KR20100097781A - Method for preparing corrosion inhibition type orsconductive coating agent unessential pre-treatment by moisture removal reaction of rust - Google Patents

Method for preparing corrosion inhibition type orsconductive coating agent unessential pre-treatment by moisture removal reaction of rust Download PDF

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KR20100097781A
KR20100097781A KR1020090016601A KR20090016601A KR20100097781A KR 20100097781 A KR20100097781 A KR 20100097781A KR 1020090016601 A KR1020090016601 A KR 1020090016601A KR 20090016601 A KR20090016601 A KR 20090016601A KR 20100097781 A KR20100097781 A KR 20100097781A
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polyaniline
acid
coating agent
doped
base
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KR101115414B1 (en
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이동복
허재철
정병남
정창남
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이동복
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

PURPOSE: A method for manufacturing an eco-friendly coating agent is provided to prevent the corrosion by forming a protective layer which is stable to air, water, and a salt and to obtain excellent corrosion resistance without a pre-treatment by forming a very strong polyurethane inactive film. CONSTITUTION: A method for manufacturing an eco-friendly coating agent using a moisture removal reaction of a rust layer comprises a step(S10) of manufacturing a polyaniline salt by doping hydracids on polyaniline and a step(S20) of synthesizing the polyaniline salt and isocyanate. A method for manufacturing the polyaniline comprises: a doping step(S11) of synthesizing the polyaniline, which is doped with the hydracids, by filtering the polyaniline after an addition reaction of the hydracids and an oxidant in an aniline aqueous solution; a first washing step(S12) of washing the synthesized polyaniline using distilled water and methanol; a dedoping step(S13) of neutralizing the polyaniline which is doped with the hydracids using a base; a second washing step(S14) of washing a filtered polyaniline base using the distilled water and the methanol; and a dispersion step(S15) of dispersing the polyaniline base on a solvent.

Description

녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법{METHOD FOR PREPARING CORROSION INHIBITION TYPE ORSCONDUCTIVE COATING AGENT UNESSENTIAL PRE-TREATMENT BY MOISTURE REMOVAL REACTION OF RUST} TECHNICAL FOR PREPARING CORROSION INHIBITION TYPE ORSCONDUCTIVE COATING AGENT UNESSENTIAL PRE-TREATMENT BY MOISTURE REMOVAL REACTION OF RUST}

본 발명은 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 관한 것으로, 보다 상세하게는 폴리아닐린이 녹이 생기는 과정에 직접 참여하여 공기와 물, 염(salt)에 상하지 않는 보호층을 형성함으로써 부식반응의 진행을 방해하도록 함과 동시에 습기를 경화제로 하는 변성 폴리우레탄 수지가 녹층의 들뜬 부분, 기포형태로 부식된 결정입계에 침입해 있는 수분을 찾아 깊숙한 순수 철 표면까지 침투해서 물분자와 반응하면서 CO2가 가스화로 방출되어 녹 그 자체를 고정시키고 아주 강한 폴리우레탄의 불활성 피막을 형성함으로써 전처리 공정이 필요없고 우수한 방청효과를 얻을 수 있는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 관한 것이다.The present invention relates to a method for preparing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment step due to the water removal reaction of the rust layer. By forming a protective layer that prevents the corrosion reaction from progressing, the modified polyurethane resin, which uses moisture as a curing agent, finds moisture that penetrates the excited part of the rust layer and the grain boundary that is corroded in the form of bubbles. CO 2 is released by gasification as it penetrates and reacts with water molecules to fix the rust itself and form an inert coating of very strong polyurethane, eliminating the need for a pretreatment process. Relates to a method for producing a corrosion-resistant conductive eco-friendly coating All.

일반적으로 산업부분에서 철강을 포함한 금속재의 부식은 가장 심각한 문제를 야기하며, 철강재의 부식으로 재산 및 산업에 막대한 손실을 가져오고 있고, 또한 매년 철 생산의 1/2을 부식된 철 구조물의 교체에 이용된다.In general, the corrosion of metals, including steel, in the industrial sector causes the most serious problems. The corrosion of steel materials causes enormous losses to property and industry, and also annually produces one-half of the production of iron for the replacement of corroded steel structures. Is used.

