TW201024462A - Surface-treating agent for galvanized steel plate - Google Patents

Abstract

Disclosed is a surface treating agent for a galvanized steel sheet that can provide a surface treated galvanized steel sheet, which has various excellent properties such as excellent corrosion resistance and corrosion resistance after alkali degreasing, particularly has a good balance among corrosion resistance, appearance, and grounding properties in a formed film, and also has well balanced excellent properties regarding anti-dew condensation properties and coatability (coating film adhesion). The surface treating agent for a galvanized steel sheet comprises zirconium ammonium carbonate (A), a compound (B), which contains in one molecule two or more functional groups (a) represented by -SiR1R2R3, in which the molecular weight per functional group (a) (average molecular weight/number of functional groups) is in the range of 100 to 5000, an organic phosphonic acid (C), a metal compound (D) containing at least one metal element selected from the group consisting of Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn, and water. The surface treating agent has a pH value of 6 to 11.

Description

[Technical Field] The present invention relates to a surface treatment agent for a galvanized steel sheet, a surface treatment method using the surface treatment agent for the plated steel sheet, and a surface treatment forging plate. [Prior Art] At present, galvanization is often performed on the surface of a steel sheet from the viewpoint of ensuring corrosion resistance of the steel sheet. Further, in order to further improve the corrosion resistance or improve the coating property, an alloyed galvanized steel sheet to which various metals are added is used. In particular, in industrial areas and other places that are affected by acid rain or soot, or in areas such as coastal areas that are affected by sea salt blowing particles, it is likely to cause extremely severe environmental corrosion of steel sheets, so it is expected to develop under the above circumstances. It can also be used to resist (4) more excellent (four) steel plates. In response to the above demand, a hot-plated Zn_5%A1 alloy steel plate and a hot-dip galvanized-Al-Mg alloy steel plate, such as a hot-dip galvanized _55% A1 alloy steel plate, have been proposed. However, even in the above various galvanized steel sheets, the corrosion resistance (white rust resistance) may be insufficient, and when used as a coated steel sheet, the compatibility with the coating may be insufficient. In the solution, a treatment containing hexavalent chromium called temporary rust-resistant chromate treatment is applied to the surface of the galvanized steel sheet. Further, in the production line (CGL: Continuous Galvanizing Line) using the temporary rust-resistant chromate-treated hot-dip galvanized steel sheet, the following method is mainly carried out: chromic acid containing chromic acid (hexavalent chromium) as a main component Salt treatment solution by spraying 201024462 on 'then with roller or air brake (air

Rational tendency. In short, it is currently expected to be able to be converted to a chromium-free surface treatment that does not use harmful hexavalent chromium, even trivalent chromium. The sprayer or sprayer is sprayed on the steel plate to adjust the coating amount, and then the lure roller '· spray wringer ' is sprayed. In the above case, many studies have been carried out in the surface treatment method without using hexavalent chromium. Improvement. For example, Patent Document i discloses a zinc-coated steel obtained by coating and drying a composition containing water-based resin, water or sulfide ions. Patent Document 2 discloses a mineral-based steel sheet covered with a water-dispersible metal surface treatment composition having a specific combined compound and a hair emulsion and a resin emulsion. Patent Document 3 discloses that a gold-based surface treatment material in which a film is formed using a water-based treatment agent containing a specific aqueous dispersion resin, ruthenium particles, and an organic inhibitor. Further, Patent Document 4 discloses a surface-treated metal sheet obtained by treating a metal material obtained by using a surface treatment composition containing a nonionic aqueous resin dispersion, a hydrolyzable titanium, an organic linonic acid compound, and a compound. Patent Document 5 discloses a water-dispersed rust-preventing paint composition containing an ionic polymer resin, a water-soluble hammer which reacts with a carboxyl group, and/or a water-soluble titanium compound. Further, Patent Document 6 discloses surface treatment of a metal material obtained by using a metal surface treatment composition containing hydrolyzable titanium, an organic phosphoric acid compound, a nonionic aqueous resin dispersion, a vanadium compound, and a zirconium compound. Gold 201024462 is a board. In the above Patent Documents 1 to 6, a method of directly coating a surface of a galvanized layer with a chromium-free organic film (resin skin) has been proposed. On the other hand, Patent Document 7 discloses a metal plate having a film containing titanium and/or zircon, a phosphoric acid compound, and a ruthenium compound. Patent Document 8 discloses a galvanized steel sheet obtained by surface treatment using a treating agent containing a water-soluble phosphate compound, a chelating agent, and a humectant inhibitor. Further, Patent Document 9 discloses a surface-treated metal material having a film formed of a metal surface treatment agent containing a metal compound such as a vanadium compound or a hammer compound. Further, Patent Document 1 discloses a steel sheet having a film composed of a tetravalent vanadium, Si, or phosphoric acid compound. In the above Patent Documents 7 to 10, a metal material coated with a film containing no chromium as an inorganic component is disclosed. In addition, there are reports in the material technology that use water-based resins to improve corrosion resistance. However, the conventional techniques of the above-mentioned Patent Documents 1 to 10, in particular, the method of coating with an organic film, the adhesion of the organic film to the galvanized layer is still insufficient, and the (4) material (4) substrate appears. The interface between the organic film and the plating layer is easily peeled off. Furthermore, it is also necessary to ensure the compatibility of the zinc-based steel sheet. In addition, it is grounded from the viewpoint that it is applied to home appliances and the like. In short, the Shangcheng 餹 button gold _ 4^ 迚 迚 plated steel plate not only needs corrosion resistance, but also has grounding and heat resistance. In the steel sheet for forming a resin film which has been etched so far, it is often necessary to set the amount of the film of the resin film to 201024462 or more. Therefore, when the amount of the film is increased in order to obtain corrosion resistance, there is a problem that the grounding property cannot be obtained. Further, in the case of the resin film, it is decomposed in a high temperature environment, and the heat resistance is insufficient in either case.

Based on the above background, a steel sheet coated with a chromium-free film in which an inorganic component is mainly used instead of an organic component has been proposed. For example, a steel sheet having a film obtained by using a composition containing phosphoric acid, titanium, erbium, or a sulphur coupling agent composed of four or more fluorine atoms has been disclosed in the patent document. Further, Patent Document 12 discloses a steel sheet having a film obtained by using a treatment agent containing an amine group-containing decane coupling agent, an epoxy group-containing decane coupling agent, and titanium hydrofluoric acid. Further, Patent Document 13 discloses a steel sheet having a film composed of a cerium sol binder, a phosphate ion, and a fluoride ion. However, the steel sheets described in the above-mentioned Patent Documents 11 to 13 have good corrosion resistance and heat resistance. However, since a film having a large amount of acid components is formed, there is a problem of grounding properties and adhesion. In addition, when the surface is a beautiful molten zinc bond, in these techniques, a film having a large amount of inorganic components is formed, and fine cracks and a film are formed on the film, and whitening (whitening) is observed, and a rainbow is also seen. The problem of interference color of color is particularly serious when whitening occurs, which may lead to misunderstanding that the galvanized surface has a white record and the value of the product is lowered. In addition, water droplets are generated on the surface of the galvanized steel sheet. When the water droplets are dry, the problem of the value of the 7 product is reduced, and ‘the solution is solved. At the time of 'constantly, the water droplets on the steel plate will remain due to condensation, and the above problems are not solved in the conventional technology of the steel plate. The temporary anti-rust chromate treatment as described above, the general system implementation 201024462 : The chromate treatment liquid is sprayed on the steel plate by a sprayer or a shower, and then the coating amount is adjusted by a roller or an air brake, and then dried by an oven or the like. This surface treatment method is very simple and highly productive. However, in the conventional technique of using chromium which has not been proposed so far, the treatment agent used is sometimes water-based, and the active ingredient concentration (or dry solid content) of the composition is the strongest, but not more than 2 〇 3 〇 mass % β. That is, in order to obtain a coating amount of lg/m2 (about the amount of the film, the amount of the coating liquid required is 4 to 5 g/m2), in order to control it, it is limited by the roll coating method (especially In the method called the reverse roll coating method, the method of treating the liquid by rotating the roller in the direction opposite to the direction of the thread is applied. Therefore, the conventional manufacturing equipment cannot be used, and it is necessary to The production line (cgl, coffee) invests in new equipment. In addition, in the case of reverse light coating, the rolls at the edge of the steel sheet at the time of coating are ground, resulting in a thread (strip) flaw corresponding to the width of the sheet at the roll. The flaw affects the appearance of the coating, so it is not produced in the order of the wider plate width to the narrower plate width, but it is a new problem in the production process of the continuous production process. As mentioned above, no matter what. No method can be used to replace the complex acid salt film. The surface treatment of steel plates, so it is currently expected to develop a kind of household

It satisfies the characteristics such as corrosion resistance, appearance, grounding, condensation resistance, and coating of Q film, and can also be applied to the conventional surface (Paper No. 1 : Special Kaiping) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 10] Japanese Laid-Open Patent Publication No. Hei. No. 2007-213. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Accordingly, it is an object of the present invention to provide a plating agent which is excellent in properties such as material properties and resistance to lysate (10). Balance of corrosion resistance, temperament, and grounding of the film It is good, and the condensation resistance and the coating property (coating film adhesion) also show excellent characteristics of balance. Further, another object of the present invention is to provide a manufacturing apparatus for a galvanized steel sheet, even if it is used in the past. A surface-treated galvanized steel sheet which can be produced by a treatment method (a showering roller or a spray squeezing roller). The present inventors have made an effort to solve the above problems, and as a result, it has been found that The present invention can solve the above problems by a compound having a predetermined functional group containing a halogen atom, a treatment agent containing 9 201024462 ammonium cerium carbonate, an organic phosphonic acid, etc., and the present invention provides the following (1) to (9). (1) A surface treatment agent for a galvanized steel sheet containing ammonium sulphate (A); a compound (B) having two or more SiWRk formulas in the i molecule, R1, R2 3 butyl ', ' The valley is self-independent, representing a functional group (3) having an alkyl group, an alkoxy group, or a hydroxyl group having a carbon number of i to 4, and the molecular weight (average molecular weight/number of functional groups) of the unit functional group (a) is at 1〇〇. ~5〇(eight)L range; general formula 1) represented by the organic acid (C);

