JP2010150626A - Posttreatment agent for galvanization and galvanized material subjected to surface treatment using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a posttreatment agent used for forming a chromium-free environment-friendly film which provides a film treatment appearance not damaging the surface appearance of a galvanized material mainly used for building materials used outdoors such as steel pipes, roads (a guardrail and a pillar), gratings, bridges, steel towers, railroad official houses and joints, and which imparts corrosion resistance and chemical conversion reactivity in the post process to the galvanized material, and to provide a galvanized material subjected to surface treatment using the posttreatment agent. <P>SOLUTION: The posttreatment agent contains: a compound (A) containing at least one kind of element selected from a group selected from among zirconium and titanium; a compound (B) containing at least one kind of element selected from the group consisting of vanadium, molybdenum and tungsten; and an inorganic compound (C) selected from phosphorous, wherein the blending ratio of the compound is limited. The galvanized steel is obtained by being subjected to film treatment with the posttreatment agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is capable of imparting corrosion resistance and chemical conversion reactivity in the subsequent process without damaging the finished appearance even after being processed on the surface of the galvanized steel material, and forming an environmentally friendly film that does not contain chromium. The present invention relates to a post-treatment agent used for the purpose and a galvanized material subjected to surface treatment using the same.

  Galvanization is a common method for making steel materials durable and extending their life. In other words, it is applied for the purpose of improving corrosion resistance, but this plating itself is oxidatively corroded by atmospheric oxygen, moisture, exhaust gas components, etc., and the appearance of zinc white rust is generated. In this case, iron red rust occurs. In addition to the durability of steel materials, temporary rust prevention properties that delay white zinc rust even a little are important. This temporary rust prevention property is considered to include not only durability but also design properties that do not impair the appearance of galvanization due to the occurrence of white rust. As a method for preventing corrosion of galvanizing, a treatment mainly composed of hexavalent chromium called a chromate treatment has been conventionally performed. The chromate treatment itself exhibits excellent corrosion resistance against plating, but since it contains hexavalent chromium, which is a recent environmentally hazardous substance, the RoHS Directive (home appliances, computers, communication equipment) mainly in the home appliance field The European Council Directive prohibits the use of harmful chemical substances in electrical and electronic equipment such as the ELV Directive (European Council Directive on Used Cars) centered on the automobile field, etc. Or it is a movement to ban.

  On the other hand, hexavalent chromium is used at this stage because there are no regulations such as the RoHS directive or ELV directive mainly in the construction field other than the home appliance and automobile fields. However, the momentum of environmental protection has been increasing day by day, and there has been a movement to voluntarily refrain from using environmentally hazardous substances. In the field of architecture that handles galvanized materials, high-strength bolt friction joining is commonly used as a fastening method for materials used for bridges, power transmission towers, road outer walls, and the like. In this method, the larger the slip coefficient of the joint surface, the less the deviation of the material and the safer. Therefore, the galvanized material is subjected to chemical conversion treatment on the joint surface to increase the slip coefficient. This chemical conversion treatment refers to a phosphate treatment. If a highly insulating film or a film that inhibits the formation of phosphate exists on the galvanizing, a crystalline phosphate film cannot be formed on the galvanizing, resulting in bolts being joined. It cannot be concluded properly. Moreover, even if it is fastened, the bolt tends to loosen after construction, which may cause a problem in safety. In this chemical conversion treatment, a coating-type phosphate treatment agent is simply sprayed or brushed at the time of construction to impart surface roughness. Therefore, it is necessary to form an appropriate film with a post-treatment agent so as to increase the slip coefficient.

  When the surface of the galvanized material is post-treated with a post-treatment agent, usually, immersion treatment is usually performed. In this immersion treatment, the galvanized material is often lifted from the post-treatment tank and naturally dried, and it is important that the appearance of the galvanized metal is not impaired in the finished appearance. That is, from the viewpoint of design properties, a technique for making the appearance after post-processing as uniform as possible is necessary.

  As a method of using a treatment liquid that does not contain hexavalent chromium, JP 2003-147544 A discloses a treatment liquid having a pH of 2.5 to 7.0 and containing trivalent chromium and a fluorine compound. However, this method has a drawback that the corrosion resistance is inferior to that of hexavalent chromium.

  As a method of using a treatment liquid that does not contain a chromium compound itself, Japanese Patent Application Laid-Open No. 10-60233 discloses a method in which an aqueous rust inhibitor containing a modified bisphenol A epoxy resin having a specific structure or a derivative thereof is applied on a steel plate and then heated. , A method of drying, Japanese Patent Application Laid-Open No. 2002-146554 discloses a method of preventing corrosion of a steel material surface by bringing an aqueous solution containing a vanadate and a water-soluble acrylic resin into contact with the surface of the galvanized steel material. However, these methods have insufficient chemical conversion reactivity in the post-process that we have been seeking. Further, the appearance of the film treatment when the immersion treatment is performed is not uniform, and the color tone of the galvanizing is impaired.

