituted with nitrogen to the aromatic compound, for example, pyrrole (pyrrole), imidazole (pyrazole), thiazole (thiazole), hexamethylene Tetramine (hexamethylenetetramine) and the like can be used. In addition, at least one selected from these compounds may be included.

상기 RYX로 표현되는 유기화합물은 히드록시기(-OH)를 포함하는 탄화수소로서 바람직하게는 알코올일 수 있다The organic compound represented by RYX may be preferably an alcohol as a hydrocarbon containing a hydroxy group (-OH).

이러한 금속부식억제 조성물은 부식억제 효과를 향상시키기 위해서는 헤테로 고리 방향족 화합물(hetero cyclic compound) 1몰에 대하여 에피크로로히드린 0.5~1.5몰, RYX로 표현되는 유기 화합물 0.7~1.4몰의 비율로 첨가하는 것이 바람직하다. RYX로 표현되는 유기 화합물의 경우 0.7~1.2 몰의 비율로 첨가하는 것이 더욱 바람직하다.In order to improve the corrosion inhibitory effect, the metal corrosion inhibitor composition is added in an amount of 0.5 to 1.5 moles of epichlorohydrin and 0.7 to 1.4 moles of an organic compound represented by RYX to 1 mole of a hetero cyclic compound. It is desirable to. In the case of the organic compound represented by RYX, it is more preferable to add in the ratio of 0.7-1.2 mol.

각 성분의 함량비율을 넘게 되면 금속표면의 국부 부식을 방지하기 위한 충분한 부식억제력을 갖는 것이 어려워진다.When the content ratio of each component is exceeded, it is difficult to have sufficient corrosion inhibitory power to prevent local corrosion of the metal surface.

상기와 같은 금속부식억제 조성물은 물에 잘 용해될 수 있는 고분자 물질에 해당하고, 안정성이 향상되어 사용수명이 증가되어 사용시에 급격하게 금속표면재료가 부식되지 않는 장점이 있다.The metal corrosion inhibitor composition as described above corresponds to a polymer material that can be well dissolved in water, and has an advantage in that stability of the metal surface material is not corroded rapidly during use due to improved stability.

또한, 계면활성제 계통이 아니기 때문에 산세정시 거품의 발생이 미미하며, 수세 공정에서도 거품 발생이 없어 주변 환경오염을 방지할 수 있으며, 고분자물질로 이루어져 있어 산세정시 발생하는 산가스의 발생을 억제하는 효과가 우수하여 작업환경도 개선될 수 있다.In addition, since it is not a surfactant system, bubbles are minimally generated during pickling, and there is no foaming in the washing process, so it is possible to prevent environmental pollution, and since it is made of a polymer material, it is effective to suppress generation of acid gas generated during pickling. Excellent work environment can be improved.

산세정시에는 상기 금속부식억제 조성물을 염산, 황산, 질산, 불화수소산, 설퍼믹 산 등의 무기산과, 구연산, 글루콘산, EDTA 등의 킬레이트제인 유기산의 수용액에 첨가하여 사용하는 것이 가능하다.At the time of pickling, the metal corrosion inhibitor composition may be added to an aqueous solution of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and sulfuric acid, and an organic acid which is a chelating agent such as citric acid, gluconic acid, and EDTA.

이 경우 본 발명에 따른 금속부식억제 조성물은 산세정액 1L에 대해서 0.1~50000mg을 사용하며, 바람직하게는 1~19000mg, 더욱 바람직하게는 1~5000mg을 사용한다. In this case, the metal corrosion inhibitor composition according to the present invention uses 0.1 to 50000 mg per 1 L of pickling solution, preferably 1 to 19000 mg, more preferably 1 to 5000 mg.

금속의 산세정시에 금속 표면의 국부적인 부식을 방지하기 위해 산세정액에는 0.1mg이상의 금속부식억제 조성물이 함유될 필요가 있으며, 50000mg을 초과하는 경우에는 부식방지력이 포화되어 더 이상 증가하지 않으며 제조시 가격상승의 원인이 될 수 있다.In order to prevent local corrosion of the metal surface during pickling of the metal, the pickling liquid needs to contain more than 0.1 mg of the metal corrosion inhibitor composition, and when it exceeds 50000 mg, the corrosion protection is saturated and does not increase any more. May cause a price increase.

본 발명에 따른 금속 산세용액을 이용하여 산세하는 경우 금속표면에 산세용액을 분사하거나 산세용액에 금속모재를 침지시켜 표면에 존재하는 산화물 피막을 제거할 수 있다.
When pickling using the metal pickling solution according to the present invention, the pickling solution may be sprayed onto the metal surface or the metal base material may be immersed in the pickling solution to remove the oxide film present on the surface.

이하 실시예를 통하여 본 발명에 대하여 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail with reference to Examples.

