TW200912047A - Stain-resistant electrogalvanized steel sheet - Google Patents

Abstract

The invention provides a non-chromate electrogalvanizing steel plate with excellent blemish resisting performance and production method thereof. The invention provides an electrogalvanizing steel plate setting the resin cover film containing 0.05-5quality percent Na instead of Cr on the electrogalvanizing layer. The electrogalvanizing layer is converted by atom to restrain Pb and TI into Pb: below 5ppm (ppm represents quality ppm, the same as follows) and TI: below 10ppm.

Description

200912047 IX. Description of the Invention The present invention relates to an electrogalvanized steel sheet excellent in stain resistance and a method for producing the same, and more particularly to an electrogalvanized steel sheet having a resin film substantially free of Cr. A technique for improving the stain resistance of the appearance unevenness (which makes it not conspicuous) which can effectively control the stain caused by Na in the resin film. The electrogalvanized steel sheet of the present invention can be suitably used, for example, in a chassis or a casing part such as a household electric appliance or an office machine, or a steel furniture such as a steel furniture. [Prior Art] An electrogalvanized steel sheet (non-chromate electrogalvanized steel sheet) having a chromium-free chemical conversion treatment film containing no hexavalent chromium is widely used from the viewpoint of restricting the use of harmful substances. Since such a non-chromate electrogalvanized steel sheet is often used without coating, it is often produced in a coil after storage, in a home appliance manufacturer or an office machine. During processing in the business, during use by the user, it may be exposed to high temperature and humidity for a long time. However, according to experiments by the present inventors, it has been clarified that if a non-chromate electrogalvanized steel sheet is left in a high temperature and humidity environment for a long period of time of more than half a month [for example, about 5 04 hours (2 1 day)], then In the form of a stain or the like, unevenness in appearance (a difference in hue) (a phenomenon in which speckle is discolored) is generated on the surface of the above-mentioned steel sheet. This phenomenon (hereinafter sometimes referred to as "staining") is not visible in the electrogalvanized steel sheet subjected to the chromate-5-200912047 gloss treatment. In addition, the following facts have been clarified: staining and white rust generated in a humid environment in the presence of chloride ions [usually evaluated at 96 hours (4 days) after the salt spray test specified in ns Z23 71], in white rust The blackening produced in the relatively mild rot environment seen before (initial) is usually represented by 5 (TC and 72 hours (3 days) under constant temperature and humidity with relative humidity above 95%). The corrosion phenomenon reported so far is different, especially by exposing a non-chromate electrogalvanized steel sheet containing Na in the film to a high temperature and humidity for a long time of about half a month or more. However, the uneven appearance of the electrogalvanized steel sheet proposed so far improves the technique for preventing blackening before white rust or white rust is generated (for example, Patent No. 3,043,6, Patent No. 3,495,454, Patent No. 3,495,543, JP-A-2004-263252, JP-A-2000-355790, JP-A-2003-5 5 790), and has not provided a technique for improving the appearance unevenness for the purpose of preventing staining. [Invention Institute] [Problem to be Solved] The present invention has been made in view of the above circumstances, and an object of the invention is to provide a non-chromate electrogalvanized steel sheet which is excellent not only in white rust resistance but also excellent in stain resistance, and a method for producing the same, and a method suitable for use in A zinc plating bath for the production of such a non-chromate electrogalvanized steel sheet. [Means for Solving the Problem] -6- 200912047 The electric ore plate of the present invention which solves the above problems is provided on the electrogalvanized layer. An electrosurgical steel sheet containing a resin film of Na 〇.〇5 to 5% (% by mass), the same as the above), and Pb and T1 in the electrogalvanized layer are controlled to Pb in atomic conversion. 5 ppm (ppm means mass ppm. The same applies hereinafter) and Tl: 1 Oppm or less. In a preferred embodiment, the electrogalvanized layer contains a material selected from the group consisting of Ni, Fe, Cr, Mo, Sn, Cu, Cd, Ag. At least one of Si, Co, In, lr and w, in atomic conversion, Ni: 60 to 6000 ppm, Fe: 60 to 600 ppm, Cr: 0 to 5 to 5 ppm, Mo: 30 to 5 to 00 ppm, Sn: 0.6 to 20ppm, Cu: 8 to 3000ppm, Cd: 0 · 0 0 0 1 ~〇· 〇2 ppm , Ag : 1.0 to 400 ppm, Si: 30 to 2000 ppm, Co: 0.0003 to 0.3 ppm 'In: 0.1 to 30 ppm, Ir: 0.01 to 1 〇 ppm, W: 0.1 to 50 ppm. In the preferred embodiment The resin film contains a carboxyl group-containing resin and a Si-based inorganic compound. As a representative example of the S i -based inorganic compound, for example, cerium oxide sol Colloidal Silica) can be mentioned. In a preferred embodiment, the above resin film further contains a decane coupling agent. The method for producing an electrogalvanized steel sheet according to the present invention which can solve the above problems includes: (1) using an electroless plating solution for controlling Pb and T1 in a plating solution to Pb: 〇.〇8 ppm or less and Tl: 0.2 ppm or less And (2) a step of forming a resin film containing 0.05 to 5% by mass of Na. In a preferred embodiment, the above acidic plating solution contains a material selected from the group consisting of Ni: 20 to 2000 ppm 'Fe2 + : 50 to 5000 ppm, Fe 3 + : 50 to 5 ppm ppm 200912047, (: r: 5 to 2000 ppm, Mo: 50 to 2000 ppm, Sn: 0.05 to 20 ppm, Cu: 0.05 to 50 ppm, Cd: 0.05 to 5 ppm, Ag: 0·05 to 5 ppm, Si: 20 to 2000 ppm, Co: 0.05 to 5 ppm, In: 0.5 to 50 ppm, Lr: 0.05 to 5 ppm and W: 0.5 to 5 ppm of at least one element in the group. In the present invention, Pb and T1 in the plating bath are controlled to be zinc plating of Pb: 0.08 ppm or less and Tl: 0.2 ppm or less. The bath is also included in the scope of the present invention. In a preferred embodiment, the zinc plating bath contains a material selected from the group consisting of Ni: 2 0 to 2 0 0 ppm, F e 2 + : 5 0 to 5 0 0 ppm, F e3 + : 5 0 to 5 0 0 0 ppm , Cr : 5 to 2000 ppm , Mo : 50 to 200 〇 ppm , Sn : 0.05 to 20 ppm , Cu : 0.05 to 50 ppm , Cd : 0.05 to 5 ppm , Ag : 0.05 to 5 ppm , Si: 20 to 2000 ppm, Co: 0.0 5 to 5 0 pp m, I n : 0.5 to 50 ppm, Ir: 0.05 to 5 ppm, and W: 0 to 5 to 50 ppm of at least one element in the group. The electrogalvanized steel of the present invention Since the plate is configured as described above, it is possible to greatly improve the white rust resistance and the stain resistance of the non-chromate gloss treated steel sheet. [Best form for carrying out the invention] "Staining phenomenon" [spotted The phenomenon of uneven appearance (difference in hue) is a phenomenon that has not been recognized in the chromate-treated steel sheet to date. According to experiments by the present inventors, especially through the chromate-free resin The electrogalvanized steel sheet containing Na in the film is exposed to high temperature and humidity for a long time (about 504 hours or so).