The Mo metal compound (D) contains at least one selected from the group consisting of zr, Ti, Co, Fe, v, Ce, Μη, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn. The above metal element; and water; and the pH is 6~11; general formula (1)

OH

C- OH

(2) The surface treatment agent for galvanized steel sheets according to (1), wherein the mass of Zr in the ammonium zirconium carbonate (A) is converted into Zr〇2 and the conversion of Si in the compound (B) to 201024462 becomes Si02. The mass ratio (A/B) of the mass is 0.01 to 6 〇; the mass ratio of the mass of the organic phosphonic acid (C) to the mass of the compound (Β) converted to SiO 2 (C/B) is 〇.〇1~5.〇; The mass ratio (D/B) of the mass of the metal element in the metal compound (D) to the mass of Si in the compound (B) is 0 〇 1~4 〇. (3) A surface treatment agent for a galvanized steel sheet according to (1) or (2), wherein the compound (B) is a decane coupling agent having a reactive functional group (bl), and has a reactivity with a reactive group (b 1) The compound of the functional group (b2) of the reaction is reacted and the one of the reactive g-energy (bl) and the pot of the functional group (匕2) is an amine group or an epoxy group. (4) The surface treatment agent for a plated steel sheet according to any one of (1) to (3) further comprising a metal alkoxide (E); the metal oxide oxide (E), which is selected from the group consisting of b, At least one metal element of the group consisting of Nb, Si, Ta, Ti, V, W, and Zr. (5) The surface treatment agent for galvanized steel sheets according to (4), wherein the mass in the compound (7)) is converted to Si〇2, and the mass of the metal element contained in the metal alkoxide (8) The ratio (9)/(1) is 〇〇1~2 〇. (6) The surface treatment agent for galvanized steel sheets according to any one of (1) to (5), further comprising a compound (F); the compound (F), at least one of the group consisting of a water-soluble polymer and an aqueous emulsion One type of resin. 11 201024462 (8) A surface treatment method for galvanized steel sheets, which is coated with a surface treatment agent for galvanized steel sheets of (1) to (7) on the surface of a galvanized steel sheet, and dried by heating, and the zinc-plated steel sheet is heated. A film having a film amount of 25 to i 〇〇〇 mg/m 2 was formed on the surface. (9) A galvanized steel sheet having a film obtained by a surface treatment method of the galvanized steel sheet of (8). Advantageous Effects of Invention Therefore, the present invention can provide a surface treatment agent for a galvanized steel sheet which can obtain a galvanized steel sheet having excellent properties such as corrosion resistance and corrosion resistance after alkali degreasing, and particularly the formed film. The balance between corrosion resistance, appearance, and grounding property is good, and the condensation resistance and the coating property (coating film adhesion) also show excellent balance characteristics. Further, the present invention can provide a surface-treated key steel sheet which can be manufactured by using a conventionally used treatment method (dip tweeting, (four) nip roller) in the manufacturing equipment of the mineral steel sheet. [Embodiment]

And a method of using the galvanized steel sheet for a galvanized steel sheet according to the present invention, a surface treatment method for the treatment agent, and a galvanized steel sheet having a film obtained from the surface. First, the surface treatment agent for galvanized steel sheets will be described. <Surface Treatment Agent for Galvanized Steel Sheet>: Ammonium Carbonate is represented by a surface treatment agent for a zinc-zinc steel sheet according to the present invention, which contains (A), a compound (B), and is used in! a functional group (a) having two or more siR1R2R3 (wherein R1, R2 and R3 are each independently, alkyl, alkoxy or hydroxy group of Table 12 201024462 4), and the molecular weight of one unit of the functional group (4) (average molecular weight/number of functional groups) is in the range of 100 to 5 mm; the organic phosphonic acid (c) represented by the formula (1); the metal compound (9) contains a compound selected from the group consisting of Zr, Ti, c, Fe, v, , M〇, heart, μ,

A metal element having at least one of a group consisting of Nl Ca W, Nb, Cr, and Zn; and water; and a treatment agent having a pH of 6 to 11. Hereinafter, each component contained in the surface treatment agent for galvanized steel sheets will be described. ❹ General formula (1) 〇 Ο HO- P-

P-P--OH

OH OH OH < Ammonium Carbonate (A) &gt; 表面 The surface imaginary agent for galvanized steel sheets of the present invention contains cerium ammonium carbonate (A). Ammonium carbonate is mainly used to impart corrosion resistance, corrosion resistance after alkali degreasing, heat resistance, refining property, continuous processability, and dew condensation resistance to the obtained skin gland secret film. More specifically, the content of carbonic acid and (4) in the strontium carbonate record is not limited, and the relative corrosion is excellent in the corrosion resistance of the obtained film, the corrosion resistance after degreasing, and the dew condensation resistance. The total solid content in the treating agent is preferably from 0.1 to 70% by mass, more preferably from 1 to 5% by mass. In addition, the total solid

The meaning is the solid component constituting the film described later, and the medicinal blade does not contain a solvent or the like. <Compound (B)> 13 201024462 The surface treatment agent for a galvanized steel sheet according to the present invention contains the compound (B), and the system has two or more knives represented by _SiRlR2R3 (wherein, R2 and R3 are each Independently, the molecular weight (average molecular weight/g energy base) of the functional group (4)' of the alkyl group, the alkoxy group or the trans) group having a carbon number of 4 is located in the range of ～. It is presumed that the compound (B) forms a film having a three-dimensional crosslinked structure by crosslinking reaction with the cerium carbonate produced by the above ammonium cerium carbonate, so that the corrosion resistance of the obtained film, the corrosion resistance after alkali degreasing, and the heat resistance can be improved. , weldability, continuous processability, and condensation resistance. Further, it is presumed that the functional group (a) of the compound (B) is excellent in adhesion to a substrate to be described later, so that the appearance and coating properties of the obtained film can be improved (coating film adhesion is further estimated to be per unit function) The molecular weight (average molecular weight/number of functional groups) of the group (a) is in the range of 1 〇〇 to 5 Å, so that the grounding property of the film and the anti-fingerprint property can be improved. By using the above compound (B) in combination with the above cesium carbonate Ammonium can improve various properties. It can be used to produce a film that exhibits excellent corrosion resistance and grounding properties that cannot be obtained by individual (4). Compound (B) has two or more in one molecule and is expressed as — SiR RR ( Wherein, r, r and R3 are each independently a functional group (a) having an alkyl group, an alkoxy group or a hydroxyl group having a carbon number of 1 to 4, and preferably 2 to 8 of them. Further, when i When there are only j functional groups (a) in the molecule, the adhesion to the surface of the zinc-plated steel sheet is lowered, which is not preferable. R, R2 and R3 are independent, and represent an alkyl group having a carbon number of i to 4, An oxy group or a hydroxy group. Among them, an alkoxy group and a hydroxyl group are preferred. Examples of the alkyl group of 1 to 4 include a methyl group, a acetophenone, a propylene 201024462 group, an isopropyl group, a butyl group and the like. Among them, a f group and an ethyl group are preferable. The compound (8) preferably has a molecular weight (average molecular weight/functional number) of the i unit functional group (4) in a range of 100 to ≤, more preferably in a range of 12 Å to 1 side. The range of 5 〇 to 3 特 is particularly good. When the molecular weight of the i unit functional group (4) is less than (10), it is difficult to synthesize a compound, and the film resistance and adhesion are deteriorated, which is not preferable. On the other hand, when the molecular weight of the unit functional group (4) exceeds 5 mm, the adhesion of the surface of the functional group (4) to the surface of the galvanized steel sheet is lowered, which is not preferable. Further, as the method for measuring the above molecular weight, it can be used. The gel is analyzed by gel permeation chromatography (GPC) or NMR. The skeleton of the compound (B) is not particularly limited, and preferably has a vinegar bond, a guanidine bond, a guanamine bond, an amino formate bond, or a urea bond. Bonding of an ethylene bond, etc. As a compound (B) The method is not particularly limited, and examples thereof include a method in which ruthenium (1) has two or more active hydrogen-containing functional groups and a gas-fired reaction; (2) copolymerization with a money coupling agent having a vinyl group; a method in which an ethylene compound is reacted (polymerized); (3) a method having a specific reactivity; a decane coupling agent capable of reacting with a compound having a functional group reactive with the reactive functional group; (4) a modification A method of using a hydrophilic group of a polyfunctional decane coupling agent, etc., wherein (2) or (3) is preferred, and (3) is preferred. Hereinafter, each production method will be described. Preferred Embodiment of Compound (B) In one case, it can be exemplified by reacting with a copolymerizable ethylene compound by a vinyl decane coupling agent having 15 201024462 (poly. The compound obtained (reaction product). Further, the method is as in the manufacturing method of the above (2). The decane coupling agent having a vinyl group is not particularly limited as long as it has a vinyl group, and examples thereof include r-methacryloxypropyltriethoxymethane, ethylene trioxane, and ethylene trimethoxydecane. Further, the vinyl compound which is copolymerizable is not particularly limited, and examples thereof include acrylic acid, butyl acrylate, methyl acrylate, and 2-hydroxyethyl methacrylate. The reaction form of the above compound is not particularly limited, and examples thereof include anionic polymerization, cationic polymerization, and radical polymerization. Among them, radical polymerization is preferred. Further, a conventional polymerization initiator or the like may be suitably used in accordance with the reaction form selected. Further, a suitable solvent may be used in the reaction, and examples thereof include methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl alcohol, water, and the like. The other preferred embodiment of the compound (B) is exemplified by a reactive functional group (b1); a cyclohexane coupling agent having a reaction with the reactive functional group (b1) A compound obtained by reacting a compound of the functional group (b2) (reaction product). The reactive functional group (b1) is not particularly limited as long as it can react with other functional groups to form a bonded group. For example, it is preferably selected from the group consisting of an epoxy group, an amine group, a thiol group, a propyloxy group, and an anthracene group. a functional group in the group consisting of a ureido group, an isodecanoic acid group, and a vinyl group. Among them, an epoxy group and an amine group are preferred. One of the preferred embodiments of the decane coupling agent having a reactive functional group (bl) is a compound represented by the formula (2). General formula (2)

