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KR20110083742A - Surface treating agent for metallic materials, method for surface treating metallic materials using the surface treating agent, and surface treated metallic materials - Google Patents

Surface treating agent for metallic materials, method for surface treating metallic materials using the surface treating agent, and surface treated metallic materials Download PDF

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KR20110083742A
KR20110083742A KR1020117013455A KR20117013455A KR20110083742A KR 20110083742 A KR20110083742 A KR 20110083742A KR 1020117013455 A KR1020117013455 A KR 1020117013455A KR 20117013455 A KR20117013455 A KR 20117013455A KR 20110083742 A KR20110083742 A KR 20110083742A
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metal
mass
surface treatment
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KR101285420B1 (en
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세이이치 사토
준이치 우치다
겐스케 미즈노
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니혼 파커라이징 가부시키가이샤
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    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
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    • C23COATING 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
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    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/40Chemical 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
    • C23C22/44Chemical 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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    • C23C22/07Chemical 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 phosphates
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    • C23C22/06Chemical 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
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    • C23C22/00Chemical 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
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    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
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    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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 fluorides or complex fluorides
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    • C23C22/00Chemical 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
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    • C23C22/06Chemical 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
    • C23C22/40Chemical 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
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Abstract

본 발명은, 금속재료 표면에 내열성, 용접성, 연속 가공성, 도전성, 내지문성이나 도장성 등을 겸비하는 지금까지 없는 신규 피막을 형성할 수 있고, 용액 안정성이 우수한 금속재료용 표면처리제를 제공하는 것을 과제로 한다.
상기 과제를 해결하기 위해 본 발명의 금속재료용 표면처리제는, 1분자 중에 -SiR1R2R3로 표시되는 관능기(a)를 2개 이상과, 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)과, Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 갖는, 1종 이상의 금속 알콕시드(B)와, 불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)과, 카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 친수성 관능기를 갖는 유기 화합물(D)과, 물을 함유하는 것을 특징으로 한다.
The present invention can provide a surface treatment agent for a metal material excellent in solution stability, capable of forming a novel new film having heat resistance, weldability, continuous workability, conductivity, anti-fingerprint property, and paintability on the surface of a metal material. It is a task.
Surface treatment agent for metal products of the present invention to solve the above problems, the two or more functional groups (a) represented by -SiR 1 R 2 R 3 in a molecule and and containing a hydrophilic functional group (b), functional groups ( b) One or more metal alkoxides having a compound (A) having a molecular weight (average molecular weight / number of functional groups) per 300 to 5000 and one element selected from the group consisting of Si, Ti and Zr ( B), at least one compound (C) selected from the group consisting of fluorine-containing compounds and phosphoric acid compounds, and an organic compound having at least one hydrophilic functional group selected from the group consisting of carboxylic acid groups, phosphonic acid groups and sulfonic acid groups (D) and water, It is characterized by the above-mentioned.

Description

금속재료용 표면처리제, 및 그것을 사용한 금속재료의 표면처리방법, 표면처리 금속재료{Surface treating agent for metallic materials, method for surface treating metallic materials using the surface treating agent, and surface treated metallic materials}Surface treating agent for metallic materials, method for surface treating metallic materials using the surface treating agent, and surface treated metallic materials

본 발명은 강(鋼), 아연계 도금 강판, 알루미늄판 등의 금속재료의 표면에 우수한 내식성(특히, 절곡부(折曲部) 내식성) 및 덧칠(上塗) 도장 밀착성을 부여할 수 있고, 내산성이나 내알칼리성 등의 내약품성도 겸비하는 피막을 형성하기 위한 금속재료용 표면처리제, 및 그것을 사용한 금속재료의 표면처리방법에 관한 것이다.INDUSTRIAL APPLICABILITY The present invention can impart excellent corrosion resistance (particularly, bend corrosion resistance) and overcoat adhesion to surfaces of metal materials such as steel, zinc-based galvanized steel sheets, and aluminum plates, The present invention relates to a surface treatment agent for metal materials for forming a coating having both chemical resistance such as alkali resistance and alkali resistance, and a surface treatment method for metal materials using the same.

아연계 도금 강판으로 대표되는 금속재료는, 자동차, 가전, 건재(建材) 등 다양한 분야에서 사용되고 있으나, 대기 중에서 부식되어 백청(white rust)이라 불리는 부식 생성물을 형성한다는 결점을 가지고 있다. 이에, 종래기술에서는 내식성을 개선할 목적으로, 금속재료의 표면에 크롬산 수용액을 포함하는 처리액을 사용하여, 6가 크롬과 3가 크롬을 포함하는 피막층을 형성시키는 크로메이트 처리로 불리는 방법이 일반적으로 행해지고 있었다.Metal materials represented by galvanized steel sheets are used in various fields such as automobiles, home appliances, building materials, etc., but have a drawback of corrosion in the air to form a corrosion product called white rust. Therefore, in the prior art, a method called a chromate treatment, which generally forms a coating layer containing hexavalent chromium and trivalent chromium, using a treatment solution containing an aqueous solution of chromic acid on the surface of a metal material for the purpose of improving corrosion resistance. It was done.

그러나, 이 크로메이트 처리에 사용하는 수용액은, 인체에 유해한 6가 크롬을 가지고 있기 때문에, 배수 처리에 있어서 수질 오탁 방지법에 규정되어 있는 특별한 처리를 실시할 필요가 있다. 이 때문에, 최근 들어, 지구적 환경보전에 대한 의식의 고양에 수반하여, 가능한 한 인체에 유해한 화합물의 사용을 피하고자 하는 움직임이 강해지고 있다.However, since the aqueous solution used for this chromate treatment has hexavalent chromium harmful to a human body, it is necessary to perform the special process prescribed | regulated by the water pollution prevention method in wastewater treatment. For this reason, in recent years, with the raising of awareness about global environmental conservation, there has been a strong movement to avoid the use of compounds harmful to the human body as much as possible.

한편, 크로메이트 처리 이외의 표면처리방법으로서는, 탄닌산을 포함하는 표면처리제에 의한 처리방법이 잘 알려져 있다. 탄닌산을 포함하는 수용액을 사용하여 처리하면, 탄닌산과 금속재료의 반응에 의해 형성되는 보호 피막이 부식물질의 침입을 방지하기 때문에, 내식성이 향상될 것으로 생각된다. 그러나, 이 피막으로는, 최근 제품의 고품질화(내식성, 도장 밀착성)에 대한 대응은 어렵다.On the other hand, as a surface treatment method other than chromate treatment, the treatment method by the surface treating agent containing tannic acid is well known. It is considered that when the treatment is performed using an aqueous solution containing tannic acid, the protective film formed by the reaction of tannic acid with the metal material prevents the intrusion of corrosive substances, thereby improving the corrosion resistance. However, with this coating, it is difficult to cope with the recent high quality of the product (corrosion resistance, paint adhesion).

한편으로, 주로 무기성분을 사용하는 기술로서는, 특허문헌 1에, 내식성, 도장 밀착성을 개선하는 방법으로서, 희박수(希薄水) 유리용액 또는 규산 소다용액, 또는 그들의 혼합액에, 특정량의 유기 실란 커플링제를 첨가한 처리액을 강재에 도포 건조하는 방법이 개시되어 있다.On the other hand, as a technique which mainly uses an inorganic component, Patent Literature 1 discloses a specific amount of organic silane in a lean water glass solution, a soda silicate solution, or a mixture thereof as a method of improving the corrosion resistance and coating adhesion. The method of apply | coating and drying the processing liquid which added the coupling agent to steel materials is disclosed.

또한, 주로 실란 커플링제를 사용하는 기술로서, 특허문헌 2에서는, 일시적인 방식효과를 얻기 위해, 저농도의 유기 관능 실란 및 가교제를 함유하는 수용액에 의한 금속판의 처리방법이 개시되어 있다. 이 방법에서는, 가교제가 유기 관능 실란을 가교함으로써, 조밀한 실록산·필름이 형성된다.Moreover, as a technique mainly using a silane coupling agent, Patent Document 2 discloses a method for treating a metal plate by an aqueous solution containing a low concentration of organic functional silane and a crosslinking agent in order to obtain a temporary anticorrosive effect. In this method, a dense siloxane film is formed by the crosslinking agent crosslinking the organic functional silane.

또한, 특허문헌 3에서는, 알콕시실란을 2개 이상 갖는 화합물과, 유기산, 인산 및 착불화물로부터 선택되는 화합물을 함유하는 표면처리제를 사용하여, 금속의 표면에 내식성과 도장 밀착성이 우수한 피막을 형성하는 방법이 개시되어 있다.In addition, Patent Document 3 uses a surface treatment agent containing a compound having two or more alkoxysilanes and a compound selected from organic acids, phosphoric acid and complex fluoride to form a film having excellent corrosion resistance and paint adhesion on the surface of the metal. A method is disclosed.

또한, 특허문헌 4에서는, 실란 커플링제(a-1)와 알콕시실란 올리고머(a-2)를 포함하는 실리카 졸 바인더(a), 인산 이온(b), 불화물 이온(c), 및 V, Ti, Zr, Zn, Mn, Mg, Al, Co, Ni, Mo, W 및 Ce로 이루어진 군으로부터 선택되는 1종 이상의 금속을 포함하는 금속 화합물(d)을 함유하는 금속 표면처리용 조성물이 개시되어 있다. 또한, 이 조성물을 사용하여, 부식성(특히 가공부의 내식성), 내알칼리성, 내열성, 내융제(ablation)성, 밀착성(덧칠 도막과의 밀착성, 기재와의 밀착성)이 우수한 피막이 얻어지는 것이 개시되어 있다.Moreover, in patent document 4, the silica sol binder (a) containing a silane coupling agent (a-1) and an alkoxysilane oligomer (a-2), a phosphate ion (b), a fluoride ion (c), and V, Ti A metal surface treatment composition containing a metal compound (d) containing at least one metal selected from the group consisting of Zr, Zn, Mn, Mg, Al, Co, Ni, Mo, W and Ce is disclosed. . Moreover, using this composition, it is disclosed that the film which is excellent in corrosiveness (especially corrosion resistance of a process part), alkali resistance, heat resistance, ablation resistance, adhesiveness (adhesiveness with a coating film, adhesiveness with a base material) is obtained.

그러나, 이들 기술은 도전성 및 내지문성 등의 성능이 현저히 결여되어 있는 것, 내식성, 및 도장 밀착성이 제품의 고품질화에 대해, 목표성능 달성이 곤란한 것 등의 문제가 있었다. 또한, 만일 내식성과 도장 밀착성이 우수한 피막을 형성하는 것이 가능해도, 용제계인 것으로 인해 환경면 및 안전면에 문제를 남기고, 수계에서 안정적으로 공급하는 것이 곤란한 등의 문제를 안고 있어, 실용화에 이르러 여전히 커다란 문제를 안고 있었다.However, these techniques have problems such as lack of remarkably lacking performances such as conductivity and fingerprint resistance, corrosion resistance, and paint adhesion, which are difficult to achieve the target performance for high quality products. In addition, even if it is possible to form a film excellent in corrosion resistance and paint adhesion, the solvent system leaves problems on the environmental and safety surfaces, and it is difficult to stably supply in the water system. I had a big problem.

한편, 특허문헌 5에는, 1분자 내에, 식 -SiR1R2R3(식 중, R1, R2 및 R3는, 알킬기, 알콕시기, 또는 수산기를 나타내고, 하나 이상은 알콕시기를 나타낸다)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함될 수 있는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 친수성 관능기(b)를 1개 이상 함유하고, 관능기(b) 1개당 분자량이 300~10000인 유기 규소 화합물을 배합해서 되는 수계 금속 표면처리제 및 처리방법이 개시되어 있다. 또한, 이 처리제를 사용함으로써, 우수한 내식성, 밀착성은 물론이고, 무기계 피막이 갖는 내열성, 용접성, 연속 가공성 및 도전성, 유기계 피막이 갖는 내지문성이나 도장성 등을 겸비하는 피막을 형성할 수 있는 것이 개시되어 있다.In Patent Literature 5, in one molecule, the formula -SiR 1 R 2 R 3 (wherein R 1 , R 2, and R 3 represents an alkyl group, an alkoxy group, or a hydroxyl group, and at least one represents an alkoxy group). From two or more functional groups represented by (a) and hydroxyl groups (separate from those which may be included in functional group (a)), amino groups, carboxyl groups, phosphoric acid groups, phosphonic acid groups, sulfone groups, polyoxyethylene chains and amide groups Disclosed are an aqueous metal surface treatment agent and a treatment method containing at least one hydrophilic functional group (b) selected and blended with an organosilicon compound having a molecular weight of 300 to 10,000 per functional group (b). In addition, it is disclosed that by using this treatment agent, a film having not only excellent corrosion resistance and adhesion but also heat resistance, weldability, continuous processability and conductivity of the inorganic coating, and anti-fingerprint and coating properties of the organic coating can be formed. .

그러나, 피막 중에 유기성분에 의한 배리어층을 가져, 도금에 대한 약품의 침입을 저지하는 유기계 피막과 비교하여, 이 기술에서는 내산성이나 내알칼리성 등의 피막의 내약품성이 떨어져 있었다. 또한 평면부 및 가공부 내식성은 우수한 성능을 가지나, 절곡부 등의 극도로 피막이 변형되는 부위의 내식성이 결여된다는 문제를 안고 있었다.However, compared with the organic coating which has a barrier layer by an organic component in the coating, and prevents the invasion of a chemical to plating, in this technique, the chemical resistance of coatings, such as acid resistance and alkali resistance, was inferior. In addition, the flat part and the processed part have excellent corrosion resistance, but suffer from the problem that the corrosion resistance of the portion where the film is extremely deformed, such as the bent part.

한편, 유기 수지 피막을 사용하는 기술로서, 특허문헌 6에서는, 수성 분산 수지를 고형분 농도로 5~30 질량%, 실리카 입자를 0.1~20 질량%, 및 유기 티타네이트 화합물을 0.01~20 질량% 배합하여, 용액 안정성이 우수하고, 아연계 피복강 또는 무피복강 등의 강재를 피복하는데 적합한 1액 타입의 강재용 수성 피복제가 개시되어 있다. 또한, 이 피복제를 사용함으로써, 내식성, 내용제성, 내알칼리성, 도장 밀착성, 피막 밀착성이 우수한 피막이 얻어지는 것이 개시되어 있다.On the other hand, as a technique using an organic resin film, Patent Literature 6 blends 5-30 mass% of aqueous dispersion resin in solid content concentration, 0.1-20 mass% of silica particles, and 0.01-20 mass% of organic titanate compound. Accordingly, an aqueous coating agent for steel of one-liquid type, which is excellent in solution stability and suitable for coating steel materials such as zinc-based coated steel or uncoated steel, has been disclosed. Moreover, by using this coating agent, it is disclosed that the film excellent in corrosion resistance, solvent resistance, alkali resistance, coating adhesiveness, and film adhesiveness is obtained.