  JP-A-8-35084 discloses a metal rust inhibitor added to an aqueous solution in contact with a metal surface, which is trisodium phosphate (anhydrous): 10 to 20 w / v%, polymerized phosphate: 5 to 15 w. / V% and 1-hydroxyethylidene-1,1-diphosphonic acid: A metal rust inhibitor prepared by adding phosphoric acid to an aqueous solution of 10 to 15 w / v% to adjust the pH to 5 to 7 is disclosed. The method has a disadvantage that the corrosion resistance is inferior to hexavalent chromium.

  JP-A-2006-9121 discloses at least one selected from the group consisting of (A) a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. Based on 100 parts by mass of the solid content of a titanium-containing aqueous liquid obtained by mixing a titanium compound with hydrogen peroxide, (B) 1 to 400 parts by mass of an organic phosphate compound, (C) water-soluble or water-dispersible organic 10 to 2,000 parts by mass of resin in solid content, (D) 1 to 400 parts by mass of vanadic acid compound, (E) 1 to 400 parts by mass of zirconium fluoride compound and (F) 1 to 400 parts by mass of zirconium carbonate compound Although the metal surface treatment composition characterized by containing is disclosed, in this method, it was difficult to achieve both corrosion resistance and chemical conversion reactivity in the subsequent step.

  Japanese Patent No. 3851106 contains at least one vanadium compound (A) and a metal compound (B) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. In order to further improve the physical properties of the metal surface treatment agent, the ratio of pentavalent vanadium ions to the total vanadium is specified, the organic compound having a specific functional group, the etching material, the water-soluble polymer or / And a metal surface treatment method and a surface treatment metal material characterized by containing an aqueous emulsion resin. In this method, it has been difficult to make the slip appearance coefficient 0.4 or more while making the appearance of the film after the surface treatment of the galvanized material uniform and imparting corrosion resistance.

Therefore, in order to form a film that is post-treated on a galvanized steel, exhibits a uniform film appearance, excellent corrosion resistance, satisfies all chemical conversion reactivity in the subsequent process, and does not contain chromium. The present condition is that the post-processing agent to be used is not obtained.
JP 2003-147544 A Japanese Patent Laid-Open No. 10-60233 JP 2002-146554 A JP-A-8-35084 Japanese Patent Laid-Open No. 2006-9121 Japanese Patent No. 3851106 Japanese Patent Laid-Open No. 2004-232040

  The present invention is for solving the problems of the prior art, and is mainly used for construction materials used outdoors such as steel pipes, roads (guardrails and columns), gratings, bridges, steel towers, railway buildings, joints, and the like. Post-treating agent used to form a coating-treated appearance that does not impair the surface appearance of the galvanized material used, to provide corrosion resistance and chemical conversion reactivity in the subsequent process, and to form an environmentally friendly coating that does not contain chromium And it aims at providing the galvanization processed material surface-treated using it.

  As a result of earnestly examining the means for solving the above-mentioned problems, the present inventor treated the galvanized steel with a post-treatment agent having a specific compound as an essential component and limiting the compounding ratio, thereby giving a finished appearance. The present inventors have found that a film having corrosion resistance and chemical conversion reactivity in a subsequent process can be obtained without damaging the present invention.

  That is, the present invention includes a compound (A) containing at least one element selected from the group consisting of zirconium and titanium, and a compound (B) containing at least one element selected from the group selected from vanadium, molybdenum and tungsten. And an inorganic compound (C) selected from phosphorus, and the mass ratio of the compounds is A / (B + C) = 0.8 to 4.5, B / (A + C) = 0.15 to 0.7 It relates to a post-treatment agent for galvanizing processing having a pH of 7-11. Moreover, it is preferable that the compound (A) is a zirconium compound, the compound (B) is a vanadium compound, and is a post-treatment agent for galvanizing which is a tetravalent vanadium compound. Further, it further contains a silicon compound (D), and the mass ratio of the compounds is preferably D / (A + B + C) = 0.1 to 5.0, and at least one selected from organic phosphonic acid and phosphate ester It further contains a compound (E), and the mass ratio of the compounds is preferably E / (A + B + C) = 0.05 to 5.0, and further contains an aqueous resin compound (F) having anionic or nonionic properties. The mass ratio of the compounds is preferably F / (A + B + C) = 0.01 to 3.5.

  The present invention also relates to a galvanized material obtained by treating the surface of a galvanized material with the post-treatment agent. Furthermore, it is preferable to perform the surface treatment by bringing the post-treatment agent having a temperature of 20 to 80 ° C. into contact, and it is preferable to form a film without washing with water after the surface treatment.

Further, the present invention relates to a galvanized material having a plated appearance that is the same as that before the treatment, after the surface treatment by bringing the post-treatment agent into contact with the surface of the galvanizing. Moreover, the zinc coating amount of one side is 80-1000 g / m < ² >, and the slip coefficient after performing a phosphate chemical conversion treatment after making it surface-treat by contacting this post-processing agent is 0.4 or more zinc It relates to a plated material.

