KR20010024643A - Chromium-free corrosion protection agent and method for providing corrosion protection - Google Patents
Chromium-free corrosion protection agent and method for providing corrosion protection Download PDFInfo
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- KR20010024643A KR20010024643A KR1020007005290A KR20007005290A KR20010024643A KR 20010024643 A KR20010024643 A KR 20010024643A KR 1020007005290 A KR1020007005290 A KR 1020007005290A KR 20007005290 A KR20007005290 A KR 20007005290A KR 20010024643 A KR20010024643 A KR 20010024643A
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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
- C23C22/40—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 containing molybdates, tungstates or vanadates
- C23C22/44—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 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
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- 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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
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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
- 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
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C23C22/40—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 containing molybdates, tungstates or vanadates
- C23C22/42—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 containing molybdates, tungstates or vanadates containing also phosphates
Abstract
아연도금강 혹은 합금 아연도금강 혹은 알루미늄 표면을 처리하기 위한 크롬 무함유 수성 방식제를 제공한다. 이 방식제는 그 필수성분으로서,Provides chromium-free, water-based anticorrosive for treating galvanized steel or alloy galvanized steel or aluminum surfaces. This anticorrosive is an essential ingredient
(가) 티타늄 (IV) 및/또는 지르코늄 (IV)의 헥사플루오로 음이온 0.5 ∼ 10 g/l,(A) 0.5 to 10 g / l hexafluoro anion of titanium (IV) and / or zirconium (IV),
(나) 바나듐 이온 5 ∼ 15 g/l,(B) 5-15 g / l of vanadium ions,
(다) 코발트 이온 0.5 ∼ 2 g/l, 및(C) 0.5-2 g / l cobalt ions, and
(라) 인산 30 ∼ 150 g/l.(D) phosphoric acid 30-150 g / l.
이 방식제는 유기피막 형성 성분, 특히 폴리아크릴레이트로 된 것을 함유하는 것이 바람직하다. 더욱이 이 방식제는 전도성 안료를 함유하는 것이 바람직하다. 이 방식제는 금속 스트립의 방식처리에 특히 적합하며, 바람직하게는 약 0.5 ∼ 약 5 g/m2의 건조중량 층이 표면에 형성되도록 도포한다.It is preferable that this anticorrosive agent contains an organic film formation component, especially what consists of polyacrylates. Moreover, it is preferable that this anticorrosive contains a conductive pigment. This anticorrosive is particularly suitable for anticorrosive treatment of metal strips and is preferably applied such that a dry weight layer of about 0.5 to about 5 g / m 2 is formed on the surface.
Description
일시적인 방식을 위한 대책으로서, 예컨대 아연도금 혹은 합금 아연도금 강대 (steel strip)가 보다 가혹한 부식조건에 노출된다고 예상될 경우에는 이들을 단순히 기름칠을 한다거나 인화처리 혹은 크롬화 처리를 한다. 그러나 염분함유 해양 분위기에서 선박으로 수송한다거나 열대성 환경하에 보관할 경우 등의 매우 부식성인 조건의 경우에서는 이들 대책은 적절하지 못하다. 선행기술에 개시된 가장 양호한 일시적인 방식대책은 크롬화 공정인데, 이 공정에서는 일반적으로 크롬을 약 5 ∼ 약 15 mg/m2의 비율로 함유한 크롬 (III) 및/또는 크롬 (VI)으로 금속표면을 도포한다. 크롬 화합물의 공지의 독성학적 문제로 인하여 작업 안정성, 생태학 및 필요로 하는 폐기대책의 관점에서 이 공정은 불리하며 경비가 많이 소요된다. 더욱이 크롬화 강금속은, 한편으로는 세척액의 크롬 오염을 유발하고, 다른 한편으로는 금속표면의 전체 면적에 걸쳐 일반적으로 인화처리가 되지 않기 때문에 그 다음의 인화 처리에는 적합하지 않다. 일시적인 방식을 위한 다른 대책으로서의 인화 처리는 바람직하지 못한 방식으로 금속표면의 외관을 변화시킨다. 더욱이 인화 처리 공정은 기재에 따라서는 인화 처리후의 추가적인 활성화 단계 및 일반적으로 비활성화 단계를 필요로 하기 때문에 장치비가 소요된다. 비활성화는 크롬함유 처리용액를 사용하여 빈번히 실시되므로 크롬함유 처리용액을 사용하는 것과 관련하여 앞서 설명한 바와 같은 여러 가지 단점이 생기기도 한다. 금속 스트립은 자동차 및 가전 산업분야에서 가공처리되는 경향이 증가하고 있는데, 이들 스트립은 스트립 제조업자가 이미 방식층을 형성해 둔 것이다. 이들 타입의 공지된 재료로서는, 예컨대 상품명으로서 Durasteel, Bonazinc 및 Durazinc 등이 있다. 이들은 전환층, 예컨대 크롬화층 혹은 안화층위에 얇은 유기 코우팅을 가지고 있다. 이 유기 코우팅은 에폭시 또는 폴리우레탄 수지, 폴리아미드 및 폴리아크릴레이트 등의 폴리머 시스템으로 되어 있다. 실리카, 아연분말 및 카본 블랙 등의 고체 첨가제는 방식효과를 개선하고 두께가 약 0.3 내지 약 5 ㎛인 층으로 도포된 금속부를 그 전기전도에 의해 전기용접 및 전해 래커 (lacquer) 처리할 수 있도록 한다. 