이러한 금속재 특히, 철강재의 부식을 방지하기 위하여 다양한 방청도료가 사용되고 있다. 통상의 방청도료는 통상 방청안료인 금속과 이들 금속을 부착시키고 부식 환경으로부터 피착물을 보호하는 유기고분자수지/무기질수지로 구성되어 있으며, 방청안료로 Pb와 Cr등을 사용하는 산화피막 형성형과 Zn을 사용하는 희생양극 방식형이 종래로부터 많이 이용되고 있다.In order to prevent corrosion of such metals, especially steel, various antirust coatings are used. Conventional rust preventive paint is composed of metal which is rust preventive pigment and organic polymer resin / inorganic resin which adheres these metals and protects the deposits from corrosive environment. A sacrificial anode type using Zn has been widely used in the past.

그러나, 산화피막 형성형 방청도료의 방청안료는 중금속으로 분류되어 용출시 또 다른 환경문제를 야기하는 단점을 가지고 있으며, 희생양극 방식형은 방청안료의 이온화 경향을 이용한 전기화학적 희생방식으로 방청기능을 발휘하는 것이므로시간이 흐를수록 희생 금속이 부식되어감에 따라 희생방식 성능이 떨어져 철강재료에 대한 보호작용을 장기간 할 수 없는 단점을 가지고 있다.However, rust preventive pigments of anodized rust preventive paints are classified as heavy metals and have the disadvantage of causing further environmental problems when eluted. The sacrificial anode type anticorrosive paints have an anti-corrosive function by using an ionization tendency of rust preventive pigments. Since the sacrificial metal is corroded over time, the sacrificial anticorrosive performance is poor, and thus the protective action on the steel material cannot be performed for a long time.

또한, 기존의 도장이나 코팅방식은 샌드블래스터, 그라인더 등으로 녹층을 제거하는 전처리 과정이 필요하기 때문에 금속분진 및 소음이 발생될 뿐만 아니라 전처리 공정에 따라 전체 도장비의 20~30%정도의 추가비용이 발생되는 문제점을 갖는다.In addition, the existing coating or coating method requires a pretreatment process to remove the rust layer with sandblaster, grinder, etc., which not only generates metal dust and noise, but also adds 20 ~ 30% of the total cost of equipment according to the pretreatment process. This has a problem that arises.

본 발명은 상기와 같은 점을 인식하여 안출된 것으로 본 발명의 목적은 폴리아닐린이 녹이 생기는 과정에 직접 참여하여 공기와 물, 염(salt)에 상하지 않는 보호층을 형성함으로써 부식반응의 진행을 방해하도록 함과 동시에 습기를 경화제로 하는 변성 폴리우레탄 수지가 녹층의 들뜬 부분, 기포형태로 부식된 결정입계에 침입해 있는 수분을 찾아 깊숙한 순수 철 표면까지 침투해서 물분자와 반응하면서 CO2가 가스화로 방출되어 녹 그 자체를 고정시키고 아주 강한 폴리우레탄의 불활성 피막을 형성함으로써 전처리 공정이 필요없고 우수한 방청효과를 얻을 수 있는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법을 제공하기 위한 것이다.The present invention was conceived by recognizing the above point, the object of the present invention is to directly participate in the process of the polyaniline rust to form a protective layer that does not damage the air, water, salt (salt) to prevent the progress of the corrosion reaction At the same time, the modified polyurethane resin, which uses moisture as a curing agent, finds moisture that penetrates the crystalline layer, which is corroded in the form of bubbles in the rust layer, penetrates deep into the pure iron surface, reacts with water molecules, and releases CO 2 by gasification. It is possible to fix the rust itself and to form a very strong inert coating of polyurethane. It is to provide.

상기와 같은 목적을 달성하기 위하여 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은, 폴리아닐린에 수소산을 도핑시켜 폴리아닐린염을 제조하는 과정과, 폴리아닐린염과 이소시아네이트를 합성시키는 과정을 포함하는 것을 특징으로 한다.In order to achieve the above object, a method of preparing a corrosion inhibiting conductive eco-friendly coating agent that does not require a pretreatment process due to a water removal reaction of a rust layer according to the present invention includes a process of preparing a polyaniline salt by doping polyaniline with hydrochloric acid, and polyaniline salt. And a process of synthesizing isocyanate with.