  By performing the surface treatment using the post-treatment agent of the present invention, it is possible to obtain a film-finished appearance with a good finish without changing the surface appearance of the galvanized material, and to impart corrosion resistance and chemical conversion reactivity in the subsequent process. In addition, an environmentally friendly film containing no chromium can be formed. Compound (A) reacts at the plating interface to form a hardly soluble salt when a film is formed on the galvanized film, and at the same time forms a metal oxide network to obtain a highly barrier film. Thereby, corrosion resistance can be improved. However, since this effect alone is insufficient, it is possible to inactivate the surface of the galvanizing by containing the metal compound (B) having a high oxidizing power and reinforce the rust prevention power. In addition, an insoluble metal salt can be formed at the interface. This makes it possible to exhibit a practical level of corrosion resistance. Furthermore, white unevenness of the coating treatment appearance due to the etching of zinc can be suppressed by suppressing the etching of galvanizing at the time of coating formation. The compound (C) is necessary for the control of chemical conversion treatment for adjusting the slip coefficient in the subsequent process. In particular, when the film to be formed and the acidic chemical conversion treatment agent come into contact with each other, a part of the film is washed away to form crystal grains of phosphate contained in the chemical conversion treatment agent so as to have roughness. When the flowability of the film is poor, the formation of phosphate is insufficient, and a desired slip coefficient cannot be obtained. Details of the effects and actions of the compounds (A), (B) and (C) of the present invention will be described later.

Examples of the compound (A) containing zirconium or titanium used in the present invention include oxides, hydroxides, complex compounds, salts with inorganic acids or organic acids, and the like. For example, as the zirconium compound, basic zirconium carbonate {Zr ₂ (CO ₃ ) (OH) ₂ O ₂ }, zirconium hydroxide, zirconium acetate {(CH ₃ CO ₂ ) _n Zr}, zirconium carbonate ammonium {(NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ]}, potassium zirconium carbonate {K ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ]}, sodium zirconium carbonate {Na ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ]}, zirconium acetate, hexafluorozirconium hydrogen acid and its salt, zirconia sol and the like.

Titanium sulfate {TiOSO ₄ }, titanium lactate, diisopropoxytitanium bisacetylacetone {(C ₅ H ₇ O ₂ ) ₂ Ti [OCH (CH ₃ ) ₂ ] ₂ }, reaction of lactic acid with titanium alkoxide Di-n-butoxy bis (triethanolaminato) titanium {Ti (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ }, titanium tetraiso Examples thereof include propoxide, hexafluorotitanium hydrogen acid and its salt, titania sol, titanium oxide and the like.

Of zirconium compounds and titanium compounds, zirconium compounds are more preferred from the viewpoint of corrosion resistance. Furthermore, among zirconium compounds, basic zirconium carbonate and its salt are particularly suitable. For example, basic zirconium carbonate {Zr ₂ (CO ₃ ) (OH) ₂ O ₂ }, zirconium ammonium carbonate {(NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ]}, potassium zirconium carbonate {K ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ]} and sodium zirconium carbonate {Na ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ]} are preferably used.

Examples of the compound (B) containing vanadium, molybdenum, and tungsten used in the present invention include oxides, hydroxides, complex compounds, salts with inorganic acids or organic acids, and the like. For example, vanadium compounds include vanadium pentoxide {V ₂ O ₅ }, metavanadate {HVO ₃ }, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride {VOCl ₃ }, vanadium trioxide {V ₂ O ₃ } , Vanadium dioxide {VO ₂ }, vanadium oxysulfate {VOSO ₄ }, vanadium oxyacetylacetonate {VO (OC (CH ₃ ) = CHCOCH ₃ )} ₂ }, vanadium acetylacetonate {V (OC (CH ₃ ) = CHCOCH _{3) 3},} vanadium trichloride {VCl _3}, phosphovanadomolybdic acid _{{H 15 -X [PV 12 -xMoxO} 40] · nH 2 O (6 <x <12, n <30)}, vanadium sulfate { VSO ₄ · 7H ₂ O}, vanadium dichloride {VCl _2}, vanadium oxide {VO}, oxalic acid acid Vanadium _{{V (C 2 O 4)} O} , and the like.

Examples of the molybdenum compound include molybdic acid (H ₂ MoO ₄ ), ammonium molybdate, sodium molybdate, and molybdophosphoric acid compounds (eg, ammonium molybdate {(NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ] · 3H ₂ O}). And sodium molybdate {Na ₃ (PO ₄ · 12MoO ₃ ) · nH ₂ O}, and the like.

Tungsten compounds include metatungstic acid {H ₆ (H ₂ W ₁₂ O ₄₀ )}, ammonium metatungstate {(NH ₄ ) ₆ (H ₂ W ₁₂ O ₄₀ )}, sodium metatungstate, paratungstic acid { H ₁₀ (W ₁₂ O ₄₆ H ₁₀ )}, ammonium paratungstate, sodium paratungstate, sodium phosphomolybdate {Na ₂ HPMo ₁₂ O · nH ₂ O}, and the like.