또한, 특허문헌 7에는, 특정 수지 화합물(A)과, 제1~3 아미노기 및 제4 암모늄염기로부터 선택되는 1종 이상의 양이온성 관능기를 갖는 양이온성 우레탄 수지(B)와, 특정 반응성 관능기를 갖는 1종 이상의 실란 커플링제(C)와, 특정 산 화합물(E)을 함유하고, 양이온성 우레탄 수지(B) 및 실란 커플링제(C)의 함유량이 소정 범위 내인 표면처리제를 사용하여 얻어지는, 내식성이 우수하고, 또한 내지문성, 내흑변성 및 도장 밀착성이 우수한 논크롬계 표면처리 강판 및 그의 제조방법이 개시되어 있다.In addition, Patent Document 7 has a specific resin compound (A), a cationic urethane resin (B) having at least one cationic functional group selected from first to third amino groups, and a fourth ammonium base group, and a specific reactive functional group. Corrosion resistance which contains at least 1 type of silane coupling agent (C) and a specific acid compound (E), and is obtained using the surface treatment agent whose content of cationic urethane resin (B) and a silane coupling agent (C) exists in a predetermined range. Disclosed are a non-chromium surface-treated steel sheet excellent in anti-fingerprint, blackening resistance, and paint adhesion, and a manufacturing method thereof.

또한, 특허문헌 8에는, (A) 가수분해성 티탄 화합물, 가수분해성 티탄 화합물의 저축합물, 수산화 티탄 및 수산화 티탄의 저축합물로 이루어진 군으로부터 선택되는 1종 이상의 티탄 화합물을, 과산화수소수와 혼합하여 얻어지는 티탄 함유 수성액의 고형분 100 중량부, (B) 유기 인산 화합물 1~400 중량부, (C) 수용성 또는 수분산성 유기 수지를 고형분으로 10~2,000 중량부, (D) 바나딘산 화합물 1~400 중량부, (E) 불화지르코늄 화합물 1~400 중량부, 및 (F) 탄산지르코늄 화합물 1~400 중량부를 함유해서 되는 것을 특징으로 하는 금속 표면처리 조성물이 개시되어 있다.Further, Patent Document 8 obtains by mixing one or more titanium compounds selected from the group consisting of (A) a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide and a titanium hydroxide, and a hydrogen peroxide solution. 100 parts by weight of the solid content of the titanium-containing aqueous liquid, (B) 1 to 400 parts by weight of the organic phosphoric acid compound, (C) 10 to 2,000 parts by weight of the water-soluble or water dispersible organic resin as a solid content, (D) vanadate compound 1 to 400 The metal surface treatment composition characterized by containing a weight part, 1-400 weight part of (E) zirconium fluoride compounds, and 1-400 weight part of (F) zirconium carbonate compounds.

그러나, 이들 기술은 유기 수지로 금속 재료 표면을 피복함으로써 내식성이나 내지문성을 발현하기 때문에, 도전성이나 스팟 용접성 등의 성능이 떨어진다는 문제가 있었다. 또한 주성분이 유기 고분자이기 때문에, 고온에 있어서의 열분해, 착색, 점성의 증가 등이 발생하기 때문에 내열용도로는 사용할 수 없는 것이 현재 상황이었다.However, these techniques exhibit corrosion resistance and fingerprint resistance by coating the surface of the metal material with an organic resin, and thus there is a problem that the performance such as conductivity and spot weldability is poor. In addition, since the main component is an organic polymer, thermal decomposition, coloring, increase in viscosity, etc. occur at high temperatures, so that it cannot be used for heat resistance.

이와 같이, 어떤 방법으로도 크로메이트 피막의 대체로서 사용할 수 있는, 내식성(특히, 절곡부의 내식성), 내약품성, 내열성, 내지문성, 도전성 등의 모든 특성을 종합적으로 만족하는 피막은 얻어지고 있지 않다.In this way, no coating has been obtained that satisfactorily satisfies all characteristics such as corrosion resistance (particularly, corrosion resistance of bent portions), chemical resistance, heat resistance, fingerprint resistance, and conductivity that can be used as a substitute for the chromate coating by any method.

특허문헌 1: 일본국 특허공개 소58-15541호 공보Patent Document 1: Japanese Patent Application Laid-open No. 58-15541

특허문헌 2: 미국특허 제5,292,549호 명세서Patent Document 2: US Patent No. 5,292,549

특허문헌 3: 일본국 특허공개 제2001-49453호 공보Patent Document 3: Japanese Patent Application Laid-Open No. 2001-49453

특허문헌 4: 일본국 특허공개 제2007-177314호 공보Patent Document 4: Japanese Patent Application Laid-Open No. 2007-177314

특허문헌 5: 국제공개 제2006-082951호 팸플릿Patent Document 5: International Publication No. 2006-082951 Pamphlet

특허문헌 6: 일본국 특허공개 제2001-353750호 공보Patent Document 6: Japanese Patent Application Laid-Open No. 2001-353750

특허문헌 7: 일본국 특허공개 제2003-105562호 공보Patent Document 7: Japanese Patent Application Laid-Open No. 2003-105562

특허문헌 8: 일본국 특허공개 제2006-009121호 공보Patent Document 8: Japanese Patent Application Laid-Open No. 2006-009121

본 발명은 종래기술이 갖는 상기 과제점을 해결하여, 금속재료 표면에 우수한 내식성, 및 내산성은 물론이고, 무기계 피막이 통상 갖는 내열성, 및 도전성이 우수하며, 유기계 피막이 통상 갖는 내지문성 등을 겸비하는 지금까지는 없었던 신규 피막을 형성할 수 있어, 용액 안정성이 우수한 금속재료용 표면처리제, 그것을 사용한 표면처리방법, 및 표면처리된 금속재료를 제공하는 것을 목적으로 하는 것이다.MEANS TO SOLVE THE PROBLEM This invention solves the said subject which the prior art has, and it is excellent in the corrosion resistance and acid resistance on the metal material surface, as well as the heat resistance which inorganic coating normally has, the electroconductivity, and the anti-fingerprint which an organic coating normally has. It is an object of the present invention to provide a novel coating film which has not been provided so far, and has excellent surface stability for a metal material, a surface treatment method using the same, and a surface treated metal material.

본 발명자들은, 이들 종래기술이 안고 있는 문제점을 해결하고자 예의 검토를 거듭한 결과, 1분자 중에 -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)과, Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 갖는, 1종 이상의 금속 알콕시드(B)와, 불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)과, 카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 친수성 관능기를 갖는 유기 화합물(D)과, 물을 함유한, 매우 안정한 금속재료용 표면처리제를 사용함으로써, 상기 과제를 해결할 수 있는 것을 발견하고, 본 발명을 완성하기에 이르렀다.MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the problem which these prior arts have, as a result, -SiR <1> R <2> R <3> (In formula, R <1> , R <2> and R <3> are respectively independently carbon number 1 in 1 molecule. Two or more functional groups (a) represented by an alkyl group, an alkoxy group, or a hydroxyl group of -4, and at least one of R 1 , R 2, and R 3 represent an alkoxy group; and a hydroxyl group (functional group (a)). And one or more hydrophilic functional groups (b) selected from amino groups, amino groups, carboxyl groups, phosphoric acid groups, phosphonic acid groups, sulfone groups, polyoxyethylene chains and amide groups, and have a molecular weight per functional group (b). At least one metal alkoxide (B) having a compound (A) having an average molecular weight / functional group in the range of 300 to 5000, one element selected from the group consisting of Si, Ti, and Zr, and fluorine At least one selected from the group consisting of containing compounds and phosphoric acid compounds A very stable surface treatment agent for metal materials containing a compound (C), an organic compound (D) having at least one hydrophilic functional group selected from the group consisting of carboxylic acid groups, phosphonic acid groups and sulfonic acid groups, and water. By using it, it discovered that the said subject could be solved and came to complete this invention.

즉, 본 발명은, 이하의 (1)~(10)을 제공한다.That is, this invention provides the following (1)-(10).

(1) 1분자 중에 -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)과,(1) -SiR <1> R <2> R <3> (In formula, R <1> , R <2> and R <3> respectively independently represents a C1-C4 alkyl group, an alkoxy group, or a hydroxyl group, R <1> , R <2> And at least one of R 3 represents an alkoxy group; two or more functional groups (a), a hydroxyl group (a separate one from the functional group (a)), an amino group, a carboxyl group, a phosphoric acid group, a phosphonic acid group, Compound (A) containing at least one hydrophilic functional group (b) selected from sulfone groups, polyoxyethylene chains and amide groups, and having a molecular weight (average molecular weight / number of functional groups) per functional group (b) in the range of 300 to 5000 (A )and,

Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 갖는, 1종 이상의 금속 알콕시드(B)와,At least one metal alkoxide (B) having one element selected from the group consisting of Si, Ti and Zr,

불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)과,At least one compound (C) selected from the group consisting of fluorine-containing compounds and phosphoric acid compounds,

카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 친수성 관능기를 갖는 유기 화합물(D)과,An organic compound (D) having at least one hydrophilic functional group selected from the group consisting of a carboxylic acid group, a phosphonic acid group and a sulfonic acid group,

물을 함유하는 금속재료용 표면처리제.Surface treatment agent for metal materials containing water.

(2) 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과, 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량의 질량비(B/A)가 0.01~5.0이고, 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 화합물(C)의 질량의 질량비(C/A)가 0.01~4.0인 (1)에 기재된 금속재료용 표면처리제.(2) The mass when the amount of Si in the compound (A) is converted into SiO 2 , and the amount of Si, Ti, and Zr in the metal alkoxide (B) are MO 2 (M is Si, Ti, or Zr). The mass ratio (B / A) of the total mass when converted into () is 0.01 to 5.0, and the mass ratio of the mass when the amount of Si in the compound (A) is converted into SiO 2 and the mass of the compound (C) ( Surface treatment agent for metal materials as described in (1) whose C / A) is 0.01-4.0.

(3) 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 화합물(C)의 질량의 질량비(B/C)가, 0.10~30.0인, (1) 또는 (2)에 기재된 금속재료용 표면처리제.(3) The total mass and the mass of the compound (C) when the amount of Si, Ti and Zr in the metal alkoxide (B) is converted into MO 2 (M represents Si, Ti, or Zr). The surface treating agent for metal materials as described in (1) or (2) whose mass ratio (B / C) is 0.10-30.0.

(4) 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 유기 화합물(D)의 질량의 질량비(B/D)가 0.10~5.0인, (1)~(3) 중 어느 하나에 기재된 금속재료용 표면처리제.4 parts by mass of the metal alkoxide (B) Si amount, Ti amount and the total weight and the organic compound when the terms of the Zr amount to MO 2 (M represents a Si, Ti, or Zr) of (D) The surface treating agent for metal materials in any one of (1)-(3) whose mass ratio (B / D) is 0.10-5.0.

(5) 상기 금속 알콕시드(B)로서, 1종 이상의 테트라알콕시실란이 함유되는 (1)~(4) 중 어느 하나에 기재된 금속재료용 표면처리제.(5) The surface treating agent for metal materials according to any one of (1) to (4), in which at least one kind of tetraalkoxysilane is contained as the metal alkoxide (B).

(6) 2종의 금속 알콕시드(B)를 사용하는, (1)~(5) 중 어느 하나에 기재된 금속재료용 표면처리제.(6) The surface treating agent for metal materials in any one of (1)-(5) using 2 types of metal alkoxides (B).

(7) 상기 화합물(C)이 Ti, Zr, Hf, Si, Al 및 B로 이루어진 군으로부터 선택되는 1종 이상의 원소를 갖는, (1)~(6) 중 어느 하나에 기재된 금속재료용 표면처리제.(7) The surface treating agent for metal materials according to any one of (1) to (6), wherein the compound (C) has at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al, and B. .

(8) 추가로, Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca 및 Li로 이루어진 군으로부터 선택되는 1종 이상의 원소를 함유하는 금속 화합물(E)(단, 상기 불소 함유 화합물은 포함되지 않는다)을 함유하고, 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 상기 금속 화합물(E)의 질량의 질량비(E/A)가 0.01~3.0인, (1)~(7) 중 어느 하나에 기재된 금속재료용 표면처리제.(8) further, a metal compound (E) containing at least one element selected from the group consisting of Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca and Li ( However, the said fluorine-containing compound is not included), and the mass ratio (E / A) of the mass when the amount of Si in the compound (A) is converted into SiO 2 and the mass of the metal compound (E) is 0.01. The surface treating agent for metal materials in any one of (1)-(7) which is -3.0.

(9) (1)~(8) 중 어느 하나에 기재된 금속재료용 표면처리제를 금속재료 표면 상에 도포, 건조시켜서, 피막량이 10~3000 ㎎/㎡인 피막을 상기 금속재료 표면 상에 형성하는, 금속재료의 표면처리방법.(9) Applying and drying the surface treatment agent for a metal material according to any one of (1) to (8) on a metal material surface to form a film having a coating amount of 10 to 3000 mg / m 2 on the metal material surface. , Surface treatment of metal materials.

(10) (9)에 기재된 금속재료의 표면처리방법에 의해 얻어지는, 표면처리된 금속재료.(10) The surface-treated metal material obtained by the surface treatment method of the metal material according to (9).

본 발명에 의하면, 금속재료 표면에 우수한 내식성, 및 내산성은 물론이고, 무기계 피막이 통상 갖는 내열성 및 도전성이 우수하며, 유기계 피막이 통상 갖는 내지문성 등을 겸비하는 지금까지는 없었던 신규 피막을 형성할 수 있고, 용액 안정성이 우수한 금속재료용 표면처리제, 그것을 사용한 표면처리방법, 및 표면처리된 금속재료를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, it is possible to form the novel film | membrane which was not present so far that it is excellent in the heat resistance and electroconductivity which inorganic coatings normally have as well as excellent corrosion resistance and acid resistance on the metal material surface, The surface treatment agent for metal materials excellent in solution stability, the surface treatment method using the same, and the surface-treated metal material can be provided.

이하에, 본 발명의 금속재료용 표면처리제, 및 그 처리제를 사용한 표면처리방법, 더 나아가서는 그 표면처리방법에 의해 얻어지는 피막을 갖는 금속재료에 대해 설명한다.Below, the surface treatment agent for metal materials of this invention, the surface treatment method using this treatment agent, Furthermore, the metal material which has a film obtained by the surface treatment method is demonstrated.

먼저, 금속재료용 표면처리제에 대해 설명한다.First, the surface treating agent for metal materials is demonstrated.

본 발명의 금속재료용 표면처리제는, 1분자 중에 -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)과, Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 갖는, 1종 이상의 금속 알콕시드(B)와, 불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)과, 카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 유기 화합물(D)과, 물을 함유한다.The surface treating agent for metal materials of the present invention is -SiR 1 R 2 R 3 (wherein R 1 , R 2 and R 3 are each independently a C 1-4 alkyl group, an alkoxy group, or a hydroxyl group in one molecule). 2 or more functional groups (a) represented by one or more of R 1 , R 2, and R 3 represent an alkoxy group, and a hydroxyl group (a separate one from the functional group (a)), an amino group, and a carboxyl group. , At least one hydrophilic functional group (b) selected from phosphoric acid group, phosphonic acid group, sulfone group, polyoxyethylene chain and amide group, and has a molecular weight (average molecular weight / number of functional groups) per functional group (b) At least one metal alkoxide (B) having one compound selected from the group consisting of a compound (A) and Si, Ti and Zr in the range of; and a fluorine-containing compound and a phosphoric acid compound At least one compound (C) and a carboxylic acid group, a phosphonic acid group and a sulfonic acid At least one organic compound (D) selected from the group consisting of groups and water.