또한 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은, 아닐린이 함유된 아닐린 수용액에 수소산과 산화제를 첨가 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하는 도핑과정과, 합성된 폴리아닐린을 증류수와 메탄올로 세척하여 과량의 용매를 감압 여과로 제거하는 1차세척과정과, 수소산으로 도핑된 폴리아닐린 수용액에서 염기를 사용하여 중화시킨 후 감압여과시키는 도핑과정과,In addition, according to the present invention, a method of preparing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process by removing the moisture of the rust layer according to the present invention is performed by adding and reacting a hydrochloric acid and an oxidizing agent to an aniline-containing aqueous solution of aniline, and then filtering the resulting polyaniline into hydrochloric acid. Doping process for synthesizing doped polyaniline, first washing process for washing the synthesized polyaniline with distilled water and methanol to remove excess solvent by reduced pressure filtration, and neutralizing with base in aqueous polyaniline solution doped with hydrochloric acid Filtering doping process,

여과된 폴리아닐린 염기를 증류수와 메탄올로 세척하는 2차세척과정과, 폴리 아닐린 염기를 용매에 분산시키는 분산과정을 포함하는 것을 특징으로 한다.And a secondary washing process of washing the filtered polyaniline base with distilled water and methanol, and a dispersion process of dispersing the polyaniline base in a solvent.

또한, 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은, 상기 수소산은 염산, 파라톨루엔슬폰산, 부틸나프탈렌슬폰산, 도데실벤젠슬폰산 중 어느 하나인 것을 특징으로 한다.In addition, the method for producing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process by the water removal reaction of the rust layer according to the present invention, the hydrochloric acid is any of hydrochloric acid, paratoluenesulfonic acid, butyl naphthalenesulfonic acid, dodecylbenzenesulfonic acid It is characterized by one.

또한, 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은, 상기 도핑과정은, 0.05M 내지 1M의 아닐린이 함유된 아닐린 수용액 1ℓ에 0.3M 내지1M의 염산과, 산화제로서 0.5M 내지 1.5M 암모늄퍼설페이트를 1 내지 2시간에 걸쳐 천천히 첨가하고, -10℃ 내지 80℃에서 30분 내지 24시간 동안 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하고, 상기 디도핑과정은, 도핑된 폴리아닐린을 염기로 NaOH, Na2CO3, NH4OH, Et3N중 어느 하나가 1% 내지 20% 정도로 용해되어 있는 수용액에 첨가한 뒤, 생성된 혼합물을 6시간 정도 반응시킨 후, 디도핑된 폴리아닐린 염기를 감압여과로 여과시며, 상기 분산과정은, 폴리에틸렌글리콜(PEG:polythyleneglycol), 폴리에틸렌글리콜 모노메틸 에테르(PEG-OMe: polythyleneglycol monomethyl ether), 폴리비닐알콜 (PVA: polyvinyl alcohol), 디옥틸프탈레이트(DOP), 유기알킬아민 중에서 하나 또는 2이상이 7중량%가 용매인 물이나 알코올에 용해된 용액에 폴리아닐린 염기를 혼합시키는 것을 특징으로 한다.In addition, the method of producing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process by the water removal reaction of the rust layer according to the present invention, the doping process, 0.3M to 1M in 1L of aniline aqueous solution containing 0.05M to 1M Hydrochloric acid and 0.5 M to 1.5 M ammonium persulfate as an oxidizing agent were slowly added over 1 to 2 hours, reacted at -10 ° C to 80 ° C for 30 minutes to 24 hours, and the resulting polyaniline was filtered and doped with hydrogen acid. Synthesized polyaniline, and the de-doping process was performed by adding doped polyaniline to an aqueous solution in which any one of NaOH, Na 2 CO 3, NH 4 OH, and Et 3 N was dissolved in an amount of about 1% to 20%, and then the resulting mixture was added for 6 hours. After the degree of reaction, the doped polyaniline base is filtered by vacuum filtration, and the dispersion process is polyethylene glycol (PEG: polythyleneglycol), polyethylene glycol monomethyl ether (PEG-OMe: polythyleneglycol monomethyl ether), polyvinyl alcohol (PVA: polyvinyl alcohol), dioctylphthalate (DOP), organoalkylamine, or one or two or more in a solution dissolved in water or alcohol in which 7% by weight is a solvent It is characterized by mixing the polyaniline base.