  Of the vanadium compounds, molybdenum compounds, and tungsten compounds, vanadium compounds are more preferred from the viewpoint of corrosion resistance, more preferably tetravalent vanadium compounds, and particularly preferably tetravalent vanadium complex compounds. When the vanadium compound is divalent to trivalent, the oxidizing power is small, and the effect of improving the corrosion resistance is small compared to tetravalent. In addition, when it is pentavalent, the oxidizing power is large, but if water is present in the formed film, it easily dissolves. Therefore, the effect of gradually flowing away in a corrosive environment and improving the corrosion resistance is small compared to tetravalent. The tetravalent has an oxidizing power, and it can be said that the runoff from the film is less than the pentavalent. Thereby, it is suitable in corrosion resistance. Further, typical vanadium compounds listed in the practice of the present invention contain yellow or brown unevenness in the appearance of the coating when at least the amount present in the coating to be formed is contained in the post-treatment agent in order to avoid it. It is necessary to reduce the blending amount. However, the effect of tetravalent is extremely small. That is, yellow or brown unevenness of the appearance of the film hardly occurs even when the abundance is large as compared with other vanadium compounds having other valences. Moreover, when an oxidizing power is large, when a post-processing agent forms a film | membrane on galvanization, the etching with respect to the zinc plating of a post-processing agent will be suppressed, and the whitening of the film | membrane to form will be suppressed. From such a point, the vanadium compound is more preferable than the molybdenum compound or the tungsten compound, and the vanadium valence is preferably 4 or more. That is, it can be said that a tetravalent vanadium compound is preferable in the compound (B) used in the present invention.

  As the inorganic compound (C) selected from phosphorus, inorganic phosphoric acid and a salt thereof are preferable. Examples thereof include orthophosphoric acid, metaphosphoric acid, condensed phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, hexametaphosphoric acid and salts thereof. For example, magnesium biphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, hydroxylammonium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, sodium dihydrogen phosphate , Disodium hydrogen phosphate, trisodium phosphate, aluminum phosphate, nickel phosphate, cobalt phosphate and the like. Among these, from the viewpoint of corrosion resistance, diammonium hydrogen phosphate, ammonium hydrogen phosphate, triammonium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, sodium dihydrogen phosphate, Disodium hydrogen phosphate and trisodium phosphate are preferable, and diammonium hydrogen phosphate, ammonium hydrogen phosphate, and triammonium phosphate are more preferable.

  The inorganic compound (C) is a component necessary for developing chemical conversion reactivity. When the inorganic compound (C) is contained in the film formed according to the present invention, it is effective for the chemical conversion reactivity carried out to adjust the friction coefficient. In the presence of the inorganic compound (C), that is, the phosphorus compound, when it comes into contact with the acidic phosphating agent (chemical conversion treatment), a part of the phosphorus compound dissolves from the film, so that phosphate crystals are likely to precipitate. . Furthermore, the galvanized surface is partially exposed in the process of dissolution of the film, and phosphate crystals are likely to precipitate at that portion. The inorganic compound (C) is required by such an action.

  By measuring the slip coefficient of the post-treatment material of the present invention after the chemical conversion reaction, strictly speaking, the chemical conversion reactivity can be judged, but it can also be judged simply by changing the appearance to gray. It is. It is preferable that the post-treatment material changes to a gray color after the chemical conversion reaction.

  The mass ratio of the compounds (A) to (C) contained in the post-treatment agent needs to be A / (B + C) = 0.8 to 4.5. In this range, it is preferable to set it as 1.0-4.0, and it is more preferable to set it as 1.2-3.5. This range is important for corrosion resistance and chemical conversion reactivity. Below this range, the barrier property of the film of the compound (A) becomes poor, and the corrosion resistance decreases. Moreover, when this range is exceeded, the solubility of an inorganic compound (C) will become scarce, and chemical conversion reactivity will fall. At the same time, the solubility of the compound (B) becomes poor and the corrosion resistance decreases. It is important to dissolve the compound (B) appropriately in order to exhibit corrosion resistance.

  Further, it is necessary to set B / (A + C) = 0.15 to 0.7. In this range, it is preferably 0.15 to 0.65, more preferably 0.15 to 0.6, and still more preferably 0.15 to 0.4. Since the compound (B) itself is a component that is easily colored, it is necessary to be within this range in order to improve the coating treatment appearance. Below this range, the oxidizing power is poor, and when the film is formed on the zinc plating, the etching of zinc becomes large, and white unevenness appears on the film processing appearance. Moreover, when it exceeds this range, the abundance of the compound (B) increases, and the degree of influence of coloring increases. Therefore, the trouble of yellow and brown unevenness arises.