이하에, 이들의 각 구성성분에 대해 각각 설명한다.Below, each of these components is demonstrated, respectively.

<화합물(A)><Compound (A)>

본 발명의 금속재료용 표면처리제에는, 1분자 중에, -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)이 포함된다. 화합물(A)이 포함됨으로써, 피막의 내식성이 부여된다. 화합물(A)은, 1종만이어도 되고, 2종 이상을 병용해도 된다.In the surface treatment agent for metal materials of the present invention, in one molecule, -SiR 1 R 2 R 3 (wherein, R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a hydroxyl group). , At least one of R 1 , R 2, and R 3 represents an alkoxy group; two or more functional groups (a), a hydroxyl group (one separate from the functional group (a)), an amino group, It contains at least one hydrophilic functional group (b) selected from a carboxyl group, a phosphoric acid group, a phosphonic acid group, a sulfone group, a polyoxyethylene chain and an amide group, and has a molecular weight (average molecular weight / number of functional groups) per functional group (b). Compound (A) in the range of 5000 is included. By containing a compound (A), the corrosion resistance of a film is provided. 1 type of compound (A) may be sufficient, and may use 2 or more types together.

화합물(A)은, 1분자 중에, -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상 갖는다. 그 중에서도, 2~7개가 바람직하다. 또한, 1분자 중에 관능기(a)를 1개밖에 포함하지 않는 경우는, 금속재료 표면에 대한 밀착성이 저하되기 때문에 바람직하지 않다.Compound (A) represents -SiR 1 R 2 R 3 (In formula, each of R 1 , R 2 and R 3 independently represents a C1-C4 alkyl group, an alkoxy group, or a hydroxyl group in one molecule. R is At least one of 1 , R 2 and R 3 represents an alkoxy group.) And has two or more functional groups (a) represented by. Especially, 2-7 pieces are preferable. Moreover, when only one functional group (a) is contained in 1 molecule, since adhesiveness to the surface of a metal material falls, it is unpreferable.

R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타낸다. 그 중에서도, 알콕시기가 바람직하다.R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a hydroxyl group. Especially, an alkoxy group is preferable.

또한, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타내고, 모두 알콕시기인 것이 바람직하다.Moreover, at least one of R <1> , R <2> and R <3> represents an alkoxy group, and it is preferable that all are alkoxy groups.

탄소수 1~4의 알킬기로서는, 예를 들면, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, sec-부틸기, t-부틸기 등을 들 수 있고, 바람직하게는 에틸기이다.As a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, etc. are mentioned, for example, Preferably it is an ethyl group. .

알콕시기로서는, 예를 들면, 탄소수 1~3의 알콕시기를 바람직하게 들 수 있다.As an alkoxy group, a C1-C3 alkoxy group is mentioned preferably, for example.

화합물(A)은, 1분자 내에, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 1개 이상 함유한다. 그 중에서도, 수산기 및 아미노기가 바람직하다.Compound (A) is one kind selected from hydroxyl groups (separate from those contained in functional group (a)), amino groups, carboxyl groups, phosphoric acid groups, phosphonic acid groups, sulfone groups, polyoxyethylene chains and amide groups in one molecule. It contains one or more of the above hydrophilic functional groups (b). Especially, a hydroxyl group and an amino group are preferable.

또한, 친수성 관능기의 수는 1~4개가 바람직하다.Moreover, as for the number of hydrophilic functional groups, 1-4 pieces are preferable.

또한, 화합물(A) 중의 관능기(b)는, 관능기(a)를 갖는 화합물과, 관능기(b)를 갖는 화합물을 반응시켜서 합성해도 된다. 관능기(b)를 갖는 화합물로서는, 히드록실아민, 다가 알코올, 아민티올아민설폰산, 히드록시포스폰산, 아민산 등을 들 수 있다.In addition, you may synthesize | combine the functional group (b) in a compound (A) by making the compound which has a functional group (a), and the compound which has a functional group (b) react. As a compound which has a functional group (b), hydroxylamine, polyhydric alcohol, amine thiolamine sulfonic acid, hydroxyphosphonic acid, an amine acid, etc. are mentioned.

화합물(A)은, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 것이 바람직하고, 보다 바람직하게는 400~3000의 범위이며, 특히 바람직하게는 500~2000의 범위이다. 관능기(b) 1개당 분자량이 300 미만인 경우는, 화합물의 합성이 어렵고, 얻어지는 피막의 특성도 떨어진다. 한편, 5000을 초과하는 경우는, 관능기(b)의 특징인 금속재료 표면에 대한 밀착성이 저하되기 때문에 바람직하지 않다.It is preferable that the compound (A) has a molecular weight (average molecular weight / number of functional groups) per functional group (b) in the range of 300-5000, More preferably, it is the range of 400-3000, Especially preferably, it is 500-2000 Range. When the molecular weight per functional group (b) is less than 300, the synthesis of the compound is difficult and the characteristics of the obtained film are also inferior. On the other hand, when it exceeds 5000, since adhesiveness with respect to the metal material surface which is the characteristic of the functional group (b) falls, it is not preferable.

또한, 상기 분자량의 측정방법으로서는, 겔투과 크로마토그래피(GPC)나 NMR을 사용하여 측정할 수 있다.In addition, as a measuring method of the said molecular weight, it can measure using gel permeation chromatography (GPC) or NMR.

또한, 화합물(A)의 골격으로서는 특별히 한정되지 않으나, 에스테르 결합, 에테르 결합, 산아미드 결합, 아미드 결합, 우레탄 결합, 우레아 결합, 비닐 결합 등의 결합을 가지고 있는 것이 바람직하다.The skeleton of the compound (A) is not particularly limited, but preferably has a bond such as an ester bond, an ether bond, an acid amide bond, an amide bond, a urethane bond, a urea bond, or a vinyl bond.

화합물(A)의 제조방법은 특별히 한정되지 않으나, 예를 들면, (1) 2개 이상의, 활성수소 함유 관능기를 갖는 화합물과 클로로실란을 반응시키는 방법, (2) 비닐기를 갖는 실란 커플링제와 공중합 가능한 비닐 화합물을 반응(중합)시키는 방법, (3) 특정의 반응성 관능기를 갖는 실란 커플링제와, 그 반응성 관능기와 반응할 수 있는 관능기를 갖는 화합물을 반응시키는 방법, (4) 다관능 실란 커플링제에 친수기를 수식하는 방법 등을 들 수 있다.Although the manufacturing method of a compound (A) is not specifically limited, For example, (1) The method of making the compound which has two or more active hydrogen containing functional groups, and chlorosilane react, (2) Copolymerization with the silane coupling agent which has a vinyl group. A method of reacting (polymerizing) a vinyl compound, (3) a method of reacting a silane coupling agent having a specific reactive functional group with a compound having a functional group capable of reacting with the reactive functional group, and (4) a polyfunctional silane coupling agent And a method of modifying a hydrophilic group.

그 중에서도, (2) 또는 (3)이 바람직하고, (3)이 가장 바람직하다. 이하에 각각의 제조방법에 대해 설명한다.Especially, (2) or (3) is preferable and (3) is the most preferable. Each manufacturing method is demonstrated below.

화합물(A)의 바람직한 실시형태의 하나로서, 비닐기를 갖는 실란 커플링제와, 공중합 가능한 비닐 화합물의 반응(중합)에 의해 얻어지는 화합물(반응 생성물)을 들 수 있다. 또한, 이 방법은 상기의 (2)의 제조방법에 해당한다.As one of preferable embodiment of a compound (A), the compound (reaction product) obtained by reaction (polymerization) of the silane coupling agent which has a vinyl group, and a copolymerizable vinyl compound is mentioned. In addition, this method corresponds to the manufacturing method of said (2).

비닐기를 갖는 실란 커플링제로서는, 비닐기를 가지고 있으면 특별히 한정되지 않으나, 예를 들면, γ-메타크릴옥시프로필트리에톡시실란, γ-메타크릴옥시프로필메틸디에톡시실란, 비닐트리에톡시실란 등을 들 수 있다.As a silane coupling agent which has a vinyl group, if it has a vinyl group, it will not specifically limit, For example, (gamma)-methacryloxypropyl triethoxysilane, (gamma)-methacryloxypropyl methyl diethoxysilane, vinyl triethoxysilane, etc. are mentioned. Can be mentioned.

또한, 공중합 가능한 비닐 화합물로서는 특별히 한정되지 않으나, 예를 들면, 아크릴산, 부틸아크릴레이트, 메틸아크릴레이트, 2-히드록시에틸메타크릴레이트 등을 들 수 있다.Moreover, it does not specifically limit as a vinyl compound which can be copolymerized, For example, acrylic acid, butyl acrylate, methyl acrylate, 2-hydroxyethyl methacrylate, etc. are mentioned.

전술한 화합물을 사용한 반응형식은 특별히 한정되지 않고, 예를 들면, 음이온 중합, 양이온 중합, 라디칼 중합 등을 들 수 있다. 그 중에서도, 라디칼 중합이 바람직하다. 또한, 선택되는 반응형식에 따라, 공지의 중합개시제 등을 적절히 사용해도 된다.The reaction format using the above-mentioned compound is not particularly limited, and examples thereof include anionic polymerization, cationic polymerization and radical polymerization. Especially, radical polymerization is preferable. Moreover, you may use a well-known polymerization initiator etc. suitably according to the reaction format chosen.

또한, 반응시에는 적절히 용매를 사용해도 되고, 예를 들면, 물, 에탄올, 이소프로필알코올 등을 들 수 있다.Moreover, at the time of reaction, you may use a solvent suitably, For example, water, ethanol, isopropyl alcohol, etc. are mentioned.

화합물(A)의 다른 바람직한 실시형태의 하나로서, 반응성 관능기(c1)를 갖는 실란 커플링제와, 그 반응성 관능기(c1)와 반응할 수 있는 관능기(c2)를 갖는 화합물의 반응에 의해 얻어지는 화합물(반응 생성물)을 들 수 있다.As one of another preferable embodiment of a compound (A), the compound obtained by reaction of the silane coupling agent which has a reactive functional group (c1), and the compound which has a functional group (c2) which can react with the reactive functional group (c1) ( Reaction products).

반응성 관능기(c1)로서는, 다른 관능기와 반응하여 결합을 형성하는 기이면 특별히 한정되지 않으나, 예를 들면, 수산기, 에폭시기, 1급 아미노기, 2급 아미노기, 메르캅토기, 이소시아네이트기, 카르복실기 및 비닐기로 이루어진 군으로부터 선택되는 관능기가 바람직하다. 그 중에서도, 에폭시기, 1급 아미노기, 2급 아미노기가 바람직하다.The reactive functional group (c1) is not particularly limited as long as it is a group that reacts with other functional groups to form a bond. For example, a hydroxyl group, an epoxy group, a primary amino group, a secondary amino group, a mercapto group, an isocyanate group, a carboxyl group, and a vinyl group A functional group selected from the group consisting of is preferred. Especially, an epoxy group, a primary amino group, and a secondary amino group are preferable.

반응성 관능기(c1)를 갖는 실란 커플링제의 바람직한 실시태양의 하나로서, 화학식 I으로 표시되는 화합물을 들 수 있다.As one of the preferable embodiment of the silane coupling agent which has a reactive functional group (c1), the compound represented by General formula (I) is mentioned.

[화학식 I][Formula I]

Figure pct00001
Figure pct00001

화학식 I 중, X는 에폭시기, 아미노기, 메르캅토기, 비닐기 및 이소시아네이트기로 이루어진 군으로부터 선택되는 어느 하나의 관능기를 나타낸다. L은 2가의 연결기, 또는 단순한 결합수(結合手)를 나타낸다. Y는 각각 독립적으로, 알콕시기를 나타낸다.In the general formula (I), X represents any one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, a vinyl group and an isocyanate group. L represents a divalent linking group or simple coupling | bonding number. Y each independently represents an alkoxy group.

화학식 I 중, X는 에폭시기, 아미노기, 메르캅토기, 비닐기 및 이소시아네이트기로 이루어진 군으로부터 선택되는 어느 하나의 관능기를 나타낸다. 그 중에서도, 에폭시기, 아미노기가 바람직하다.In the general formula (I), X represents any one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, a vinyl group and an isocyanate group. Especially, an epoxy group and an amino group are preferable.

화학식 I 중, L은 2가의 연결기, 또는 단순한 결합수를 나타낸다.In the formula (I), L represents a divalent linking group or a simple bond number.

L로 표시되는 연결기로서는, 예를 들면, 알킬렌기(탄소수 1~20이 바람직하다), -O-, -S-, 아릴렌기, -CO-, -NH-, -SO2-, -COO-, -CONH-, 또는 이들을 조합한 기를 들 수 있다. 그 중에서도, 알킬렌기가 바람직하다. 단순한 결합수의 경우, 화학식 I의 X가 Si(규소원자)와 직접 결합하는 것을 가리킨다.As the linking group represented by L, for example, an alkylene group (having a carbon number of 1 to 20 is preferred), -O-, -S-, an arylene group, -CO-, -NH-, -SO 2 - , -COO- , -CONH-, or a combination thereof. Especially, an alkylene group is preferable. In the case of a simple bond water, X in formula (I) refers to the direct bond with Si (silicon atoms).

화학식 I 중, Y는, 각각 독립적으로, 알콕시기를 나타낸다. 그 중에서도, 탄소수 1~3의 알콕시기가 바람직하다.In general formula (I), Y represents an alkoxy group each independently. Especially, a C1-C3 alkoxy group is preferable.

반응성 관능기(c1)를 갖는 실란 커플링제로서는, 예를 들면, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 및 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등의 에폭시실란, N-(2-아미노에틸)3-아미노프로필메틸디메톡시실란, N-(아미노에틸)3-아미노프로필트리메톡시실란, 및 3-아미노프로필트리에톡시실란 등의 아미노실란, 3-메르캅토프로필트리메톡시실란 등의 메르캅토실란, 3-이소시아네이트프로필트리메톡시실란, 3-이소시아네이트프로필트리에톡시실란 등의 이소시아네이트실란, 비닐트리에톡시실란, p-스티릴트리메톡시실란 등의 비닐기 함유 실란 등을 들 수 있다.Examples of the silane coupling agent having a reactive functional group (c1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl). Epoxysilanes such as ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxy Isocyanate silane, such as amino silanes, such as a silane, and mercaptosilanes, such as 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane, vinyl triethoxysilane, p Vinyl group containing silanes, such as styryl trimethoxysilane, etc. are mentioned.

관능기(c2)를 갖는 화합물 중에 있어서의 관능기(c2)는, 상기의 반응성 관능기(c1)와 반응 가능하면 특별히 한정되지 않고, 예를 들면, 상기의 반응성 관능기(c1)에서 열거된 관능기 등을 바람직하게 들 수 있다.The functional group (c2) in the compound having a functional group (c2) is not particularly limited as long as it can react with the reactive functional group (c1). For example, the functional groups listed in the reactive functional group (c1) are preferable. It can be heard.