상기와 같은 구성에 의하여 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은 폴리아닐린이 녹이 생기는 과정에 직접 참여하여 공기와 물, 염(salt)에 상하지 않는 보호층을 형성함으로써 부식반응의 진행을 방해하도록 함과 동시에 습기를 경화제로 하는 변성 폴리우레탄 수지가 녹층의 들뜬 부분, 기포형태로 부식된 결정입계에 침입해 있는 수분을 찾아 깊숙한 순수 철 표면까지 침투해서 물분자와 반응하면서 CO2가 가스화로 방출되어 녹 그 자체를 고정시키고 아주 강한 폴리우레탄의 불활성 피막을 형성함으로써 전처리 공정이 필요없고 우수한 방청효과를 얻을 수 있는 장점을 갖는다.By the above configuration, the method for preparing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process due to the water removal reaction of the rust layer according to the present invention does not injure the air, water, and salt by directly participating in the process of forming polyaniline. By forming a protective layer that prevents the corrosion reaction from progressing, the modified polyurethane resin, which uses moisture as a curing agent, finds moisture that penetrates the excited part of the rust layer and the grain boundary that is corroded in the form of bubbles. By penetrating and reacting with water molecules, CO 2 is released by gasification to fix rust itself and to form an inert coating of very strong polyurethane, which does not require a pretreatment process and has an excellent antirust effect.

이하에서는 도면 및 실시예를 참조하여 본 발명에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법을 보다 상세하게 설명하기로 한다.Hereinafter, with reference to the drawings and examples will be described in more detail a method for producing a corrosion-resistant conductive eco-friendly coating agent does not require a pretreatment process by the water removal reaction of the rust layer according to the present invention.

도면을 참조하면 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은 폴리아닐린 제조과정(S10)과, 폴리아닐린과 이소시아네이트를 합성시키는 합성과정(S20)과, 경화제 및 첨가제를 첨가하는 과정(S30)을 포함하여 구성된다.Referring to the drawings, a method of preparing a corrosion-inhibiting conductive eco-friendly coating agent that does not require a pretreatment process due to a water removal reaction of a rust layer according to an embodiment of the present invention includes a polyaniline manufacturing process (S10) and a synthetic process of synthesizing polyaniline and isocyanate ( S20) and the step of adding the curing agent and the additive (S30).

상기 폴리아닐린 제조과정(S10)은 폴리아닐린에 수소산을 도핑시켜 폴리아닐린염을 제조하는 과정으으로 도핑과정(S11), 1차세척과정(S12), 디도핑과정(S13), 2차세척과정(S14), 분산과정(S15)을 포함하여 구성된다.The polyaniline manufacturing process (S10) is a process of preparing a polyaniline salt by doping polyacid with hydrogen acid. The doping process (S11), the first washing process (S12), the dedoping process (S13), and the second washing process (S14). , Including the dispersion process (S15).

상기 도핑과정(S11)은 아닐린이 함유된 아닐린 수용액에 수소산과 산화제를 첨가 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하는 과정이다. 상기 수소산으로는 염산, 파라톨루엔슬폰산, 부틸나프탈렌슬폰산, 도데실벤젠슬폰산 중 어느 하나가 사용되어 질 수 있으나 염산이 가장 바람직하다.The doping process (S11) is a process of synthesizing polyaniline doped with hydrogen acid by filtration of the resulting polyaniline after addition and reaction of hydrogen acid and an oxidizing agent to the aqueous solution of aniline containing aniline. As the hydrochloric acid, any one of hydrochloric acid, paratoluenesulfonic acid, butylnaphthalenesulfonic acid, and dodecylbenzenesulfonic acid may be used, but hydrochloric acid is most preferred.