In order to further improve the appearance of the film treatment, it is preferable to contain the silicon compound (D) in the post-treatment agent. For example, wet silica sol or dry silica sol dispersed SiO ₂ in water, SiO ₂ · nMb ₂ O (where, n is 1 to 5, Mb is an alkali metal) inorganic silicon compound represented by vinyl trichlorosilane , Vinyltris (2-methoxyethoxysilane), vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxypropyl) trimethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glyoxydoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-Aminopropylmethyldimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, ureidopropyltriethoxysilane, Examples thereof include tetra- or trimethoxysilane such as tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and n-propyltrimethoxysilane. Also, containing glycidyl group obtained by demethanol reaction of tetra- or trimethoxysilane such as tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, or tetra- or trimethoxysilane such as n-propyltrimethoxysilane and glycidol It may be a partial condensate of methoxysilane.

  About content of a silicon compound (D), when mass ratio is the range of D / (A + B + C) = 0.1-5.0, it is preferable when expressing an effect. Below this range, a sufficient effect cannot be obtained. On the other hand, if it exceeds this range, the continuity of the film is lost and it becomes brittle, which may reduce the corrosion resistance. Therefore, this range is suitable for improving the appearance of the film treatment.

  In order to improve the appearance of the film treatment, it is preferable to contain any compound (E) of organic phosphonic acid or phosphate ester in the post-treatment agent. When the compound (E) is contained, the degree of yellow or brown of the film formed by chelating with the compound (B) can be suppressed, and the film treatment appearance is improved. For example, aminotri (methylenephosphonic acid), 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, 1-hydroxyethylene- 1,1-diphosphonic acid, 2-hydroxyphosphonoacetic acid, aminotri (methylenephosphonic acid), ethylenediamine-N, N, N ′, N′-tetra (methylenephosphonic acid), hexamethylenediamine-N, N, N ′ , N′-tetra (methylenephosphonic acid), diethylenetriamine-N, N, N ′, N ″, N ″ -penta (methylenephosphonic acid), 2-phosphonic butane-1,2,4-tricarboxylic acid, Organic phosphonic acids such as inositol hexaphosphonic acid, phytic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, ethyl Emissions diamine tetra (methylene phosphonic acid), and organic phosphoric acids such as phytic acid.

  About content of a compound (E), when mass ratio of a compound is the range of E / (A + B + C) = 0.05-5.0, it is preferable when expressing an effect. Below this range, a sufficient effect cannot be obtained. On the other hand, if it exceeds this range, the continuity of the film is lost and it becomes brittle, which may reduce the corrosion resistance. Therefore, this range is suitable for improving the appearance of the film treatment.

  In order to improve the corrosion resistance, it is preferable to contain an anionic or nonionic aqueous resin compound (F) in the post-treatment agent. Although it does not specifically limit, For example, an acrylic resin, a urethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyolefin resin, a phenol resin etc. are mentioned. In this, it is more preferable to use an acrylic resin, a urethane resin, and an epoxy resin.

  About content of a compound (F), when mass ratio of a compound is the range of E / (A + B + C) = 0.05-5.0, it is preferable when expressing an effect. Below this range, a sufficient effect cannot be obtained. Moreover, when it exceeds this range, it is preferable from the viewpoint of corrosion resistance, but since the barrier property of the film is improved, the chemical conversion treatment property is lowered. Therefore, it is preferable to be within this range in order to improve the corrosion resistance and maintain the chemical conversion treatment property.

  Here, it is preferable that both the compound (A) and the compound (C), which are essential components in the post-treatment agent for galvanizing processing according to the present invention, are ammonium salts. And as a more suitable aspect, as a compound (A), a compound (B), and a compound (C), ammonium salt of basic zirconium carbonate (for example, zirconium carbonate ammonium), a tetravalent vanadium compound, ammonium of inorganic phosphate, respectively Examples thereof include salts (for example, triammonium phosphate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate). The reason is that if the counter cations of the compound (A) and the compound (C) are ammonium ions, they are volatilized at the time of film formation, so that the continuity of the film is hardly lost. Therefore, desired performance is easily obtained in the corrosion resistance and the film-treated appearance.

  Water is suitable as the liquid medium for the post-treatment agent of the present invention. When the liquid medium is water, the liquid medium may contain an aqueous solvent other than water (for example, a water-soluble alcohol as described later). When the liquid medium is water, the compounds (A) to (C) that are essential components described above are typically present in water in a dissolved state. However, there may be an embodiment in which some are not dissolved or in a dispersed state (for example, a colloidal state).

  The post-treatment agent of the present invention needs to have a pH of 7 to 11 (preferably pH 7.5 to 10, more preferably 8 to 9.5) in order to prevent white unevenness in outdoor exposure. In the case of acidic post-treatment, if the water is not washed after the post-treatment, the acid component remains and the film treatment material for the post-treatment is oxidized under actual use (exposure test in the present invention). This is because, by etching, zinc oxide is generated or the continuity of the film is lost, thereby causing a problem of whitening. Furthermore, when the pH is high, the post-treatment agent and the galvanizing are excessively etched and whitening occurs. If the pH is low, it is difficult to ensure post-processing stability. In addition, it is necessary to maintain long-term liquid stability. When the pH is low, when water is interposed in the formed film, the acid component etches a part of the surface of the galvanizing, leading to a decrease in corrosion resistance.