기재를 도포하고 있는 표면은 일반적으로 장비면에서 비용이 소요되는 2단계 공정으로 실시되는데, 첫번째로는 무기 전환층을 생성시킨 다음, 두번째 단계에서는 유기 폴리머 피막을 도포한다.As a countermeasure for a temporary approach, for example, galvanized or alloyed galvanized steel strips are simply oiled, ignited or chromed if they are expected to be exposed to more severe corrosive conditions. However, these measures are not appropriate in the case of very corrosive conditions, such as when transporting by ship in a salty marine atmosphere or when stored under a tropical environment. The best temporary anticorrosion measures disclosed in the prior art is the chromization process, in which the metal surface is generally chromium (III) and / or chromium (VI) containing chromium in a ratio of about 5 to about 15 mg / m 2 . Apply. Due to the known toxicological problems of chromium compounds, this process is disadvantageous and costly in view of working stability, ecology and the disposal measures required. Furthermore, chromium steels are unsuitable for subsequent ignition because they, on the one hand, cause chromium contamination of the wash liquor and, on the other hand, are not generally ignited over the entire area of the metal surface. As a countermeasure for the temporary mode, the ignition process changes the appearance of the metal surface in an undesirable way. Furthermore, the printing process requires equipment costs because, depending on the substrate, an additional activation step and generally a deactivation step after the printing process are required. Deactivation is frequently carried out using chromium-containing treatment solutions, which may lead to several disadvantages as described above with regard to the use of chromium-containing treatment solutions. Metal strips tend to be processed in the automotive and consumer electronics industries, where strip strips already have anticorrosive layers. Known materials of these types include, for example, Durasteel, Bonazinc and Durazinc as trade names. They have a thin organic coating on the conversion layer, such as a chromized layer or a stabilized layer. This organic coating consists of a polymer system such as epoxy or polyurethane resin, polyamide and polyacrylate. Solid additives such as silica, zinc powder and carbon black improve the anticorrosive effect and allow metal parts coated in layers with a thickness of about 0.3 to about 5 μm to be subjected to electrowelding and electrolytic lacquer treatment by their conduction. . The surface to which the substrate is applied is generally carried out in a two-step process, which is expensive in terms of equipment. First, an inorganic conversion layer is produced, and then, in the second step, an organic polymer film is applied.
종래의 기술에서는 무기전환 처리 및 유기 폴리머에 의한 표면도포를 단일의 처리액을 사용하여 실시하는 단일단계 표면 도포법을 개시하고 있다. 예컨대 US-A-5 344 504에는 붕소, 실리콘, 티타늄 및 지르코늄의 테트라 혹은 헥사플루오르산 혹은 플루오르화 수소산 0.1 ∼ 10 g/l, 코발트, 구리, 철, 망간, 니켈, 스트론튬 혹은 아연 등의 양이온 약 0.015 ∼ 약 6 g/l 및 폴리아크릴산, 폴리메타크릴산 및 이들의 에스테르로 된 군으로부터 선택되는 폴리머 약 3 g/l의 조성을 가진 처리액과 기재를 접촉시키는 아연도금강의 표면 코우팅법이 개시되어 있다. 이 처리액의 pH는 약 4 내지 약 5의 범위이다.The prior art discloses a single step surface coating method in which inorganic conversion treatment and surface coating with an organic polymer are carried out using a single treatment liquid. US Pat. No. 5,344,504, for example, contains about 0.1 to 10 g / l of tetra or hexafluoric acid or hydrofluoric acid of boron, silicon, titanium and zirconium, cobalt, copper, iron, manganese, nickel, strontium or zinc. Disclosed is a surface coating method of a galvanized steel in which a substrate is brought into contact with a treatment liquid having a composition of 0.015 to about 6 g / l and a polymer of about 3 g / l selected from the group consisting of polyacrylic acid, polymethacrylic acid and esters thereof. It is. The pH of this treatment liquid is in the range of about 4 to about 5.