수소산으로 염산을 이용하는 경우 0.05M 내지 1M의 아닐린이 함유된 아닐린 수용액 1ℓ에 0.3M 내지1M의 염산과, 산화제로서 0.5M 내지 1.5M 암모늄퍼설페이트를 1 내지 2시간에 걸쳐 천천히 첨가하고, -10℃ 내지 80℃에서 30분 내지 24시간 동안 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하게 된다.When using hydrochloric acid as hydrochloric acid, 0.3 M to 1 M hydrochloric acid and 0.5 M to 1.5 M ammonium persulfate as an oxidizing agent were slowly added to 1 L of an aqueous solution of aniline containing 0.05 M to 1 M of aniline over -1 hour, -10 After the reaction for 30 minutes to 24 hours at ℃ to 80 ℃ the resulting polyaniline is filtered to synthesize a polyaniline doped with hydrogen acid.

상기 1차세척과정(S12)은 상기 도핑과정(S11)에서 합성된 폴리아닐린을 증류수와 메탄올로 세척하여 과량의 용매를 감압 여과로 제거하는 과정이다.The first washing process (S12) is a process of removing the excess solvent by vacuum filtration by washing the polyaniline synthesized in the doping process (S11) with distilled water and methanol.

상기 디도핑과정(S13)은 수소산으로 도핑된 폴리아닐린 수용액에서 염기를 사용하여 중화시킨 후 감압여과시키는 과정이다. 디도핑과정(S13)은 도핑된 폴리아닐린이 완전히 건조되기 전에 이루어지는 것이 바람직하며, 도핑된 폴리아닐린을 염기로 NaOH, Na2CO3, NH4OH, Et3N중 어느 하나가 1% 내지 20% 정도로 용해되어 있는 수용액에 첨가한 뒤, 생성된 혼합물을 6시간 정도 반응시킨 후, 디도핑된 폴리아닐린 염기를 감압여과로 여과시켜 이루어진다.The dedoping process (S13) is a process of neutralization using a base in a polyaniline aqueous solution doped with hydrochloric acid and then filtration under reduced pressure. The dedoping process (S13) is preferably performed before the doped polyaniline is completely dried, and the doped polyaniline is added to an aqueous solution in which any one of NaOH, Na 2 CO 3, NH 4 OH, and Et 3 N is dissolved in an amount of about 1% to 20%. Thereafter, the resulting mixture is allowed to react for about 6 hours, followed by filtration of the doped polyaniline base by vacuum filtration.

상기 2차세척과정(S14)은 여과된 폴리아닐린 염기를 증류수와 메탄올로 세척 하는 과정이다.The second washing process (S14) is a process of washing the filtered polyaniline base with distilled water and methanol.

상기 분산과정(S15)은 폴리아닐린 염기를 용매에 분산시키는 과정이다. 즉, 상기 분산과정(S15)은 폴리에틸렌글리콜(PEG:polythyleneglycol), 폴리에틸렌글리콜 모노메틸 에테르(PEG-OMe: polythyleneglycol monomethyl ether), 폴리비닐알콜 (PVA: polyvinyl alcohol), 디옥틸프탈레이트(DOP), 유기알킬아민 중에서 하나 또는 2이상이 7중량%가 용매인 물이나 알코올에 용해된 용액에 폴리아닐린 염기를 혼합시킨다. 용매로는 에탄올이 바람직하다.The dispersing process (S15) is a process of dispersing a polyaniline base in a solvent. That is, the dispersion process (S15) is polyethylene glycol (PEG: polythyleneglycol), polyethylene glycol monomethyl ether (PEG-OMe: polythyleneglycol monomethyl ether), polyvinyl alcohol (PVA: polyvinyl alcohol), dioctylphthalate (DOP), organic One or more of the alkylamines is mixed with a polyaniline base in a solution dissolved in water or alcohol in which 7% by weight is a solvent. Ethanol is preferred as the solvent.

상기와 같이 제조된 폴리아닐린 염은 폴리아닐린이 녹이 생기는 과정에 직접 참여하여 공기와 물, 염(salt)에 상하지 않는 보호층을 형성함으로써 부식반응의 진행을 방해함으로써 부식을 억제시키게 된다.The polyaniline salt prepared as described above directly inhibits the corrosion by inhibiting the progress of the corrosion reaction by forming a protective layer that does not damage the air, water, and salts by directly participating in the process of the polyaniline rusting.