Na is mainly added for the purpose of improving the strength of the chromate-free resin film and improving the abrasion resistance (damage resistance) (described later), so that a non-chromate resin film containing Na can be widely used. Non-chromate gloss treated steel sheet. Therefore, the inventors of the present invention have made it possible to provide a technique for preventing uneven appearance (not conspicuous) of "staining" which is generated when a non-chromate electrogalvanized steel sheet is stored in a high-temperature and high-humidity environment for a long time. In the case of an impurity element which is inevitably present in Zn which is a raw material, and an impurity element which is inevitably deposited in the electrogalvanized layer by dissolution of an anode material or the like at the time of electroplating, it is repeatedly examined. As a result, it has been found that if (A) Pb and T1, among the impurity elements contained in the plating layer, are controlled to a predetermined level or less, the stain resistance can be improved, and if (B) is selected from Ni, Fe, Cr, When the content of at least one of the groups of Mo, Sn, Cu, Cd, Ag, Si, Co, In, Ir, and W (hereinafter collectively referred to as "stain resistance improving element") is controlled within a predetermined range, The stain resistance can be further improved, thereby completing the present invention. The T1 in the above (A) is an element which has not been paid attention to so far in the field of the electrogalvanized steel sheet for non-chromate which the present inventors have as an investigation object, and the present inventors exceeded the usual detection limit. After carefully examining the various unavoidable impurities contained in the galvanized raw material, it was found for the first time that 'the same as P b for the improvement of the stain resistance, T1 is an element that should be controlled (controlled). As shown in the following detailed description, Pb and T1 specified in the above (A) are elements which adversely affect the improvement of the stain resistance (if the relationship with the stain resistance is 200912047, it is a harmful element, and it can be relative to the above ( The stain resistance improving element of B) is called a stain resistance deterioration element.) If both of these elements are not controlled within a predetermined range, the desired characteristics cannot be obtained. The fewer these elements, the better. The most thorough case is that the best setting is Oppm. In contrast, the antifouling improving element of the above (B), which is a component selected in the present invention, is an element which can contribute to further improvement of the stain resistance by being added in a predetermined amount or more (if it is resistant to staining). The relationship is a useful element), and the addition effect is different from Pb and T1 of (A) above. Moreover, although it is not the technique for improving the stain resistance of the present invention, it has been proposed in the above-mentioned prior patent documents to improve the white rust resistance by controlling the content of a predetermined element in the electrogalvanized layer. method. However, even if these patent documents are examined in detail, there is no record of T1. As described in the examples to be described later, if T1 is not controlled below the level of the present invention, the desired stain resistance cannot be obtained. Further, in the above-mentioned patent documents, although there is an example of controlling Pb in the electroplated zinc layer, it is not sufficient to control Pb only within the scope of the present invention, as described in the following examples, if Pb and The control of both sides of T1 within the scope of the present invention does not provide the desired stain resistance. Further, in the present invention, for example, in the present invention, for example, in the present invention, the present invention is disclosed in the patent application No. 304,336, the patent No. 3,494,344, the patent No. 3,495,543, the Japanese Patent Application No. 2004-263252. The stain resistance used improves a number of partially repeating elements of the element. Specifically, in order to prevent uneven appearance such as white rust, in the patent No. 3 043 3 6 , the patent No. 34 995 44 , and the patent No . 3 49 9543 , the addition of the ratio to the plating bath is disclosed in October 2009. A more expensive element of Zn (Ni, In, Cu, Ag, Co) is disclosed in JP-A-2004-263252, which discloses the addition of a poorly soluble hydrogen in an alkaline region dissolved in Zn in a plating bath. Oxide elements (Fe, Co, Ni, Mn, Mg, Al, Ce, In), elements that are stable in the neutral region and can be stably present in a corrosive environment (Si, Ti, V, Mo, Zr) )Methods. However, the appearance unevenness of the two as the object of study is as follows, and the causes of their occurrence are different, and the mechanism (mechanism) is also different. In other words, in the present invention, the uneven appearance of the "stain" of the object to be investigated is caused by the exposure of the non-chromate electrogalvanized steel sheet to a high temperature and high humidity for a long time, and it is considered that the mechanism and mechanism are The white rust generated in a salt water mist atmosphere differs in appearance unevenness due to short-term exposure to high temperature and high humidity. In addition, it is considered that the above-mentioned "stain" is a phenomenon which is observed when Na is contained in the non-chromate chemical conversion treatment film, and the mechanism of occurrence is also uneven with the appearance of white rust or blackening. different. Even if these patent documents are examined in detail, there is no description of the use of a Na-containing non-chromate film. In addition, as shown in the examples to be described later, the type and content of the stain resistance improving element used in the invention of the present invention include the improvement of white rust resistance confirmed by the facts described in the above-mentioned patent documents. When the types and contents of the elements are different, it is difficult to directly apply the method described in the above patent documents to the technique for improving the stain resistance. Although the details of the mechanism for generating stain on the Na contained in the non-chromate film are not clear', it can be estimated as shown below. When an electrogalvanized steel sheet containing Na in a non-chromate film of -11 - 200912047 is placed in a humid atmosphere of a high temperature and humidity environment, water first dews on the surface of the film. The soluble Na in the film dissolves and precipitates in the condensation portion. When the water containing Na is dried, the Na agglomerated portion where Na is agglomerated and the Na non-agglomerated portion where Na is not agglomerated are mixed in the film. presence. In the Na condensed part, since the corrosion reaction of zinc is promoted by Na ions, an amorphous oxide deviating from the chemical theoretical composition of ΖηχΟ^χ is formed on the surface of the shovel zinc under the film, and the surface of the plating layer becomes black. Color (tea brown). On the other hand, in the non-agglomerated portion of Na, the above discoloration is not produced. In this way, it can be considered that the stained image is only partially discolored by the agglomerated portion of Na, and therefore, as a whole of the film, it appears to be a patch-like pattern. Hereinafter, the electrogalvanized steel sheet of the present invention will be described in detail. The electrogalvanized steel sheet according to the present invention is an electrogalvanized steel sheet in which a resin film containing 0.05 to 5% of Na is substantially contained without containing Cr, and Pb and T1 contained in the electrogalvanized layer are converted by atomic conversion. It is controlled to Pb: 5 ppm or less and Tl: 1 Oppm or less. As shown in the later-described embodiment, if only one of Pb or T1 is controlled within the above range, the desired characteristics cannot be exhibited, and when both of Pb and T1 are controlled within the above range, the desired function is started. characteristic. The content of Pb and T1 is preferably as small as possible, and is preferably controlled to be Pb: l.Oppm or less, and Tl: Ι.Ορρπι or less, preferably controlled to be Pb: 0.3 ppm or less and Tl: 0.5 ppm or less. The electrogalvanized layer described above contains at least one element (soil resistance improving element) selected from the group consisting of Ni, Fe, Cr, Mo, Sn, Cu, Cd, Ag, Si, Co, In, lr, and w. , Fe: 60 to 600 ppm, Cr: 0.5 -12-200912047 to 5 ppm, Mo: 30 to 5 00 ppm, Sn: 0 · 6 to 2 Oppm ' C u : 8 to 3000 ppm, Cd: 0.000 1 - 〇.〇2 ppm 'Ag : 1.0 to 400 ppm, Si: 3 〇 to 2000 ppm, Co: 0 · 0 0 0 3 〜 0 · 3 ppm, In: 0.1-3 Oppm, Ir: 0.01 to lOppm, W: 0.1 to 50 ppni in the vehicle bH It is better. Although the mechanism for effectively preventing staining by the addition of the above-described stain resistance improving element is not clear 'but it can be considered that the zinc plating layer is formed by the provision of an electrogalvanized layer containing a predetermined amount of the above elements. The crystal form and the surface oxide (for example, a gas oxide layer of zinc including the above-mentioned additive element which is inevitably formed on the surface of the zinc plating layer) are affected, and thus the Na agglomerated portion and the Na non-agglomerated portion can be substantially eliminated. The difference in hue. As a result, it is possible to eliminate the uneven appearance caused by the stain. Although the above elements have the effect of improving the stain resistance, they can be roughly classified into (1) elements more expensive than Zn (Ni, Fe, Sn, Cd). Ir, In, Cu, Ag, Co) and (2) are not more expensive elements than Zn but are oxide-forming elements (Cr, Mo, Si, W). These elements may be used alone or in combination of two or more. In order to effectively exhibit the effect of improving the stain resistance of the above-mentioned elements, the content of each element contained in the electrogalvanized layer is set to be 60 ppm or more (preferably 600 ppm or more) of Ni and 60 ppm or more of Fe (in terms of atomic conversion). Preferably, it is 80 ppm or more), Cr is 〇.5 ppm or more (preferably 〇.8 ppm or more), Mo is 30 ppm or more (preferably 〇〇ppm or more), and Sn is 0.6 ppm or more (preferably 1-5 ppm or more). Above ppm (preferably l〇〇ppm or more), Cd is above O.OOOlppm (more preferably o. oippm or more), Ag is above 1.0 ppm, and then from -13 to 200912047 (more preferably, more than 30 ppm), and Si is above 30 ppm ( Preferably, it is 80 ppm or more), Co is 0.0003 ppm or more (preferably 〇.0 〇lppm or more), In is 〇丨ppm or more (preferably 1.0 ppm or more), and ΐΓ is 0.01 ppm or more (preferably 〇lppm or more). W is at 0.1 ppm or more (preferably i.0 ppm or more) (refer to Examples described later). Where 'when added too much, the following bad situation will occur. First, when Fe or S i is excessively added, the effect of improving the stain resistance is lowered, and the corrosion resistance (especially the white rust resistance) is also lowered. On the other hand, when the stain resistance improving element other than F e or S i is excessively added, the stain resistance is good, but the white rust resistance is lowered. In order to satisfy the characteristics of both the stain resistance and the white rust resistance, an excellent surface appearance is obtained, and the content of each element contained in the electrogalvanized layer is set to be 6000 ppm or less and Fe to 600 ppm or less. 5.0 ppm or less, Mo is 50 〇ppm or less, Sn is 20 ppm or less, 'Cu is 3,000 ppm or less' Cd is 〇.