  The post-treatment agent of the present invention may contain a pH adjuster for stabilization of the post-treatment liquid. The pH adjuster is not particularly limited, and examples thereof include ammonia water, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, sulfuric acid, ammonium sulfate, hydrochloric acid, ammonium chloride and the like. It is done.

  The post-treatment agent of the present invention contains a thickener, a leveling agent, a wettability improver, an antifoaming agent, a surfactant, a water-soluble alcohol, a cellosolve solvent, etc. for the purpose of adjusting coating properties. It doesn't matter. Moreover, you may contain antiseptic | preservative, an antibacterial agent, a coloring agent, a damage prevention agent, a lubricant, etc. Moreover, you may contain a benzotriazole, a guanidine type compound, a hindered amine, etc. In addition, it is suitable for the post-processing agent of this invention not to contain organic acids including organic acids having an aromatic ring such as tannic acid and gallic acid. When such an organic acid is present in the composition, the appearance of the film treatment is deteriorated. Here, “does not contain” means “does not contain substantially” and includes not only the case where it is not completely contained, but also the case where it is present in a trace amount.

  The treatment agent of the present invention can obtain the appearance of film treatment, corrosion resistance and chemical conversion reactivity in the post-process by combining the compound (A), the compound (B) and the compound (C), but these compounds are simply mixed. In addition, the post-treatment agent may be adjusted using a known chemical reaction.

  Next, the surface treatment method of the post-treatment agent of the present invention is not particularly limited, and examples include immersion treatment, spray treatment, brush painting treatment, electrostatic coating treatment, and the like performed in the cooling step after plating. . In these treatments, it is preferable to clean the surface state by washing with an alkaline degreasing agent or an acidic degreasing agent and then washing with hot water or water when oil or dirt adheres to the surface of the steel material. . In addition, it does not specifically limit as a plating processing method of the zinc plating processed material which applies the processing agent of this invention, and plating components other than zinc. Aluminum, magnesium, silicon or the like may be contained as an alloy component.

  In addition, the shape of the galvanized material is not particularly limited. For example, H steel, guardrail, corrugated pipe, building columns and beams, soundproof wall columns, sign columns, lighting columns, large bridge girder bridges, All building materials that are galvanized, such as bridges such as overpasses, steel bars, small parts such as bolts and nuts used in power towers, small wind power generators such as solar cells, outdoor exposed steel frames, etc. Is mentioned.

  As the drying method of the post-treatment agent, the most economical method is to use preheating after the plating process, and it can be dried by immersing the galvanized material and leaving it as it is. That is, there is no need for a washing step such as water washing after the post-treatment. You may send the wind for flying away the water | moisture content adhering to the surface of a galvanization processed material in the case of drying efficiently. In addition, the post-treatment agent itself can be heated to increase production efficiency. Although it does not specifically limit as temperature of the post-treatment agent in that case, 20-80 degreeC is preferable, 30-80 degreeC is more preferable, Especially preferably, it is 35-75 degreeC. When it is difficult to use preheating after the galvanizing process, it is preferable to use a drying facility that can evaporate water contained in the post-treatment agent. In this case, the drying equipment is not particularly limited, and examples thereof include hot air drying equipment, induction heating drying equipment, infrared heater drying equipment, near infrared heater drying equipment, and the like. Although it does not specifically limit as drying temperature at the time of using these drying facilities, It is preferable that it is 40-200 degreeC as reach | attainment temperature on the surface of a zinc plating processed material, More preferably, it is 40-150 degreeC.

  Regardless of the surface treatment method and the drying process, the film-treated appearance formed by the post-treatment agent can have a uniform film-treated appearance without impairing the appearance of the galvanizing.

The film formed by the post-treatment agent is the slip strength after the chemical conversion reaction (according to the building construction standard specification JASS6 steel construction). With the post-treatment agent of the present invention, the slip coefficient is 0.4 or more, and the slip strength is increased. Can be obtained.

The coating weight of the film formed by the treating agent is preferably from 0.05 to 10 g / ^{m 2} on a dry film weight, more preferably 0.05-5 g / ^{m 2.} When the dry film mass is less than 0.1 g / m ^2, sufficient corrosion resistance cannot be obtained. On the other hand, when the dry film mass exceeds 10 g / m ² , cracks occur in the film and the adhesion of the film itself is reduced, resulting in corrosion resistance. It may cause a decrease. In addition, the appearance of the film treatment may be deteriorated.

  Although it does not specifically limit as total solid content concentration of a post-processing agent, It is preferable that it is the range of 1-500 g / L, More preferably, it is 1-400 g / L. When the total solid concentration of the treatment agent is less than 1 g / L, the corrosion resistance is insufficient. On the other hand, when it exceeds 500 g / L, the coating obtained by the post-treatment agent is cracked, and the adhesion of the coating itself May decrease.