표1은 상기와 같이 제조된 폴리아닐린의 도판트별 전도도 및 에탄올에 유기알킬아민 중 하나인 N-메틸피롤리돈을 용해시킨 용액과, 에탄올에 N-메틸피롤리돈과 트리에탄올아민(TEA)을 용해시킨 용액에 대한 용해도를 정리한 것이다.Table 1 shows the conductivity of polyaniline prepared as described above and the solution of N-methylpyrrolidone which is one of organic alkylamines in ethanol and N-methylpyrrolidone and triethanolamine (TEA) in ethanol. The solubility of the prepared solution is summarized.

도판트Dopant 전도도
(S/Cm)conductivity
(S / Cm) 용해도(g/l)Solubility (g / l)
비고
Remarks N-메틸피롤리돈N-methylpyrrolidone N-메틸피롤리돈+TEAN-methylpyrrolidone + TEA 염산Hydrochloric acid 0.80.8 0.1750.175 9.789.78 파라톨루엔슬폰산Paratoluenesulfonic acid 2.42.4 1.8571.857 5.875.87 부틸나프탈렌슬폰산Butyl naphthalenesulfonic acid 1.51.5 5.2485.248 9.459.45 도데실벤젠슬폰산Dodecylbenzenesulfonic acid 0.70.7 0.0450.045 6.546.54

상기 합성과정(S20)은 상기와 같이 제조된 폴리아닐린염과 이소시아네이트를 배합 합성시키는 과정이다. 이소시아네이트는 습기를 경화제로 하여 녹층의 들뜬 부분, 기포형태로 부식된 결정입계에 침입해 있는 수분을 찾아 깊숙한 순수 철 표면까지 침투해서 물분자와 반응하면서 CO2가 가스화로 방출되어 녹 그 자체를 고정시키고 아주 강한 폴리우레탄의 불활성 피막을 형성하게 된다.The synthesis process (S20) is a process of compounding the polyaniline salt and isocyanate prepared as described above. Isocyanate uses moisture as a curing agent to find moisture that penetrates the crystalline layer of the rust layer and the grains corroded in the form of bubbles, penetrates deep into the pure iron surface, reacts with water molecules, and releases CO 2 by gasification to fix the rust itself. And an inert coating of very strong polyurethane.

상기 첨가제 및 경화제 첨가과정(S30)은 코팅제의 경화를 촉진시키기 위한 경화제 및 습윤제, 소포제, 흐름성 및 표면조절제, 자외선 안정제, 산화방지제, 필러 등을 첨가하여 코팅제의 성능을 향상시키기 위한 과정이다.The additive and curing agent addition process (S30) is a process for improving the performance of the coating agent by adding a curing agent and a wetting agent, an antifoaming agent, a flow and surface control agent, a UV stabilizer, an antioxidant, a filler and the like to promote the curing of the coating agent.

도 2는 상기와 같이 제조된 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 의해 제조된 코팅제로 강판을 코팅시킨 상태를 도시한 사진이고, 도 3은 본 발명에 따른 코팅제가 코팅된 상태에서 자외선 노출을 시험하는 상태를 나타낸 사진이며, 도 4는 본 발명에 따른 코팅제가 코팅된 상태에서 박리 시험한 결과를 나타낸 사진이다.Figure 2 shows a state in which the steel sheet is coated with a coating prepared by the method for producing a corrosion-resistant conductive eco-friendly coating agent does not require a pretreatment process by the water removal reaction of the rust layer according to an embodiment of the present invention prepared as described above It is a photograph, Figure 3 is a photograph showing a state of testing the UV exposure in the coating state is coated with a coating according to the present invention, Figure 4 is a photograph showing the results of the peel test in a state in which the coating according to the present invention is coated.

앞에서 설명되고 도면에 도시된 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법은 본 발명을 실시하기 위한 하나의 실시예에 불과하며, 본 발명의 기술적 사상을 한정하는 것으로 해석되어서는 안된다. 본 발명의 보호범위는 이하의 특허청구범위에 기재된 사항에 의해서만 정하여지며, 본 발명의 요지를 벗어남이 없이 개량 및 변경된 실시예는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 자명한 것인 한 본 발명의 보호범위에 속한다고 할 것이다.The method for preparing a corrosion inhibiting conductive eco-friendly coating agent, which does not require a pretreatment process due to the water removal reaction of the rust layer described above and illustrated in the drawings, is merely one embodiment for carrying out the present invention, which is intended to limit the technical spirit of the present invention. It should not be construed as. The scope of protection of the present invention is defined only by the matters set forth in the claims below, and the embodiments which have been improved and changed without departing from the gist of the present invention will be apparent to those skilled in the art. It will be said to belong to the protection scope of the present invention.