〇2 ppm or less 'Ag is 400 ppm or less 'Si is 200 〇ppm or less, c 〇 is 0.3 ppm or less 'In 3 〇ppm or less, Ir is less than 10 〇 ppm, and it is under the “claw. Among the above elements, the elements excellent in the improvement of the stain resistance are preferably Ni, Fe, Cr, Mo, Si, Cu, Co, W. , In, Cu, Ag, more preferably Ni, Fe, Mo, Cr, W. The amount of the anti-fouling improving element contained in the electro-galvanized layer can be, for example, atomic absorption spectrometry or inductively coupled electric paddle emission spectrometry Analytical method (ICP) or inductively coupled plasma mass spectrometry (ICP-MS), etc. The detailed analysis method is described in the section of the examples described later. Moreover, in the analysis: -14- 200912047 In order to eliminate the matrix of Zn, Na, S, etc. contained in the ore solution (mat The measurement error due to the element of rix) is preferably carried out by diluting the plating layer with hydrochloric acid or the like. The dilution ratio is appropriately controlled to a suitable range according to the concentration of the matrix element and the amount of the stain resistance improving element to be measured. In the example described later, 'the content of the element in the ore layer is analyzed after diluting the plating layer by diluting twice the hydrochloric acid. For the adhesion amount of the electrogalvanized zinc, consider the zinc single crystal deposited on the surface of the plating layer. The crystal size is preferably 40 g/m 2 or less, preferably 30 g/m 2 or less. Further, although the lower limit is not particularly limited based on the above viewpoint, if the sacrificial corrosion prevention effect of zinc is considered, The upper part is preferably 3 g/m 2 , and more preferably 10 g/m 2 . The electrogalvanized layer may be provided on at least one surface of the steel sheet as the base material, and may be provided only on one side of the steel sheet or on both sides. (non-chromate resin film) contains about 0.05 to 5% (more preferably 0.1% or more and 3% or less, preferably 1% or less) of Na. Na is usually used to improve a non-chromate resin film (containing a carboxyl group-containing resin and Dioxane The strength of the Si-based inorganic compound such as cerium sol is added to the above-mentioned carboxyl group-containing resin or cerium oxide sol. When the content of Na is less than 5%, for example, in a carboxyl group-containing resin Na is not sufficiently formed between the carboxyl group and Na, and the strength of the film is lowered. On the other hand, when the content of Na exceeds 5%, the amount of soluble Na contained in the film is increased. The amount of Na contained in the resin film may be the sum of the amounts of Na in the solid portion of each component (resin component, Si-based inorganic compound, decane coupling agent or the like which is required to be contained, etc.) constituting the resin film. To indicate that -15-200912047 resin film does not contain Cr in nature. Here, "substantially not contained" means the amount of Cr which can be allowed to be inevitably mixed in the production process of the resin film. For example, in the present invention, a trace amount of Cr is added to the plating layer as a stain resistance improving element, but Cr in the plating layer is mixed into the resin film. Further, for example, in the process of preparing and coating a treatment liquid used in a non-chromate resin film, when a small amount of a CR compound is dissolved and precipitated from a production container, a coating device, or the like, C r may be It is mixed into the resin film. In this case, the amount of Cr contained in the resin film is also preferably in the range of substantially 0.01% or less. The resin film preferably contains a resin component containing a carboxyl group-containing resin and a Si-based inorganic compound (typically a cerium oxide sol). Corrosion resistance, alkali degreasing property, coating property, and the like are improved by the film of the resin film containing such a film. The carboxyl group-containing resin is not particularly limited, and examples thereof include a monomer having a carboxyl group such as an unsaturated carboxylic acid as a part or all of a raw material, and a polymer synthesized by polymerization or a reaction using a functional group. A carboxylic acid-modified resin or the like. A commercially available product can also be used as the carboxyl group-containing resin, and examples thereof include HITECS 3141 (manufactured by Toho Chemical Co., Ltd.). The resin component may contain an organic resin other than the above-mentioned carboxyl group-containing resin. Examples of the Si-based inorganic compound include citrate and/or ruthenium dioxide. These may be used alone or in combination of two or more. In the case of the bismuth hydride, for example, potassium ruthenate or lithium niobate is used as the cerium oxide, and examples thereof include cerium oxide sol and scaly cerium oxide. Further, dry cerium oxide such as pulverized cerium oxide, vapor phase cerium oxide, cerium oxide sol (silica s?), and fumed silica such as fumed silica may also be used. Among them, it is preferred to use a cerium oxide sol in particular. Thereby, the strength of the resin film can be improved, and in addition, in the corrosive environment, cerium oxide is concentrated on the scar portion of the film to control the corrosion of Zn, thereby further improving the corrosion resistance. Commercially available products can also be used as the cerium oxide sol. For example, the SNOWTEX series "ST-40", "ST-XS", "ST-N", and "ST-20L" manufactured by Nissan Chemical Industries, Ltd. , "ST-UP", "ST-ZL", "ST-SS", "ST-O", "ST-AK", etc. These usually contain Na. The mass ratio of the resin component constituting the resin film to the Si-based inorganic compound (typically cerium oxide sol) is substantially in the resin component: Si-based inorganic compound = 5 parts to 4 5 parts: 5 5 parts to 9 parts The range is better. When the content of the resin component is small, the uranium resistance, the degreasing resistance, the coating property, and the like tend to be lowered. On the other hand, when the content of the resin component is large, abrasion resistance, electrical conductivity, and the like are obtained. It will decrease. In addition, when the content of the Si-based inorganic compound is small, the abrasion resistance 'conductivity and the like tend to be lowered. When the content of the Si-based inorganic compound is large, the resin component is reduced. The film forming property is lowered and the corrosion resistance is lowered. -17- 200912047 The resin film may also contain a decane coupling agent. Since the above-mentioned carboxyl group-containing resin and the s i-based inorganic compound are strongly bonded by the addition of the decane coupling agent, the dissolution and precipitation of Na ions are reduced, and the stain resistance is further improved. The decane coupling agent is preferably a material having a lower alkoxy group such as an alkyl group, an allyl group or an aryl group having 1 to 5 carbon atoms. Specific examples include, for example, r-glycidoxypropyltrimethoxydecane, r-glycidoxypropylmethyldimethoxydecane, and r-glycidoxypropyltriethyl. a glycidyloxydecane coupling agent such as oxydecane or 7-glycidoxymethyldimethoxydecane; r-aminopropyltrimethoxydecane, r-aminopropyltriethoxydecane An amino-containing decane coupling agent such as n-(spot-aminoethyl)-r-aminopropyltrimethoxydecane, n-(A-aminoethyl)-r-aminopropylmethyldimethoxydecane a vinyl-containing decane coupling agent such as vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(/5-methoxyethoxy)decane; r-methacryloxypropylpropyl a methacrylic decyloxydecane coupling agent such as trimethoxydecane; a mercapto-containing decane coupling agent such as r-mercaptopropyltrimethoxydecane or r-mercaptopropylmethyldimethoxydecane; A halogen-containing decane coupling agent such as propyl methoxy decane or 7-chloropropyltrimethoxy decane. These decane coupling agents may be used singly or in combination of two or more. The above-mentioned glycidyloxydecane coupling agent is preferably used because it is highly reactive, excellent in corrosion resistance and alkali resistance. A commercially available product may be used as the decane coupling agent, and examples thereof include r-cyclopropoxypropyltrimethoxydecane "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd., -18-200912047). The content of the decane coupling agent is preferably in the range of substantially 5 parts by mass to 25 parts by mass or less based on 100 parts by mass of the total of the resin component and the Si-based inorganic compound. When the content of the decane coupling agent is small, the reactivity of the carboxyl group-containing resin and the Si-based inorganic compound is lowered, and the abrasion resistance and the coating property are deteriorated. Corrosion resistance, etc. are reduced. On the other hand, when the content of the decane coupling agent is large, the stability of the coating liquid used in the production of the resin film is lowered, and gelation is caused. Further, since the amount of the decane coupling agent which does not participate in the reaction increases, the adhesion between the galvanized layer and the resin film may be lowered. Hereinafter, a case where the following resin film is used as a representative non-chromate resin film used in the present invention will be described. Hereinafter, the configuration and preparation method of the resin film will be briefly described. However, the resin film used in the present invention is not limited thereto. Further, the resin film is a modified film of a urethane resin disclosed in the application of the present inventors, and the details are as described in JP-A-2000-439.1, (for example, refer to [0 0 2 0]. ] Section ~ [〇〇7 1] paragraph). The resin film can be obtained from the following aqueous resin solution. In the aqueous resin solution, 'as a nonvolatile resin component, 5 to 45 parts by mass of an aqueous dispersion of a carboxyl group-containing polyurethane resin and an aqueous dispersion of an ethylene-unsaturated carboxylic acid, and the aqueous solution of the resin contains an average particle diameter of 4 5 to 9 parts by mass of cerium oxide particles of ～20 nm, and a total of 10 parts by mass of the cerium oxide particles in the total amount of 5 to 25 parts by mass in the aqueous resin solution The coupling agent' and the above-mentioned non-volatile resin of the aqueous polyurethane resin are formed into a ratio of the non-volatile component (EC) of the aqueous dispersion of the above-mentioned ethylene-unsaturated carboxylic acid copolymer to -19-200912047 parts (PU). The ratio is PU: EC = 9 : 1 to 2 • 1 ° First, the aqueous solution containing carboxyl group polyurethane is explained. As the aqueous carboxyl group-containing polyurethane liquid, either an aqueous dispersion containing a carboxyl group-containing urethane resin or an aqueous solution in which the carboxyl group-containing urethane resin is dissolved in an aqueous medium can be used. The aqueous medium may contain a hydrophilic solvent such as a trace amount of alcohol, N-methylpyrrolidone or acetone in addition to water. The carboxyl group-containing urethane resin preferably has a resin obtained by chain-growth reaction of a urethane prepolymer with a chain extender, and the urethane prepolymer can be reacted, for example, with a polyisocyanate component described later. And get it. The polyisocyanate component constituting the urethane prepolymer is at least selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and dicyclohexylmethane diisocyanate (hydrogenated MDI). 1 kind of polyisocyanate. Here, as the polyol component constituting the urethane prepolymer, all three kinds of polyols using 1,4-cyclohexanedimethanol, a polyether polyol, and a polyol having a carboxyl group are used, and all three are set to three. Glycol. Further, the polyether polyol is not particularly limited as long as it has at least two or more hydroxyl groups in the molecular chain, and the main skeleton is composed of an alkylene oxide unit, and examples thereof include polyethylene oxide, polyoxypropylene glycol, and polyoxybutylene. The polyvalent tetramethylene glycol or the like is not particularly limited, and the chain extender is a chain extender of the above-mentioned urethane prepolymer. , alkanolamine and the like. The aqueous solution containing a carboxyl group-containing urethane resin can be produced by a known method, for example, by neutralizing a carboxyl group of a carboxyl group-containing urethane prepolymer with a base, emulsifying and dispersing in an aqueous medium, and performing a chain extension reaction. A method in which a carboxyl group-containing urethane resin is emulsified and dispersed under high shear force to carry out a chain extension reaction in the presence of a solvent. Hereinafter, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer will be described. The aqueous dispersion of the ethylene-unsaturated carboxylic acid copolymer is not particularly limited as long as it is a liquid in which an ethylene-unsaturated carboxylic acid copolymer is dispersed in an aqueous medium, and the ethylene-unsaturated carboxylic acid copolymer is not ethylene or ethylene. A copolymer of a saturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, and itaconic acid, and one or more of these may be known from ethylene. The high temperature and high pressure polymerization method or the like is polymerized to obtain a copolymer. The above-mentioned ethylene monounsaturated carboxylic acid copolymer has a carboxyl group, and an aqueous dispersion can be formed by neutralizing the carboxyl group with an organic base (e.g., an amine having a boiling point of 100 ° C or lower) or a monovalent metal ion such as Na. Here, the monovalent metal ion is used for neutralization as described above, but is also effective in improving solvent resistance or film hardness. The compound of the monovalent metal is preferably one or more selected from the group consisting of sodium, potassium and lithium, and preferably a hydroxide, a carbon oxide or an oxide of the metal. Among them, NaOH, KOH, LiOH, etc. are preferred, and NaOH -21 - 200912047 is optimal. The present invention is an invention for improving the staining phenomenon caused by the NaOH. The amount of the quinone metal compound is 0.02 to 0.4 mol (2 to 40) with respect to the carboxyl group 1 molar in the ethylene monounsaturated carboxylic acid copolymer. The range of Moll%) is better. When the amount of the above metal compound is less than 0.0 2 mol, the emulsion stability becomes insufficient, and when it exceeds 0.4 mol, the hygroscopicity of the obtained resin film (especially for an alkaline solution) The increase in corrosion resistance after the degreasing step is deteriorated, which is not preferable. The lower limit of the amount of the preferred metal compound is 〇.