Si-L-一~-X In the formula (7), it is selected from the group consisting of an epoxy group, an amine group, a thiol group, a propyloxy group, an anthracene group, an isocyanate group, and a vinyl group. Any g month of the giant base. Among them, an epoxy group and an amine group are preferred. In the formula (2), L represents a divalent linking group or only a bonding. Examples of the linking group represented by L include an alkyl group (carbon 敖 〜 20 is preferable), - 〇 ·, _S_, an extended aryl group, _c 〇 ·, _NH·, _s 〇 2, -CONH-, or The basis of these combinations. Among them, an alkyl group is preferred. When only the bond is indicated, X representing the formula (2) is directly bonded to Si (germanium atom). In the formula (2), Y is each independently, and represents an alkyl group having a carbon number of 丨4, a decyloxy group, or a hydroxyl group. Among them, an alkoxy group having a carbon number of 1 to 3 and a mesogenic group are preferred. Examples of the decane coupling agent having a reactive functional group (bl) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 2 Epoxy decane such as (3,4-epoxycyclohexyl)ethyltrimethoxydecane; N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(aminoethyl) 3-aminopropyltrimethoxydecane, and amino decane such as 3-aminopropyltriethoxydecane; thiol decane such as 3-thiolpropyltrimethoxydecane; 3-isoindole Acid propyl trimethoxy decane, 3-isohydro acid ester propyl triethyl 17 201024462 Oxygen monoxide and other isohydro acid (tetra) burning; ethylene triethoxy sulphur, p-phenylethylene dimethoxy Hard-boiled, etc. The functional group (10) in the compound having a functional group (10) is not particularly limited as long as it can react with the above-mentioned reactive functional group (10), and is preferably an epoxy group, an amine group, a thiol group, a propyloxy group, an anthracene group, or the like. An oleic acid group, an ethylene group or the like is preferably an epoxy group or an amine group. The oxime may preferably be a functional group different from the above reactive functional group (bi). Examples of the compound having a functional group (b2) include a decane coupling agent exemplified as the above-described decane coupling agent having a reactive functional group (bl), or an amine compound such as ethylenediamine or aminopropanethiol; An ether compound such as hydroxymethylpropane polyepoxypropyl ether or neopentyl alcohol polyepoxypropyl ether. Further, a decane coupling agent exemplified by a decane coupling agent having a reactive functional group (bl) is preferred. That is, the compound (B) is preferably a reaction product of a dreaming coupling agent having a reactive functional group (bi) and a decane coupling agent having a functional group (b2) reactive with a functional group (b1). The reaction ratio of the decane coupling agent having a reactive functional group (bl) to the compound having a functional group (b2) is not particularly limited, and is preferably a decane coupling agent: Θ compound (mol ratio) = 9 : 1 to 1 : 9, better for 7: 3~3: 7. The reaction conditions are selected according to the compound to be used, and the optimum conditions are selected. Further, a solvent (for example, an alcohol or the like) or the like may be used in the reaction. The content of the compound (B) in the surface treatment agent for a zinc-zinc steel sheet is not particularly limited, and the relative treatment of the film obtained from the viewpoint of the survivability, the anti-fingerprint property, the appearance, the grounding property, and the coating property is relatively high. The total solid content in the agent is preferably from 0.1 to 70% by mass, more preferably from 1 to 50% by mass. 18 201024462 &lt;Organic phosphonic acid (c) &gt; The surface treatment agent for a zinc-zinc steel sheet of the present invention is an organic phosphonic acid. Lifting the yang yang, A difficult eight (the shackles of the sputum, the material and the steel sheet react to form the insoluble coating, and the coating property ((4) close, in order to stabilize the metal compound (9) described later) The organic phosphonic acid is required to dissolve in the water, so it gives the storage stability of the agent. (4) (4) Surface treatment ❹ General formula (1) HO-