WO 95/14117에 있어서도 아연 또는 알루미늄 혹은 이들의 합금의 표면 처리법이 개시되어 있다. 여기서는 표면을 금속 옥시이온 및 기타의 이온으로부터 생성된 착화합물을 함유하는 pH 3 미만의 처리액과 기재를 접촉시키고 있다. 금속 옥시이온은 몰리브데이트, 텅스테이트 및 바나데이트로부터 선택된다. 기타의 이온은 인, 알루미늄, 실리콘, 망간, 마그네슘, 지르코늄, 티타늄, 주석, 세륨 및 니켈로부터 선택된다. 더욱이 처리액에는 용액중에서 기타 성분과 상용성이 있는 유기피막 형성 성분을 함유한다. 폴리아크릴레이트류, 특히 예컨대 메틸 메타크릴레이트, n-부틸 아크릴레이트, 히드록시에틸 아크릴레이트 및 글리세린프로폭시 트리아크릴레이트 등은 피막형성 성분으로서 적합하다.WO 95/14117 also discloses a surface treatment method of zinc or aluminum or alloys thereof. Here, the substrate is brought into contact with a treatment liquid having a pH of less than 3 containing a complex formed from metal oxy ions and other ions. Metal oxyions are selected from molybdate, tungstate and vanadate. Other ions are selected from phosphorus, aluminum, silicon, manganese, magnesium, zirconium, titanium, tin, cerium and nickel. Furthermore, the treatment liquid contains an organic film-forming component that is compatible with the other components in the solution. Polyacrylates, in particular methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate, glycerin propoxy triacrylate and the like are suitable as film forming components.
EP-A-694 593에서는 단량체 그룹 0.5 내지 8%가 알루미늄, 칼슘, 세륨, 코발트, 몰리브덴, 실리콘, 바나듐, 지르코늄, 티타늄, 3가 크롬 및 아연의 금속이온, 착양이온 혹은 음이온을 생성할 수 있는 유기 폴리머 또는 공중합체, 산화제 (예: 질산, 과염소산 혹은 과산화 수소) 및 산 (예: 옥살산, 아세트산, 붕산, 인산, 황산, 질산 혹은 염산)을 함유하는 처리액에 의한 금속표면의 처리를 권장하고 있다.In EP-A-694 593, 0.5 to 8% of monomer groups are capable of producing metal ions, cationic ions or anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zirconium, titanium, trivalent chromium and zinc. Treatment of metal surfaces by treatment solutions containing organic polymers or copolymers, oxidizing agents (e.g. nitric acid, perchloric acid or hydrogen peroxide) and acids (e.g. oxalic acid, acetic acid, boric acid, phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid) is recommended. have.
WO 95/04169에는 적어도 다음의 각종 성분, 즉 티타늄, 지르코늄, 하프늄, 실리콘, 알루미늄 및 붕소의 플루오르 착화합물, 코발트, 마그네슘, 망간, 아연, 니켈, 주석, 구리, 지르코늄, 철 및 스트론튬으로부터 선택되는 금속의 이온, 인산염 혹은 포스폰산염 및 수용성 또는 불분산성 유기피막 형성 성분을 함유하는 처리액에 의한 금속표면의 처리가 개시되어 있다.WO 95/04169 contains at least the following various components: fluorine complexes of titanium, zirconium, hafnium, silicon, aluminum and boron, cobalt, magnesium, manganese, zinc, nickel, tin, copper, zirconium, iron and strontium The treatment of metal surfaces with a treatment liquid containing ions, phosphates or phosphonates and water-soluble or non-dispersible organic film-forming components is disclosed.
EP-A-792 922에는 피막형성 유기 폴리머와, (i) 희토류 금속과 알칼리 금속의 에스테르 또는 알칼리 토금속 바나데이트로부터 선택되는 염과, (ii) 알칼리 토금속의 붕산염을 함유하는 크롬 무함유의 부식억제용 코우팅 조성물이 개시되어 있다. 바람직한 폴리머의 예로서는 폴리이미드계 에폭시드 등의 에폭시드류, 폴리우레탄, 아크릴 폴리머 및 알키드계 시스템을 들고 있다. 따라서 이 표면 코우팅용 조성물은 유기피막 형성 성분외에도 적어도 붕산염 및 기타의 성분, 즉 바나데이트를 함유해야만 한다.EP-A-792 922 contains chromium-free corrosion inhibitors containing an encapsulating organic polymer, (i) salts selected from rare earth metals and alkali metal esters or alkaline earth metal vanadates, and (ii) borate salts of alkaline earth metals. A coating composition for use is disclosed. Examples of preferred polymers include epoxides such as polyimide epoxides, polyurethanes, acrylic polymers, and alkyd-based systems. Thus, the surface coating composition should contain at least borate and other components, ie vanadate, in addition to the organic coating-forming component.
이들 선행기술이 있음에도 불구하고 적어도 무기 비활성화층과 바람직하게는 유기 폴리머층을 금속표면에 동일한 처리단계에서 도포하는 금속표면의 개선된 표면 코우팅을 아직까지도 필요로 하고 있다. 이 코우팅에 의하여 도포된 금속 스트립으로 된 구조부의 펀칭 아웃과 성형을 용이하게 할 수 있어야 한다. 더욱이 각 층은, 예컨대 차체 혹은 가전제품 등의 제품을 조립한 후에 실시되는 세척 및 인화처리 등의 손상을 주지않는 종래의 처리단계에서도 견디어 낼 수 있고, 또한 직접 래커처리를 할 수 있는 것이어야 한다. 환경을 보호하고 작업 안전성의 이유로 해서 크롬 화합물을 사용하지 않고, 또한 가능하다면 유기용제를 사용하지 않고서도 처리공정을 실시할 수 있어야 한다.Despite these prior arts there is still a need for improved surface coating of metal surfaces which at least applies an inorganic deactivation layer and preferably an organic polymer layer to the metal surface in the same processing step. It should be possible to facilitate punching out and forming of structural parts made of metal strips applied by this coating. Furthermore, each layer must be able to withstand conventional processing steps that do not cause damage such as cleaning and ignition after the assembly of a product such as a car body or a home appliance, and also can be directly lacquered. It should be possible to carry out the treatment process without the use of chromium compounds and, where possible, without the use of organic solvents for environmental protection and operational safety reasons.