〇3 mole, and the lower limit is preferably 0.1 mole. The upper limit of the optimum amount of the metal compound is 0.5 mole, and the particularly preferred upper limit is 0.2 mole. When the total amount (neutralization amount) of the above-mentioned organic base (the amine having a boiling point of 100 ° C or less) or the monovalent metal compound is too large, the viscosity of the aqueous dispersion may rapidly rise and solidify. Further, since an excessive amount of the alkali portion causes deterioration of corrosion resistance, it requires a large amount of energy in order to volatilize it, which is not preferable. However, since the amount of neutralization is too small, the emulsifiability is poor, and therefore it is not ideal. Therefore, the total amount of the organic base and the monovalent metal compound used is preferably in the range of 0.3 to 1.0 mol with respect to the carboxyl group 1 mol in the ethylene-unsaturated carboxylic acid copolymer. The aqueous dispersion of the ethylene-unsaturated carboxylic acid copolymer is emulsified by using an organic base and a monovalent metal ion in combination, and it is possible to obtain an extremely small particle (oil droplet) having an average particle diameter of 5 to 50 nm. The liquid in the medium. From this, it is estimated that the film formability of the obtained resin film, the adhesion to the metal plate, and the densification of the film can be improved to improve the corrosion resistance. In the above aqueous medium, a hydrophilic solvent such as alcohol or ether-22-200912047 may be contained in addition to water. Further, the particle diameter of the resin particles of the above aqueous dispersion can be measured, for example, by a laser diffraction method using a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd.). As a method of preparing an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid copolymer is introduced together with an aqueous medium into, for example, a homogenizer apparatus or the like, and heated at 70 to 25 Torr as needed. Next, a compound having an boiling point of i 0 (an amine such as an amine below TC and a monovalent metal (first adding an amine having a boiling point of 1 〇〇 or less) or a boiling point of less than 100 ° C is appropriately added in the form of an aqueous solution or the like. The amine is added almost simultaneously with the compound of the monovalent metal), and is stirred with high shear force. Then, the aqueous solution of the carboxyl group-containing polyurethane resin obtained by the above method and the copolymer of the ethylene-unsaturated carboxylic acid are dispersed. The liquid is mixed with the cerium oxide particles and the decane coupling agent in a predetermined amount, and if necessary, a wax, a crosslinking agent, or the like is added to obtain a desired aqueous resin liquid, cerium oxide particles, a decane coupling agent, a wax, a crosslinking agent, and the like. It may be added at any stage. However, in order to prevent crosslinking and gelation after the addition of the crosslinking agent and the decane coupling agent, it is preferred not to carry out heating. In the resin film, in addition to the above components, components which are usually contained (for example, anti-skinning agent, leveling agent, defoaming) may be contained within a range not impairing the effects of the present invention. Agent, penetrant, emulsifier, film forming aid, coloring pigment, lubricant, surfactant, conductive additive for imparting conductivity, tackifier, dispersant, desiccant, stabilizer, mold inhibitor, Anti--23- 200912047 preservative, antifreeze, etc.) The thickness of the resin film is preferably in the range of 0.1 to 2 μm, preferably in the range of 〇.2 to Ι.Ομπι. When the thickness of the resin film is less than 〇 In the case of .ιμιη, the corrosion resistance is lowered. However, when it exceeds 2 μm, the conductivity is lowered on the resin film to improve the corrosion resistance (especially white rust resistance) or the coating property. A film such as an organic resin film, an organic inorganic composite film, an inorganic film, or an electrodeposition coating film may be provided. Here, examples of the organic resin film include a urethane resin and an epoxy resin. An olefin-based resin such as a fat, an acrylic resin, a polyethylene, a polypropylene or an ethylene-acrylic acid copolymer, a styrene resin such as polystyrene, a polyester, a copolymer or a modified product thereof, or the like, which is known as a coating material. A film formed by combining a cerium oxide sol, a solid lubricant, a crosslinking agent, or the like as needed. The organic-inorganic composite film is typically a water glass such as the above-mentioned organic resin or sodium citrate. The film formed by the combination of the components is typically a water glass film or a film formed of lithium niobate. The following is a method for producing a non-chromate electric shovel zinc steel sheet according to the present invention. First, the base steel sheet (electroplated original sheet) to be used as a base material is used. The base IS _ plate is not particularly limited as long as it is a steel sheet generally used in an electrogalvanized steel sheet. For example, an ordinary steel sheet or an aluminum deoxidized steel sheet can be used. A1 — -24- 200912047 killed steel sheet), various steel sheets such as high-strength steel sheets. It is preferable that the electroplated original plate is subjected to pre-treatment such as degreasing or pickling in the case of electro-galvanizing. Then, an electrogalvanized steel sheet is produced by forming an electrogalvanized layer on the base steel sheet by an electrogalvanizing method. In the acidic bath used for electrogalvanizing, in order to form a desired plating layer, Pb and T1 in an acidic liquid such as sulfuric acid or hydrochloric acid are controlled to a range of Pb: 0.08 ppm or less and Tl: 0.2 ppm or less. As will be described in the examples to be described later, when the amount of addition of Pb and T1 exceeds the above upper limit, the required stain resistance cannot be exhibited. The smaller the amount of Pb and T1 added, the better, and it is preferably controlled in the range of Pb: 0.05 ppm or less and Tl: O.lppm or less, and the control is in the range of Pb: 〇. 〇 3 ppm or less and Tl: 0.05 ppm or less. Better. In addition, in order to control Pb and T1 in the electroplated zinc layer within the range prescribed by the present invention, in addition to controlling the addition amount of Pb and T1 in the acidic liquid as described above, attention is paid to the raw material of Zn or electrogalvanized. The anode material or the like used in the method is preferred. Specifically, it is preferable to control Pb and T1 in Zn which are raw materials to be about 15 ppm or less and about 10 ppm or less, respectively. In addition, when a pb alloy such as a Pb—In—Ag alloy or a Pb—Sn alloy is used as an anode material, the amount of Pb in the zinc ore layer may increase due to dissolution and precipitation of the anode material, so that it is used. An anode material (for example, a ruthenium oxide electrode) which does not substantially contain P b is preferred. Further, in the acidic bath used in electrogalvanizing, in an acidic liquid such as sulfuric acid or hydrochloric acid, it may be selected from Ni: 20 to 20 00 Ppm, ρ ε 2 : 50 to 5 000 ppm, Fe 3 + : 50 to 5000 ppm, and Cr : 5 〜 20〇〇ppm, M〇-25- 200912047:50~2000ppm, Sn: 0.05~20ppm, Cu: 0.05~5〇ppm, Cd: 0.05~5ppm, Ag '·0.05 ～5ppm, Si: 20~2000ppm, Co : 0.05 to 50 ppm, In: 0.5 to 50 ppm, lr: 〇.〇5 to 5 ppm, and W: 0·5 to 50 ppm of at least one element in the group, whereby the stain resistance is further improved. When the amount of addition of each element is less than the above lower limit, the stain resistance cannot be effectively exhibited. However, when the amount of each element added exceeds the above upper limit, properties such as stain resistance and white rust resistance are caused. Yu. The preferable addition amount of each element is Ni: 200 ppm or more and 2000 ppm or less, Fe2+ · _ 200 ppm or more and 20 〇〇 ppm or less, Fe3+: 500 ppm or more and 2000 ppm or less, Cr: 50 ppm or more and 2 〇〇〇 ppm or less, and Mo: 200 ppm or more and 2000 ppm. Hereinafter, Sn: 〇·5ρρπ1 or more and 5 ppm or less, Cu: 2 ppm or more and 50 ppm or less, cd: 0.5 ppm or more and 5 ppm or less, Ag: 5. 5 ppm or more and 5 ppm or less, Si: 5 〇 ppm or more and 800 ppm or less, c 〇: 0.5 ppm or more 5 ppm or less, in: 2 ppm or more and 20 ppm or less, ir: 5 ppm or more and 5 ppm or less, and w: 2 ppm or more and 50 ppm or less. The above-mentioned elements (Pb and τ1 and the stain resistance improving element) are not particularly limited in the form of addition in the plating bath, and any form can be adopted as long as the atomic conversion amount of each element satisfies the above range. For example, it may be added to the plating solution in a metal state such as a metal powder or a metal box or may be added in the form of a metal salt such as a sulfate, a chloride salt, an acid salt of a phthalate or an oxide salt. In the case of being added in the form of a metal salt, the valence of the element is not particularly limited. A ruthenium which can be generally used can be used. For example, it may be 3 or 6 valence. M〇 or w, etc. can be *price or 6 price. As described in the examples of -26-200912047 to be described later, the above elements may be added in the form of a hydrate. In the plating solution, in addition to the above elements, other components which are generally added may be added. For example, a conductive auxiliary agent such as Na2S04, (NH4)2S04, KC1, or NaCl may be added for the purpose of improving conductivity and reducing power consumption. The zinc plating bath described above used in the present invention is novel and is included in the scope of the present invention. In other words, (A) is controlled to have a zinc plating bath of Pb: 0.08 ppm or less and Tl: 0.2 ppm or less, and (B) in the above (A), control is Pb: 0.08 ppm or less and Tl: 0.2 ppm or less, and contains From Ni: 20 to 2000 ppm, F e 2 + : 5 0 to 5 0 0 Opp m , Fe3+ : 50 to 5000 ppm, Cr: 5 to 2000 pp m, Mo: 50 to 2 0 0 ppm, S n · 0.05 to 20 ppm ' Cu : 0.05 - , 5 Oppm , Cd : 0,05 to 5 ppm, Ag · 0.05 to 5 ppm, Si: 20 to 2000 ppr n, Co: 0.05 to 50 ppm, In : 0.5 to 50 ppm ' Ir : 0.05 to 5 ppm and W : A zinc electroplating bath of at least one element in the group of 0.5 to 50 ppm is also included in the scope of the present invention. The zinc plating bath of the present invention has the following characteristics in a zinc plating bath which is generally used in electrogalvanizing or the like, that is, the amount of addition of Pb and T1 is controlled to the above-described level, or the amount of addition of the stain resistance improving element is also improved. The control is within the above range. 'The components in the other plating bath are not particularly limited. In the present invention, 'the zinc plating bath which is generally used, for example, a zinc sulfate bath (a zinc sulfate bath containing zinc sulfate and sulfuric acid, a zinc sulfate bath containing zinc sulfate and sodium sulfate, and the like) may be used in an acid zinc plating bath. , add the above elements. The zinc plating bath of the present invention may contain, in addition to the above elements, an additive component (for example, the above-mentioned conductive auxiliary agent) which is usually added to the zinc plating bath. -27- 200912047 Specifically, the following zinc plating baths can be used in addition to the zinc plating bath described in the examples to be described later. (Zinc sulfate bath...one)