관능기(c2)를 갖는 화합물로서는, 반응성 관능기(c1)를 갖는 실란 커플링제를 바람직하게 들 수 있다. 즉, 화합물(A)은, 반응성 관능기(c1)를 갖는 실란 커플링제끼리의 반응 생성물인 것이 바람직하다.As a compound which has a functional group (c2), the silane coupling agent which has a reactive functional group (c1) is mentioned preferably. That is, it is preferable that a compound (A) is a reaction product of silane coupling agents which have a reactive functional group (c1).

관능기(c2)를 갖는 화합물로서는, 상기의 반응성 관능기(c1)를 갖는 실란 커플링제로 예시한 실란 커플링제나, 에틸렌디아민, 아미노프로판티올 등의 아민 화합물, 트리메틸올프로판폴리글리시딜에테르, 펜타에리스리톨폴리글리시딜에테르 등의 에테르 화합물 등을 들 수 있다.As a compound which has a functional group (c2), the silane coupling agent illustrated by the silane coupling agent which has said reactive functional group (c1), amine compounds, such as ethylenediamine and amino propane thiol, trimethylol propane polyglycidyl ether, penta Ether compounds, such as erythritol polyglycidyl ether, etc. are mentioned.

반응성 관능기(c1)를 갖는 실란 커플링제와, 관능기(c2)를 갖는 화합물의 반응비는, 특별히 제한되지 않으나, 실란 커플링제:화합물(몰비)=5:1~0.5:1이 바람직하고, 3:1~1:1이 보다 바람직하다.The reaction ratio of the silane coupling agent having a reactive functional group (c1) and the compound having a functional group (c2) is not particularly limited, but silane coupling agent: compound (molar ratio) = 5: 1 to 0.5: 1 is preferable, and 3 : 1-1: 1 are more preferable.

반응조건은, 사용되는 화합물에 따라 적절히 최적의 조건이 선택된다. 또한, 반응시에, 용매(예를 들면, 알코올 등) 등을 사용해도 된다.The reaction conditions are appropriately selected as appropriate depending on the compound used. In addition, you may use a solvent (for example, alcohol) etc. at the time of reaction.

본 발명의 금속재료용 표면처리제 중에 있어서의 화합물(A)의 함유량은 특별히 한정되지 않으나, 얻어지는 피막의 모든 특성이 보다 우수한 관점에서, 처리제 중의 전체 고형분에 대해, 40~90 질량%가 바람직하고, 60~80 질량%가 보다 바람직하다. 또한, 전체 고형분이란, 후술하는 피막을 구성하는 고형성분을 의미하며, 용매 등은 포함되지 않는다.Although content of the compound (A) in the surface treating agent for metal materials of this invention is not specifically limited, 40-90 mass% is preferable with respect to the total solid in a treating agent from a viewpoint which all the characteristics of the obtained film are more excellent, 60-80 mass% is more preferable. In addition, all solid content means the solid component which comprises the film mentioned later, and a solvent etc. are not contained.

<금속 알콕시드(B)><Metal alkoxide (B)>

본 발명의 금속재료용 표면처리제는, Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나 이상의 원소를 갖는, 1종 이상의 금속 알콕시드(B)를 갖는다. 금속 알콕시드(B)와 화합물(A)을 처리제 중에 함유함으로써, 관능기간의 강고한 가교반응이 발생하여, 치밀한 망목구조를 갖는 피막 형성이 가능하다고 추찰된다. 또한, 금속 알콕시드(B)를 함유하여 형성한 화합물(A)의 결합은, 무기계 피막이 통상 갖는 내열성, 용접성, 연속 가공성 및 도전성이 우수할뿐 아니라, 내약품성도 갖는다.The surface treatment agent for metal materials of this invention has 1 or more types of metal alkoxides (B) which have one or more elements chosen from the group which consists of Si, Ti, and Zr. By incorporating the metal alkoxide (B) and the compound (A) in the treatment agent, a strong crosslinking reaction occurs during the functional period, and it is inferred to be possible to form a film having a dense network structure. Moreover, the bond of the compound (A) formed containing the metal alkoxide (B) is not only excellent in the heat resistance, weldability, continuous workability, and electroconductivity which an inorganic coating normally has, but also has chemical-resistance.

금속 알콕시드(B)는, Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 가지고, 알콕시기를 가지고 있으면 특별히 제한되지 않으며, 종래부터 공지의 것을 적절히 선택하여 사용할 수 있다. 상기 금속 알콕시드는, 금속에 직접 결합하는 알콕시기가 가수분해된 수산기여도 상관없다.The metal alkoxide (B) is not particularly limited as long as it has one element selected from the group consisting of Si, Ti and Zr, and has an alkoxy group, and conventionally known ones can be appropriately selected and used. The said metal alkoxide may be a hydroxyl group in which the alkoxy group which couple | bonds with the metal directly is hydrolyzed.

그 중에서도, 식 Me(OR)4(식 중, R은 각각 독립적으로, 알킬기 또는 수소원자를 나타내고, R 중 하나 이상은 알킬기를 나타낸다. Me는 Si, Ti, 또는 Zr을 나타낸다.)로 나타내어지는 화합물이 바람직하다.Among them, represented by the formula Me (OR) 4 (wherein R each independently represents an alkyl group or a hydrogen atom, and at least one of R represents an alkyl group. Me represents Si, Ti, or Zr.) Compound is preferred.

알킬기로서는 탄소수 1~3이 바람직하고, 탄소수 1~2가 보다 바람직하다.As an alkyl group, C1-C3 is preferable and C1-C2 is more preferable.

금속 알콕시드(B)로서는, 예를 들면, 티탄테트라이소프로폭시드, 티탄테트라에톡시드, 티탄부톡시드다이머, 티탄테트라-2-에틸헥소시드, 지르코늄에톡시드, 지르코늄테트라에톡시드, 지르코늄테트라프로폭시드, 테트라메톡시실란, 테트라에톡시실란, 테트라-n-프로폭시실란, 메틸트리메톡시실란, 메틸트리에톡시실란, 디메틸디메톡시실란, 디메틸디에톡시실란, 메틸트리에톡시실란, 메틸디메톡시실란, 메틸디에톡시실란, 디메틸에톡시실란, 시클로헥실메틸디메톡시실란, n-헥실트리메톡시실란, 디페닐디메톡시실란, 디페닐디에톡시실란, 페닐트리메톡시실란, 페닐트리에톡시실란, 데실트리메톡시실란, 옥타데실트리메톡시실란, 옥타데실트리에톡시실란, 이소부틸트리메톡시실란, 비닐메톡시실란, 비닐에톡시실란, 비닐트리클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, β-(3,4에폭시시클로헥실)에틸트리메톡시실란, γ-글리시독시프로필트리메톡시실란, γ-글리시독시프로필메틸디에톡시실란, γ-글리시독시프로필트리에톡시실란, N-β(아미노에틸)γ-아미노프로필메틸디메톡시실란, N-β(아미노에틸)γ-아미노프로필메틸트리메톡시실란, γ-아미노프로필트리메톡시실란, γ-아미노프로필트리에톡시실란, γ-메타크릴옥시프로필메틸디메톡시실란, γ-메타크릴옥시프로필메틸트리메톡시실란, γ-메타크릴옥시프로필메틸디에톡시실란, γ-메타크릴옥시프로필메틸트리에톡시실란, γ-메르캅토프로필메틸디메톡시실란, γ-메르캅토프로필메틸트리메톡시실란, p-스티릴트리메톡시실란, γ-아크릴옥시프로필트리메톡시실란, N-페닐-γ-아미노프로필트리메톡시실란, γ-우레이도프로필트리에톡시실란, γ-클로로프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설피드, γ-이소시아네이트프로필트리에톡시실란, γ-트리에톡시실릴-N-(1,3-디메틸-부틸리덴)프로필아민, N-(비닐벤질아민)-β-아미노에틸-γ-아미노프로필트리메톡시실란을 들 수 있고, 그 중에서도 테트라메톡시실란, 테트라에톡시실란, 테트라-n-프로폭시실란 등이 보다 바람직하다.As the metal alkoxide (B), for example, titanium tetraisopropoxide, titanium tetraethoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, zirconium ethoxide, zirconium tetraethoxide, Zirconium tetrapropoxide, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriethoxy Silane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, cyclohexylmethyldimethoxysilane, n-hexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, isobutyltrimethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinyltrichlorosilane, vinyltri Me Methoxysilane, vinyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-gly Cydoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyl Triethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyltrimethoxysilane, p-styryltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatepropyltriethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N- (vinylbenzylamine) -β-aminoethyl-γ-aminopropyltrimethoxysilane, among which tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, etc. More preferred.

금속 알콕시드(B)의 바람직한 실시형태로서는, 테트라알콕시실란을 바람직하게 들 수 있다.As preferable embodiment of a metal alkoxide (B), tetraalkoxysilane is mentioned preferably.

테트라알콕시실란으로서는, 예를 들면, 테트라에톡시실란, 테트라메톡시실란, 테트라-n-프로폭시실란 등을 들 수 있다.As tetraalkoxysilane, tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane, etc. are mentioned, for example.

상기 화합물을 사용하면, 굽힘부의 내식성이나 내산성의 측면에서 바람직하다.When the said compound is used, it is preferable at the point of corrosion resistance and acid resistance of a bending part.

금속 알콕시드(B)는, 2종 이상(바람직하게는 2~4종)을 병용하는 것이 바람직하고, 특히 2종이 바람직하다. 2종 이상을 병용함으로써, 가공부 내식성이나 굽힘부 내식성의 측면에서 바람직하다.It is preferable to use 2 or more types (preferably 2-4 types) together, and, as for a metal alkoxide (B), 2 types are especially preferable. By using 2 or more types together, it is preferable from a viewpoint of a process part corrosion resistance and a bending part corrosion resistance.

2종 이상 병용하는 경우의 금속 알콕시드(B)의 1종으로서, 테트라알콕시실란을 사용하는 것이 바람직하다. 또한, 2종 병용하는 경우의 바람직한 조합으로서는, 테트라알콕시실란과 지르코늄알콕시드(예를 들면, 지르코늄테트라프로폭시드)의 조합을 들 수 있다.It is preferable to use tetraalkoxysilane as 1 type of metal alkoxide (B) in the case of using together 2 or more types. Moreover, as a preferable combination in the case of using together 2 types, the combination of a tetraalkoxysilane and a zirconium alkoxide (for example, zirconium tetrapropoxide) is mentioned.

본 발명의 금속재료용 표면처리제 중에 있어서의 금속 알콕시드(B)의 합계 함유량은 특별히 한정되지 않으나, 얻어지는 피막의 모든 특성이 보다 우수한 관점에서, 처리제 중의 전체 고형분에 대해, 5~80 질량%가 바람직하고, 10~50 질량%가 보다 바람직하다.Although the total content of the metal alkoxide (B) in the surface treating agent for metal materials of this invention is not specifically limited, From 5 to 80 mass% with respect to the total solid in a processing agent from a viewpoint that all the characteristics of the film obtained are more excellent. It is preferable and 10-50 mass% is more preferable.

<화합물(C)><Compound (C)>

본 발명의 금속재료용 표면처리제에는, 불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)이 포함된다.The surface treating agent for metal materials of the present invention includes at least one compound (C) selected from the group consisting of fluorine-containing compounds and phosphoric acid compounds.

불소 함유 화합물로서는, 불화물, 착불화물, 기타 불소를 함유하는 화합물이면 특별히 한정되지 않는다. 예를 들면, 불화수소산, 그의 암모늄염, 그의 알칼리금속염; 불화주석, 불화망간, 불화 제1철, 불화 제2철, 불화알루미늄, 불화아연, 불화바나듐 등의 금속 불화물; 산화불소, 불화아세틸, 불화벤조일 등의 산불화물을 들 수 있다.The fluorine-containing compound is not particularly limited as long as it is a compound containing fluoride, complex fluoride and other fluorine. For example, hydrofluoric acid, its ammonium salt, its alkali metal salt; Metal fluorides such as tin fluoride, manganese fluoride, ferrous fluoride, ferric fluoride, aluminum fluoride, zinc fluoride and vanadium fluoride; Acid fluorides, such as fluorine oxide, acetyl fluoride, and benzoyl fluoride, are mentioned.

또한, 불소 함유 화합물로서, Ti, Zr, Hf, Si, Al 및 B로 이루어진 군으로부터 선택되는 원자의 1종 이상의 원소를 갖는 것이 바람직하게 사용된다. 구체적으로는, 예를 들면, (TiF6)2-, (ZrF6)2-, (HfF6)2-, (SiF6)2-, (AlF6)3-, (BF4OH)- 등의 음이온에 수소원자가 1~3원자 부가된 착체, 이들 음이온의 암모늄염, 이들 음이온의 금속염 등을 들 수 있다. 착불화물은, 불소에 의한 에칭효과 외에, 착불화물에 사용되고 있는 금속에 의한 킬레이트 작용을 갖기 때문에, 피막의 내식성이 향상된다.As the fluorine-containing compound, one having at least one element of an atom selected from the group consisting of Ti, Zr, Hf, Si, Al and B is preferably used. Specifically, for example, (TiF 6) 2-, ( ZrF 6) 2-, (HfF 6) 2-, (SiF 6) 2-, (AlF 6) 3-, (BF 4 OH) - , etc. Complexes having 1 to 3 atoms of hydrogen atoms added to an anion thereof, ammonium salts of these anions, metal salts of these anions, and the like. In addition to the etching effect by fluorine, the complex fluoride has a chelate action by the metal used for the complex fluoride, so that the corrosion resistance of the film is improved.

또한, 불소 함유 화합물은, 단독 또는 2종 이상을 조합해서 사용된다.In addition, a fluorine-containing compound is used individually or in combination of 2 or more types.

인산 화합물은, 아연계 도금 표면에 극히 약간이지만 인산아연계 화성피막을 형성하기 때문에 내식성이 향상된다. 인산 화합물로서는, 예를 들면, 인산, 메타인산, 피로인산, 오르토인산, 삼인산, 사인산, 및 이들의 암모늄염, 알루미늄염, 마그네슘염 등을 사용할 수 있다. 상기 기재 이외의 산, 예를 들면, 질산, 황산, 염산과 같은 강산에서는, 금속재료 표면에 대한 에칭력이 지나치게 강하기 때문에, 내식성이 저하되는 경우가 있다. 또한, 이들 강산은, 금속재료 표면 상에서 부동태화 피막을 형성하기 때문에, 도전성이 저하되는 경우가 있어 바람직하지 않다.Although the phosphoric acid compound forms a zinc phosphate chemical conversion coating on the zinc-based plating surface very little, corrosion resistance is improved. As the phosphoric acid compound, for example, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, triacid, and ammonium salts, aluminum salts, magnesium salts, and the like thereof can be used. In acids other than the above-described base materials, for example, strong acids such as nitric acid, sulfuric acid, and hydrochloric acid, the etching force on the surface of the metal material is too strong, which may lower corrosion resistance. Moreover, since these strong acids form a passivation film on the metal material surface, electroconductivity may fall and it is unpreferable.