C

-OH

〇H OH OH (4) Steel (4) Surface treatment of organic materials ((4) content is not particularly important in terms of the resistance of the obtained film, the acid resistance after degreasing, and the better the condensation, the relative treatment The solid content of the agent is preferably - mass%, more preferably. M = <metal compound (D)&gt; The surface treatment agent for galvanized steel sheets of the present invention contains a material selected from the group consisting of Zr, ^:°, Fe, v, Ce, M°, Mn, mCa, :, ::: at least one or more of the compounds (9) of the group consisting of CP and Zn. The metal compound (9) is the organic squarate described above. Therefore, it is presumed that the organic film is organic. The immobilization of the phosphonic acid (c) enhances the film's resistance to dew condensation and coating (coating adhesion). 201024462 D,::::: b) As long as it contains the above metal elements, there is no particular limit of sulphate. , money salt two: such as metal deletion, sulfate, acetate, more specifically, as a true ▲ 士 7 叙, for example, can lead blood with metal compounds, in addition to carbonation, sulfuric acid Examples of the oxygen recording, the acetic acid oxygenation, and the wrong fluorine include water-soluble salts, helium gas, and oxidized insoles. In addition, it is also an acid and a salt thereof. Examples of the metal compound of the acid oxime obtained by the ion exchange or the neutralization of the liquid include, for example, oxysulfate sulfate, succinyldithioacetic acid, and the like. In addition, the metatitanic acid obtained by thermal hydrolysis is decomposed and the salts thereof. As a metal compound containing Co, cobalt, carbonic acid drill, cobalt phosphate, gasified ruthenium, iron as a metal compound containing #Fe, iron carbide, iron phosphate, iron oxide, as a metal compound containing V, acidity, hunger _ , three oxygenated bismuth titanium, titanium gasification, grass gasification, oxidized sol, oxidation "potassium oxalate titanate, titanium lactate, ethyl acetonide titanium, diiso can also be cited as aqueous titanyl sulfate solution or experience neutralization Examples of the ortho-titanic acid produced include cobalt sulfate, cobalt nitrate, cobalt hydroxide, etc. Examples thereof include iron sulfate, iron nitrate iron, iron powder, and the like. Examples thereof include vanadium pentoxide, a sharp partial oxidation, and a dioxane. Vanadium oxychloride vanadium oxysulfate, oxyethylene hydrazine - 9 % bismuth, two bismuth vanadium ruthenium acetonide acetone vanadium, acetamidine propyl vanadium vanadium 'phosphorus bismuth acid, vanadium sulphate, etc. m ^ e metal compounds, for example Examples thereof include cerium nitrate, acetyl chloride, vaporized hydrazine, hydrazine sol, etc. Flat 201024462 As a metal compound containing Mo, for example, ammonium molybdate, sodium molybdate, potassium molybdate, ammonium molybdate, sodium molybdate, etc. As a metal compound containing Μη, Examples thereof include sulphate acid, ammonium sulphate, sodium permanganate, permanganate, or lanthanum L 醆 manganese, manganese nitrate, manganese oxide, manganese carbonate, manganese hydride, manganese phosphate, etc. The metal compound, for example, ί π Γ exemplifies magnesium sulfate, magnesium nitrate, magnesium carbonate, magnesium phosphate, magnesium sulfide, magnesium oxide, magnesium hydroxide, etc. Hydrogen oxygen as the metal compound containing ruthenium 1, for example, oxidized aluminum Examples of the metal compound containing Ni, such as aluminum sulfate, aluminum nitrate, aluminum phosphate, and chlorinated, include nickel oxide, nickel sulfate, nickel nitrate, nickel phosphate, nickel vapor, etc. "Hydrogen and oxygen as Ca-containing" Examples of the metal compound include oxidized calcium, calcium sulfate, calcium nitrate, calcium phosphate, and calcium carbonate. Examples of the metal compound containing W include a benzoic acid, a sodium metabensate, a abietic acid, a paratungstic acid, a ursolic acid, and a sodium benzoate. ❹ Examples of the metal compound containing Nb include ruthenium oxalate and ruthenium sol. Examples of the metal compound containing Cr include a trivalent complex, chromium sulfate, chromium nitrate, chromium chloride, chromium hydroxide, and an oxidized U acid complex. Examples of the metal compound containing Zn include zinc oxide, nitrogen oxide m μ zinc, zinc vapor, zinc sulphate, and ethyl ruthenium. Other aspects are due to the fact that zinc is an amphoteric metal and a sodium or an acid. Therefore, among the zinc acids generated by the inspection, it is preferable that 21 201024462 is a metal compound containing V, Mg, A or Zn, and the salt thereof. . The content of the metal compound (D) in the surface treatment agent for galvanized steel sheets is not particularly limited, and is excellent in corrosion resistance of the obtained film, corrosion resistance after alkali degreasing, weldability, continuous processability, appearance, and dew condensation resistance. In view of the above, the total solid content in the treating agent is preferably 〇〇1 to 4% by mass, more preferably 0.1 to 30% by mass. &lt;Water&gt; The surface treatment agent for a galvanized steel sheet according to the present invention contains water as a solvent. The content of the water in the surface treatment agent for the plated steel sheet is not particularly limited, and the total amount of the treatment agent is preferably from 30 to 99% by mass, more preferably 4%, from the viewpoint of easier use of the treatment agent. ~95% by mass. &lt;pH&gt; The pH of the surface treatment agent for galvanized steel sheets of the present invention is preferably 6 to Η, more preferably 7 to 10. When ρ Η is less than 6, the ammonium cerium carbonate may not be stably dissolved, and the stability of the surface treatment agent for the plated steel sheet may be deteriorated. When ρ Η exceeds 1 ^, the workability is deteriorated due to the significant bond odor, and the obtained film performance is also poor. The adjustment of the pH is preferably carried out using ammonia, carbonic acid, acetic acid, nitric acid or the like. In addition, it is presumed that the pH is adjusted to 6 to u, which suppresses excessive etching of the zinc-coated steel sheet caused by the treatment agent, and improves the grounding property of the surface-treated galvanized steel sheet. In the treatment agent, the mass ratio of the mass of the Zr (Zr mass) in the ammonium cerium carbonate (A) to the mass in the case of Zr02 and the mass of (4) in the compound (B) is (A). B) is preferably 〇〇1 to 6〇, more preferably 〇1 to 4.0. If it is less than 0.01', the amount of components which are easily dissolved may increase, and the corrosion resistance and the dew condensation resistance of the film after alkali degreasing may decrease. On the other hand, if it exceeds 6 〇, 22 201024462 j, the film may become hard, and coatability (coating adhesion) may fall. The mass ratio (C/B) of the mass of the above organic phosphonic acid (c) to the mass of the compound (B) converted to Si〇2 in the compound (B) is preferably 〇·01 more preferably 〇 .05~4.0, the best is 0.05~3.0. If it is not full (Η, the resistance of the film may deteriorate. If it exceeds 5Q, the corrosion resistance and the dew condensation resistance of the film after degreasing may be deteriorated. ❹ In the treatment agent, the above metal compound (9) The mass ratio of the metal element to the mass in the compound (B) is preferably "1 to 4. G., more preferably U5 to 3.0". In the case of screening, the skin may not be able to obtain the resistance (4). If it exceeds 4.0, the skin may become more and more difficult, and the corrosion resistance of the film may be lowered. In addition to the above compounds, the zinc plating of the present invention. The surface treatment agent for steel sheets may contain at least one of the following metal alkoxides (8) and a group of water-soluble polymers and emulsion resins. [Following the following] Metal alkoxide (E)&gt; The surface treatment agent for a zinc-zinc steel sheet of the present invention may further contain a metal-fired oxide (8). More specifically, it may contain a material selected from the group consisting of B, Nb, & τ T:v, At least β metal element in the group consisting of w and Zr: metal alkane telluride (Ε) The surface treatment agent for a zinc-zinc steel sheet according to the present invention provides a film-fired oxide which is more excellent in corrosion resistance (particularly in a processed portion) by containing a metal material (8) (it is presumed that the crosslinking reaction of the above compound (8) is promoted. A film having a denser mesh structure. The reason is still d, but it is preferably selected from the group consisting of si and Ti from the viewpoint of improving resistance (4). As the metal oxide oxide (8), as long as it has The compound which is directly bonded to the metal of the metal is not particularly limited, and a conventionally known one may be appropriately selected. The alkoxy group directly bonded to the metal may also be a hydrolyzed radical. Preferably, it is a general formula of Me(0R)n (wherein R is independently and represents an alkyl group or a hydrogen atom, at least one of which is an alkyl group. n represents a valence of the metal. Me represents the metal) The compound represented by R is preferably a hospital base having a hindrance of the number 4. The metal alkoxide (E) may, for example, be tetraisopropoxide, tetra-titanium oxide or titanate. Polymer, tetra- 2 -ethylhexyl titanium oxide, oxygen three Vanadium oxide, triisopropyloxide hunger, acetylation error, tetraethoxy ruthenium oxide, ruthenium tetrapropoxide, tetramethoxy decane oxime, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, Trimethoxy decane, decyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl triethoxy decane, cyclohexyl methyl dimethoxy decane, n-Hexyltrimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, phenyltrimethoxydecyl, phenyltriethoxydecane, decyltrimethoxydecane, octadecyl A dimethoxy decane, an octadecyl triethoxy decane, an isobutyl trimethoxy decane, etc. As a preferred embodiment of the metal-fired oxide (E), the corrosion resistance of the obtained film and the alkali degreasing From the viewpoint of further excellent corrosion resistance, an alkoxysilane containing a Si element is preferable, and a tetraalkyloxane of a formula of Si(〇R) 4 (R represents an alkyl group) is more preferable. 24 201024462 The content of the metal alkoxide (E) in the surface treatment agent for a zinc-zinc steel sheet is not particularly limited, and the total solid content in the treatment agent is S' from the viewpoint of further improving the corrosion resistance of the obtained film. It is preferably 〇.〇1 to 5〇, preferably 0.1 to 30% by mass. The mass ratio (E / B) of the mass of the metal element contained in the metal alkoxide (E) to the mass in the compound (B) converted to SiO 2 in the treatment agent is preferably 〇〇1~ 2 〇, more preferably 〇乃~} $. If it is less than 〇1, the corrosion resistance of the film may not be obtained in some cases. If it exceeds 2. 〇, the amount of dissolved components in the film will increase, and the corrosion resistance will decrease. &lt;Water-soluble polymer and/or aqueous emulsion resin&gt; The surface treatment agent for a zinc-zinc steel sheet according to the present invention may further contain at least one compound (F) of a group consisting of a water-soluble high-knife and a water-based emulsion resin. . By the addition of these components, the anti-fingerprint property, corrosion resistance, and lubricity of the film can be improved. The water-soluble polymer and/or the water-based emulsion resin are not particularly limited, and examples thereof include a water-soluble polymer such as polyacrylic acid, polymethacrylic acid, polypropylene decylamine, and polyethylene glycol, and are dispersed in water. Acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin, polyolefin resin, ethylene-acrylic resin, polybutyraldehyde resin, fluororesin, and the like. The total content of the compound (F) in the surface treatment agent for a galvanized steel sheet is not particularly limited, and the obtained skin enamel is more excellent in corrosion resistance, fingerprint resistance, dew condensation resistance, and coating property. The total solid content in the treating agent is preferably from 0.1 to 90% by mass, more preferably from 1 to 70% by mass. In the treatment agent, the mass ratio (F/B) of the mass of the compound (F) to the mass of the compound (B) converted to Si〇2 in the compound (B) is preferably 0 01 to 30, more preferably 0.1. ~20. If it is less than 0.01 Å, the fingerprint and lubricity of the film may not be improved. If it exceeds 30, the corrosion resistance and heat resistance of the film may be lowered. &lt;Fluoride Compound&gt; The surface treatment agent for the wrought zinc steel sheet of the present invention may optionally contain a gasification product. In particular, in a hot-dip galvanized steel sheet in which a surface oxide film is formed thick, if a fluoride is added to enhance the laborability of the treatment agent, the reaction layer (non-conductive layer) on the surface of the material becomes thicker, and it is expected to be more The corrosion resistance of the step is improved. However, when the fluoride is added to the treating agent, the etching property is increased, so that the grounding property is lowered as the portion other than the surface oxide film is dissolved. In addition, the amount of Zn or Fe mixed in the aqueous treatment liquid may increase, and the stability of the surface treatment agent for the galvanized steel sheet may be lowered, and the treatment for generating fluorine in the disposal of the liquid may be caused. Therefore, it is preferably implemented within the scope of the above problems. The content of the fluoride in the surface treatment agent for a galvanized steel sheet according to the present invention is not particularly limited. The upper limit of the fluorine in the treatment agent lkg is preferably a core. Further, examples of the fluoride include ammonium fluoride, ammonium hydride fluoride, ammonium titanium fluoride, and ammonium fluoride. &lt;Defoaming agent&gt; The surface treatment agent for the zinc ore steel plate of the moon may also contain a surface treatment agent for descaling (3) of a zinc ore steel sheet having a size of 13⁄4 / xiaobuqi1, preferably in the form of a mineralizer. The surface of the steel sheet is formed into a film by spraying or immersing it on a galvanized steel sheet, and then adjusting the coating amount by a roller or an air brake. The amount is then 50 to 25 (rc is used as the highest reaching plate temperature for drying). The antifoaming agent is not particularly limited, and may be a type which has been subjected to stable emulsification such as mineral oil, fatty acid or dioxo, or a type of water-soluble active agent. The two may be used in combination. The defoaming in the treating agent is selected in accordance with the type to be used, and the appropriate amount is preferably selected in the range of 0, 1 to 3. 〇g per treatment liquid. If the content of the antifoaming agent is too small, the defoaming property cannot be obtained; if the content is too large, the coating property is not good. <Lubricant> The surface treating agent for the plated steel sheet of the present invention may optionally contain a lake smoothing property. Additives (lubricants). Anti-slip agents improve the surface treatment of the film Slip resistance to prevent injury is effective for reducing the damage of the steel plate during processing. 〃As a lake slip agent, for example, polyethylene oxime, oxidized polyethylene butterfly, oxidized polypropylene wax, carnauba wax, paraffin wax (paraffin), a solid lubricant such as a lignite ant iron, and a solid lubricant such as a sorghum (s. ss.) can also be used in the surface treatment agent for galvanized steel sheets of the present invention. The content of the agent is not particularly limited, but it is preferably at most 50 g per kg of the treatment liquid. If the value exceeds this value, not only the stability may be added, but also the original purpose may be hindered. The surface treatment agent for the galvanized steel sheet of the present invention is also The solvent for the surface treatment agent for the galvanized steel sheet of the present invention is not particularly limited. For example, ammonium zirconium carbonate (A) can be used in a mixer such as a mixing homogenizer. , a substance (B) organic phosphonic acid (c), metal compound (7)), other additives, 27 201024462 water is sufficiently mixed to produce β &lt; surface treatment method &gt; Table of surface treatment agent for zinc zinc steel sheet of the present invention The treatment method is not particularly limited, but it is preferably a surface treatment method in which the surface treatment agent for the plated steel sheet is applied onto the surface of the galvanized steel sheet and dried, and the amount of the film formed on the surface of the galvanized steel sheet is 25 ~1〇〇〇mg/m2 of the film. Hereinafter, the surface treatment method will be described.