본 발명은 크롬 무함유 방식제 및 용융침지 아연도금강 혹은 전기 아연도금강, 합금 아연도금강 또는 알루미늄 및 이들의 합금의 표면을 처리하는 방식방법에 관한 것이다. 특히, 본 발명은 컨베이어 시스템을 사용하는 표면처리에 적합하다.The present invention relates to a chromium-free anticorrosive and an anticorrosive method for treating the surface of a hot dip galvanized steel or electro galvanized steel, an alloy galvanized steel or aluminum and alloys thereof. In particular, the present invention is suitable for surface treatment using a conveyor system.
본 발명은 물과,The present invention is water,
(가) 티타늄 (IV) 및/또는 지르코늄 (IV)의 헥사플루오로 음이온 0.5 ∼ 10 g/l,(A) 0.5 to 10 g / l hexafluoro anion of titanium (IV) and / or zirconium (IV),
(나) 바나듐 이온 5 ∼ 15 g/l,(B) 5-15 g / l of vanadium ions,
(다) 코발트 이온 0.5 ∼ 2 g/l,(C) 0.5-2 g / l cobalt ions,
(라) 인산 30 ∼ 150 g/l, 및(D) 30 to 150 g / l phosphoric acid, and
(마) 임의로 기타 활성물질 혹은 보조물질을 함유한 크롬 무함유 방식제에 관한 것이다.(E) Chromium-free anticorrosive, optionally containing other active substances or auxiliary substances.
상기한 성분 (가) ∼ (다)의 바람직한 농도범위는 다음과 같다.Preferred concentration ranges of the above-mentioned components (A) to (C) are as follows.
(가) 티타늄 (IV) 및/또는 지르코늄 (IV)의 헥사플루오로 음이온 1 ∼ 3 g/l,(A) 1 to 3 g / l hexafluoro anion of titanium (IV) and / or zirconium (IV),
(나) 바나듐 이온 6 ∼ 10 g/l,(B) 6-10 g / l vanadium ions,
(다) 코발트 이온 0.6 ∼ 1.2 g/l.(C) cobalt ion 0.6-1.2 g / l.
방식제의 pH 범위는 0.5 ∼ 2.5, 바람직하게는 1.0 ∼ 2.1, 특히 1.4 ∼ 2.0이다. 이러한 종류의 물질은 금속표면을 용해하므로 작업용 처리욕중에는 피처리 기재로부터 생성되는 추가의 양이온을 함유하여도 좋다. 이러한 예로서는 아연 및 알루미늄과 임의로 기타의 합금성분, 예컨대 철, 니켈 및 구리를 들 수 있다.The pH range of an anticorrosive is 0.5-2.5, Preferably it is 1.0-2.1, Especially 1.4-2.0. This kind of material dissolves the metal surface, so the working bath may contain additional cations generated from the substrate to be treated. Examples include zinc and aluminum and optionally other alloying components such as iron, nickel and copper.
당업자라면 상기한 성분들이 서로간에 반응에 참여하며, 처리액중에서 상기한 pH 조건하에서 안정한 형태로 존재한다는 것을 인식하게 된다. 예컨대 헥사플루오로 음이온은 간혹 유리산 형태로 존재할 때도 있다. 바나듐 이온은 대개 VO2 +양이온으로 존재하지만, 때로는 축합하여 폴리양이온 (polycation)을 생성하기도 한다.Those skilled in the art will recognize that the above components participate in the reaction with each other and are present in a stable form in the treatment liquid under the above pH conditions. For example, hexafluoro anions sometimes exist in free acid form. Vanadium ions are typically present in the VO 2 + cation, but sometimes it may produce a condensed polycation (polycation).
이 방식제는 기타의 활성물질 혹은 보조물질을 함유해도 좋은데, 예컨대 추가의 활성물질로서는 약 0.5 ∼ 약 10 g/l, 특히 약 1 ∼ 약 5 g/l의 비착화(非錯化) 플루오라이드 이온을 함유해도 좋다. 이들을 플루오르화 수소산, 혹은 알칼리 금속 또는 암모늄 플루오라이드 등의 가용성 플루오라이드로 하여 도입한다. 사용된 화합물과는 독립하여 플루오라이드 이온은 대체적으로 방식제의 pH에서 미해리 플루오르화 수소산으로서 존재한다.The anticorrosive may contain other active substances or auxiliary substances, for example, from about 0.5 to about 10 g / l, in particular about 1 to about 5 g / l, of non-complexing fluorides as further active substances. It may contain ions. These are introduced as soluble fluorides such as hydrofluoric acid or alkali metal or ammonium fluoride. Independent of the compound used, fluoride ions are generally present as undissociated hydrofluoric acid at the pH of the anticorrosive.