본 발명의 금속재료용 표면처리제 중에 있어서의 화합물(C)의 함유량은 특별히 한정되지 않으나, 얻어지는 피막의 모든 특성이 보다 우수한 관점에서, 처리제 중의 전체 고형분에 대해, 0.1~50 질량%가 바람직하고, 0.5~30 질량%가 보다 바람직하다.Although content of the compound (C) in the surface treating agent for metal materials of this invention is not specifically limited, 0.1-50 mass% is preferable with respect to the total solid in a processing agent from the viewpoint which all the characteristics of the obtained film are more excellent, 0.5-30 mass% is more preferable.

<유기 화합물(D)><Organic Compound (D)>

본 발명의 금속재료용 표면처리제에는, 카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 친수성 관능기를 갖는 유기화합물(D)이 포함된다. 유기화합물(D)을 함유함으로써, 금속 알콕시드(B)와 화합물(A)이 형성하는 실록산 결합의 형성이 촉진되는 동시에, 화합물(A)의 -SiR1R2R3로 표시되는 관능기(a)의 반응성이 제어되어, 화합물(A)을 수중에서 안정화할 수 있다.The surface treating agent for metal materials of the present invention includes an organic compound (D) having at least one hydrophilic functional group selected from the group consisting of carboxylic acid groups, phosphonic acid groups and sulfonic acid groups. By containing the organic compound (D), the formation of the siloxane bond formed by the metal alkoxide (B) and the compound (A) is promoted, and at the same time, the functional group represented by -SiR 1 R 2 R 3 of the compound (A) (a) ) Can be controlled to stabilize compound (A) in water.

유기 화합물(D)로서는, 예를 들면, 포름산, 초산, 부티르산, 옥살산, 숙신산, 락트산, L-아스코르브산, 타르타르산, 구연산, DL-말산, 말론산, 말레산, 프탈산, 니트릴로트리스메틸렌포스폰산, 니트릴로트리스프로필렌포스폰산, 니트릴로디에틸메틸렌포스폰산, 니트릴로프로필비스메틸렌포스폰산메탄, 메탄-1-히드록시-1,1-디포스폰산, 에탄-1-히드록시-1,1-디포스폰산, 프로판-1-히드록시-1,1-디포스폰산, 설폰산, 벤젠설폰산 등을 들 수 있다.As the organic compound (D), for example, formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, L-ascorbic acid, tartaric acid, citric acid, DL-malic acid, malonic acid, maleic acid, phthalic acid, nitrilotris methylenephosphonic acid , Nitrilotrispropylenephosphonic acid, nitrilodiethylmethylenephosphonic acid, nitrilopropylbismethylenephosphonic acid methane, methane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1- Diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid, sulfonic acid, benzenesulfonic acid and the like.

본 발명의 금속재료용 표면처리제 중에 있어서의 유기 화합물(D)의 함유량은 특별히 한정되지 않으나, 얻어지는 피막의 모든 특성이 보다 우수한 관점에서, 처리제 전량에 대해, 0.1~20 질량%가 바람직하고, 0.5~10 질량%가 보다 바람직하다.Although content of the organic compound (D) in the surface treating agent for metal materials of this invention is not specifically limited, 0.1-20 mass% is preferable with respect to processing agent whole quantity from the viewpoint which all the characteristics of the obtained film are more excellent, and 0.5 10 mass% is more preferable.

<물><Water>

본 발명의 금속재료용 표면처리제에는, 용매로서 물이 포함된다.The surface treating agent for metal materials of the present invention contains water as a solvent.

본 발명의 금속재료용 표면처리제 중에 있어서의 물의 함유량은 특별히 한정되지 않으나, 처리제의 취급이 보다 용이한 관점에서, 처리제 전량에 대해, 30~99 질량%가 바람직하고, 40~95 질량%가 보다 바람직하다.Although the content of water in the surface treating agent for metal materials of this invention is not specifically limited, 30-99 mass% is preferable with respect to treatment agent whole quantity, and 40-95 mass% is more preferable from a viewpoint of handling of a processing agent more easily. desirable.

처리제 중에 있어서의 상기 화합물(A) 중의 Si량(규소성분)을 SiO2로 환산했을 때의 질량과, 상기 금속 알콕시드(B) 중의 Si량(규소성분), Ti량(티탄성분), 및 Zr량(지르코늄성분)을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량의 질량비(B/A)가, 0.01~5.0인 것이 바람직하고, 0.5~3.0인 것이 보다 바람직하다. 상기 범위 내이면, 내산성의 측면에서 바람직하다.The compound (A) of the Si content (silicon component) in the Si content by weight and when converted to a (silicon component) in SiO 2, the metal alkoxide (B), Ti amount (titanium component) in the treatment agent, and The mass ratio (B / A) of the total mass when the amount of Zr (zirconium component) is converted to MO 2 (M represents Si, Ti, or Zr) is preferably 0.01 to 5.0, and preferably 0.5 to 3.0. More preferred. If it is in the said range, it is preferable at the point of acid resistance.

처리제 중에 있어서의 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 상기 화합물(C)의 질량의 질량비(C/A)는, 0.01~4.0인 것이 바람직하고, 0.05~2.0인 것이 보다 바람직하다. 0.01 미만이면, 산화막을 제거하는 효과가 작고, 4.0을 초과하면 에칭력이 지나치게 강해, 피막의 내식성을 저하시키는 경우가 있다.The mass ratio (C / A) of the mass when the amount of Si in the compound (A) in the treating agent is converted into SiO 2 and the mass of the compound (C) is preferably 0.01 to 4.0, and is 0.05 to 2.0. It is more preferable. If it is less than 0.01, the effect of removing an oxide film is small, and if it exceeds 4.0, etching force may become too strong and the corrosion resistance of a film may fall.

처리제 중에 있어서의 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 화합물(C)의 질량의 질량비(B/C)가, 0.1~30인 것이 바람직하고, 5~20이 보다 바람직하다. 상기 범위 내이면, 도전성의 측면에서 바람직하다.Total mass and mass of the compound (C) when the amount of Si, Ti and Zr in the metal alkoxide (B) in the treating agent was converted into MO 2 (M represents Si, Ti, or Zr). It is preferable that mass ratio (B / C) of is 0.1-30, and 5-20 are more preferable. If it is in the said range, it is preferable from a viewpoint of electroconductivity.

처리제 중에 있어서의 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti 및 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 유기 화합물(D)의 질량의 질량비(B/D)가, 0.1~5.0인 것이 바람직하고, 0.5~3.0이 보다 바람직하다. 상기 범위 내이면, 안정성, 도전성의 측면에서 바람직하다.By weight of the total weight and the organic compound (D) when converted to the metal alkoxides Si content, Ti amount and the Zr content in (B) in the treatment agent to the MO 2 (M represents a Si, Ti and Zr) It is preferable that mass ratio (B / D) of is 0.1-5.0, and 0.5-3.0 are more preferable. If it is in the said range, it is preferable from a viewpoint of stability and electroconductivity.

전술한 화합물 이외에, 본 발명의 금속재료용 표면처리제는, 본 발명의 효과를 손상시키지 않는 범위에서, 다른 첨가제를 함유하고 있어도 된다. 이하에, 각각의 성분에 대해 설명한다.In addition to the above-mentioned compounds, the surface treating agent for metal materials of the present invention may contain other additives within a range that does not impair the effects of the present invention. Below, each component is demonstrated.

<금속 화합물(E)><Metal Compound (E)>

본 발명의 금속재료용 표면처리제에는, Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca 및 Li로 이루어진 군으로부터 선택되는 1종 이상의 원소를 함유하는 금속 화합물(E)(단, 불소 함유 화합물은 포함되지 않는다)이 포함되어 있어도 된다. 금속 화합물(E)을 함유함으로써, 피막의 내식성이 추가적으로 향상된다.In the surface treating agent for metal materials of the present invention, a metal compound containing at least one element selected from the group consisting of Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca and Li (E) (however, the fluorine-containing compound is not included) may be included. By containing a metal compound (E), corrosion resistance of a film further improves.

금속 화합물(E)로서는, 예를 들면, 상기 금속의 탄산염, 산화물, 수산화물, 질산염, 유기산염, 유기 화합물 등을 들 수 있다. 또한, 금속 화합물(E)은, 친수성 관능기를 갖는 유기 화합물(D)에서, 수중에서 안정화되는 것이 바람직하다.As a metal compound (E), the carbonate, oxide, hydroxide, nitrate, organic acid salt, an organic compound, etc. of the said metal are mentioned, for example. In addition, the metal compound (E) is preferably stabilized in water in the organic compound (D) having a hydrophilic functional group.

금속 화합물(E)로서는, 예를 들면, 메타텅스텐산암모늄, 탄산지르코늄암모늄, 몰리브덴산암모늄, 오산화바나듐, 바나딘산암모늄, 바나딘산나트륨, 바나딜아세틸아세토네이트, 옥살산바나듐, 옥시황산바나듐, 티탄아세틸아세토네이트, 티탄테트라아세틸아세토네이트, 질산티탄, 중인산알루미늄, 질산알루미늄, 중인산마그네슘, 인산이수소망간, 질산니켈, 질산코발트, 질산망간, 아세틸아세톤아연, 아세틸아세톤니켈, 아세틸아세톤코발트 등을 들 수 있다.As a metal compound (E), for example, ammonium metatungstate, ammonium zirconium carbonate, ammonium molybdate, vanadium pentoxide, ammonium vanadate, sodium vanadate, vanadil acetylacetonate, vanadium oxalate, vanadium oxysulfate, Titanium acetylacetonate, titanium tetraacetylacetonate, titanium nitrate, aluminum phosphate, aluminum nitrate, magnesium phosphate, manganese dihydrogen phosphate, nickel nitrate, cobalt nitrate, manganese nitrate, acetylacetone zinc, acetylacetone nickel, acetylacetone cobalt Etc. can be mentioned.

본 발명의 금속재료용 표면처리제 중에 있어서의 금속 화합물(E)의 함유량은 특별히 한정되지 않으나, 얻어지는 피막의 모든 특성이 보다 우수한 관점에서, 처리제 중의 전체 고형분에 대해, 1~40 질량%가 바람직하고, 5~40 질량%가 보다 바람직하다.Although content of the metal compound (E) in the surface treating agent for metal materials of this invention is not specifically limited, 1-40 mass% is preferable with respect to the total solid in a processing agent from the viewpoint which all the characteristics of the film obtained are more excellent. , 5-40 mass% is more preferable.

처리제 중에 있어서의 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 상기 금속 화합물(E)의 질량의 질량비(E/A)는, 0.01~3.0인 것이 바람직하고, 0.5~2.0인 것이 보다 바람직하다. 0.01 이상이면, 충분한 내식성 향상효과가 얻어진다. 3.0 이하이면, 안정성의 측면에서 바람직하다.Mass and mass mass ratio of the metal compound (E) when converted to the compound Si content in (A) in the treating agent to SiO 2 (E / A) is 0.01 to 3.0, is preferable, and 0.5 to 2.0 It is more preferable that is. If it is 0.01 or more, sufficient corrosion resistance improvement effect will be acquired. If it is 3.0 or less, it is preferable from a viewpoint of stability.

본 발명의 금속재료용 표면처리제에는, 추가로, 피도면에 균일한 피막을 형성시키기 위한 습윤성 향상제로 불리는 계면활성제나, 증점제, 도전성 향상제, 의장성 향상을 위한 착색 안료, 조막성(造膜性) 향상을 위한 조막 보조제 등이 포함되어 있어도 된다.The surface treatment agent for metal materials of the present invention further includes a surfactant called a wettability enhancer for forming a uniform coating on the surface to be coated, a thickener, a conductivity improver, a coloring pigment for improving designability, and film forming properties. The film-forming adjuvant etc. for improvement may be included.

본 발명의 금속재료용 표면처리제에는, 추가적인 내식성 향상을 위해, 유기 인히비터로 불리는 1분자 중에 C=O기, C=C기, C≡C기, C=N기, C≡N기 및 N=N기로 이루어진 군으로부터 선택되는 1종 이상의 불포화기, 또는, N-N기 또는 S원소를 갖는 관능기로 이루어진 군으로부터 선택되는 1종 이상의 관능기를 갖는 화합물이 포함되어 있어도 된다.In the surface treatment agent for metal materials of the present invention, in order to further improve the corrosion resistance, in one molecule called an organic inhibitor, C = O group, C = C group, C≡C group, C = N group, C≡N group and N The compound which has at least 1 sort (s) of unsaturated group selected from the group which == N group, or at least 1 sort (s) of functional group selected from the group which consists of a functional group which has NN group or S element may be contained.

이들 관능기를 갖는 화합물로서는 특별히 한정되지 않으나, 포름알데히드, 아세트알데히드 등의 알데히드류, 아세톤, 메틸에틸케톤 등의 케톤류 등의 C=O기 함유 화합물, 벤젠 및 그의 유도체, 나프탈렌 및 그의 유도체, 아크릴산 및 메타크릴산 및 그의 유도체, 알킬카르복실산에스테르, 알킬알데히드 등의 C=C기 함유 화합물, 아세틸렌알코올이나 아세틸렌 유도체 등의 C≡C기 함유 화합물, 아진, 트리아진, 옥사존 염료, 트리페닐메탄 염료, 퀴니딘, 피리미딘, 피라졸, 이미다졸, 피리디늄 및 퀴놀리늄 화합물 등의 C=N기 함유 화합물, 에틸렌시아노히드린 등의 C≡N 함유 화합물, 히드라진 화합물 및 그의 유도체 등의 N-N기 함유 화합물, 아조 염료 등의 N=N기 함유 화합물, 설폰산, 설포네이트, 설포아미드, 티오요소 및 환상 티오요소 등의 S원소 함유 화합물 등을 들 수 있다.Although the compound which has these functional groups is not specifically limited, C = O group containing compound, such as aldehydes, such as formaldehyde and acetaldehyde, ketones, such as acetone and methyl ethyl ketone, benzene, its derivatives, naphthalene and its derivatives, acrylic acid, C = C group-containing compounds such as methacrylic acid and derivatives thereof, alkylcarboxylic acid esters and alkylaldehydes, C≡C group-containing compounds such as acetylene alcohol and acetylene derivatives, azine, triazine, oxazone dyes, triphenylmethane C = N group-containing compounds such as dyes, quinidine, pyrimidine, pyrazole, imidazole, pyridinium and quinolinium compounds, C 화합물 N-containing compounds such as ethylenecyanohydrin, hydrazine compounds and derivatives thereof N = N group-containing compounds such as NN group-containing compounds and azo dyes, S element-containing compounds such as sulfonic acids, sulfonates, sulfoamides, thioureas and cyclic thioureas A compound etc. are mentioned.

본 발명의 금속재료용 표면처리제에는, 추가적인 내식성 향상을 위해, 수계 수지(수용성 수지, 또는 수분산성 또는 에멀젼형 수지를 사용)가 포함되어 있어도 된다.In order to further improve corrosion resistance, the surface treating agent for metal materials of the present invention may contain an aqueous resin (a water-soluble resin or a water dispersible or emulsion type resin).