ZnS04 · 7H20 3 5 Og/L

H2S04 3 Og/L (zinc sulfate bath...second)

ZnS04 * 7H20 3 50g/L

Na2S04 70g/L

(NH4)2S〇4 3 0 g/L The production method of the present invention is characterized in that Pb and T1 in the plating solution are controlled to a predetermined level, and it is preferable to use a plating solution in which a predetermined amount of the stain resistance improving element is added. In order to form an electrogalvanized layer, other plating conditions can be appropriately determined within a range that does not impair the effects of the present invention, and for example, it is preferably controlled as shown below. The pH of the plating solution is preferably in the range of 0.5 to 4.0, preferably in the range of 1. 〇 to 2.0, in view of the relationship with the current efficiency or the burn phenomenon of the plating layer. The temperature of the plating solution is approximately 50 to 7 (best in the range of TC. The relative flow rate of the plating solution is preferably in the range of 0.3 to 5 m/SeC. Here, the relative flow rate means the flow direction of the plating solution. The difference between the speed and the speed of the plate in the plate as the plated original plate. The type of the electrode (anode) used in the plating is not particularly limited as long as it is generally used -28-200912047, for example, in addition to the P b - S η electrode, Examples of the lead-based electrode such as P b — I η electrode, Pb—Ag electrode, and Pb—In—Ag electrode include a ruthenium oxide electrode, a fresh electrode, etc. The plating tank may use any of a vertical type and a horizontal type. The method of electroplating zinc is not particularly limited, and examples thereof include a constant current plating method, a pulse plating method, and the like. After the plating layer is formed as described above, a resin film (non-chromate film) is formed as shown below. Before the formation of the film, for the purpose of improving the film adhesion, improving the corrosion resistance, and controlling the appearance, the surface of the plating layer may be made of, for example, an amine such as Co, Ni, Mo, V, phosphate or nitrate. Specifically, first, a chromium-free chemical conversion treatment liquid containing a predetermined amount of a carboxyl group-containing resin component and a Si-based inorganic compound, and a predetermined amount of a decane coupling agent (hereinafter sometimes referred to simply as "treatment liquid" is prepared. The treatment liquid is a liquid in which the following components are dissolved and dispersed in an aqueous solvent (for example, hydrochloric acid or a nitric acid solution) which can be completely dissolved. The resin component contained in the treatment liquid and the quality of the Si-based inorganic compound. The ratio is roughly the resin component: Si-based inorganic compound = 5 parts to 45 parts: preferably in the range of 5 5 parts to 95 parts. When the amount of the resin component such as a carboxyl group-containing resin is small, there is corrosion resistance and resistance. When the amount of the resin component is large, the abrasion resistance, the electrical conductivity, and the like are lowered. When the amount of the cerium oxide sol is small, the amount of the cerium oxide sol is small. There is a tendency for abrasion resistance and electrical conductivity to decrease. When the amount of the cerium oxide sol is large, the resin composition is reduced, so that the film formation property of the resin film is lowered -29-200912047, and corrosion resistance is low. reduce. The treatment liquid may further contain a decane coupling agent. The content of the alkane coupling agent contained in the treatment liquid is generally 100 parts by mass based on the total of the tree component and the Si-based inorganic compound, as shown in Examples described later. The range of 5 parts by mass is preferably. When the content of the decane coupling agent is small, in addition to the effect of effectively improving the stain resistance, the reactivity of the carboxyl group-containing resin with the Si inorganic compound is also lowered, thereby making the wear resistant. On the other hand, when the content of the decane coupling agent is large, the stability of the coating liquid used in the production of the resin film is lowered, and gelation is caused. Since the amount of the decane coupling which does not participate in the reaction increases, the adhesion between the zinc plating layer and the resin film may be lowered. In the treatment liquid, in addition to the above components, a wax or a crosslinking agent or the like may be added as needed. Further, in the treatment liquid, it is also possible to contain a component (for example, an anti-skin agent, a leveling agent, an antifoaming agent, a penetrating agent, an emulsifier, a film-forming auxiliary agent) which is usually contained in a range which does not impair the effects of the present invention. Pigments, lubricants, surfactants, conductive additives for imparting conductivity, tackifiers, dispersants, desiccants, stabilizers, anti-fungal preservatives, antifreezes, etc.). When the treatment liquid containing the above components is used, a known method is used, and the method is applied by a roll coating method, a spray coating method, a curtain coating method, a knife coating method, a bar coating method, a dip coating method, a brush coating method, or the like. When one side or both sides of a metal plate is heated and dried, a desired resin film galvanized steel sheet can be obtained. The heating/drying temperature is a temperature at which the crosslinking reaction of the -30-200912047 compound which is low after the use of the carboxyl group-containing resin and the Si-based inorganic oxime is low (for example, The plate temperature is approximately 90 to 1 00 ° C). In addition, in the case of using a spherical polyethylene wax as a lubricant, since the processing property in the subsequent processing step becomes good if the spherical shape is maintained, it is preferably about 70 to 1 30 t. Drying is carried out within the range. [Embodiment] The present invention will be more specifically described by the following examples. However, the present invention is not limited by the following examples, and may be appropriately selected in the scope of the above-described subject matter. It is implemented by making a change, and such a mode is also included in the technical scope of the present invention. [Embodiment 1] In this embodiment, the effects of Pb and T1 contained in the plating layer on stain resistance and white rust resistance were examined. Here, a resin film was produced in the same manner as in the method described in Example 1 of the above-mentioned JP-A No. 20 04 -2 2 44 54. (1) Preparation of aqueous resin solution Here, a resin film was prepared from an aqueous resin liquid containing an aqueous solution of a carboxyl group-containing urethane resin, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer, cerium oxide particles and a decane coupling agent. The specific production method is as follows -31 - 200912047 (1 - 1) Preparation of aqueous solution containing carboxyl group-containing urethane resin In a synthetic device having a content of 0.8 L with a stirrer, a thermometer, and a temperature controller, it is added as a polyol component to the Baogu Valley. Chemical Industry Co., Ltd. produces polytetramethylene ether glycol (average molecular weight l〇〇〇) 60g, 1,4-cyclohexanedimethanol Mg, dimethylolpropionic acid 2〇g, and then N-methylpyrrolidone 3〇.〇g was added as a reaction solvent. To the isocyanate component, 1 4 g of toluene diisocyanate (hereinafter sometimes abbreviated as "TDI") was added, from 80. (: The temperature was raised to 85 ° C, and the reaction was carried out for 5 hours. The obtained prepolymer had an NC Ο content of 8.9%. Then, 16 g of triethylamine was added for neutralization, and ethylenediamine 16 g and water 4 8 0 were added. The mixed aqueous solution of g was emulsified at 50 ° C for 4 hours, and subjected to a chain extension reaction to obtain an aqueous dispersion of a polyurethane resin (the nonvolatile resin component was 2 9 _ 1 % 'acid value was 4 1.4). 1) Preparation of an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer in an autoclave equipped with an emulsifier having a content of 0.8 L of a stirrer, a thermometer, and a temperature controller, and adding 626 parts by mass of water, an ethylene-acrylic acid copolymer (20% by mass of acrylic acid, 300: melt index (MI)) 160 parts by mass, adding 40 mol% of triethylamine, 15 mol% of sodium hydroxide' to 150 of the carboxyl group 1 molar of the ethylene-acrylic acid copolymer High-speed stirring was carried out in an atmosphere of ° C and 5 Pa, and the mixture was cooled to 40 ° C to obtain an aqueous dispersion of an ethylene-acrylic acid copolymer. In the above aqueous dispersion, 4,4'-double was added as a crosslinking agent. Ethyleneimidocarbonylamino)diphenylmethane (manufactured by Japan Catalyst, CH EMITITE DZ—22E, “CHEMITITE” is the registrar-32-200912047), which is 5 parts by mass relative to the non-volatile resin component of the ethylene-acrylic acid copolymer. (1 - 3 ) In the preparation of the aqueous resin solution, the aqueous solution of the carboxyl group-containing urethane resin obtained in the above description, the aqueous dispersion of the ethylene-acrylic acid copolymer, the silica dioxide sol ("ST-XS" manufactured by Nissan Chemical Industries Co., Ltd., and the average particle size) The diameter is 4 to 6 nm), and 100 parts by mass is added in total in terms of nonvolatile components, and they are brought to 5 parts by mass: 25 parts by mass: an addition ratio of 70 parts by mass, and 1 part by mass relative to the total amount Further, 1 part by mass of 7•-glycidoxypropyltrimethoxydecane ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a decane coupling agent to prepare a resin aqueous solution. (2) Preparation of an electrogalvanized steel sheet For the electroplating original plate, an A1 aluminum deoxidized steel plate produced by a conventional method is used. After degreasing and pickling, a reflow type plating apparatus having a plating area of 180 mm x 300 rnm is used, and a sulfate bath is used, in the following strip Electroplating was carried out to obtain an electrogalvanized steel sheet. (Polyplating liquid composition) The plating of the elements (Pb/Tl) shown in Table 1 was added in the range shown in Table 1 in the form of sulfate in the following composition. In addition, a plating solution in which these elements are not added at all is prepared.