더욱이 이 방식제에는 추가적인 활성물질로서 전도성 안료를 약 1 ∼ 약 30 g/l, 특히 약 10 ∼ 약 25 g/l 함유해도 좋다. 이렇게 함으로써 방식제로 처리된 물질의 전기 용접능과 전해 래커 (lacquer)처리능을 개선한다. 적당한 전도성 안료의 예로서는 인화철, 주석 혹은 안티몬으로 도핑된 황산 바륨, 카본 블랙, 흑연, 황화 몰리브덴 등이 있으며, 이중에서 인화철 [페로포스 (Ferrophos, Fe2P)]이 특히 바람직하다. 바람직한 사용량은 약 20 g/l이다.Furthermore, the anticorrosive may contain from about 1 to about 30 g / l, in particular from about 10 to about 25 g / l, of a conductive pigment as an additional active substance. This improves the electrical welding and electrolytic lacquer treatment of the material treated with the anticorrosive. Examples of suitable conductive pigments include barium sulfate, carbon black, graphite, molybdenum sulfide and the like doped with iron phosphide, tin or antimony, among which iron phosphide [Ferrophos, Fe 2 P] is particularly preferred. The preferred amount of use is about 20 g / l.
또한 이 방식제에는 추가적인 활성물질로서 폴리에틸렌 왁스를 약 0.5 ∼ 약 50 g/l 함유해도 좋다. 이 왁스는 도포막을 미끄럽게 하므로 방식제로 처리된 기재의 성형거동을 개선한다. 이것은 성형공정 도중에 표면에 성형용 오일을 도포할 필요가 없다는 것을 의미한다.The anticorrosive may also contain from about 0.5 to about 50 g / l polyethylene wax as an additional active material. This wax makes the coating film slippery, thereby improving the molding behavior of the substrate treated with the anticorrosive. This means that it is not necessary to apply the molding oil to the surface during the molding process.
또한 이 방식제에는 유기피막 형성 성분을 약 15 ∼ 약 200 g/l, 특히 약 50 ∼ 약 150 g/l 함유하는 것이 바람직하다. 따라서 처리된 금속표면에 방식제 사용도중에 혼합 무기/유기 도포막이 형성되기 때문에 프라이머로서의 기능은 물론이고 방식제로서의 기능을 수행한다. 따라서 예비처리된 금속부를 직접 그 위에다 래커처리할 수 있다. 이것과는 별도로 유기피막 형성성분은 방식제의 작용으로 인해 형성된 방식층중의 성분들이 세척공정에서 침출해나오지 못하도록 한다. 폴리에틸렌 왁스를 병용함으로써 유기피막 형성제도 형성거동을 개선한다.In addition, the anticorrosive agent preferably contains about 15 to about 200 g / l, particularly about 50 to about 150 g / l, of an organic coating-forming component. Therefore, since the mixed inorganic / organic coating film is formed on the treated metal surface during use of the anticorrosive agent, it functions not only as a primer but also as an anticorrosive agent. Thus, the pretreated metal part can be lacquered directly on it. Apart from this, the organic film forming component prevents the components in the formed anticorrosive layer from leaching due to the action of the anticorrosive. By using polyethylene wax in combination, the organic film former also improves the formation behavior.
유기피막 형성성분을, 예컨대 에폭시드 수지, 폴리우레탄 수지, 및 스티렌, 부타디엔, 아크릴산, 메타크릴산 및/또는 말레산 및 이들 산의 에스테르의 폴리머 혹은 공중합체로부터 선택되거나, 또는 이들 폴리머의 선구물질로부터 선택된다. 피막형성 성분은 180℃ 이하, 특히 170℃ 이하에서 가교하는 것들이 바람직하다. 유기피막 형성제를 방식제중에 용해 혹은 분산시킨다. 그 한가지 예로서는 폴리아크릴산 나트륨과 폴리아크릴산의 수성 혼합물인데, 이것은 고형분 함량이 51 wt.%이고 pH 범위가 2 ∼ 3인 시판품으로서 입수할 수 있다. 아크릴산 및/또는 메타크릴산 및 이들의 에스테르와 탄소원자수 1 내지 6의 알코올로 된 피막형성 성분이 바람직하다. 이들 폴리머 혹은 공중합체의 유리전이 온도는 20℃ ∼ 25℃의 범위인 것이 바람직하다.The organic film forming component is selected from, for example, epoxide resins, polyurethane resins, and polymers or copolymers of styrene, butadiene, acrylic acid, methacrylic acid and / or maleic acid and esters of these acids, or precursors of these polymers. Is selected from. The film forming component is preferably those which are crosslinked at 180 ° C or lower, particularly at 170 ° C or lower. The organic film-forming agent is dissolved or dispersed in the anticorrosive. One example is an aqueous mixture of sodium polyacrylate and polyacrylic acid, which can be obtained as a commercial product having a solid content of 51 wt.% And a pH range of 2-3. Preference is given to the film forming component of acrylic acid and / or methacrylic acid and esters thereof and alcohols having 1 to 6 carbon atoms. It is preferable that the glass transition temperature of these polymers or copolymers is 20 degreeC-25 degreeC.