수지의 종류로서는, 소부 경화형(baking hardening type)이면 특별히 한정되는 것은 아니나, 예를 들면, 에폭시계 수지, 페놀계 수지, 아크릴계 수지, 우레탄계 수지, 올레핀-카르복실산계 수지, 나일론계 수지, 폴리옥시알킬렌 사슬을 갖는 수지, 폴리비닐알코올, 폴리글리세린, 카르복시메틸셀룰로오스, 히드록시메틸셀룰로오스, 히드록시에틸셀룰로오스 등을 바람직하게 들 수 있다.The kind of resin is not particularly limited as long as it is a baking hardening type, but for example, an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, an olefin-carboxylic acid resin, a nylon resin, or a polyoxy Resin which has an alkylene chain, polyvinyl alcohol, polyglycerol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose etc. are mentioned preferably.

본 발명의 금속재료용 표면처리제는, 필요에 따라, 물 이외의 용매(예를 들면, 알코올 등)를 함유해도 된다.The surface treating agent for metal materials of this invention may contain solvents (for example, alcohol etc.) other than water as needed.

본 발명의 금속재료용 표면처리제의 조제방법은 특별히 한정되지 않는다. 예를 들면, 화합물(A), 금속 알콕시드(B), 화합물(C), 유기 화합물(D), 기타 첨가제, 물을, 혼합 믹서 등의 교반기를 이용하여 충분히 혼합함으로써 제조할 수 있다.The preparation method of the surface treating agent for metal materials of this invention is not specifically limited. For example, it can manufacture by fully mixing a compound (A), a metal alkoxide (B), a compound (C), an organic compound (D), other additives, and water using a stirrer, such as a mixing mixer.

<표면처리방법><Surface Treatment Method>

본 발명의 금속재료용 표면처리제를 사용한 표면처리방법은 특별히 한정되지 않으나, 전술한 금속재료용 표면처리제를 금속재료 표면 상에 도포, 건조시켜서, 피막량이 10~3000 ㎎/㎡인 피막을 금속재료 표면 상에 형성하는 표면처리방법이 바람직하다.Although the surface treatment method using the surface treating agent for metal materials of this invention is not specifically limited, The above-mentioned surface treating agent for metal materials is apply | coated and dried on the surface of a metal material, and the film | membrane of 10-3000 mg / m <2> coats the metal material. The surface treatment method formed on the surface is preferable.

이하에, 그 표면처리방법에 대해 설명한다.Below, the surface treatment method is demonstrated.

처리제를 도포하기 전에, 필요에 따라, 금속재료 표면 상의 유분이나 오염을 제거할 목적으로, 금속재료에 전처리를 실시해도 된다. 금속재료는, 방청(anti-rust) 목적으로 방청유가 도포되어 있는 경우가 많다. 또한, 방청유로 도유(塗油)되어 있지 않은 경우에도, 작업 중에 부착된 유분이나 오염 등이 있다. 전처리를 실시함으로써, 금속재료 표면 상을 청정하여, 본 발명의 처리제에 의해 금속재료 표면이 균일하게 젖기 쉬워진다. 또한, 유분이나 오염 등이 없어, 본 발명의 처리제로 재료 표면이 균일하게 젖는 경우는, 전처리 행정(行程)은 특별히 필요는 없다.Before applying the treatment agent, the metal material may be pretreated as necessary for the purpose of removing oil or dirt on the metal material surface. The metal material is often coated with rust preventive oil for the purpose of rust prevention. Moreover, even when it is not oiled with rust preventive oil, there exists an oil, contamination, etc. which adhered during work. By carrying out the pretreatment, the surface of the metal material is cleaned and the surface of the metal material is easily wetted by the treatment agent of the present invention. In addition, when there is no oil, a contamination, etc., and the material surface wets uniformly with the processing agent of this invention, a pretreatment stroke is not necessary in particular.

또한, 전처리의 방법으로서는 특별히 한정되지 않고, 탕세(湯洗), 용제 세정, 알칼리 탈지 세정 등의 방법을 들 수 있다.Moreover, it does not specifically limit as a method of pretreatment, The methods, such as hot water washing | cleaning, solvent washing | cleaning, and alkali degreasing washing | cleaning, are mentioned.

적용하는 금속재료는 특별히 한정되지 않으나, 아연 함유 금속 도금 강판, 알루미늄판, 스테인리스 강판이 바람직하다. 이들 금속재료 표면에는 사전에 인산염 처리, 크로메이트 처리 등의 전처리가 실시되어 있어도 된다.The metal material to be applied is not particularly limited, but a zinc-containing metal plated steel sheet, an aluminum sheet, or a stainless steel sheet is preferable. The surface of these metal materials may have been previously subjected to pretreatment such as phosphate treatment or chromate treatment.

금속재료 표면에 도포하는 방법은 특별히 제한은 없고, 침지법, 스프레이법, 롤코트법 등의 방법을 사용할 수 있다.There is no restriction | limiting in particular in the method of apply | coating to the metal material surface, The methods, such as an immersion method, a spray method, and a roll coat method, can be used.

또한, 처리(도포)온도, 처리(도포)시간에 대해서도 특별히 제한되지 않으나, 일반적으로 처리(도포)온도는 10~40℃인 것이 바람직하고, 처리(도포)시간은 0.1~10초인 것이 바람직하다.The treatment (coating) temperature and the treatment (coating) time are not particularly limited, but in general, the treatment (coating) temperature is preferably 10 to 40 ° C, and the treatment (coating) time is preferably 0.1 to 10 seconds. .

금속재료 표면 상에 도포되어 형성된 도막을 건조함으로써, 용매, 즉 물 또는 알코올이 휘발되어, 목적하는 피막이 형성된다. 건조방법으로서는 특별히 한정되지 않고, 열풍이나 인덕션 히터, 적외선, 근적외선 등에 의해 가열하여, 건조하면 된다.By drying the coating film applied and formed on the metal material surface, a solvent, that is, water or an alcohol, is volatilized, and a desired film is formed. It does not specifically limit as a drying method, What is necessary is just to heat and dry by hot air, an induction heater, infrared rays, near infrared rays, etc.

건조온도는 도달판온도로서 30~300℃인 것이 바람직하고, 40~250℃인 것이 보다 바람직하며, 60~200℃인 것이 특히 바람직하다. 건조시간은 도달판온도가 상기 조건을 만족하고 있으면, 특별히 제한되지 않는다.It is preferable that drying temperature is 30-300 degreeC as an arrival board temperature, It is more preferable that it is 40-250 degreeC, It is especially preferable that it is 60-200 degreeC. The drying time is not particularly limited as long as the reaching plate temperature satisfies the above conditions.

금속재료 표면 상에 형성되는 피막의 피막량은 10~3000 ㎎/㎡의 범위이고, 100~1000 ㎎/㎡가 보다 바람직하다. 상기 범위 내이면, 내식성과 도전성의 측면에서 바람직하다.The film amount of the film formed on the metal material surface is 10-3000 mg / m <2>, and 100-1000 mg / m <2> is more preferable. If it is in the said range, it is preferable from a viewpoint of corrosion resistance and electroconductivity.

또한, 이들 피막량은, 강판 등의 판상물의 경우는, 편면당 피막량을 가리킨다.In addition, these coating amounts indicate the coating amount per single side in the case of plate-shaped objects, such as a steel plate.

전술한 표면처리방법에 의해 형성된 피막 상에, 건조 후의 막두께가 0.1~3.0 ㎛가 되도록 유기 고분자막을 형성하여, 추가적으로 고도의 내식성이나 내지문성, 윤활성을 부여할 수 있다. 이와 같은 유기 고분자막은 공지의 아크릴, 우레탄, 에폭시 등 수지 에멀젼이나, 이것에 실리카, 방청제, 자외선 흡수제, 안료 등이 첨가된 것을 사용할 수 있다.On the film formed by the above-mentioned surface treatment method, an organic polymer film is formed so that the film thickness after drying may be 0.1-3.0 micrometers, and it can additionally provide high corrosion resistance, fingerprint resistance, and lubricity. As such an organic polymer film, resin emulsions, such as a well-known acryl, urethane, and epoxy, and what added silica, a rust preventive agent, a ultraviolet absorber, a pigment, etc. to this can be used.

전술한 표면처리방법에 의해 처리된 금속재료는, 각종 용도로 적용할 수 있다. 예를 들면, 가전제품용 강판, 건재용 강판, 자동차용 강판 등을 들 수 있다.The metal material processed by the above-mentioned surface treatment method can be applied to various uses. For example, the steel plate for home appliances, the steel plate for building materials, the steel plate for automobiles, etc. are mentioned.

본 발명의 금속재료용 표면처리제를 사용하면, 금속재료 표면에 우수한 내식성, 밀착성 및 내산성은 물론이고, 무기계 피막이 통상 갖는 내열성, 용접성, 연속 가공성 및 도전성, 유기계 피막이 통상 갖는 내지문성이나 도장성 등을 겸비하는 신규한 피막이 얻어진다.When the surface treatment agent for metal materials of the present invention is used, it is excellent in corrosion resistance, adhesion and acid resistance to the surface of the metal material, as well as heat resistance, weldability, continuous workability and conductivity that inorganic coatings usually have, and fingerprinting and coating properties that organic coatings usually have. The new film which combines is obtained.

이 이유는 이하와 같이 추측되나, 본 발명은 이와 같은 추측에 제한되지 않는다. 본 발명의 금속재료용 표면처리제를 사용하여 형성되는 피막은, 주로 화합물(A)과 금속 알콕시드(B)에 의한 것이다. 먼저, 화합물(A)의 일부가 건조 등에 의해 농축되었을 때 금속 알콕시드(B)가 촉매가 되어, 연속 피막을 성막하는 것, 일부가 가수분해되어 생성된 -OR기가 금속 표면과 Si-O-M 결합(M: 피도물 표면의 금속원소)을 형성함으로써, 현저한 배리어효과가 발휘되어, 내식성이 향상되는 것으로 추정된다.This reason is estimated as follows, but the present invention is not limited to such a guess. The film formed using the surface treating agent for metal materials of this invention mainly consists of a compound (A) and a metal alkoxide (B). First, when a part of the compound (A) is concentrated by drying or the like, the metal alkoxide (B) becomes a catalyst to form a continuous film, and the -OR group formed by hydrolysis of a part of the metal surface and the Si-OM bond By forming (M: a metal element on the surface of the workpiece), a remarkable barrier effect is exhibited and corrosion resistance is estimated to improve.

한편, 본 발명의 금속재료용 표면처리제를 사용한 피막은, 주로 규소를 주성분으로 하여 형성된다. 그 구조에 대해서는, 규소-유기 사슬의 배열이 규칙적이고, 또한 유기 사슬이 비교적 짧은 것으로부터, 피막 중의 매우 미소(微小)한 구역에, 규칙적이고 치밀하게 규소 함유부와 유기물부, 즉 무기물과 유기물이 배열되어 있는 것으로 생각된다. 그 때문에, 무기계 피막이 통상 갖는 내열성, 용접성, 연속 가공성 및 도전성, 유기계 피막이 통상 갖는 내지문성이나 도장성 등을 겸비하는 신규한 피막의 형성이 가능해질 것으로 추정된다.On the other hand, the film using the surface treating agent for metal materials of this invention is formed mainly using silicon as a main component. As for the structure, since the arrangement of the silicon-organic chains is regular and the organic chains are relatively short, the silicon-containing portions and the organic matter portions, i.e. inorganic and organic matters, are regularly and precisely in very minute regions in the coating. It is assumed that this is arranged. Therefore, it is presumed that the formation of a novel coating having both heat resistance, weldability, continuous workability and conductivity, and anti-fingerprint and coating properties, which the inorganic coating usually has, can be achieved.

또한, 피막 중의 규소 함유부에 있어서는, 규소의 약 80%가 실록산 결합을 형성하고 있는 것이 분석으로 확인되고 있다.Moreover, in the silicon containing part in a film, about 80% of silicon forms the siloxane bond by analysis.

실시예Example

이하에 본 발명의 실시예 및 비교예를 들어 본 발명을 구체적으로 설명하나, 본 발명은 이들에 의해 한정되지 않는다. 시험판의 조제, 실시예 및 비교예, 및 금속재료용 표면처리제의 도포의 방법에 대해 하기에 설명한다.Although an Example and a comparative example of this invention are given to the following, this invention is concretely demonstrated to it, but this invention is not limited by these. The preparation of the test plate, the examples and the comparative examples, and the method of coating the surface treatment agent for a metal material will be described below.

시험판의 조제Trial

(1) 시험 소재(1) test material

하기에 나타낸 시판의 소재를 사용하였다.Commercially available materials shown below were used.

·전기 아연 도금 강판(EG):판두께=0.8 ㎜, 도금량=20/20(g/㎡)Electro galvanized steel sheet (EG): plate thickness = 0.8 mm, plating amount = 20/20 (g / ㎡)

·5% 알루미늄 함유 용융 아연 도금 강판(GF):판두께=0.8 ㎜, 도금량=90/90(g/㎡)5% aluminum-containing hot dip galvanized steel sheet (GF): plate thickness = 0.8 mm, plating amount = 90/90 (g / ㎡)

·아연 니켈 합금 도금 강판(Zn/Ni):판두께=0.8 ㎜, 도금량=20/20(g/㎡)Zinc nickel alloy plated steel sheet (Zn / Ni): plate thickness = 0.8 mm, plating amount = 20/20 (g / ㎡)

·용융 55% 아연 합금 도금 강판(GL):판두께=0.8 ㎜, 도금량=90/90(g/㎡)Molten 55% zinc alloy coated steel plate (GL): plate thickness = 0.8 mm, plating amount = 90/90 (g / m2)

·합금화 (Zn-Fe) 용융 아연 도금 강판(GA):판두께=0.8 ㎜, 도금량=60/60(g/㎡)Alloying (Zn-Fe) hot dip galvanized steel sheet (GA): plate thickness = 0.8 mm, plating amount = 60/60 (g / ㎡)

·용융 아연 도금 강판(GI):판두께=0.8 ㎜, 도금량=60/60(g/㎡)Hot-dip galvanized steel sheet (GI): Plate thickness = 0.8 mm, Plating amount = 60/60 (g / m 2)

·A-1100계 알루미늄판(AL):판두께=0.8 ㎜A-1100 series aluminum plate (AL): Plate thickness = 0.8 mm

또한, 도금량은 각각의 강판의 주면(主面) 상으로의 도금량을 나타내고 있다. 예를 들면, 전기 아연 도금 강판의 경우는, 20/20(g/㎡)이고, 강판 양면의 각각에 20 g/㎡의 도금을 갖는 것을 의미한다.In addition, the plating amount has shown the plating amount on the main surface of each steel plate. For example, in the case of an electrogalvanized steel sheet, it means 20/20 (g / m <2>) and it means having 20 g / m <2> plating in each of both surfaces of a steel plate.