ZnS04 * 7H2〇 3 5 0g/L -33- 200912047

Na2S04 70g/L

H2S04 20g/L Other plating conditions are as follows. - Current density: 1 00 A/dm2 • Plating bath temperature: 60 ± 5 乞 • Plating solution flow rate: 1.3 m/Sec • Electrode (anode): IrOx electrode • Plating adhesion: 20 g/m2 (3) Plating with resin film Preparation of zinc steel sheet The aqueous resin liquid obtained in the above (1) was applied by a rolling method (single-sided coating) to the zinc plating layer obtained in the above (2), and in a laboratory furnace, at a furnace temperature of 2 2 The plate was heated and dried at 0 ° C at 0 ° C to obtain an electrogalvanized steel sheet having a resin film (non-chromate film) having a thickness of 0.4 μm. The resin film thus obtained contains a resin component, a cerium oxide sol, and a brothel coupling agent in terms of a mass ratio, which is substantially a resin component: cerium oxide sol: decane coupling agent = 30 parts: 70 parts : 10 copies. In addition, it was confirmed by atomic absorption spectrophotometry (device: SOLARA-M6 manufactured by Jarrel-Ash Co., Ltd.), and the result was 1.2% by mass. Specifically, the content of Na contained in the resin component constituting the resin film is 0 to 55 mass%, and the content of Na contained in the cerium oxide sol is 1 to 7 mass%. (4) Analysis of the stain resistance improving element in the plating layer -34- 200912047 The amount of the stain resistance improving element contained in the plating layer thus obtained was analyzed by the following method. First, an analysis sample in which the electrogalvanized steel sheet obtained as described above is cut at a size of 50 × 50 mm is prepared, and this is added to a hydrochloric acid liquid diluted to twice, and immersed until the dissolution reaction of Ζ η is completed. The immersion liquid (1). In the present embodiment, in order to eliminate the measurement error caused by the precipitation of the surface of the steel sheet as the base material by the temporarily dissolved stain resistance improving element, the sample is pulled up immediately after the dissolution reaction of Ζη is completed, and again in the new The prepared hydrochloric acid liquid (2-fold dilution) was immersed for 30 seconds to obtain an immersion liquid (2). Then, the immersion liquids (1) and (2) obtained as described above were combined and brought to volume, and then Pb and Τ1 and the improvement of the stain resistance were analyzed using an ICP-MS analyzer (PLASMAQUAD type manufactured by VGI Corporation). The amount of element (except Cu). For the CU, an ICP analyzer (ICPV - 1 000 manufactured by Shimadzu Corporation) was used for analysis. Further, the detection limit of Pb and T1 in the present embodiment is Pb: O.lppin, Tl: O.lppm. (5) Evaluation of stain resistance Each of the electrogalvanized steel sheets obtained as described above was placed in a constant temperature and humidity test apparatus having a temperature of 50 ° C and a relative humidity of 95% or more and stored for 504 hours. The appearance of the surface was visually observed, and the stain resistance was evaluated based on "photograph of the stain evaluation evaluation" (5 cm X 5 cm) in Fig. 1A to Fig. 1E. 1A to 1E correspond to the following evaluation criteria 1 to 5, respectively. In the present embodiment, the evaluation criteria are "1" to "3", and it is judged as pass, and "4" or "5" is judged as unacceptable. 35- 200912047 (Evaluation Criteria) 1 : Case where there is no stain at all (Fig. 1 A) 2 : Case where little stain is generated (Fig. 1 B) 3: Case where stain is generated (Fig. 1C) 4: Obviously produced Case of staining (Fig. 1 D) 5 : Case where stains are severely generated (Fig. 1 E) Here, if Fig. 1B (evaluation 2) and Fig. 1C (evaluation 3) are compared, it is understood that in Fig. 1 C, More spot-like spots are clearly produced compared to Figure 1B. In addition, if FIG. 1C (Evaluation 3) and FIG. 1D (Evaluation 4) are compared, it can be seen that in FIG. 1D, the overall color tone is blacker than that of FIG. 1C, which can be considered because of the Na condensation portion. The degree of blackening of the area that is blackish is increased, and as a result, the difference in stains between the two becomes conspicuous. In addition, if FIG. 1D (evaluation 4) and FIG. 1E (evaluation 5) are compared, it can be seen that in FIG. 1E, the hue is further blackened as compared with FIG. 1D, which can be considered because of the blackening of the Na-condensed portion. The degree is excessively exacerbated. The degree of blackening can be, for example, the L値 of the Hunter-Lab color method (using a color solid coordinate system composed of three coordinate axes of the L-axis, the a-axis, and the b-axis to divide the color into three elements and use the number値) expressed by the method of performance/metering. Thus, in the present embodiment, the degree of blackening was comprehensively evaluated for the stain resistance. (6) Evaluation of white rust resistance The respective galvanized steel sheets obtained as described above were subjected to the salt spray test specified in JIS Z2371, and white rust generation after -36-200912047 after 96 hours was determined by the following criteria. The area ratio was evaluated for white rust resistance. In the present embodiment, the evaluation criterion is "◎" or "〇", and the judgment is acceptable (example of the present invention). ◎: less than 5% 〇: 5% or more and less than 10% △: 10% or more and less than 50% X: 50% or more These results are recorded in Table 1. In Table 1, "one" indicates that it is below the detection limit (measurement limit). -37- 200912047 [Table l]

No. Pb T Evaluation of concentration in plating solution (ppm) Concentration in plating layer (PPm) Concentration in plating solution (ppm) Concentration in plating layer (ppm) Stain resistance White rust resistance 1 — — — — 3 ◎ 2 0.01 0.1 — — 3 ◎ 3 0.03 0.4 — — 3 ◎ 4 0.05 1.1 — — 3 ◎ 5 0.1 8.7 — — 4 〇6 0.3 17.4 — — 4 〇7 0.5 25 — — 4 Δ 8 1 37.8 — — 4 Δ 9 3 119 — — 5 X 10 5 224 — — 5 X 11 10 450 — — 5 X 12 — — 0.01 0.6 3 ◎ 13 — — 0.03 2.2 3 ◎ 14 — — 0.05 3.1 3 ◎ 15 — — 0.1 7.2 3 ◎ 16 — — 0.3 27 4 〇17 — — 0.5 44 4 〇18 — — 1 60 4 Δ 19 — — 3 168 4 X 20 — — 5 287 5 X 21 — — 10 650 5 X 22 0.06 2.2 0.04 2.5 3 ◎ 23 0.07 3.5 0.08 5.5 3 ◎ 24 0.07 4.4 0.15 9.2 3 ◎ 25 0.1 6.2 0.05 3.8 4 〇26 0.12 8 0.09 6.7 5 Δ 27 0.2 12 0.14 8.8 4 X 28 0.06 2.5 0.3 13 4 X 29 0.07 4.1 0.28 12.5 4 Δ 30 0.07 4.8 0.4 15 5 X -38- 200912047 According to Table 1, it can be examined as shown below.

No. 1 is an example in which a plating solution in which both Pb and T1 are not added is used, and both Pb and T1 in the plating layer are controlled to be below the detection limit of the present embodiment; No. 2 to 4 are in the plating solution. The Pb in the plating layer is controlled within the scope of the present invention, and the T1 in the plating layer is controlled to be below the detection limit of the present embodiment; No. 12 to 15 is to control the T1 in the plating solution and in the plating layer in the present invention. In the range, and the Pb in the plating layer is controlled below the detection limit of the present embodiment; N 〇. 2 2 to 2 4 is to control both Pb and T1 in the plating solution and in the plating layer within the scope of the present invention. For example, both stain resistance and white rust resistance are improved. On the other hand, Nos. 5 to 11 are examples in which the T1 in the plating layer is controlled below the detection limit of the present embodiment, but the content of Pb in the plating solution and the plating layer is large; Ν ο · 1 6 to 2 1 Although Pb in the plating layer is controlled below the detection limit of the present embodiment, the content of T1 in the plating solution and the ore layer is large; No. 25 to 30 are both Pb and T1 in the plating solution and in the plating layer. In addition to the reduction in stain resistance, there are examples in which the white rust resistance is lowered. [Embodiment 2] In the present embodiment, the influence of the addition of the stain resistance improving element on the stain resistance and white rust resistance was examined. Specifically, a resin film (non-chromic acid) was produced in the same manner as in Example 1 except that the plating solution containing the additive (stain resistance improving element) described in Tables 2 to 9 was used as in Example 1. Galvanized steel of the salt film) - 39 - 200912047 The board was evaluated for stain resistance and white rust resistance in the same manner as in Example 1. Ni, Fe, Sn, Cu, C d, C o, and W in the stain resistance improving element are added as sulfates, and M 〇 is added as sodium molybdate.