  The viscosity of the post-treatment agent is not particularly limited, but it is desirable that the variation in dry film mass is reduced by immersing the galvanized material, and the viscosity (B-type viscometer) is as follows. It is preferably 500 mPa · s or less, more preferably 250 mPa · s or less, and still more preferably 100 mPa · s or less. When the viscosity of the treatment agent exceeds 500 mPa · s, a liquid pool portion is likely to be generated when the plated building material is dipped and then pulled up, and the variation of the dry film mass is increased, which is not preferable.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this Example is a mere example and does not limit this invention. The galvanized steel materials, compounds, post-treatment agents, galvanized steel materials surface-treated with the post-treatment agents and evaluation methods used in Examples and Comparative Examples are as follows.

1. Materials The materials used are listed below. Normally, galvanized products for building materials are mostly shaped products, but plates were used as raw materials in this test. It should be noted that even if the shape of the material changes, the effect of the present invention is not affected.

a: Hot-dip galvanized steel sheet (according to JIS H8641 HDZ35), small spangle Dimension: 700 mm × 150 mm × 1.6 mm (plate thickness) Double-sided plating adhesion 360 g / m ²
b: Hot-dip galvanized steel sheet (according to JIS H8641 HDZ55)
Dimensions: 700 mm x 150 mm x 6 mm (plate thickness) Double-sided plating adhesion amount 720 g / m ²
c: Hot-dip galvanized steel sheet (commercially available)
Dimensions: 700 mm x 150 mm x 1 mm (plate thickness) Double-sided plating adhesion 160 g / m ²

2. Compound The compound (A) used is described below.
A1: potassium zirconium carbonate A2: ammonium zirconium carbonate A3: zirconia sol A4: diisopropoxytitanium bisacetylacetone A5: titanium lactate ammonium salt

The compound (B) used is described below.
B1: ammonium metavanadate B2: vanadyl acetylacetonate B3: vanadium oxysuccinate B4: ammonium molybdate B5: ammonium metatungstate

The compound (C) used is described below.
C1: triammonium phosphate C2: diammonium hydrogen phosphate C3: sodium pyrophosphate

The compound (D) used is described below.
D1: Colloidal silica D2: Gas phase silica D3: 3-Glyoxydoxypropyltrimethoxysilane

The compound (E) used is described below.
E1: 1-hydroxyethylidene 1, 1-diphosphonate ammonium E2: nitrilotris (methylenephosphonate ammonium)
E3: ammonium 2-phosphonbutanetricarboxylate

The compound (F) used is described below.
F1: Acrylic resin (manufactured by Nippon Shokubai Co., Ltd., Aquaric HL)
F2: acrylic resin (manufactured by Showa Polymer Co., Ltd., Polyzol AP-1058)
F3: Urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex E2500)
F4: Ethylene acrylic acid copolymer (manufactured by Toho Chemical Co., Ltd., Hitech S3121)

3. Post-treatment agent Details of the post-treatment agent are shown in Table 1. The treatment liquid was produced by sequentially adding the compounds (A) to (F) to deionized water and adjusting the solid content concentration to 15 g / L. Each time (A) to (F) was added, the mixture was stirred with a propeller stirrer for 30 minutes.

4). Method for Producing Treatment Material A method for producing the treatment material is described below.
(1) Degreasing In order to clean the surface of the material, the dirt attached to the surface of the material is removed with Fine Cleaner FC-315 (20g / L building bath, 60 ° C, 30 seconds spray, immersion) manufactured by Nihon Parkerizing Co. did. Subsequently, it was immersed in running water for 10 seconds, further immersed in warm water at 75 ° C. for 30 seconds, and naturally dried. This cleaned the galvanized surface.
(2) Treatment method of treatment agent of the present invention Treatment I: The material was immersed in a treatment agent heated to 60 ° C. for 1 minute, then taken out, and naturally dried in a suspended state.
Treatment II: The material was immersed in a treatment agent heated to 20 ° C. for 1 minute, then taken out, and naturally dried in a suspended state.
Treatment III: The material was immersed in a treatment agent heated to 80 ° C. for 1 minute, then taken out, and naturally dried in a suspended state.
When the amount of wet with which the post-treatment agent adhered to the surface of the material was calculated with a precision balance, the amount of wet was 25 g / m ^{2 on} one side. Therefore, the dry film amount after the post-treatment agent can be calculated as 0.4 g / m ² .