For coating, it is also possible to pre-treat the zinc-zinc steel plate as needed to achieve the removal of oil or dirt on the surface of the galvanized steel sheet. Plated steel plate base; anti-rust purpose and often coated with anti-rust oil. Even if the anti-rust oil is not coated, there will be oil or dirt adhering to the operation. The surface of the zinc-plated steel sheet is washed by pre-treatment, and the surface of the zinc-zinc steel sheet can be simply wetted by the surface treatment agent for the zinc-zinc steel sheet of the present invention. Further, in the case where the surface treatment agent for the zinc-coated steel sheet of the present invention is used to wet the surface of the material without oil or the like, there is no particular need for a pretreatment step.

Further, the method of the pretreatment is not particularly limited, and examples thereof include a method of hot washing, solvent washing, and degreasing washing. As the zinc-zinc steel plate to be used, a molten zinc-zinc steel plate (GI), an alloyed molten zinc-zinc steel plate after goldation, and a molten 5/oAI alloy steel plate (GF) and glazed galvanized _ 5External alloy electric recording steel plate (10)), electric final nickel alloy steel plate (zn_gang. This (external) can be applied to iron plates not plated. As the treatment agent of the present invention, coated galvanized steel sheet The method is not particularly limited as long as the treatment agent is uniformly applied to the surface of the galvanized steel sheet, and may be, for example, a roll coating method, a dipping method, a spray coating method, etc. Further, regarding the treatment (coating) temperature and treatment ( The coating time is also not particularly limited. Generally, the treatment (coating) temperature is preferably 10 to 40 t: and the treatment (coating) time is preferably 0.1 to 1 sec. as formed on the surface of the dry galvanized steel sheet. The heating temperature at the time of coating the film is preferably 50 to 250 ° C, more preferably 60 to 180. (The method of heating and drying is not particularly limited, and may be carried out by hot air, induction heater, ultraviolet ray, near infrared ray, or the like. Heating to dry the treatment agent. In addition, the heating time is based on The optimum conditions are selected in accordance with the type of the compound in the surface treatment agent for the plated steel sheet, etc. From the viewpoint of productivity, etc., it is preferably 〇.丨~6〇sec, more preferably 1~3. The amount of the film formed on the surface of the galvanized steel sheet is preferably 25 to 1 〇〇〇 mg / m, more preferably 50 to 800 mg / m 2 , most preferably 1 〇〇 6 〇〇 mg / m 2 .

When the thickness is less than 25 mg/m2, the galvanized steel sheet cannot be uniformly applied to the surface of the steel sheet by the surface treatment agent, so that various properties such as the desired workability and the steep coating resistance cannot be uniformly achieved. If it exceeds 10,000 mg/m2, the appearance will be lowered, and the coatability will be deteriorated. Further, the grounding property and the solubility are deteriorated. In addition, in the pressurization plus: L·, the amount of separation of the good film will increase, and it will not cause an obstacle in the formation of the calendar, and the manufacturing cost will also increase. Further, the above film amount means the amount of skin sputum on one side of the steel sheet. On the film formed by the above surface treatment method, an organic ruthenium molecular film having a film thickness of 0·1 3 · 0 //La Xigu drag 1 is formed on the film formed by the above surface treatment method, thereby imparting higher corrosion resistance and anti-fingerprint Sex, lubrication. , +, + 丨 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士Agents, UV absorbers, pigments, etc. By surface treatment using a surface treatment agent for a galvanized steel sheet according to the present invention, a surface treatment film having corrosion resistance, heat resistance, splicability, continuous processability, grounding property, and anti-fingerprint property can be formed on the surface of a galvanized steel sheet. In particular, the formed film not only has good corrosion resistance and appearance, but also exhibits excellent balance characteristics in terms of condensation resistance and coating property (coating film adhesion).

The coating amount in the spray and winch coating method is usually about 1 to 3 g/m2. Further, from the viewpoint of usability (uniform coating), a treatment liquid in which the solid content concentration of the surface treatment agent is adjusted to 10 to 20% by mass is used. When the surface treatment agent is applied in an amount of from 1 to 20% by mass in this way, a film of from 100 to 600 g/m2 can be obtained, and the degree of evaporation of moisture in drying is sufficient. In short, since the objective performance can be obtained with the amount of the film, the surface-treated galvanized steel sheet of the present invention can be utilized.