Si is added as a cerium oxide sol, Ag is added as silver nitrate, and in is added as a hydroxide to add Ir as a bromide. The results of these are recorded in Table 2 to Table 9. The results of N 〇 . 1 of Table 1 for reference are also recorded in Tables 2 to 9. -40- 200912047 【2撇】 IM White rust resistance ◎ ◎ ◎ ◎ 〇 XX ◎ 〇〇<3 XX ◎ 〇〇〇XX ΙίϊΙπ Stain resistance m »—Η f ·Η cn ΓΠ inch 1—Η m inch 1 1 Η (Ν inch^Τ) Concentration in the plating (ppm) 1 880 3100 5500 950 3200 5450 120 200 500 310 550 00 200 Ο Ο 1 < 310 480 Concentration in the bath (ppm) 1 300 ι_____ ... 1000 1500 300 1000 1500 300 1000 3000 300 1000 3000 ο 1000 3000 ο 1—Η 1000 3000 Type 1 NiS04 · 6Η20 FeS04 · 7Η20 Fe2(S〇4)3 · ηΗ^Ο Concentration in the coating (ppm) 1 (Ν Ο οο ο (Ν ί ί ί Ο Ν Ν Ν Ν Ν Ν Ν Ν Ν 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 ι—Η 0.01 0.03 0.05 ο Η Ο 1—^ 0.01 0.03 0.05 I-^ ο Ο d Z τ 1 Η (Ν mmm 00 m ο Ο] rn -41 - 200912047 u嗽] Evaluation of white rust resistance ◎ ◎ ◎ 〇 〇XX ◎ 〇〇〇XX ◎ ◎ 〇〇XX Stain resistance m ί—Η Τ—Η ^-Η rH ΓΠ Inch CN m Concentration in the coating of the additive (ppm) 1 ο ο Ο 1—i r-^ p ·Η (Ν inch 180 310 440 200 330 470 § οο 450 Ό m (N 酽— concentration in 420 plating bath (ppm) 1 Ο 300 1000 Ο r—H 300 1000 300 1000 1500 300 1000 1500 Ο m ο r—H Ο m Ο m 〇1—^ 300 Type 1 Cr2(S04)3 Na2Mo042H20 Si〇2 £ Concentration in plating (ppm) 1 CN Ο r- o ΓΝ inch \ό Ο Ό 389 ι_ Ο Ο CN m Ο 400 ο ο m ro 398 Concentration in plating solution (PPm) 1 0.01 0.03 0.05 Ο Ο 0.01 0.03 0.05 1 '< Ο Ο 0.01 0.03 0.05 oo 〇Γ·Η o in (Ν m Yr) iT) 00 Ον ir> m Ό -42- 200912047 [Table 4]

No. Pb Additive evaluation of concentration in plating solution (ppm) Concentration in plating layer (ppm) Concentration in type plating solution (ppm) Concentration in plating layer (ppm) Stain resistance White rust resistance 1 — — — — — 3 ◎ 67 0.01 0.1 SnS〇4 0.1 1.3 1 ◎ 68 0.03 1.1 1 3.0 1 ◎ 69 0.05 3.9 3 6.0 1 〇70 0.1 7.3 0.1 1.1 4 〇71 1 39 1 4.0 5 X 72 10 322 3 8.0 5 X 73 0.01 0.2 CuS04 0.1 18 1 ◎ 74 0.03 0.8 1 88 1 〇75 0.05 4.0 3 250 2 〇76 0.1 7.5 0.1 25 4 Δ 77 1 50 1 110 4 X 78 10 380 3 220 5 X 79 0.01 0.1 C0SO4 0.1 0.0005 2 ◎ 80 0.03 0.5 1 0.0020 1 ◎ 81 0.05 2.9 3 0.0070 1 〇82 0.1 7.0 0.1 0.0006 4 〇83 1 42 1 0.0030 5 X 84 10 400 3 0.0070 5 X 85 0.01 0.2 W2S04 1 0.9 2 ◎ 86 0.03 1.3 3 2.5 1 〇87 0.05 3.3 10 12 1 〇88 0.1 7.8 1 1.2 4 〇89 1 67 3 3.0 4 X 90 10 403 10 10 5 X -43- 200912047

[Table 5] No. Pb Additive evaluation of concentration in plating solution (ppm) Concentration in plating layer (ppm) Concentration in type plating solution (ppm) Concentration in plating layer (ppm) Stain resistance White rust resistance 1 — — —— 3 ◎ 91 0.01 0.1 In(OH)3 1 0.7 2 ◎ 92 0.03 1 3 1.5 1 ◎ 93 0.05 4 10 4 1 ◎ 94 0.1 8.2 1 0.8 3 〇95 1 34 3 2 4 X 96 10 398 10 4.2 5 X 97 0.01 0.1 CdS04 0.1 0.0003 2 ◎ 98 0.03 0.8 1 0.0027 1 〇99 0.05 3.8 3 0.008 1 〇100 0.1 9 0.1 0.0002 4 〇101 1 44 1 0.0033 5 X 102 10 421 3 0.009 5 X 103 0.01 0.1 AgN03 0.1 8 2 ◎ 104 0.03 0.5 1 58 1 〇105 0.05 2.9 3 200 1 〇106 0.1 8.1 0.1 10 4 〇107 1 66 1 65 4 X 108 10 411 3 350 5 X 109 0.01 0.1 IrBr3 · 4H2〇0.1 0.03 2 ◎ 110 0.03 0.8 1 0.7 1 〇111 0.05 3.2 3 3.1 1 〇112 0.1 7.3 0.1 0.02 3 〇113 1 60 1 0.9 5 X 114 10 336 3 3.5 5 X -44 - 200912047 [Table 6]

No. 添加剂 Additive evaluation of the concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Stain resistance White rust resistance 1 — — — 3 ◎ 115 0.01 0.5 NiS04-6H20 100 320 1 ◎ 116 0.03 2 300 850 1 ◎ 117 0.05 3.5 1000 3100 1 ◎ 118 0.1 8 1500 5200 1 ◎ 119 0.3 20 100 298 3 〇 120 0.5 50 300 810 3 〇 121 1 82 1000 2890 4 △ 122 10 530 1500 5450 5 X 123 0.01 0.2 FeS04-7H20 100 67 1 ◎ 124 0.03 1.8 300 90 1 ◎ 125 0.05 4 1000 120 1 ◎ 126 0.1 6.9 3000 550 1 ◎ 127 0.3 18 100 70 3 〇128 0.5 45 300 88 3 〇 129 1 66 1000 135 4 Δ 130 10 580 3000 570 5 X 131 0.01 0.4 Fe2(S〇4)3 · nH2〇100 80 1 ◎ 132 0.03 2.8 300 120 1 ◎ 133 0.05 5 1000 210 1 ◎ 134 0.1 7 3000 500 1 ◎ 135 0.3 22 100 75 3 〇 136 0.5 50 300 90 3 〇 137 1 77 1000 220 4 Δ 138 10 540 3000 560 5 X -45 - 200912047

[Table 7] No. 添加剂 Evaluation of concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Stain resistance White rust resistance 1 —— — 3 ◎ 139 0.01 0.6 Cr2(S04)3 30 0.7 1 ◎ 140 0.03 2.2 100 1.5 1 ◎ 141 0.05 3.1 300 3 1 ◎ 142 0.1 8.5 1000 4.2 1 ◎ 143 0.3 25 30 0.8 3 〇144 0.5 53 100 2 3 〇145 1 60 300 3.9 4 Δ 146 10 580 1000 4.5 5 X 147 0.01 0.3 Na2Mo〇42H2〇100 45 1 ◎ 148 0.03 3 300 180 1 ◎ 149 0.05 4.5 1000 320 1 ◎ 150 0.1 7.7 1500 470 1 ◎ 151 0.3 21 100 60 3 〇 152 0.5 44 300 123 3 〇 153 1 70 1000 326 4 Δ 154 10 657 1500 450 5 X 155 0.01 0.5 Si02 30 45 1 ◎ 156 0.03 2 100 130 1 ◎ 157 0.05 3.7 300 430 1 ◎ 158 0.1 7.6 1000 1200 1 ◎ 159 0.3 25 30 69 3 〇160 0.5 53 100 157 3 〇161 1 76 300 398 4 Δ 162 10 590 1000 1320 5 X -46- 200912047 [Table 8] 添加剂 Additive evaluation No. In the plating solution in the ore solution The concentration of the concentration in the plating solution is concentration-concentrated White rust resistance (ppm) (ppm) (ppm) (PPm) 1 — — — 3 ◎ 163 0.01 0.4 0.1 1.3 1 ◎ 164 0.03 2.8 1 2.7 1 ◎ 165 0.05 4.2 3 6 1 ◎ 166 0.1 8.7 SnS04 10 15 1 ◎ 167 0.3 30 0.1 1.2 3 〇 168 0.5 58 1 3 3 〇 169 1 77 3 5.7 4 Δ 170 10 620 10 10 5 X 171 0.01 0.5 0.1 12 1 ◎ 172 0.03 2.4 1 68 1 ◎ 173 0.05 3.6 3 210 1 ◎ 174 0.1 8.1 CuS04 10 724 1 ◎ 175 0.3 19 0.1 15 3 〇 176 0.5 55 1 70 3 〇 177 1 82 3 236 4 Δ 178 10 590 10 630 5 X 179 0.01 0.6 0.0006 1 ◎ 180 0.03 2.5 1 0.003 1 ◎ 181 0.05 4 3 0.008 1 ◎ 182 0.1 7.2 CoS04 10 0.09 1 ◎ 183 0.3 28 0.1 0.0005 3 〇184 0.5 44 1 0.005 3 〇185 1 90 3 0.01 4 Δ 186 10 645 10 0.1 5 X 187 0.01 0.4 W2S〇4 1 0.5 1 ◎ -47- 200912047