(실시예)(Example)

250ml 용량의 둥근 플라스크에 물 30g을 투입하고, 교반하면서 피롤(Pyrrole) 30g을 투입하였다. 여기에 에탄올 20g을 가하고 완전히 용해될 때까지 교반하였다. 완전히 용해된 후 에피크로로히드린(Epichlorohydrin) 41.3g을 서서히 첨가하고, 약 90℃에서 3시간 동안 유지시켜 부식억제 조성물을 제조하였다. 30 g of water was added to a 250 ml round flask, and 30 g of pyrrole was added while stirring. 20 g of ethanol was added thereto and stirred until completely dissolved. After completely dissolved, 41.3 g of epichlorohydrin was slowly added, and maintained at about 90 ° C. for 3 hours to prepare a corrosion inhibiting composition.

이와 마찬가지로, 각 성분의 함량을 조절하여 하기 표1과 같이 동일한 방법으로 부식억제물을 제조하였다.Likewise, by controlling the content of each component to prepare a corrosion inhibitor in the same manner as shown in Table 1.

구분division 헤테로 고리 방향족
질소 화합물Heterocyclic aromatic
Nitrogen compound 에탄올
(g)ethanol
(g) 물
(g)water
(g) 에피크로로히드린
(g)Epichlorohydrin
(g) 온도
(℃)Temperature
(° C) 시간
(hr)time
(hr) 실시예1Example 1 피롤 30g30 g of pyrrole 2020 3030 41.341.3 9090 33 실시예2Example 2 이미다졸 40gImidazole 40g 2525 3333 3333 9090 33 실시예3Example 3 피라졸 25g25 g of pyrazole 2525 3737 3737 9090 33 실시예 4Example 4 티아졸 25gThiazole 25g 3030 3232 3232 9090 33 실시예 5Example 5 헥사메칠렌테트라민 50gHexamethylenetetramine 50g 2020 3333 3333 9090 33 실시예 6Example 6 트리아진Triazine 1515 2727 3030 9090 33

본 발명의 실시예에 따른 금속부식억제제에 대하여 국부부식을 평가하기 위하여 부식량 측정 및 백색도 측정을 하였다.Corrosion amount and whiteness were measured to evaluate local corrosion of the metal corrosion inhibitor according to the embodiment of the present invention.

부식량 측정은 염산 100g과 제1 철이온 50g, 제2 철이온 1g을 포함한 산세정 수용액 1L에 부식억제제를 약 100mg을 첨가한 후 약 80℃까지 온도를 상승시킨 후에 열간압연강판을 180번의 연마지로 연마한 시편을 10분간 침지하였다.Corrosion measurement was performed by adding 100 mg of a corrosion inhibitor to 1 L of an acid-cleaned aqueous solution containing 100 g of hydrochloric acid, 50 g of ferrous ions, and 1 g of ferric ions, raising the temperature to about 80 ° C, and polishing the hot rolled steel plate 180 times. The specimen ground with paper was immersed for 10 minutes.

이 때 측정되는 부식량은 시험편의 단위 면적당 침지하기 전과 후의 중량차이로 표현될 수 있다.The amount of corrosion measured at this time can be expressed as the weight difference before and after immersion per unit area of the test piece.

한편 백색도 측정은 산세정액 1L에 금속부식억제제를 약 100mg을 첨가하고 80℃까지 가열한 후 산화피막이 있는 열간압연강판을 침지해 산화철을 완전히 제거한 후 수세하고 전기아연도금 후 MINOLTA 측색색차계로 측정하였다. On the other hand, whiteness was measured by adding 100mg of metal corrosion inhibitor to 1L of pickling solution, heating it to 80 ℃, immersing the hot rolled steel plate with oxide film, completely removing iron oxide, washing with water, and electroplating and measuring with MINOLTA colorimetry.

표2및 도1에 부식량 측정 및 백색도 측정 결과를 나타내었다. 여기서 비교예1은 부식억제제를 첨가하지 않고 실시예와 같은 방법으로 부식량 및 백색도를 측정하였고, 비교예2는 남동화학에서 판매하고 있는 제품명 '안티코'라는 기존의 폴리에틸렌글리콜, 하이드록시아세트산나트륨, 이미다졸을 포함하는 종래의 부식억제제를 100mg을 첨가하여 부식량 및 백색도를 측정하였다.Table 2 and Figure 1 shows the results of the measurement of corrosion and whiteness. Here, Comparative Example 1 measured the amount of corrosion and whiteness by the same method as Example without adding a corrosion inhibitor, and Comparative Example 2 was a conventional polyethylene glycol, sodium hydroxyacetate, which is sold by Namdong Chemical. , 100 mg of a conventional corrosion inhibitor including imidazole was added to measure the amount of corrosion and whiteness.