(2) 시험판의 제작(2) Production of trial

상기 시험 소재를, 실리케이트계 알칼리 탈지제의 파인 클리너 4336(등록상표: 니혼 파커라이징(주) 제조)을 사용하여, 농도 20 g/L, 온도 60℃의 조건으로 2분간 스프레이 처리하고, 순수로 30초간 수세한 후에 건조한 것을 시험판으로 하였다. 이 시험판에 후술하는 금속재료용 표면처리제를 바코터로 도포하고, 열풍 건조로를 사용하여, 도달온도를 90℃가 되도록 건조하였다.The test material was sprayed for 2 minutes under conditions of a concentration of 20 g / L and a temperature of 60 ° C using Fine Cleaner 4336 (trademark: manufactured by Nippon Parker Co., Ltd.) of a silicate-based alkali degreasing agent, followed by pure water for 30 seconds. After washing with water, the dried one was used as a test plate. The surface treatment agent for metal materials mentioned later was apply | coated to this test board with the bar coater, and it dried so that the arrival temperature might be 90 degreeC using the hot air drying furnace.

(3) 금속재료용 표면처리제의 구성성분(3) Components of Surface Treatment Agents for Metal Materials

화합물(A)로서, 이하의 화합물 A1~A9을 사용하였다.As the compound (A), the following compounds A1 to A9 were used.

[화합물 A1][Compound A1]

트리메톡시클로로실란 2 몰과, 트리메틸올프로판 1 몰을, 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.2 mol of trimethoxychlorosilane and 1 mol of trimethylolpropane were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 수산기를 가지고 있고, 1분자 중의 관능기(a) 수는 2개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 530이었다.The obtained product had a hydroxyl group, the number of functional groups (a) in one molecule was two, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 530.

[화합물 A2][Compound A2]

비닐트리메톡시실란 2 몰과, 설포에틸아크릴레이트 1 몰을, 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.2 mol of vinyl trimethoxysilane and 1 mol of sulfoethyl acrylate were made to react in ethanol, and the product was obtained. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 설폰산기를 가지고 있고, 1분자 중의 관능기(a) 수는 2개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 320이었다. The obtained product had a sulfonic acid group, the number of functional groups (a) in one molecule was two, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 320.

[화합물 A3][Compound A3]

3-글리시독시프로필트리메톡시실란 2 몰과, 3-아미노프로필트리에톡시실란 1 몰을, 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.2 mol of 3-glycidoxypropyltrimethoxysilane and 1 mol of 3-aminopropyltriethoxysilane were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 아미노기, 수산기를 가지고 있고, 1분자 중의 관능기(a) 수는 3개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 700이었다.The obtained product had an amino group and a hydroxyl group, the number of functional groups (a) in one molecule was three, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 700.

[화합물 A4][Compound A4]

N-(아미노에틸)3-아미노프로필트리메톡시실란 2 몰과, 3-이소시아네이트프로필트리메톡시실란 1 몰을, 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다. 2 mol of N- (aminoethyl) 3-aminopropyltrimethoxysilane and 1 mol of 3-isocyanatepropyltrimethoxysilane were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 아미노기를 가지고 있고, 1분자 중의 관능기(a) 수는 2개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 800이었다. The obtained product had an amino group, the number of functional groups (a) in one molecule was two, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 800.

[화합물 A5][Compound A5]

3-메르캅토트리메톡시실란 4 몰과, 2-(3,4에폭시시클로헥실)에틸트리메톡시실란 4 몰과 디메틸올프로피온산 1 몰을 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.4 mol of 3-mercaptotrimethoxysilane, 4 mol of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 1 mol of dimethylolpropionic acid were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 수산기, 카르복실기를 가지고 있고, 1분자 중의 관능기(a) 수는 4개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 1900이었다.The obtained product had a hydroxyl group and a carboxyl group, the number of functional groups (a) in one molecule was four, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 1900.

[화합물 A6][Compound A6]

3-글리시독시프로필트리메톡시실란 4 몰과, 에틸렌디아민 1 몰을 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.4 mol of 3-glycidoxypropyltrimethoxysilane and 1 mol of ethylenediamine were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 아미노기, 수산기를 가지고 있고, 1분자 중의 관능기(a) 수는 4개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 약 500이었다.The obtained product had an amino group and a hydroxyl group, the number of functional groups (a) in one molecule was four, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was about 500.

[화합물 A7][Compound A7]

3-아미노프로필트리에톡시실란 3 몰과, 트리메틸올프로판폴리글리시딜에테르 1 몰을, 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.3 mol of 3-aminopropyltriethoxysilane and 1 mol of trimethylolpropanepolyglycidyl ether were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 아미노기, 수산기를 가지고 있고, 1분자 중의 관능기(a) 수는 3개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 300이었다.The obtained product had an amino group and a hydroxyl group, the number of functional groups (a) in one molecule was three, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was 300.

[화합물 A8][Compound A8]

3-메르캅토트리메톡시실란 7 몰과, 펜타에리스리톨폴리글리시딜에테르 1 몰과, 2-아미노프로판티올 1 몰을 에탄올 중에서 반응시켜 생성물을 얻었다. 그 후, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.7 mol of 3-mercaptotrimethoxysilane, 1 mol of pentaerythritol polyglycidyl ether, and 1 mol of 2-aminopropanethiol were reacted in ethanol to obtain a product. Then, it mixed with pure water and adjusted so that solid content might be 10 mass%.

얻어진 생성물은 아미노기를 가지고 있고, 1분자 중의 관능기(a) 수는 7개이며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)은 1500이었다.The obtained product had an amino group, the number of functional groups (a) in one molecule was seven, and the molecular weight (average molecular weight / number of functional groups) per functional group (b) was 1500.

[화합물 A9][Compound A9]

3-글리시독시프로필트리메톡시실란 175.1 질량부와 3-아미노프로필트리메톡시실란 58.5 질량부를 혼합시킨 실란 커플링제에, 순수와 혼합하여, 고형분이 10 질량%가 되도록 조정하였다.The silane coupling agent which mixed 175.1 mass part of 3-glycidoxy propyl trimethoxysilane and 58.5 mass part of 3-aminopropyl trimethoxysilane was mixed with pure water, and it adjusted so that solid content might be 10 mass%.

얻어진 생성물의 1분자 중의 관능기(a) 수는 1개이고, 관능기(a) 1개당 분자량(평균 분자량/관능기 수)은 약 230으로, 화합물(A)의 범위 밖이었다.The number of functional groups (a) in one molecule of the obtained product was one, and the molecular weight (average molecular weight / number of functional groups) per one functional group (a) was about 230, which was outside the range of the compound (A).

<금속 알콕시드(B)><Metal alkoxide (B)>

B1: 티탄테트라이소프로폭시드B1: titanium tetraisopropoxide

B2: 테트라메톡시실란 B2: tetramethoxysilane

B3: 테트라에톡시실란 B3: tetraethoxysilane

B4: 테트라-n-프로폭시실란B4: tetra-n-propoxysilane

B5: 지르코늄테트라프로폭시드 B5: zirconium tetrapropoxide

<화합물(C)><Compound (C)>

C1: 티탄불화수소산C1: titanium hydrofluoric acid

C2: 지르콘불화수소산C2: Zirconic Hydrofluoric Acid

C3: 규불화수소산 C3: hydrofluoric acid

C4: 하프늄불화수소산C4: hafnium hydrofluoric acid

C5: 티탄불화암모늄C5: ammonium titanium fluoride

C6: 지르콘불화암모늄C6: ammonium zircon fluoride

C7: 불화암모늄 C7: ammonium fluoride

C8: 인산C8: phosphoric acid

C9: 피로인산C9: pyrophosphate

C10: 인산수소이암모늄 C10: diammonium hydrogen phosphate

<유기 화합물(D)><Organic Compound (D)>

D1: 초산D1: acetic acid

D2: 타르타르산D2: tartaric acid

D3: 프탈산D3: phthalic acid

D4: 에탄-1-히드록시-1,1-디포스폰산D4: ethane-1-hydroxy-1,1-diphosphonic acid

D5: 설폰산D5: sulfonic acid

<금속 화합물(E)><Metal Compound (E)>

E1: 메타텅스텐산암모늄E1: ammonium metatungstate

E2: 탄산지르코늄암모늄E2: Zirconium Ammonium Carbonate

E3: 바나딜아세틸아세토네이트E3: vanadilacetylacetonate

E4: 티탄아세틸아세토네이트E4: titanium acetylacetonate

E5: 바나딘산암모늄E5: ammonium vanadate

E6: 중인산알루미늄E6: aluminum phosphate

E7: 중인산마그네슘E7: Magnesium phosphate

E8: 인산이수소망간E8: Manganese Dihydrogen Phosphate

E9: 질산니켈E9: Nickel Nitrate

E10: 질산알루미늄E10: aluminum nitrate

전술한 화합물(A), 금속 알콕시드(B), 화합물(C), 유기 화합물(D), 물, 및 금속 화합물(E)을 표 1에 나타내는 소정량으로 수중에서 배합하여, 금속재료용 표면처리제를 조제하였다. 표 1 중의 성분 (A)~(E)의 배합량은, 처리액 1 ㎏ 중에 배합되는 양(g)을 나타낸다. 또한, 각 처리제에 포함되는 성분 (A)~(E) 이외의 성분은, 주로 물이다. 또한, 표 1 중에 있어서의 화합물(A)의 배합량은, 화합물(A) 중의 Si량(규소성분)을 SiO2로 환산했을 때의 질량을 의미한다. 또한, 표 1 중에 있어서의 금속 알콕시드(B)의 배합량은, 금속 알콕시드(B) 중의 Si량(규소성분), Ti량(티탄성분), 및 Zr량(지르코늄성분)을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량을 의미한다. 또한, 표 1 중, 2종의 화합물을 병용하는 경우의 비율은, 질량비(g)를 의미한다.The compound (A), the metal alkoxide (B), the compound (C), the organic compound (D), the water, and the metal compound (E) mentioned above are mix | blended in water in the predetermined amount shown in Table 1, and the surface for metal materials Treating agent was prepared. The compounding quantity of components (A)-(E) in Table 1 shows the quantity (g) mix | blended in 1 kg of process liquids. In addition, components other than components (A)-(E) contained in each processing agent are mainly water. In addition, the amount of the compound (A) in the Table 1, means the weight when converted to the amount of Si (silicon component) in the compound (A) with SiO 2. Further, the blending amount of the metal alkoxide (B) in the Table 1, the metal alkoxide (B) a of Si content (silicon source), Ti amount (the titanium component) and Zr amount (zirconium component) MO 2 (M Means Si, Ti, or Zr). In addition, in Table 1, the ratio at the time of using two types of compounds together means mass ratio (g).

조제된 처리제를, 표 1에 나타내는 시험판의 표면에, 소정의 피막량이 되도록 바코트 도포하고, 도달판온도가 90℃가 되도록 건조하여 피막을 형성하였다.The prepared treatment agent was coated on the surface of the test plate shown in Table 1 so as to have a predetermined coating amount, and dried so that the reaching plate temperature became 90 ° C to form a film.

[표 1-1]Table 1-1

Figure pct00002
Figure pct00002

[표 1-2]TABLE 1-2

Figure pct00003

Figure pct00003

(5) 평가시험의 방법(5) Method of evaluation test

(5-1) 평면부 내식성(5-1) Flat part corrosion resistance

얻어진 각 표면처리 시험판에 대해, JIS-Z-2371에 의한 염수 분무 시험을 120시간 행하였다. 다음으로, 백청 발생 면적률을 육안으로 측정하여 평가를 행하였다. 여기에서 백청 발생 면적률이란, 관찰 부위의 면적(50 ㎝×120 ㎝)에 대한 백청 발생 부위의 면적의 백분율이다. 평가기준은 이하와 같다.About each obtained surface treatment test board, the salt spray test by JIS-Z-2371 was performed for 120 hours. Next, the white rust-generating area ratio was visually measured and evaluated. Here, the white rust-generating area ratio is a percentage of the area of the white rust-generating site with respect to the area of the observation site (50 cm x 120 cm). Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=백청 발생이 전체 면적의 3% 미만◎ = White rust is less than 3% of total area

○=백청 발생이 전체 면적의 3% 이상 10% 미만○ = White rust outbreak is less than 10% more than 3% of total area

△=백청 발생이 전체 면적의 10% 이상 30% 미만△ = White rust occurrence is more than 10% and less than 30% of the total area

×=백청 발생이 전체 면적의 30% 이상X = White rust is more than 30% of the total area

(5-2) 알칼리 탈지 후 내식성(5-2) Corrosion resistance after alkali degreasing

알칼리 탈지제 CL-N364S(니혼 파커라이징(주) 제조)를 2 질량%의 농도로 순수에 용해하고, 60℃로 가온하였다. 이 알칼리용액에 각 샘플을 2분간 침지하고, 꺼내어 수세하여 건조하였다. 각 샘플에 대해, JIS-Z-2371에 의한 염수 분무 시험을 72시간 행하고, 백청 발생상황을 관찰하였다. 여기에서 백청 발생 면적률이란, 관찰 부위의 면적(50 ㎝×120 ㎝)에 대한 백청 발생 부위의 면적의 백분율이다. 평가기준은 이하와 같다.Alkali degreasing agent CL-N364S (manufactured by Nippon Parker Co., Ltd.) was dissolved in pure water at a concentration of 2% by mass, and heated to 60 ° C. Each sample was immersed in this alkaline solution for 2 minutes, taken out, washed with water and dried. About each sample, the salt spray test by JIS-Z-2371 was done for 72 hours, and the white blue color development condition was observed. Here, the white rust-generating area ratio is a percentage of the area of the white rust-generating site with respect to the area of the observation site (50 cm x 120 cm). Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=백청 발생이 전체 면적의 3% 미만◎ = White rust is less than 3% of total area

○=백청 발생이 전체 면적의 3% 이상 10% 미만○ = White rust outbreak is less than 10% more than 3% of total area

△=백청 발생이 전체 면적의 10% 이상 30% 미만△ = White rust occurrence is more than 10% and less than 30% of the total area

×=백청 발생이 전체 면적의 30% 이상X = White rust is more than 30% of the total area

(5-3) 가공부 내식성(5-3) Machining part corrosion resistance

얻어진 각 표면처리 시험판에 대해, 에릭슨 시험(7 ㎜ 압출)을 행한 후, JIS-Z-2371에 의한 염수 분무 시험을 72시간 행하였다. 다음으로, 백청 발생 면적률을 육안으로 측정하여 평가를 행하였다. 평가기준은 이하와 같다.After performing the Ericsson test (7 mm extrusion) about each obtained surface treatment test board, the salt spray test by JIS-Z-2371 was done for 72 hours. Next, the white rust-generating area ratio was visually measured and evaluated. Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=백청 발생이 전체 면적의 10% 미만◎ = White rust is less than 10% of total area

○=백청 발생이 전체 면적의 10% 이상 20% 미만○ = white rust outbreak is less than 20% more than 10% of the total area

△=백청 발생이 전체 면적의 20% 이상 30% 미만△ = White rust occurrence is more than 20% and less than 30% of the total area

×=백청 발생이 전체 면적의 30% 이상X = White rust is more than 30% of the total area

(5-4) 굽힘부 내식성(5-4) Bending part corrosion resistance

얻어진 각 표면처리 시험판에 대해, 에릭슨 시험(2 ㎜ 절곡부(折曲部))을 행한 후, JIS-Z-2371에 의한 염수 분무 시험을 72시간 행하였다. 다음으로, 백청 발생 면적률을 육안으로 측정하여 평가를 행하였다. 평가기준은 이하와 같다.After performing the Ericsson test (2 mm bent part) about each obtained surface treatment test board, the salt spray test by JIS-Z-2371 was performed for 72 hours. Next, the white rust-generating area ratio was visually measured and evaluated. Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=백청 발생이 전체 면적의 10% 미만◎ = White rust is less than 10% of total area

○=백청 발생이 전체 면적의 10% 이상 20% 미만○ = white rust outbreak is less than 20% more than 10% of the total area

△=백청 발생이 전체 면적의 20% 이상 30% 미만△ = White rust occurrence is more than 20% and less than 30% of the total area

×=백청 발생이 전체 면적의 30% 이상X = White rust is more than 30% of the total area

(5-5) 내산성(5-5) acid resistance

얻어진 각 표면처리 시험판을 1 중량%의 황산 수용액 중에 60분간 침지하고, 이어서 수세 건조하였다. 피막 외관 변화 및 금속 표면의 변색(부식) 정도로, 내산성을 육안 평가하였다.Each obtained surface treatment test board was immersed for 60 minutes in 1weight% of sulfuric acid aqueous solution, and then it was washed with water and dried. Acid resistance was visually evaluated to the extent of film appearance change and the discoloration (corrosion) of the metal surface.