And other methods of manufacturing. In this way, it is possible to manufacture the required board without the need for new production equipment and without reducing the productivity of the compact production line (CGL, EGL). According to the present invention, it is possible to form a galvanized steel sheet by surface treatment, especially for the formation of the skin, the heat, the fusion, the continuous processing, and the grounding property. Good value for money and appearance, good (and) (4) Condensation and applicability (coating adhesion) also showed excellent balance characteristics. Such steel plates in various fields such as electrical and automotive can be effectively used for materials used in construction 30 201024462. In addition, it is more effective in the production of the CGL, because it can be produced using the same processing equipment as the conventional temporary rust-resistant chromate treatment. EXAMPLES Hereinafter, the effects of the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples, and designs which are changed as conditions change are also included in the technical scope of the present invention. (1) Test materials The following commercially available materials were used as test materials. (1) Electro-zinc steel plate (EG): plate thickness 〇8 mm, plating amount = 20/20 (g/m2) (ii) galvanized steel plate (GI): plate thickness 〇.8 mm, plating amount = 60/60(g /m2) (iii) Alloyed molten ore zinc plate (GA): plate thickness 〇8mm, mineral deposit = 40 / 40 (g / m2) In addition, 'the amount of the bell is expressed in the steel plate The amount of plating on the main surface. For example, in the case of an electrogalvanized steel sheet, 2 〇 / 2 〇 (g / m 2 ) means that the both sides of the steel sheet have a plating layer of 20 g / m 2 , respectively. (2) Pretreatment (washing) The test panel is prepared by first treating the surface of the above test material with Palklin N364S manufactured by Nihon Parkerizing Co., Ltd., and applying the oil on the surface. Parts and dirt removal. Then, it was washed with tap water, and it was confirmed that 1% of the surface of the plated steel plate was wetted with water, then rinsed with pure water, and the water was removed in an oven at 100 ° C ambient atmosphere, and then 31 201024462 was used as a test plate. (3) Preparation of treatment agent for galvanized steel sheet The respective components were mixed in water in the amounts shown in Table 1 (Examples 1 to 49 and Comparative Examples 50 to 65) to prepare a treatment liquid. Further, the blending amount of the components (A) to (F) in Table 1 indicates the blending amount (g) in the surface treatment liquid for galvanized steel sheets of ikg. Further, the components other than the components (A) to (F) contained in the respective treatment liquids are mainly water. The compounding amount of the component (A) in Table 1 means Zr (Zr mass) in ammonium cerium carbonate (A). ) The mass (g) when converted to Zr 〇 2 . The blending amount of the component (B) in Table 1 indicates the mass (g) when Si (Si mass) in the compound (B) is converted into Si〇2. The compounding amount of the component (D) in Table 1 means the mass (g) of the metal element in the metal compound (D). The compounding amount of the metal alkoxide (E) in Table 1 means the mass (g) of the metal element contained in the metal alkoxide (E). Further, the mass ratio (A/B) in Table 1 indicates the mass in the case where Zr in the carbonic acid misplacement (a) is converted into Zr〇2, and the mass in the compound (B) is converted into the mass in Si〇2. Quality ratio. The mass ratio (C/b) is a mass ratio of the mass of the organic phosphonic acid (the mass of ruthenium to the mass of Si in the compound (B). The mass ratio of the ruthenium (D/B) means a metal compound ( The mass ratio of the metal element in D) to the mass in the case of Si in the compound (B), and the mass ratio (E/B) means the metal contained in the metal alkoxide (E). The mass ratio of the element to the mass in the case where Si in the compound (B) is converted to Si 〇 2. The mass ratio (F/B) indicates the mass of the compound (F), and is converted into the sum of the compound (7)). Mass ratio of mass at Si〇2. 32 201024462 (^sw^·010 Dad i#w^3nl ^长^:1^-)-H)J&lt; Surface treatment agent ffi 〇00 Ο 00 〇00 o 00 so 00 o 00 ο οό ο οό ο οό ο Οό ο οό S ο οό ο οό 2 〇00 ο οό ο 00 ο 10.0 ο οό ο οό 〇00 s Mass ratio (F)/(B) 0.35 0.35 1 I 0.35 '0.35 :0.35 0.35 0.35 0.13 0.20 0.40 0.13 0.20 0.40 0.35 0.35 I- 0.35 0.35 0.35 0,35 0.40 0.35 0.35 0.40 0.20 0.13 Mass ratio 1 1 i- 1 0.46 i- 0.46 , 0.46 0.46 0.46 0.76 1.14 2.30 0.77 ν» 2,28 1 1 1 1 1 1 0.53 0.46 1 0.53 0.26 0.18 mass ratio (D) / (B) 0.26 0.26 1 i 0.44 0.26 1 L 0.26 0.26 0.26 0.17 0.15 0.30 0.26 0.44 0.26 0.26 0.26 0.26 1 0.30 0.26 0.26 0.30 0.26 0.26 0.30 0.25 0.10 mass ratio \(Ρ)ΛΒ)\ 0.38 0.38 ST 0.38 1 i 0.38 0.38 0.38 0.07 0.10 0.20 0.07 0.10 0.43 1 I_0.38 0.38 0.38 0.38 0.01 0.05 0.43 0.38 0,11 0.43 0.22 0.14 Mass ratio Ι(Α)/(Β)Ι 0.01 0.11 1.96 1.96 1.96 1.96 1.96 0.33 1.00 3.00 0.33 1.00 3.00 1.00 3.98 5.98 7.02 1.96 1.96 2.24 1.96 1.96 6.00 1.00 0.17 Composition (F) Quantity 〇ρ — q 'St p — p — o — p — ο q τι· ρ — ρ — ο — ρ ο — ρ 七 ρ — p — ρ — ρ — ρ — ο ρ — ο ί* pp — Ζ Ζ ιΖ £ £ ΪΖ Ε Ζ Ζ U: U : u: Ε JZ EE Ε U: Ε u: E component (E) compounding amount t 1 in cn vi m in »n cn »〇22.8 22.8 3+20 3+20 3+20 22.8 I 1 f [ 1 1 rr , &gt;τΐ ΓΟ uS 1 m vS m *n ro wS Category 1 1 S &lt;N (NS fS m Ξ Ξ Ε1+Ε2 Ε1+Ε2 Ε1+Ε2 Ξ I 1 1 t 1 1 fv| ω 1 cs ω SS Ingredient (D) compounding amount ο ro o ro 4+1 〇r*S 〇rn SO ro 4+1 ο ο ο ΓΟ ο rn ο rn ο r**i 4 O ΓΟ O ΓΟ ο rn ο ΓΟ ο ΓΠ ο ο 4+1 o Category 5 Q D1+D3 SSQ 5 D1+D3 SSQSSQ D1+D3 Q 5 5 SS 5 &lt;Ν ;Q D1+D3 s Component (C) Complex amount — rn CO Tf cn — m rn — — ο (Ν Ο CS ο (Ν ο (Ν Ο cn — CO — — co — rn Tf *—Η ο ν〇Ο cn — rn — (Ν cn — m r&quot;) Type U 〇VUUU υ UU Ο 0 Ο UU uu υ UUUGUU Composition (B) ί Formulation amount 11. 11.4 11.4 ”Π 4.4 '11.4 11.4 1 11.4 30.0 20.0 10.0 30.0 1 20 .0 10.0 1 11.4 11.4 I ;Π.4 11.4 1- 11.4 11.4 1 ! 10.0 11.4 11.4 10.0 20.0 | 30.0 Type Ξ Ξ &lt;N PQ cn CQ S CQ S Ξ Ξ mm CQ &lt; m Ξ S m CQ ffl cn CQ S component (A) compounding amount d cs 22.4 22.4 22.4 22.4 22.4 10.0 20.0 30.0 10.0 20.0 30.0 Π.4 45.4 68.2 80.0 22.4 22.4 22.4 22.4 22.4 | 60.0 20.0 Type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt;&gt; £ 00 σ \ &lt; N * Ti &lt; s embodiment i embodiment embodiment embodiment embodiment embodiment 1 embodiment embodiment 1 embodiment embodiment 1 embodiment embodiment embodiment embodiment embodiment embodiment embodiment Embodiment 1 Embodiment 实施 Embodiment 1 Embodiment 实施 Embodiments Embodiments Examples 201024462 («ί3ν&lt;!»·25 Friends»w shouting 35π#'κ·&lt;:φι·4ηΐΒ) (fs蚌)ι&lt Surface treatment 剤〇00 〇00 ο οό Ο οό ο οό o 00 o 00 o 00 o 00 ο οό Ο od Ο οό ο οό ο οό ο οό o od o 00 ο οό ο od ο 10.0 o 〇〇o 〇〇〇od mass ratio 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 1 0.01 0.20 0.20 0.20 0.05 2.19 7.11 29.6 0.35 mass ratio (E)/(B) 1 1 I 1 1 0.46 0.46 1 1 1 1 0.01 0.50 2.02 2.34 1 1 1.00 1.00 1.00 1 1 1 1 0.53 Mass ratio (D)/(B) 0.26 0.26 0.26 0.01 0.05 0.44 0.26 3.01 4.01 4.58 0.26 0.26 0.26 0.26 0.26 0.26 0.25 0.40 0.50 0.26 0.44 0.26 0.26 0.26 Mass ratio (C)/(B) 2.98 4.04 5.26 0.38 0.38 0.38 0.38 0,38 i 038 0.38 1 0.38 ;0.38 0.38 0.38 :0.38 0.38 0.22 i 0.22 0.25 0.79 0.38 0.38 0.38 0.38 by mass ratio (A)/(B) 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 Ό Os 1.96 1.96 1.96 1.96 1.96 2 1.12 CN 1.96 1.96 1.96 1.96 1.96 Composition (F) Quantity p — ρ — ρ — ο a ρ rr po — Pp — ο — ρ ο 对 · ρ ο 1 op — ρ 对 · Ο — Ό Ο 25.0 81.0 337.5 o — Type Ζ s: Ε EE EEEU: Ε U: 1 u: ΪΖ Ε s: Ε iZ component (Ε) Quantity 1 1 1 I 1 m wS »n 1 1 1 Ο 3+20 26.7 1 1 20.0 20.0 20.0 1 I 1 1 o Type 1 1 1 1 1 s ω 1 1 1 Ξ a ! Ε1+Ε2 Ξ 1 1 ssa 1 1 1 1 Ξ Component (D) Quantity 〇〇rn ο rS ο Ό Ο 5 O 34.4 1 1 45.7 52.2 ο rn ο ρό ο μ ο r*S ο o rn 4+1 ο οό 10.0 ο rn 4+1 o r&lt;io — oc«*i Category 5 S 5 SS D1+D3 s 3 5 SS 5 SS 5 s D1+D3 S s Ξ D1+D3 S 5 5 Composition (C) Formulation amount 34.0 46.0 60.0 m — — cn — ro — ΡΟ rn — ro 七 — — o tri Ο α\ fO — — rn — type UU υ UUU o 5 UUUU 5 u U 〇UG u U u G u Composition (Β) Compounding amount 11.4, 11.4 11.4 11.4 11.4 11.4 Π.4 11.4 11.4 1 11.4 i 11.4 11.4 11.4 1 1 11.4 11.4 20.0 20.0 20.0 11.4 11.4 : 11.4 11.4 11.4 Type m S s rs QQ S s S Ξ CQ S CD m S Ξ s S m S PQ S Ξ S Component (Α) Complex amount 22.4 i 22.4 22.4 I 22.4 i 22.4 22.4 22.4 22.4 22.4 22.4 1 : 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 22.4 Type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; 1 - Η &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; test 00 (Ν ON CM ro fS rr> • η ms〇r^i Ρ; 00 CO 〇 ΓΛ o - 5 «ο a; Example 1 Example 1 Example 1 Example 1 Example 1 1 Implementation EXAMPLES EXAMPLES EXAMPLES EXAMPLES Example 1 Example Example 1 Example Example 1 Example Implementation Example Example Example Example Example Example 1 Example Example 201024462 © (^sw ^-ss 茫^^^351--^^^::1:^-) (£妹)1&lt;Surface treatment agent 〇〇〇ο οό ο οό Ο 〇6 ο οό ο οό Ο οό ο οό ο 〇ό ο οό Ο οό ο οό ο 00 ο οό ο 12.0 Mass ratio (F)/(B) 1 1 1 1 I 1 1 1 1 Γ^Γ 0.35 0.35 0.35 0.35 0.35 0.01 Mass ratio (E)/(B) 1 1 1 1 1 1 1 1 1 1 0.46 0.46 1 1 0.46 0.46 Mass ratio (D)/(B) 1 1 1 1 1 1 1 1 1 0.26 0.26 0.26 0.26 1 0.44 0.26 Mass ratio (Q/Φ) 1 1 1 1 1 1 1 1 1 0.38 0.38 0.38 1 0.38 ι- 1 0.38 0.38 Mass ratio (eight) / (B) j 1 1 1 1 1 1 ! 1 1 1 1.96 1.96 1.96 1.96 1.96 1.96 Ingredient (F) Mixing amount 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100,0 ρ seven ο — ρ ο — ρ ρ — ο — Type U: ΪΖ U: Ξ 5: ΣΙ: Ingredient (E) 组合 quantity vS 卜卜Γ - »η 卜 〇 in in 3+3 卜&gt;〇1 »η m in 1 1 m ι〇 Ξ ω ω Ξ Ξ Ε Ε 1+Ε2 Ε1+Ε2 ω ι a ΓΜ ID ι 1 a CA » Composition (D) Quantities 〇ο γ0 ο ro ο cn ο ο rn ο ΓΟ ο rn ο γ0 ο Rn ο cn Ο ΓΠ 5 1 4+1 Ο Category 5 5 SSS 5 Q 5 5 5 Ξ Q 5 1 D1+D3 S Composition (C) Quantity cn ΓΛ ΓΛ — m — cn — CO — CO — — ο οό 16.0 — Γ〇— cn — ι rn ¥ ro τ|* 种类 Type U υ υ - υ Ο UU 5 UU ι U Ό ο Composition (B) Quantity 1 1 1 1 1 1 1 1 1 11.4 1 11.4 11.4 1 11.4 11.4 1 11.4 11.4 Type 1 1 1 1 1 1 1 1 1 ω Ό m SS Component (A) Complex amount ο in 10.0 15.0 15.0 15.0 20.0 ο iri 1 1 1 22.4 22.4 22.4 22.4 22.4 22.4 Type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; 1 1 1 &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; Cn Ό S Comparative example comparison example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 201 024 462 The following 'will be described using the compounds shown in Table 1. < Ammonium Carbonate (A) &gt; : Ammonium Carbonate <Compound (B) &gt; Reaction of hexamethylene fluorenyl oxime with glycidoxypropyltrimethoxy ketone 2 in ethanol Get the product. Thereafter, the mixture was diluted with deionized water to have a solid content concentration of 5% by mass.