구분division 부식량(mg/m2)Corrosion amount (mg / m 2 ) 백색도Whiteness 실시예1Example 1 0.50.5 8787 실시예2Example 2 0.10.1 8989 실시예3Example 3 0.30.3 8888 실시예4Example 4 0.20.2 8888 실시예5Example 5 1One 8686 비교예1Comparative Example 1 3030 8383 비교예2Comparative Example 2 1010 8484

표2및 도1에 나타난 바와 같이 실시예1 내지 실시예5를 부식억제제로 첨가한 경우 부식억제제를 첨가하지 않은 비교예 1 과 종래의 부식억제제를 첨가한 비교예2보다 발생되는 부식량이 현저하게 감소된 것을 알 수 있었다. 또한 전기아연도금을 수행하였을 때도 백색도가 향상되며, 표면이 미려하게 도금이 된 것을 알 수 있었다.
As shown in Table 2 and FIG. 1, when Examples 1 to 5 were added as corrosion inhibitors, the amount of corrosion generated was significantly higher than that of Comparative Example 1 without addition of corrosion inhibitors and Comparative Example 2 with addition of conventional corrosion inhibitors. It was found to be reduced. In addition, the degree of whiteness is improved when the electroplating is performed, and the surface was beautifully plated.

이상 본 발명의 실시예를 설명하였지만, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명이 그 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다.While the present invention has been described in connection with certain exemplary embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변경된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.
It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (6)

헤테로 고리 방향족 질소 화합물, 에피크로로히드린 및 RYX로 표현되는 유기 화합물을 포함하며,
상기 RYX에서 R은 C1~C12, Y는 H2~H24, X는 하이드록실기이고
상기 2이상의 탄소간의 결합은 단일, 2중 및 3중 결합 중 어느 하나인 것을 특징으로 하는 금속부식억제 조성물을 무기산 또는 유기산의 산 수용액에 첨가하여 제조되는 아연도금강판용 산세정액으로서,
상기 헤테로 고리 방향족 화합물 1몰당 상기 에피크로로히드린은 0.5 몰, 상기 RYX로 표현되는 유기화합물은 0.5~1.4 몰을 포함하는 것을 특징으로 하는 아연도금강판용 산세정액.
Heterocyclic aromatic nitrogen compounds, epichlorohydrin and organic compounds represented by RYX,
In RYX, R is C1-C12, Y is H2-H24, and X is a hydroxyl group.
As the bond between the two or more carbons is a pickling liquid for galvanized steel sheet prepared by adding a metal corrosion inhibitor composition, characterized in that any one of a single, double and triple bond to an acid solution of an inorganic acid or an organic acid,
The epichlorohydrin is 0.5 mole per mole of the heterocyclic aromatic compound, and the organic compound represented by the RYX is 0.5-1.4 mole acid pickling solution for galvanized steel sheet.
청구항 1에 있어서,
상기 헤테로 고리 방향족 질소 화합물은 피롤, 이미다졸, 피라졸, 티아졸 및 헥사메틸렌테트라아민 중에서 적어도 어느 하나 이상을 포함하는 것을 특징으로 하는 금속부식억제 조성물.
The method according to claim 1,
The heterocyclic aromatic nitrogen compound metal corrosion inhibitor composition comprising at least one of pyrrole, imidazole, pyrazole, thiazole and hexamethylenetetraamine.
청구항 1에 있어서,
상기 RYX로 표현되는 유기 화합물은 알코올인 것을 특징으로 하는 금속부식억제 조성물.

The method according to claim 1,
The organic compound represented by the RYX is metal corrosion inhibitor composition, characterized in that the alcohol.

삭제delete 삭제delete 청구항 1에 있어서,
상기 금속부식억제 조성물의 첨가량은 산 수용액 1리터 당 0.1 ~ 50000mg인 것을 특징으로 하는 금속 산세용액.
The method according to claim 1,
The metal acid pickling solution, characterized in that the addition amount of the metal corrosion inhibitor composition is 0.1 ~ 50000mg per liter of the aqueous acid solution.
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KR20190076109A (en) * 2017-12-22 2019-07-02 주식회사 포스코 Etching composition and pickling composition comprising the etching composition
KR102457605B1 (en) * 2022-01-28 2022-10-20 김영량 Phosphate free corrosion inhibitor composition for acid cleaning

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KR20000063056A (en) * 1999-03-31 2000-10-25 고사이 아끼오 Corrosion inhibitor for metals, cleaning liquid composition comprising the same and cleaning method using the same
KR20120091145A (en) * 2009-09-30 2012-08-17 이 아이 듀폰 디 네모아 앤드 캄파니 An anticorrosion coating composition, an anticorrosion film and an anticorrosive article

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KR20120091145A (en) * 2009-09-30 2012-08-17 이 아이 듀폰 디 네모아 앤드 캄파니 An anticorrosion coating composition, an anticorrosion film and an anticorrosive article

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KR20190076109A (en) * 2017-12-22 2019-07-02 주식회사 포스코 Etching composition and pickling composition comprising the etching composition
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