더욱이 유기피막 형성제는 경화제가 첨가된 단일성분 혹은 별도의 경화제를 가진 2성분으로 하여 배합해도 좋은 에폭시드 수지이어도 좋은데, 물희석계가 바람직하다. 에폭시드 수지용의 경화제로서는 아민이나 폴리아민이 특히 바람직하다. 에폭시드 수지는 일반적으로 수지 함량이 약 50 내지 60%의 범위인 수성 분산물로서 시판되고 있다. 이들 분산물은 일반적으로 이소프로판올 또는 메톡시프로판올 등의 유기용제를 소량 함유한다. 더욱이 이들은 일반적으로 에폭시드 수지에 직접 융합하는 유화제를 함유한다. 이들 종류의 2성분 에폭시드 수지를 본 발명에서 사용하면 한편으로는 무기 방식성분과, 다른 한편으로는 경화제 성분과 혼합된 에폭시드 분산물을 두개의 별도의 용기에 저장하였다가, 작업장에 운반하여 사용해도 좋다. 두가지 성분을 서로 혼합한 즉시 도포한다. 이들 2성분 배합의 다른 예로서는 경화제가 첨가되어 있는 단일성분 에폭시드 수지계이다. 첨가된 경화제의 예로서는 아민 부가생성물이 있는데, 이것은 가열시에 유리 아민만을 방출하여 경화공정을 개시하는 것이다.Furthermore, the organic film forming agent may be a single component to which a curing agent is added or an epoxide resin which may be blended into two components having a separate curing agent, but a water dilution system is preferable. As a hardening | curing agent for epoxide resin, an amine and a polyamine are especially preferable. Epoxide resins are generally commercially available as aqueous dispersions with a resin content in the range of about 50 to 60%. These dispersions generally contain small amounts of organic solvents such as isopropanol or methoxypropanol. Moreover, they generally contain emulsifiers that fuse directly to the epoxide resin. When these kinds of two-component epoxide resins are used in the present invention, the epoxide dispersion mixed with the inorganic anticorrosive component on the one hand and the hardener component on the other hand is stored in two separate containers and transported to the workplace. You may use it. Apply the two ingredients immediately after mixing. Another example of these two-component blends is a single component epoxide resin system to which a curing agent is added. An example of an added curing agent is an amine adduct, which releases only the free amine upon heating to initiate the curing process.
또한, 이 방식제에는 추가적인 활성물질 혹은 보조물질로서 실란계 접착 촉진제를 약 0.5 내지 약 2 wt.% 함유해도 좋은데, 그 예로서는 아미노프로필트리에톡시실란 및 글리시독시프로필-트리메톡시실란이 있다.The anticorrosive may also contain from about 0.5 to about 2 wt.% Of a silane adhesion promoter as an additional active or auxiliary substance, such as aminopropyltriethoxysilane and glycidoxypropyl-trimethoxysilane. .
또한, 본 발명은 표면을 상기한 본 발명의 방식제와 2초 내지 60초 동안 접촉시킨 다음, 물로 중간 수세처리하거나 하지 않고서 50 ∼ 180℃ 범위의 기재온도 ("피이크 금속온도")에서 건조하는 것을 특징으로 하는, 아연도금강 혹은 합금 아연도금강 혹은 알루미늄 혹은 이들의 합금의 표면의 방식처리 방법에 관한 것이다.In addition, the present invention is to contact the surface with the above-described anticorrosive agent of the present invention for 2 to 60 seconds, and then dried at a substrate temperature ("peak metal temperature") in the range of 50 to 180 ℃ without intermediate washing with water It is related with the galvanized steel, alloy galvanized steel, aluminum, or these alloys.
따라서 한편으로는 아연도금강 혹은 합금 아연도금강에 이 방법을 사용하여도 좋다. 강에 대해서는 전해법 혹은 용융침지법으로 아연 혹은 아연합금으로 피복해도 좋다. 특히 적당한 아연합금으로서는 아연/니켈, 아연/철 및 아연/알루미늄 등의 합금이다. 다른 한편으로는 이 방법은 알루미늄 혹은 이들의 합금의 표면처리에 적합하다. 순수한 알루미늄 보다는 알루미늄 합금이 일반적으로 자동차 및 가전제품 산업 등에 사용된다. 가장 중요한 합금성분은 아연, 마그네슘, 실리콘 및 구리이다.Therefore, on the one hand, this method may be used for galvanized steel or alloy galvanized steel. The steel may be coated with zinc or zinc alloy by electrolytic or melt dipping. Particularly suitable zinc alloys are alloys such as zinc / nickel, zinc / iron and zinc / aluminum. On the other hand, this method is suitable for the surface treatment of aluminum or their alloys. Aluminum alloys, rather than pure aluminum, are generally used in the automotive and consumer electronics industries. The most important alloy components are zinc, magnesium, silicon and copper.