Further, the number of functional groups (4) in the produced product i molecule is 2 '1 unit functional groups (4), and the molecular weight (average molecular weight/number of functional groups) is about B2: a double-type epoxy resin (# 828 type) The oxime epoxy resin was loosely charged with 1 mol, and reacted with r-aminopropyltriethoxydecane 2 mol in N methyl _2 &quot; than oxime ketone to obtain a product. Thereafter, deionized water was added to form a solid concentration of 5 mass 〇/〇. The number of functional groups (a) in the product produced by the above-mentioned product is 2 '1. The molecular weight (average molecular weight/functional group number) of the 1st functional group (4) is about 4 1 1 〇' B3: acrylic acid! Mole, butyl acetoacetate 5 mol, acid methyl known 5 mol and methacryl oxime propyl triethoxy decane 3 molar water emulsion polymerization, the product is obtained. After that, diluted with deionized water The concentration of the solid component is 5% by mass. The number of functional groups (4) in the molecule of the product obtained is 3 = the molecular weight of the earlier molecule (8) (the average molecular weight of the eight-energy base) is about 36 201024462 B4 : Aminopropyltriethoxydecane oxime is reacted with r • glycidoxypropyltrimethoxydecane 2 molar in ethanol to obtain a product. Thereafter, deionized water is added to deionize The water is diluted to a solid concentration of 5% by mass. Further, the number of functional groups (a) in the produced oxime molecule is 2 '1 unit functional group (a) molecular weight (average molecular weight / functional group number) 894 ° OB5 : 1 part by mass relative to bis(trimethoxy propyl propyl)amine 200 parts by mass of water-based amino phthalate resin (registered trademark: ADEKA BONTIGHTER-HUX-760, manufactured by Asahi Kasei Co., Ltd.) having a tertiary and a quaternary amine group. Then 'diluted to a solid concentration by deionized water The amount of the functional group (a) in the molecule i obtained is 2 '1 unit functional group (a), the molecular weight (average molecular weight / functional group number) is about 171, double (three The weight ratio (A)/(B) of the oxymercaptopropylamine (A) to the urethane resin is 1/2. 0 B6: 50 mol of acrylic acid, 100 mol of butyl acrylate,曱S曰100 mM methacrylate, 2-hydroxyethyl methacrylate 1 〇〇 molar, and γ-methyl propylene methoxypropyltriethoxy decane oxime in emulsion polymerization in deionized water The product was obtained, and then diluted with deionized water to have a solid concentration of 5% by mass. Further, the number of functional groups (a) in the produced oxime molecule was i, and the molecular weight of one unit of the functional group (4) was obtained. (Average molecular weight/number of functional groups) is about 40,000 'based on the functional group of the compound (B) B7: Relative to 7-thiolpropyltrimethoxydecane, the concentration of deionized water is 37. The concentration of the functional group (a) in the molecule of compound 1 is 5% by mass. One is outside the scope of the present invention. <Organic phosphonic acid (C)&gt;

Cl : 1-hydroxyethylidene-1,1_diphosphonic acid <metal compound (D)&gt; D1: ammonium mevanovadate D2: magnesium nitrate D3: aluminum nitrate® D4: zinc oxide &lt;metal alkoxide ( E)&gt;

El: titanium isopropoxide E2: tetraethoxy decane &lt; compound (F) &gt; F1. acrylic resin (manufactured by Showa Polymer Co., Ltd., p〇lyz〇le am_2386) (4) Treatment method The surface treatment agent was applied to each test plate by a bar coating method or a spray &amp; squeegee coating method, and then washed without being washed, and directly placed in a glow box 'drying at a drying temperature shown in Table 2, A film of the amount of the film shown in Table 2 was formed. Further, the amount of the film means the amount of the film on one side of the steel sheet. The drying temperature is adjusted in accordance with the ambient temperature in the tank and the time of the oven. Further, the drying temperature means the temperature at which the surface of the test plate reaches. Rod coating method and spray traitor h. The specific method of the Peel &amp; winch coating method is as follows. Bar coating method: The treatment agent: 3⁄4 4 ~ water ~ drops were added to the test plate, and coated with # 3~5 coating 38 201024462 rod. The amount of the coating film is adjusted to a predetermined amount depending on the thickness of the coating bar to be used and the concentration of the treatment liquid. Spray &amp; squeegee coating method: spraying the treatment liquid on the surface of the test plate to wet the surface as a whole, and then removing more liquid by a roller composed of two flat rubber rollers to adjust the coating amount . The amount of water removed by the roller and the concentration of the treatment liquid are adjusted to a predetermined amount of film.

39 201024462 Table 2 (1) Test plate treatment method Coating method Film drying temperature type type mg/m2 °C Example 1 (1) Bar coating method 400 100 Example 2 (1) Bar coating method 400 100 Example 3 (1) Bar coating Method 400 100 Example 4 (1) Bar coating method 400 100 Example 5 (1) Bar coating method 400 100 Example 6 (1) Bar coating method 400 100 Example 7 (1) Bar coating method 400 100 Example 8 (ϋ) Bar coating method 600 100 Example 9 (ϋ) Bar Coating Method 600 100 Example 10 (ϋ) Bar Coating Method 600 100 Example 11 (iii) Bar Coating Method 600 100 Example 12 (iii) Bar Coating Method 600 100 Example 13 (iii) Bar Coating Method 600 100 Example 14 (1) Spray &amp; Wrench Coating Method 300 100 Example 15 (i) Spray &amp; Wrench Coating Method 300 100 Example 16 (1) Spray &amp; 300 100 Example 17 (i) Spray &amp; Wrench Coating Method 300 100 Example 18 (1) Spray &amp; Wrench Coating Method 300 100 Example 19 (1) Spray &amp; Wrench Coating Method 300 100 Implementation Example 20 (1) Spray &amp; Wrench Coating Method 400 100 Example 21 (i) Spray &amp; Wrench Coating Method 25 100 Example 22 (i) Spray &amp; Wrench Coating Method 400 100 Example 23 (i) Spray &amp; Wrench Coating Method 400 100 Example 24 (i) Spray &amp; Wrench Coating Method 400 100 Example 25 (1) Spray &amp; Wrapping Coating Method 400 100 201024462 Table 2 (Part 2) Material Processing Method Coating Method Film Drying Temperature Kind Type mg/m2 °c Example 26 (1) Bar Coating Method 400 100 Example 27 (1) Bar coating method 400 100 Example 28 (1) Bar coating method 400 100 Example 29 (1) Bar coating method 400 100 Example 30 (1) Bar coating method 400 100 Example 31 (1) Bar coating method 400 100 Example 32 (1) Bar coating method 400 100 Example 33 (1) Bar coating method 400 100 Example 34 (1) Bar coating method 400 100 Example 35 (1) Bar coating method 400 100 Example 36 (1) Bar coating method 400 100 Example 37 (1) Bar coating method 400 100 Example 38 (1) Bar coating method 400 100 Example 39 (1) Bar coating method 400 100 Example 40 (1) Spray &amp; squeegee coating method 400 100 Example 41 (1) Spray &amp; squeegee coating method 400 100 Example 42 (1) Spray Fog &amp; Wrench Coating Method 400 100 Example 43 (1) Spray &amp; Wrench Coating Method 400 100 Example 44 (1) Spray &amp; Wrench Coating Method 400 100 Example 45 (1) Spray &amp; Wrench Coating Method 400 100 Example 46 (1) Bar Coating Method 400 100 Example 47 (1) Bar coating method 800 100 Example 48 (1) Bar coating method 1000 100 Example 49 (1) Bar coating method 400 100 41 201024462 Table 2 (3) Material processing method Coating method Film amount Drying temperature type type mg/ M2 °C Comparative Example 50 (1) Bar coating method 400 100 Comparative Example 51 (1) Bar coating method 400 100 Comparative Example 52 (1) Bar coating method 400 100 Comparative Example 53 (ϋ) Bar coating method 600 100 Comparative Example 54 (iii) Bar coating method 600 100 Comparative Example 55 (1) Spray &amp; Wrench Coating Method 400 100 Comparative Example 56 (1) Spray &amp; Wrench Coating Method 400 100 Comparative Example 57 (1) Spray &amp; Wrench Coating Method 400 100 Comparative Example 58 (1) Spray &amp; Wrench Coating Method 400 100 Comparative Example 59 (1) Bar coating method 400 100 Comparative Example 60 (1) Bar coating method 400 100 Comparative Example 61 (1) Bar coating method 400 100 Comparative Example 62 (1) Bar coating method 400 100 Comparative Example 63 (1) Bar coating method 400 100 Comparative example 64 (1) Bar coating method 400 100 Comparative Example 65 (1) Bar coating method 400 100 (5) Evaluation test method (5-1) Corrosion resistance (corrosion resistance after alkali degreasing) The obtained surface-treated galvanized steel sheet was cut into a size of 70 x 150 mm, and the inside was cut. A cell paper was attached to the end portion as a test piece, and a salt spray test prescribed in JIS Z237 1 was carried out to evaluate the time required to produce white rust of 5% (area ratio). Further, the corrosion resistance after alkali degreasing was carried out by an alkali degreasing agent (Palklin N364s, manufactured by Pike 42 201024462 Nagisa Co., Ltd.), 2 〇g/L at 6 Torr. After the spray for 2 minutes, the K-treated surface-treated mineral zinc-based steel sheet was subjected to the same evaluation. The evaluation criteria at this time are as follows. ◎ *It takes more than 120 hours to produce 5% white rust. It takes more than 48 hours to produce 5% white rust and less than 12 hours △. It takes more than 24 hours to produce 5% white rust, less than 48 hours X: 5% white rust is less than 24 hours and on the other hand produces 〇: produces X: produces (5-2) appearance