도 1은 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법을 도시한 흐름도1 is a flow chart illustrating a method for preparing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process due to the water removal reaction of the rust layer according to an embodiment of the present invention.

도 2는 상기와 같이 제조된 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 의해 제조된 코팅제로 강판을 코팅시킨 상태를 도시한 사진Figure 2 shows a state in which the steel sheet is coated with a coating prepared by the method for producing a corrosion-resistant conductive eco-friendly coating agent does not require a pretreatment process by the water removal reaction of the rust layer according to an embodiment of the present invention prepared as described above Picture

도 3은 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 의해 제조된 코팅제가 코팅된 상태에서 자외선 노출을 시험하는 상태를 나타낸 사진3 is a photograph showing a state in which UV exposure is tested in a coated state prepared by a method of preparing a corrosion-protective conductive eco-friendly coating agent that does not require a pretreatment process due to a moisture removal reaction of a rust layer according to an embodiment of the present invention.

도 4는 본 발명의 일실시예에 따른 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법에 의해 제조된 코팅제가 코팅된 상태에서 박리 시험한 결과를 나타낸 사진Figure 4 is a photograph showing the results of peeling test in a state in which the coating prepared by the method of producing a corrosion-protective conductive eco-friendly coating agent is not required for the pretreatment process by the water removal reaction of the rust layer according to an embodiment of the present invention

Claims (4)