이 방법은 컨베이어 벨트 시스템위에서 금속 스트립을 처리하는데 특히 적합하다. 건조공정을 시작하기 까지의 처리제에 노출시키는 시간은 몇초 범위인데, 예컨대 약 2초 내지 약 20초, 특히 약 4초 내지 약 12초이다. 각종 공지의 방법을 사용하여 금속표면에 방식제를 도포한다. 예컨대 방식제를 금속표면에 분무하다거나 표면을 처리제에 침지하여 표면을 습윤시킨다. 이들 두가지 경우에 있어서 과잉량의 처리액을 사용하여 소정의 습윤피막 도포를 함으로써 약 0.5 ∼ 약 5 g/m2, 특히 약 0.8 ∼ 약 3 g/m2의 소요의 건조중량 도포를 하도록 하는 것이 바람직하다. 이 방식제를, 예컨대 Chemocoaters 등의 공지의 것과 유사한 도포 로울러를 사용하여 금속 스트립에 도포하는 것이 바람직하다. 이들을 사용할 경우, 습윤피막의 두께를 직접 조정할 수 있다. 모든 경우에 있어서, 방식제는 스트립위에서 소요의 습윤피막 두께로 잔존하며 중간 세척공정없이 건조된다. 건조는 예열로(豫熱爐) 혹은 적외선 조사에 의하여 실시하여 기재가 약 50 내지 약 180℃, 특히 약 100 내지 약 170℃의 온도 ("피이크 금속온도")에 도달하도록 한다. 임의로 사용된 유기피막 형성제를 이 공정도중에 경화시킨다.This method is particularly suitable for processing metal strips on conveyor belt systems. The exposure time to the treatment to the start of the drying process ranges from a few seconds, for example from about 2 seconds to about 20 seconds, in particular from about 4 seconds to about 12 seconds. Anticorrosive is applied to the metal surface using various known methods. For example, the anticorrosive is sprayed onto the metal surface or the surface is immersed in the treating agent to wet the surface. In these two cases, it is desirable to apply the desired wet film using an excess amount of the treatment liquid so that dry weight application of required 0.5 to about 5 g / m 2 , in particular about 0.8 to about 3 g / m 2 is achieved. desirable. It is preferable to apply this anticorrosive to the metal strip, for example using an application roller similar to that known in the art such as Chemocoaters. When using these, the thickness of a wet film can be adjusted directly. In all cases, the anticorrosive remains on the strip to the desired wet film thickness and dries without intermediate cleaning. Drying is carried out by preheating or infrared irradiation to allow the substrate to reach a temperature of about 50 to about 180 ° C., in particular about 100 to about 170 ° C. (“peak metal temperature”). The organic film former, optionally used, is cured during this process.
본 발명에 의한 처리를 강대의 전해 아연도금 혹은 용융침지 아연도금 직후에 실시하게 되면, 이 강대를 더 세척하지 않고 본 발명의 처리액과 접촉시킨다. 그러나 피처리 금속 스트립이 저장 및/또는 운송된 후에 본 발명에 의하여 도포되었다면 이들은 일반적으로 방식유로 처리되었거나 적어도 너무 오염되어 있기 때문에 본 발명에 의한 처리를 하기전에 세척할 필요가 있다. 이것은 종래기술로부터 이미 공지되어 있는 약 내지 강 알칼리 세척제를 사용하여 실시해도 좋다. 알루미늄 및 그 합금의 경우에 있어서 산성 세척제를 사용해도 좋다.When the treatment according to the present invention is carried out immediately after electrolytic galvanizing or hot dip galvanizing of steel strip, the steel strip is brought into contact with the treatment liquid of the present invention without further washing. However, if the metal strips to be treated have been applied according to the invention after they have been stored and / or transported, they are generally treated with anticorrosive oil or at least too contaminated and therefore need to be cleaned before the treatment according to the invention. This may be carried out using a weak to strong alkaline detergent already known from the prior art. In the case of aluminum and its alloys, an acidic cleaner may be used.
표 1에는 본 발명에 의한 방식제의 각 실시예가 나와 있다. 이들은 실온에서 주어진 순서로 각 성분을 혼합하여 제조한 것이다. 용융침지 아연도금강 및 전기 아연도금강으로 제조된 금속판을 기재로 사용하였다. 이들 각 판을 세척한 후에 시판의 강 알칼리 세척제를 사용하는 방식제로 처리하였다. 용액을 550 rpm의 래커처리기를 사용하여 금속표면에 도포하였다. 건조시작까지의 노출시간을 15초이었다. 도막의 건조/소성은 100℃의 기재온도 ("피이크 금속온도")에서 실시하였다. 이러한 목적으로 도포판을 300℃의 순환공기 캐비넷속에서 20초 동안 방치하였다.Table 1 shows each example of the anticorrosive agent according to the present invention. These are prepared by mixing each component in the order given at room temperature. Metal plates made of hot dip galvanized steel and electrogalvanized steel were used as substrates. Each of these plates was washed and then treated with an anticorrosive using a commercially available strong alkaline cleaner. The solution was applied to the metal surface using a lacquer at 550 rpm. The exposure time until the start of drying was 15 seconds. Drying / firing of the coating film was carried out at a substrate temperature of 100 ° C. (“peak metal temperature”). The coated plate was left for 20 seconds in a circulating air cabinet at 300 ° C for this purpose.