<평가기준><Evaluation Criteria>

◎=피막 외관 변화 및 금속 표면의 변색이 보이지 않음◎ = No change in coating appearance or discoloration of metal surface

○=부분적으로 약간의 피막 박리(용해도 포함한다), 또는 금속 표면의 변색이 보임(Circle) a little film peeling (we include solubility) or discoloration of metal surface is seen in part

△=거의 전면으로 퍼지는 부분적인 피막 박리(용해도 포함한다), 또는 금속 표면의 현저한 변색이 보임(Triangle | delta) = partial film peeling (including solubility) which spreads to almost the front surface, or a significant discoloration of the metal surface is seen

×=피막이 박리 또는 용해됨으로써 거의 잔존하고 있지 않고, 금속 표면의 변색도 현저함X = The film hardly remains due to peeling or melting, and the discoloration of the metal surface is also remarkable.

(5-6) 도전성(5-6) conductivity

층간 저항 시험기(도에이 공업 주식회사 제조, 장치명 LRT-1A)에 의해, 얻어진 표면처리 시험판의 층간 저항을 측정하였다.The interlayer resistance of the obtained surface treatment test plate was measured by an interlayer resistance tester (Toei Industries Co., Ltd., apparatus name LRT-1A).

<평가기준><Evaluation Criteria>

◎=층간 저항이 1.0 Ω 미만◎ = Interlayer resistance is less than 1.0 Ω

○=층간 저항이 1.0 Ω 이상 2.0 Ω 미만○ = interlayer resistance is 1.0 Ω or more and less than 2.0 Ω

△=층간 저항이 2.0 Ω 이상 3.0 Ω 미만△ = interlayer resistance 2.0 Ω or more and less than 3.0 Ω

×=층간 저항이 3.0 Ω 미만X = interlayer resistance is less than 3.0 Ω

(5-7) 내열성(5-7) heat resistance

얻어진 표면처리 시험판을 오븐에서 200℃로 2시간 가열 후, 평면부 내식성 JIS-Z-2371에 의한 염수 분무 시험을 48시간 행하여, 백청 발생상황을 관찰하였다. 여기에서 백청 발생 면적률이란, 관찰 부위의 면적(6 ㎝×6 ㎝)에 대한 백청 발생 부위의 면적의 백분율이다. 평가기준은 이하와 같다.After heating the obtained surface treatment test board at 200 degreeC in oven for 2 hours, the salt spray test by the flat part corrosion resistance JIS-Z-2371 was performed for 48 hours, and the white blue development condition was observed. Here, the white rust-generating area ratio is a percentage of the area of the white rust-generating site with respect to the area (6 cm x 6 cm) of the observation site. Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=백청 발생이 전체 면적의 3% 미만◎ = White rust is less than 3% of total area

○=백청 발생이 전체 면적의 3% 이상 10% 미만○ = White rust outbreak is less than 10% more than 3% of total area

△=백청 발생이 전체 면적의 10% 이상 30% 미만△ = White rust occurrence is more than 10% and less than 30% of the total area

×=백청 발생이 전체 면적의 30% 이상X = White rust is more than 30% of the total area

(5-8) 내지문성(5-8) anti-fingerprint

얻어진 표면처리 시험판에 바셀린을 도포하고, 색차계(닛폰덴쇼쿠 공업 주식회사 제조, color meter ZE2000)로, 바셀린 도포 전후의 L값 증감(△L)을 측정하였다. 평가기준은 이하와 같다.Vaseline was applied to the obtained surface treatment test plate, and L value increase and decrease (ΔL) before and after petroleum jelly was measured with a color difference meter (Nippon Denshoku Industries Co., Ltd., color meter ZE2000). Evaluation criteria are as follows.

<평가기준><Evaluation Criteria>

◎=△L이 0.5 미만◎ = △ L is less than 0.5

○=△L이 0.5 이상 1.0 미만○ = △ L is more than 0.5 and less than 1.0

△=△L이 1.0 이상 2.0 미만△ = △ L is 1.0 or more and less than 2.0

×=△L이 2.0 이상× = △ L is 2.0 or more

(5-9) 안정성(5-9) stability

금속재료용 표면처리제를 40℃의 고온조에서 방치하고, 겔화될 때까지의 경과일수로, 처리제의 안정성을 평가하였다.The surface treatment agent for metal materials was left to stand in a high temperature bath at 40 degreeC, and the stability of a treatment agent was evaluated by the elapsed days until it gelled.

<평가기준><Evaluation Criteria>

◎=겔화 없음◎ = No gelation

○=겔화 일수가 90일 이상 120일 미만○ = gelation days more than 90 days less than 120 days

△=겔화 일수가 60일 이상 90일 미만△ = gelation days more than 60 days less than 90 days

×=겔화 일수가 60일 미만X = gelation days less than 60 days

실시예 1~40, 및 비교예 1~6에 기재된 금속재료용 표면처리제를 사용하여, 상기의 처리방법으로 얻어지는 표면처리 시험의 (5-1)~(5-9)의 평가를 행한 결과를, 표 2에 나타낸다.The result of having evaluated (5-1)-(5-9) of the surface treatment test obtained by said processing method using the surface treating agent for metal materials of Examples 1-40 and Comparative Examples 1-6 And Table 2 are shown.

또한, 실용상의 관점에서, 상기 평가항목에 있어서 「×」가 없는 것이 필요로 된다.In addition, from a practical point of view, it is necessary that there is no "x" in the said evaluation item.

[표 2-1]TABLE 2-1

Figure pct00004
Figure pct00004

[표 2-2]Table 2-2

Figure pct00005
Figure pct00005

표 1의 실시예 1~40은, 크로메이트 피막과 동등한 내식성을 나타내고, 무기계와 동등 이상의 도전성 및 내열성을 나타내며, 유기계와 동등한 내지문성을 보유하고, 절곡부 내식성과 내약품성을 구비한, 매우 안정한 금속재료용 표면처리제인 것을 알 수 있었다.Examples 1-40 of Table 1 show the corrosion resistance equivalent to a chromate film, the electroconductivity and heat resistance equivalent to an inorganic type, and have the same anti-fingerprint as an organic type, and are highly stable metal provided with the corrosion resistance and chemical resistance of a bend part. It turned out that it is a surface treating agent for materials.

또한, 실시예 10 및 실시예 11과의 비교로부터, 금속 알콕시드를 2종 병용함으로써, 내식성이 더욱 향상되는 것을 알 수 있었다.In addition, the comparison with Example 10 and Example 11 showed that corrosion resistance further improves by using two types of metal alkoxides together.

또한, 실시예 33 및 실시예 34와의 비교로부터, 금속 알콕시드로서 테트라에톡시실란(테트라알콕시실란)을 사용하면, 내식성, 도전성 등 각종 특성이 향상되는 것을 알 수 있었다.Moreover, when comparing with Example 33 and Example 34, when tetraethoxysilane (tetraalkoxysilane) is used as a metal alkoxide, it turned out that various characteristics, such as corrosion resistance and electroconductivity, improve.

한편, 비교예에 있어서는, 어느 하나의 항목에 있어서 「×」가 포함되어 있어, 실용적인 관점에서 문제가 있었다. 또한, 비교예 4에서는, 피막량이 소정 범위 밖이었기 때문에, 굽힘부 내식성만이 떨어지는 결과가 되었다.On the other hand, in the comparative example, "x" was contained in any one item, and there existed a problem from a practical viewpoint. In Comparative Example 4, since the coating amount was outside the predetermined range, only the bending portion corrosion resistance was inferior.

Claims (10)

1분자 중에 -SiR1R2R3(식 중, R1, R2 및 R3는 각각 독립적으로, 탄소수 1~4의 알킬기, 알콕시기, 또는 수산기를 나타내고, R1, R2 및 R3 중 하나 이상은 알콕시기를 나타낸다.)로 표시되는 관능기(a)를 2개 이상과, 수산기(관능기(a)에 포함되는 것과는 별개의 것), 아미노기, 카르복실기, 인산기, 포스폰산기, 설폰기, 폴리옥시에틸렌 사슬 및 아미드기로부터 선택되는 1종 이상의 친수성 관능기(b)를 함유하며, 관능기(b) 1개당 분자량(평균 분자량/관능기 수)이 300~5000의 범위에 있는 화합물(A)과,
Si, Ti 및 Zr로 이루어진 군으로부터 선택되는 하나의 원소를 갖는, 1종 이상의 금속 알콕시드(B)와,
불소 함유 화합물 및 인산 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물(C)과,
카르복실산기, 포스폰산기 및 설폰산기로 이루어진 군으로부터 선택되는 1종 이상의 친수성 관능기를 갖는 유기 화합물(D)과,
물을 함유하는 금속재료용 표면처리제.
In one molecule, -SiR 1 R 2 R 3 (wherein R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a hydroxyl group, and R 1 , R 2 and R 3 At least one of two or more functional groups (a) represented by an alkoxy group), a hydroxyl group (one separate from the functional group (a)), amino group, carboxyl group, phosphoric acid group, phosphonic acid group, sulfone group, A compound (A) containing at least one hydrophilic functional group (b) selected from a polyoxyethylene chain and an amide group and having a molecular weight (average molecular weight / number of functional groups) per functional group (b) in the range of 300 to 5000,
At least one metal alkoxide (B) having one element selected from the group consisting of Si, Ti and Zr,
At least one compound (C) selected from the group consisting of fluorine-containing compounds and phosphoric acid compounds,
An organic compound (D) having at least one hydrophilic functional group selected from the group consisting of a carboxylic acid group, a phosphonic acid group and a sulfonic acid group,
Surface treatment agent for metal materials containing water.
제1항에 있어서,
상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과, 상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량의 질량비(B/A)가 0.01~5.0이고,
상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 화합물(C)의 질량의 질량비(C/A)가 0.01~4.0인 금속재료용 표면처리제.
The method of claim 1,
The mass when the amount of Si in the compound (A) is converted into SiO 2 , and the amount of Si, Ti and Zr in the metal alkoxide (B) are represented by MO 2 (M represents Si, Ti, or Zr). The mass ratio (B / A) of the total mass when converted to is 0.01 to 5.0,
The compound (A) the surface treatment agent in the amount of Si to SiO mass mass ratio of the mass of the compound (C) when converted into the second metal (C / A) 0.01 to 4.0 material.
제1항 또는 제2항에 있어서,
상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 화합물(C)의 질량의 질량비(B/C)가 0.10~30.0인, 금속재료용 표면처리제.
The method according to claim 1 or 2,
The metal alkoxide (B) in Si content, Ti amount and the Zr amount to MO 2 mass mass ratio of the total weight and the compound (C) when converted into the (M represents an Si, Ti, or Zr) (B / C) surface treatment agent for metal materials, 0.10 to 30.0.
제1항 내지 제3항 중 어느 한 항에 있어서,
상기 금속 알콕시드(B) 중의 Si량, Ti량 및 Zr량을 MO2(M은 Si, Ti, 또는 Zr을 나타낸다)로 환산했을 때의 합계 질량과 상기 유기 화합물(D)의 질량의 질량비(B/D)가 0.10~5.0인, 금속재료용 표면처리제.
4. The method according to any one of claims 1 to 3,
The metal alkoxide (B) in Si content, Ti amount and the Zr amount to MO 2 mass mass ratio of the total weight and the organic compound (D) when converted into the (M represents an Si, Ti, or Zr) ( Surface treatment agent for metal materials whose B / D) is 0.10-5.0.
제1항 내지 제4항 중 어느 한 항에 있어서,
상기 금속 알콕시드(B)로서, 1종 이상의 테트라알콕시실란이 함유되는 금속재료용 표면처리제.
The method according to any one of claims 1 to 4,
Surface treatment agent for metal materials containing 1 or more types of tetraalkoxysilanes as said metal alkoxide (B).
제1항 내지 제5항 중 어느 한 항에 있어서,
2종의 금속 알콕시드(B)를 사용하는, 금속재료용 표면처리제.
The method according to any one of claims 1 to 5,
Surface treatment agent for metal materials using 2 types of metal alkoxides (B).
제1항 내지 제6항 중 어느 한 항에 있어서,
상기 불소 함유 화합물이 Ti, Zr, Hf, Si, Al 및 B로 이루어진 군으로부터 선택되는 1종 이상의 원소를 갖는, 금속재료용 표면처리제.
The method according to any one of claims 1 to 6,
A surface treating agent for a metal material, wherein the fluorine-containing compound has at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al, and B.
제1항 내지 제7항 중 어느 한 항에 있어서,
추가로, Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca 및 Li로 이루어진 군으로부터 선택되는 1종 이상의 원소를 함유하는 금속 화합물(E)(단, 상기 불소 함유 화합물은 포함되지 않는다)을 함유하고, 상기 화합물(A) 중의 Si량을 SiO2로 환산했을 때의 질량과 상기 금속 화합물(E)의 질량의 질량비(E/A)가 0.01~3.0인, 금속재료용 표면처리제.
The method according to any one of claims 1 to 7,
Further, a metal compound (E) containing at least one element selected from the group consisting of Ti, Zr, V, W, Ni, Co, Fe, Zn, Mg, Al, Mn, Ca and Li, provided that Fluorine-containing compound is not included), and the mass ratio (E / A) of the mass when the amount of Si in the compound (A) is converted into SiO 2 and the mass of the metal compound (E) is 0.01 to 3.0. , Surface treatment agent for metal materials.
제1항 내지 제8항 중 어느 한 항에 기재된 금속재료용 표면처리제를 금속재료 표면 상에 도포, 건조시켜서, 피막량이 10~3000 ㎎/㎡인 피막을 상기 금속재료 표면 상에 형성하는, 금속재료의 표면처리방법.The metal which apply | coats and dries the surface treating agent for metal materials as described in any one of Claims 1-8 on the metal material surface, and forms the film whose film amount is 10-3000 mg / m <2> on the said metal material surface. Method of surface treatment of materials. 제9항에 기재된 금속재료의 표면처리방법에 의해 얻어지는, 피막을 갖는 금속재료.The metal material which has a film obtained by the surface treatment method of the metal material of Claim 9.
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