The evaluation criteria for GA are as follows. 5% white rust is required for more than 24 hours for 5% white rust, 24 hours or more, less than 48 hours, 5% white rust, more than 12 hours, less than 24 hours, 5% white rust, less than 12 hours. The surface of the surface of the surface-treated galvanized steel sheet was evaluated as follows. : Price ◎ : No whitening > Interference color 〇: Very thin whitening \ Interference color Δ : Whitening interference color X : Significant whitening interference color (5 - 3 ) Dew condensation resistance The surface treated galvanized system When the steel plate is placed in the cold storage tank, it is then placed in a high-temperature and constant-humidity tank (5 (TC, humidity 95%) 2 small 昧 small treated ore zinc-based steel plate placed in a high-temperature and constant-humidity tank, confirming the surface treatment of galvanizing Water droplets (condensation) were generated on the surface of the steel plate (de-contained in the freezer, 43 201024462 hours). It is confirmed that the surface of the surface-treated galvanized steel sheet is dry when taken out from the high-temperature and constant-humidity tank (when it is not dry, continue to be placed) The surface of the surface-treated galvanized steel sheet was visually evaluated for the water droplets (condensation) on the surface of the galvanized steel sheet. The evaluation criteria at this time are as follows: ◎: No water droplets were observed: the water droplets were not easily visible △: visible X: Significantly visible (5-4) Applicability After surface-treated galvanized steel sheet coated with melamine-based paint ("Aramaic #l〇〇〇" manufactured by Kansai Paint Co., Ltd.), it was burned at i6〇〇c After the coating film thickness was 20 # m. After coating for 1 hour in boiling water, 1 方形 1 mm square grid was cut on the coating film, and extruded by 5 mm using an Aristotle embossing tester. The tape was peeled off, and the residual ratio of the lattice was evaluated. The evaluation criteria at this time are as follows: ◎: residual ratio 91 to 100% 〇: residual ratio 71 to 90% Δ: residual ratio 51 to 70% X: residual ratio 〇~50% (5·5) Grounding The surface treated galvanized interlayer resistance material was measured by an interlayer resistance meter. The evaluation was performed on the basis of the following. The ◎ of the board was less than 1 Ω 〇 · 1 Ω or more , less than 2 Ω 201024462 △ : 2 Ω or more, less than 3 Ω X : 3 Ω or more (5-6) Resistance to blackening The surface of the test surface of the obtained surface-treated galvanized steel sheet is combined with each other 'wrapped on one side Ethylene kraft paper, and put it into 5 〇. (: Humidity and humidity device with a humidity of 9.8 %. At this time, the 矿kg was applied to the test piece after packing for the treatment of the zinc-based steel plate for fixing and sealing surface. The weight of the galvanized steel sheet after the removal of the surface is maintained for 1 day. Evaluation by visual inspection ◎: No change in appearance 〇: visible slight discoloration Δ: visible overall slight blackening, or partial blackening X: visible significant blackening with respect to Examples 1 to 49, and Comparative Example 5 The surface-treated galvanized steel sheet obtained by using the surface treatment agent for mineral steel sheets described in ～65, and the evaluation results of the above (5-1) to (5-6) are shown in Table 3. From the viewpoint of practical use, it is necessary to have no "X" in the evaluation item. Further, in Comparative Example 64, the treatment liquid could not form a film due to instability, and thus various measurements could not be performed. 45 201024462 Table 3 (1) Normal appearance, dew condensation, coating, grounding resistance, blackening, no degreasing, degreasing, Example 1 〇Δ ◎ 〇 ◎ ◎ ◎ Example 2 〇〇 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 8 〇 Δ ◎ ◎ ◎ ◎ 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施实施 ◎ ◎ ◎ Example 14 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Example 15 ◎ 〇 ◎ ◎ ◎ ◎ Example 16 ◎ 〇〇 ◎ Δ ◎ 〇 Example 17 〇〇 Δ ◎ Δ ◎ Δ Example 18 Δ Δ ◎ ◎ ◎ ◎ 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Example 25 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 24 Example ◎ ◎ ◎ ◎ ◎ 23 ◎ ◎ ◎ ◎ Δ ◎ ◎ embodiment ◎ embodiment

46 201024462 Table 3 (2)

Fortune appearance, condensation resistance, coating property, grounding resistance, blackening resistance, degreasing, degreasing, Example 26 ◎ 〇 ◎ ◎ ◎ ◎ Example 27 ◎ 〇〇〇 ◎ 〇 ◎ Example 28 ◎ Δ Δ Δ Δ Δ ◎ Example 29 〇 Δ ◎ ◎ ◎ ◎ Example 30 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 34 ◎ Δ ◎ 〇〇 ◎ Example 35 〇 Δ ◎ Δ Δ ◎ ◎ Example 36 ◎ ◎ ◎ ◎ ◎ ◎ Example 37 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 38 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Implementation Example 39 〇 △ ◎ ◎ ◎ ◎ Example 40 ◎ ◎ ◎ ◎ ◎ ◎ Example ◎ ◎ ◎ ◎ ◎ ◎ Example 42 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 43 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Implementation Example 44 ◎ ◎ ◎ ◎ ◎ ◎ Example 45 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Example 46 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Example 47 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Example 48 ◎ Example 49 ◎ square ◎ ◎ ◎ ◎ ◎ Δ ◎ ◎ ◎ ◎ ◎ embodiment 47201024462 Table 3 (part 3)

Dry appearance, condensation resistance, coating property, grounding resistance, blackening resistance, no degreasing, degreasing, Comparative Example 50 XX 〇〇 ◎ X ◎ Comparative Example 51 〇X 〇〇 ◎ X ◎ Comparative Example 52 〇X 〇〇◎ X ◎ Comparative Example 53 〇X 〇〇◎ X ◎ Comparative Example 54 ΔX 〇〇 ◎ X ◎ Comparative Example 55 〇Δ 〇〇 ◎ X ◎ Comparative Example 56 〇Δ 〇〇 ◎ X ◎ Comparative Example 57 Δ XX 〇 ◎ X ◎ Comparative Example 58 Δ XX 〇 ◎ X ◎ Comparative Example 59 XX 〇 X Δ X 〇 Comparative Example 60 Δ X 〇 Δ X Δ ◎ Comparative Example 61 Δ X 〇 △ X △ ◎ Comparative Example 62 XX 〇〇〇 Δ ◎ Comparative Example 63 XX 〇X 〇 Δ ◎ Comparative Example 64 — — — — — — — Comparative Example 65 Δ 〇〇〇 ◎ X ◎ As shown in Table 3, surface treatment plating by treating the various components defined in the present invention at a predetermined ratio is known. The zinc-based steel sheet has excellent corrosion resistance and corrosion resistance after alkali degreasing, and exhibits more excellent balance characteristics in terms of appearance, seizure resistance, coatability (coating film adhesion), and grounding property. Further, it is also known that an excellent surface-treated galvanized steel sheet can be produced in the spray &amp; In particular, the treatment agents of the components (A) to (F) contained in a quantitative amount exhibited excellent properties in all of the above items. Further, from the comparison between Example 3 and Example 48 9 201024462 Example 31, it is understood that the component Β obtained by reacting the decane coupling agents in the component (Β) exhibits superior performance. Further, from the comparison between Example 37 and Example 49, it is understood that when alkoxysilane is used as the metal alkoxide, the obtained film properties (corrosion resistance) are further excellent. In the comparative examples, the surface-treated galvanized steel sheets in which the characteristics were comprehensively satisfactory were not obtained. For example, in Comparative Examples 5 to 56, which did not contain the component 3, the comparative example 59 which did not contain the component 亦 was also poor in corrosion resistance and grounding property, and the corrosion resistance and the grounding property were all the same, and the component A was used. Skin with excellent composition of component B. Not good. On the other hand, the present invention containing the component A can obtain corrosion resistance and connection. [Simplified description of the drawing] None [Main component symbol description] None

49

Claims (1)

201024462 VII. Patent application scope: i A surface treatment agent for galvanized steel sheets, containing ammonium amide (A); compound (B), which has two or more molecules in one molecule, expressed as - SiRW (in the formula , R, r2, and r3 are each a functional group independently representing an alkyl group, an alkoxy group, or a hydroxyl group having a carbon number of ～4, and the molecular weight (average molecular weight/number of functional groups) of the unit functional group (4) is at 1〇. 〇~5_ range; The organic phosphonic acid (C" Zr, Ti, Co, Fe, V, Ce, metal compound (D) represented by the formula (1) is selected from the group consisting of Zn and Zn. At least one metal element of Mo, Μη, Mg, A, Ni, Ca, W, Nb, Cr; and water; and pH is 6 to 11; General formula (1) 〇Ο II 丨丨 HO 『-P—oh OH OH OH is a surface treatment agent for a plated steel sheet according to item 1 of the patent application scope, wherein the Zr in the ammonium carbonate (4) is converted into Si in the adduct (B). 2, with the chemical 0.0W6.0; "quantity of the mass ratio (A / B) is the mass of the organic phosphonic acid (C), the spot weight of the human... weight and the Si in the compound (B) The mass ratio (C/Β) of the mass at 50 24 2 2010 is 0.001 to 5.0; the mass of the metal element in the metal compound (D) is converted to S1 〇 2 in the case of S1 in the compound (B) The mass ratio (D/B) of the mass is 0.01 to 4.0. 3. The surface treatment agent for a plated steel sheet according to the first or second aspect of the patent application, wherein the compound (B) is composed of a reactive functional group. a (bl) decane oxime agent which is reacted with a compound having a functional group (b2) reactive with a reactive functional group (b1), and the reactive functional group (b) and the official One of the sulfhydryl groups (b2) is an amine group or an epoxy group. 4. A surface treatment agent for galvanized steel sheets according to item 1 or 2 of the patent application scope of the patent application. (E); the metal compound telluride (E) contains at least one metal element selected from the group consisting of b, Nb, Si, Ta, Ti, v W, and Zr. The surface treatment agent for galvanized steel sheets according to item 4, wherein the mass ratio of the mass of the compound (8) to Si〇2 and the mass of the metal element contained in the metal alkoxide (E) is 〇(1) 〜2·0. 6 'For the surface treatment agent for galvanized steel sheets according to item 1 or 2 of the patent scope, wherein the step (b) is contained in the step; At least one of the group of the water-soluble polymer and the water-based emulsion resin. 7. The surface treatment agent for a galvanized steel sheet according to Item 6 of the claim, wherein the Si in the compound (B) is converted into bismuth The mass ratio of the mass to the mass of the compound (F) (F/B) is 0.01 to 30. 8. A surface treatment method of a galvanized steel sheet, which is attached to a galvanized steel sheet. Surface 51 201024462 The surface treatment agent for a zinc-zinc steel sheet according to any one of claims 1 to 7 is coated and dried by heating, and a film having a film amount of 25 to 1000 mg/m 2 is formed on the surface of the galvanized steel sheet. Eight, schema: no flaw 52