처리된 시험판을 추가로 래커처리를 하지 않고 DIN 5002155에 따라 염수분무 시험을 하였다. 48시간 동안 시험후 동일한 방법으로 처리된 시험판 3개 각각에 대해 부식정도를 육안으로 평가하였다. 부식발생이 없는 판을 0점, 부식이 50% 이상인 판을 5점으로 하였다. 그 결과는 표 2에 나와 있다.The treated test plates were subjected to a salt spray test according to DIN 5002155 without further lacquering. Corrosion degree was visually evaluated for each of the three test plates treated in the same manner after testing for 48 hours. The plate without corrosion occurred at 0 points and the plate having corrosion at least 50% was set at 5 points. The results are shown in Table 2.
[표 1] 방식제의 비교 (중량부)[Table 1] Comparison of anticorrosive agents (parts by weight)
1) 탄소원자수 1 내지 6의 알코올과 아크릴산 및 메타크릴산의 에스테르의 공중합체의 수성 분산물, 고형분 46%1) Aqueous dispersion of copolymer of alcohol having 1 to 6 carbon atoms with ester of acrylic acid and methacrylic acid, solid content 46%
(2) 총 배합에 대하여 고형분 10 중량%에 해당함.(2) Corresponds to 10% by weight of solids relative to the total formulation.
[표 2] 방식제의 효과 (48시간 염수분무 시험후의 부식도)[Table 2] Effect of anticorrosive agent (corrosion degree after 48 hours salt spray test)
1) HDG = 용융침지 아연도금강1) HDG = Hot dip galvanized steel
EG = 전해 아연도금강EG = electrolytic galvanized steel
Claims (11)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19754108.9 | 1997-12-05 | ||
| DE1997154108 DE19754108A1 (en) | 1997-12-05 | 1997-12-05 | Chromium-free anti-corrosion agent and anti-corrosion process |
| PCT/EP1998/007643 WO1999029927A2 (en) | 1997-12-05 | 1998-11-26 | Chromium-free corrosion protection agent and method for providing corrosion protection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20010024643A true KR20010024643A (en) | 2001-03-26 |
Family
ID=7850931
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020007005290A KR20010024643A (en) | 1997-12-05 | 1998-11-26 | Chromium-free corrosion protection agent and method for providing corrosion protection |
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| Country | Link |
|---|---|
| EP (1) | EP1036215A2 (en) |
| JP (1) | JP2001526324A (en) |
| KR (1) | KR20010024643A (en) |
| AR (1) | AR010965A1 (en) |
| AU (1) | AU2050299A (en) |
| CA (1) | CA2312807A1 (en) |
| DE (1) | DE19754108A1 (en) |
| WO (1) | WO1999029927A2 (en) |
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-
1997
- 1997-12-05 DE DE1997154108 patent/DE19754108A1/en not_active Withdrawn
-
1998
- 1998-11-26 KR KR1020007005290A patent/KR20010024643A/en not_active Application Discontinuation
- 1998-11-26 WO PCT/EP1998/007643 patent/WO1999029927A2/en not_active Application Discontinuation
- 1998-11-26 JP JP2000524493A patent/JP2001526324A/en active Pending
- 1998-11-26 CA CA002312807A patent/CA2312807A1/en not_active Abandoned
- 1998-11-26 AU AU20502/99A patent/AU2050299A/en not_active Abandoned
- 1998-11-26 EP EP98965188A patent/EP1036215A2/en not_active Ceased
- 1998-12-04 AR ARP980106158 patent/AR010965A1/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100900639B1 (en) * | 2002-07-02 | 2009-06-02 | 주식회사 포스코 | Aqueous coating composition for galvanized steel |
| KR100485469B1 (en) * | 2002-07-13 | 2005-04-27 | 대스캡피시엠주식회사 | Coat method of the aluminium surface containing with boric acid |
| US8241745B2 (en) | 2003-10-23 | 2012-08-14 | Basf Se | Essentially chromium-free method for passivating metallic surfaces consisting of Zn, Zn alloys, Al or Al alloys |
| WO2017138714A1 (en) * | 2016-02-11 | 2017-08-17 | 주식회사 노루코일코팅 | Alkaline conversion treatment composition for magnesium and magnesium alloy, and method for performing surface treatment on magnesium and magnesium alloy material by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2050299A (en) | 1999-06-28 |
| DE19754108A1 (en) | 1999-06-10 |
| AR010965A1 (en) | 2000-07-12 |
| WO1999029927A2 (en) | 1999-06-17 |
| WO1999029927A3 (en) | 1999-08-12 |
| JP2001526324A (en) | 2001-12-18 |
| EP1036215A2 (en) | 2000-09-20 |
| CA2312807A1 (en) | 1999-06-17 |
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