폴리아닐린에 수소산을 도핑시켜 폴리아닐린염을 제조하는 과정과,Preparing a polyaniline salt by doping polyaniline with hydrogen acid, 폴리아닐린염과 이소시아네이트를 합성시키는 과정을 포함하는 것을 특징으로 하는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법.A method for producing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process by removing water from the rust layer, characterized in that it comprises a process of synthesizing a polyaniline salt and an isocyanate. 제1항에 있어서,The method of claim 1, 아닐린이 함유된 아닐린 수용액에 수소산과 산화제를 첨가 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하는 도핑과정과,A doping process of synthesizing the polyaniline doped with hydrogen acid by filtering the resulting polyaniline by adding and reacting the hydrogen acid and the oxidizing agent to an aqueous solution of aniline containing aniline, 합성된 폴리아닐린을 증류수와 메탄올로 세척하여 과량의 용매를 감압 여과로 제거하는 1차세척과정과,Washing the synthesized polyaniline with distilled water and methanol to remove excess solvent by vacuum filtration; 수소산으로 도핑된 폴리아닐린 수용액에서 염기를 사용하여 중화시킨 후 감압여과시키는 디도핑과정과,A de-doping process in which a polyaniline aqueous solution doped with hydrochloric acid is neutralized with a base and filtered under reduced pressure; 여과된 폴리아닐린 염기를 증류수와 메탄올로 세척하는 2차세척과정과,A secondary washing process in which the filtered polyaniline base is washed with distilled water and methanol, 폴리아닐린 염기를 용매에 분산시키는 분산과정을 포함하는 것을 특징으로 하는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법.A method for producing a corrosion-resistant conductive eco-friendly coating agent that does not require a pretreatment process by a water removal reaction of a rust layer, characterized in that it comprises a dispersion process of dispersing a polyaniline base in a solvent. 제1항 또는 2항에 있어서,The method according to claim 1 or 2, 상기 수소산은 염산, 파라톨루엔슬폰산, 부틸나프탈렌슬폰산, 도데실벤젠슬폰산 중 어느 하나인 것을 특징으로 하는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법.The hydrogen acid is hydrochloric acid, paratoluenesulfonic acid, butylnaphthalenesulfonic acid, dodecyl benzenesulfonic acid, characterized in that any one of the method of producing a corrosion-resistant conductive eco-friendly coating agent by the water removal reaction of the rust layer is not necessary. 제2항에 있어서,The method of claim 2, 상기 도핑과정은, 0.05M 내지 1M의 아닐린이 함유된 아닐린 수용액 1ℓ에 0.3M 내지1M의 염산과, 산화제로서 0.5M 내지 1.5M 암모늄퍼설페이트를 1 내지 2시간에 걸쳐 천천히 첨가하고, -10℃ 내지 80℃에서 30분 내지 24시간 동안 반응시킨 후 생성된 폴리아닐린을 여과해서 수소산으로 도핑된 폴리아닐린을 합성하고,In the doping process, 0.3 M to 1 M hydrochloric acid and 0.5 M to 1.5 M ammonium persulfate as an oxidizing agent were slowly added to 1 L of an aniline solution containing 0.05 M to 1 M of aniline over 1 to 2 hours. After the reaction for 30 minutes to 24 hours at -80 ℃ to filter the resulting polyaniline to synthesize a polyaniline doped with hydrogen acid, 상기 디도핑과정은, 도핑된 폴리아닐린을 염기로 NaOH, Na2CO3, NH4OH, Et3N중 어느 하나가 1% 내지 20% 정도로 용해되어 있는 수용액에 첨가한 뒤, 생성된 혼합물을 6시간 정도 반응시킨 후, 디도핑된 폴리아닐린 염기를 감압여과로 여과시며,In the dedoping process, the doped polyaniline is added to an aqueous solution in which any one of NaOH, Na 2 CO 3, NH 4 OH, and Et 3 N is dissolved in an amount of about 1% to 20%, and the resulting mixture is reacted for about 6 hours. The doped polyaniline base is filtered by vacuum filtration, 상기 분산과정은, 폴리에틸렌글리콜(PEG:polythyleneglycol), 폴리에틸렌글리콜 모노메틸 에테르(PEG-OMe: polythyleneglycol monomethyl ether), 폴리비닐알콜 (PVA: polyvinyl alcohol), 디옥틸프탈레이트(DOP), 유기알킬아민 중에서 하나 또는 2이상이 7중량%가 용매인 물이나 알코올에 용해된 용액에 폴리아닐린 염기를 혼합시키는 것을 특징으로 하는 녹층의 수분 제거 반응으로 전처리 공정이 필요없는 부식억제형 전도성 친환경 코팅제의 제조 방법.The dispersion process is one of polyethylene glycol (PEG: polythyleneglycol), polyethylene glycol monomethyl ether (PEG-OMe: polythyleneglycol monomethyl ether), polyvinyl alcohol (PVA: polyvinyl alcohol), dioctylphthalate (DOP), organic alkylamine Or a polyaniline base in a solution dissolved in water or an alcohol in which at least 2 wt% of the solvent is 7% by weight.
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KR101374723B1 (en) * 2014-01-09 2014-03-19 (주)에스시아이 Method for manufacturing corrosion inhibition type conductive coating agent that removal of rust and moisture is unnecessary
JPWO2020195905A1 (en) * 2019-03-27 2020-10-01

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KR100525772B1 (en) 2002-07-03 2005-11-03 삼화페인트공업주식회사 Anti-corrosion paint for steel by polyaniline
KR20040045972A (en) * 2002-11-26 2004-06-05 주식회사 포스코 A Method for Preparing Corrosion Resistive Coating Composition Comprising Water Dispersed Polyaniline and A Steel Sheet Having Corrosion Resistive Coating Prepared From The Composition
KR100547285B1 (en) * 2004-05-20 2006-01-31 학교법인 포항공과대학교 Process for the preparation of high glutinous conductive polyaniline blend and conductive coating solution comprising the blend
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KR101374723B1 (en) * 2014-01-09 2014-03-19 (주)에스시아이 Method for manufacturing corrosion inhibition type conductive coating agent that removal of rust and moisture is unnecessary
JPWO2020195905A1 (en) * 2019-03-27 2020-10-01
WO2020195905A1 (en) * 2019-03-27 2020-10-01 出光興産株式会社 Solution composition containing conductive polymer
CN113573899A (en) * 2019-03-27 2021-10-29 出光兴产株式会社 Solution composition containing conductive polymer

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