5). Evaluation Method (1) Film Treatment Appearance The treatment appearance of the film formed with the treatment agent was visually evaluated.
Evaluation criteria: Above are practical levels. ◎ +: Almost the same as the plating appearance, and hardly changes even after coating treatment. ◎: Almost the same as the plating appearance, but there is slight color unevenness depending on the viewing angle.
○: Almost the same as the plating appearance, but there is a slight color unevenness.
(Triangle | delta): There exists a site | part different from a plating external appearance, and the site | part is light white or yellow.
X: There are many parts different from the plating appearance, and it is clearly white or yellow.
(2) Salt spray test A salt spray test was performed based on JIS-Z-2371, and the white rust generation area after 24 hours was evaluated.
Evaluation criteria: White rust generation area ○ Above is practical level ◎ +: Less than 5%, ◎: 5% to less than 10%, ○: 10% to less than 30% △: 30% to less than 60%, ×: 60% or more (3) Outdoor exposure test The condition of white rust occurrence after exposure to outdoor exposure for 30 days was examined and evaluated by the white rust occurrence area.
Evaluation criteria: Area where white rust is generated ○ Above is practical level ◎ +: No white rust is generated, ◎: Light white rust is less than 1%, ○: White rust is less than 1% △: White rust is 1% or more and less than 5%, ×: 5% or more (4) Chemical conversion reactivity (4) -1 Appearance change Treated with Nippon Parkerizing Co., Ltd. phosphate treatment chemical Palbond L15C (A agent 250 g / L + B agent 250 g / L, 30 ° C., brush coating) Then, it was allowed to stand for 5 minutes, and the surface condition of the brushed portion was evaluated. The higher the discolored area, the more the film formed with the rough post-treatment agent is partially dissolved by the phosphate treatment, and the phosphate film is formed to exhibit a gray color tone.
Evaluation criteria: Gray discoloration area of the brush coating portion ○ Above is practical level ◎ +: 100%, ◎: 95% or more and less than 100%, ○: 80% or more and less than 95% △: 50% or more and less than 80%, ×: 50 Less than% (4) -2 Slip coefficient (4) The slip coefficient was calculated by the slip strength test (by the building construction standard specification JASS6 steel frame work) for the gray discolored part subjected to the chemical conversion treatment in item -1.
Evaluation criteria: Slip coefficient ○ is practical level ○: 0.40 or more, x: less than 0.39

Table 1 shows the contents of the post-treatment agents used in the examples and comparative examples. Table 1 shows the evaluation results of the treated materials. The film treatment material formed from the compound (A) of the present invention and the treatment agent (Examples 1 to 31) containing the compound (B) is coated film appearance, corrosion resistance (salt spray test, outdoor exposure test) and chemical conversion reaction. It can be seen that it exhibits properties (appearance after chemical conversion, slip coefficient). In comparison, Comparative Examples 1 to 3 that do not contain the compound (A), the compound (B), or the compound (C) are inferior in performance. In addition, Comparative Examples 4 to 8 which are out of the scope of the present invention and Comparative Examples 9 to 10 shown in the patent literature are inferior in performance. Moreover, although the comparative example 11 which is a chromate process satisfies all performance, since it contains hexavalent chromium, it is not preferable from a viewpoint of environmental conservation.
The post-treatment agent of the present invention is an environment-friendly treatment solution that does not contain chromium, and the galvanized material surface-treated on the galvanized material by the post-treatment agent of the present invention has a coating treatment appearance, corrosion resistance, chemical conversion reactivity, The post-treatment agent of the present invention and the galvanized material after the post-treatment using this have extremely high industrial utility value.

Claims (11)

  A compound (A) containing at least one element selected from the group consisting of zirconium and titanium, a compound (B) containing at least one element selected from the group selected from vanadium, molybdenum and tungsten, and phosphorus Inorganic compound (C), and the mass ratio of the compounds is A / (B + C) = 0.8 to 4.5, B / (A + C) = 0.15 to 0.7, pH 7 A post-treatment agent for galvanizing processing consisting of ˜11.   The post-treatment agent for galvanization processing according to claim 1, wherein the compound (A) is a zirconium compound.   The post-treatment agent for galvanization processing according to claim 1 or 2, wherein the compound (B) is a vanadium compound.   The post-treatment agent for galvanization processing according to any one of claims 1 to 3, wherein the compound (B) is a tetravalent vanadium compound.   The post-treatment agent for galvanization processing according to any one of claims 1 to 4, further comprising a silicon compound (D), wherein the mass ratio of the compounds is D / (A + B + C) = 0.1 to 5.0. .   6. The composition according to claim 1, further comprising at least one compound (E) selected from an organic phosphonic acid and a phosphate ester, wherein the mass ratio of the compounds is E / (A + B + C) = 0.05 to 5.0. The post-treatment agent for galvanizing processing according to claim 1.   The aqueous resin compound (F) having an anionic property or nonionic property is contained, and the mass ratio of the compound is F / (A + B + C) = 0.01 to 3.5. 7. Post-treatment agent for galvanizing.   A galvanized material that has been surface-treated by contacting the post-treatment agent according to any one of claims 1 to 7.   The galvanized material according to claim 8, wherein the surface treatment is a coating type treatment in which the post-treatment agent is brought into contact with the surface of the galvanizing and is not washed with water. Zinc plated material according to claim 8 or 9 zinc coating weight of one surface is 80~1000g / ^{m 2.}   The slip coefficient of the galvanized material further subjected to phosphate conversion treatment after bringing the post-treatment agent into contact with the surface of the galvanizing surface is 0.4 or more. The galvanized material described.