188 0.03 2.4 3 2.5 1 ◎ 189 0.05 3.9 10 12 1 ◎ 190 0.1 8.5 40 38 1 ◎ 191 0.3 22 1 0.8 3 〇192 0.5 53 3 3.2 3 〇193 1 88 10 9 4 Δ 194 10 570 40 40 5 X - 48- 200912047 [Table 9] No. 添加剂 Evaluation of concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Concentration in the plating solution (ppm) Concentration in the plating layer (ppm) Stain resistance White rust resistance 1 — — — 3 ◎ 195 0.01 0.4 In(OH)3 1 0.4 1 ◎ 196 0.03 2.9 3 2 1 ◎ 197 0.05 4 10 5 1 ◎ 198 0.1 7.2 40 22 1 ◎ 199 0.3 25 1 0.5 3 〇200 0.5 50 3 2.2 3 〇201 1 70 10 5.2 4 Δ 202 10 610 40 25 5 X 203 0.01 0.6 CdS04 0.1 0.0004 1 ◎ 204 0.03 2.5 1 0.003 1 ◎ 205 0.05 3.8 3 0.007 1 ◎ 206 0.1 8 4 0.014 1 ◎ 207 0.3 32 0.1 0.0003 3 〇208 0.5 53 1 0.0031 3 〇209 1 85 3 0.008 4 Δ 210 10 650 4 0.012 5 X 211 0.01 0.6 AgN03 0.1 4 1 ◎ 212 0.03 2.1 1 70 1 ◎ 213 0.05 4 3 230 1 ◎ 214 0.1 7.7 4 379 1 ◎ 215 0.3 24 0.1 4.8 3 〇216 0.5 50 1 74 3 〇217 1 78 3 207 4 Δ 218 10 598 4 350 5 X 219 0.0 1 0.7 IrBr3-4H20 0.1 0.03 1 ◎ -49- 200912047

220 0.03 2.9 1 1.1 1 ◎ 221 0.05 4 3 3 1 ◎ 222 0.1 7.9 4 7.7 1 ◎ 223 0.3 19 0.1 0.04 3 〇 224 0.5 54 1 0.9 3 〇 225 1 89 3 2.7 4 Δ 226 10 710 4 8 5 X First Table 2 to Table 5 are examined. In these tables, it is summarized that ΤΙ is controlled to be below the detection limit of the present embodiment, and the effect of adding the stain resistance improving element to various changes in the amount of Pb in the plating solution and in the plating layer is summarized. Here, the stain resistance improving elements are all varied within the optimum range of the present invention. Among them, Νο·31~33 (Ni contains examples), Νο·37~39 (Fe 曰), 1^〇.43~45 (?^ + contains examples), 1^〇.49~51 (( :]* contains examples), - 55 to 57 (& included examples), >^〇.61 to 63 (31 contains examples), >^〇.67 to 69 (Sn contains examples), No. 73 ～75 (Cu containing example), No_79~81 (Co containing example), 1^〇.85~87 (\¥included example), 1^〇_91~93 (111 containing example), No.97 to 99 ( C; d contains examples), Νο·1〇3 to 105 (Ag containing examples), and ]^〇.109~111 (11' containing examples) satisfying the present invention in both 1>1) and "1'1 In the plating solution of the main component, the above-described example of the stain resistance improving element is added to the optimum range of the present invention, and the stain resistance is further improved as compared with the case of the first embodiment in which the stain resistance is not improved. . In contrast, No. 34 to 36 (Ni-containing examples), N〇_40 to 42 (Fe2 +-containing examples), N〇_46 to 48 (Fe3 +-containing examples), and No. 52 to 54 (Cr-containing examples) ), No. 58 to 60 (M〇6+ containing examples), N〇·64 to 66 (Si containing examples), -50-200912047 Νο·70 to 72 (Sn containing examples), Νο·76 to 78 (Cu Examples include, No. 82 to 84 (Co-containing examples), Νο·88 to 90 (W-containing examples), No. 94 to 96 (In-containing examples), and >^〇.100 to 102 (€£1 contains In the plating solution containing the amount of Pb which does not satisfy the range of the present invention, the cores 106 to 108 ("containing examples") and "not included in the present invention" are added to the best range of the present invention. In the above examples of the stain resistance improving element, the degree of stain resistance or white iron resistance tends to be lowered. The results are shown in Tables 6 to 9. In the tables, it is summarized that Pb is controlled. In addition to the detection limit of the present embodiment, the effect of adding the stain resistance improving element to the amount of T1 in the plating solution and the plating layer is variously changed. Here, the stain resistance improving element is the best in the present invention. Within the scope of change. Among them, No_ 115 to 117 (Ni containing examples), No. 123 to 125 (Fe2 + containing examples), No. 131 to 133 (Fe3 + containing examples), No. l39 to 141 (Cr containing examples), Νο. 147 to 149 ( Mo contains examples), Νο·155 to 157 (Si containing examples), No. 163 to 165 (Sn containing examples), No. 171 to 173 (Cu containing examples), and ^'〇.179 to 181 ((:〇 contains Examples), 1^〇.187~189 (\^ containing examples), No.195~197 (ln containing examples), No. 203 to 205 (Cd containing examples), No_211 to 213 (Ag containing examples), No. 219 to 221 (Ir-containing examples) are examples in which both the Pb and the T1 satisfy the requirements of the present invention, and the above-described antifouling improving element is added to the best range of the present invention, and the anti-staining is not added. In contrast to the case of the first embodiment, the stain resistance is further improved. In contrast, >}〇.118~122(>^ contains examples), ^〇.126~-51 - 200912047 13〇 (Fe2+ containing example), No_134 to 138 (Fe3+ containing example), No_142 to 146 (Cr containing example), Νο·150 to 154 (Mo containing example), No. 158 to 162 (81 containing example), ^_166 to 170 (311 contains examples), ^1〇.174~178 ((:11 contains Example):: 〇. 182 to 186 ((: 〇 contains examples), > ^ 〇, 190 ～ 194 (W contains examples), No. 198 to 202 (In contains examples), NO. 206 to 210 (Cd Inclusion Examples), Nos. 214 to 218 ("Inclusion Examples", N〇.222 to 22 6 (Ir-containing Examples) are all in the plating solution in which the amount of T1 does not satisfy the range of the present invention, and are in the optimum range of the present invention. In the example in which the above-described stain resistance improving element is added, the degree of stain resistance or white rust resistance is reduced. Example 3 In the present example, the stain resistance due to the addition of the decane coupling agent Sexual improvement has been studied. Herein, a non-chromate electrogalvanized steel sheet having four resin films having different addition ratios of a resin component to a cerium oxide sol was produced as follows, and a non-chromate electroplated zinc was prepared for each non-chromate coupling agent. The influence of the steel plate. (No. 227 to 230) In the above-described Example 1, the aqueous solution of the carboxyl group-containing urethane resin, the aqueous dispersion of the ethylene-acrylic acid copolymer, and the cerium oxide in the preparation of the "(1 - 3) resin aqueous liquid preparation" In a total of 1 part by mass of the sol (addition ratio = 5 parts by mass: 25 parts by mass: 7 parts by mass), as shown in Table 10, it is in the range of 0, 10 parts by mass, 20 parts by mass, and 30 parts by mass. A resin film was produced in the same manner as in Example 1 except that a coupling agent was further added with a decane-52-200912047 coupling agent. In addition, in the "(2) Preparation of galvanized steel sheet" of the above-described Example 1, an electrogalvanized steel sheet was produced in the same manner as in Example 1 except that the plating solution containing all the elements described in Table 7 was used. Each element described in Table 11 is an element added in the form described in the above first embodiment. Then, a non-chromate electrogalvanized steel sheet was produced in the same manner as in Example 1, and the stain resistance and white rust resistance were evaluated. (No. 23 1 to 23 4) In the above-described Example 1, except that in the preparation of "〇-2" aqueous dispersion of an ethylenically unsaturated carboxylic acid copolymer, sodium hydroxide was not added, and "(1) - 3) Preparation of Resin Aqueous Solution" As a cerium oxide sol, "ST-AK" manufactured by Nissan Chemical Industries Co., Ltd. was used, and an aqueous solution containing a carboxyl group-containing urethane resin and an aqueous dispersion of an ethylene-acrylic acid copolymer ( The addition ratio of Na) and the cerium oxide sol is set to 5 parts by mass: 3 parts by mass: 65 parts by mass, and the total of 1 part by mass of these is shown in Table 6, in 〇, 10 A resin film was produced in the same manner as in Example 1 except that a decane coupling agent was further added in a range of 20 parts by mass or 30 parts by mass. In addition, in the production of the (2) electrogalvanized steel sheet of the first embodiment, an electrogalvanized steel sheet was produced in the same manner as in the example 1 except that the plating solution containing all the elements described in Table 7 was used. Each of the elements described in Table 1 is an element added in the form described in the above Example 1. Then, a non-chromate electrogalvanized steel sheet -53-200912047 was produced in the same manner as in Example 1, and the stain resistance and white rust resistance were evaluated. (No. 23 5 - 23 8) In the above-mentioned Example 1, the product of Nissan Chemical Industry Co., Ltd. was used as the cerium oxide sol in the preparation of the "(1 - 3) resin aqueous liquid preparation". In the ST-XS", 5.1% by mass of a cerium oxide sol of Na Ο 添加 is added for the purpose of improving strength, and an aqueous solution of a carboxyl group-containing urethane resin, an aqueous dispersion of an ethylene-acrylic acid copolymer, and a cerium oxide sol are added. The addition ratio is set to 6 parts by mass: 34 parts by mass: 60 parts by mass, and as a total of 100 parts by mass, as shown in Table 6, in 〇, 1 〇 parts by mass, 20 parts by mass, 30% by mass A resin film was produced in the same manner as in Example 1 except that a decane coupling agent was further added to the portion. In addition, in the "(2) Preparation of galvanized steel sheet" of the above-mentioned Example 1, an electroplated steel sheet was produced in the same manner as in Example 1, except that a plating solution containing all the elements described in Table 7 was used. Each element described in Table 1 is an element added in the form described in the above first embodiment. Then, a non-chromate electrogalvanized steel sheet was produced in the same manner as in Example 1, and the stain resistance and white rust resistance were evaluated. The results of these are recorded in Table 10. Further, in the 'Table 10', the resin component constituting the resin film and the Na content contained in the cerium oxide sol and the Na content contained in the resin film are described. -54- 200912047 [Table 10] Resin film component resin film evaluation No. Resin component SiO 2 矽 coupling agent Na content Stain resistance White rust resistance (mass parts) (mass parts) (mass parts) (% by mass) 227 0 1.4 2 〇228 30 70 10 1.2 1 〇229 (Na 0.55%) (Nal.7°/〇) 20 1.1 1 〇230 30 1.0 Gelation 231 0 0.13 2 〇232 35 65 10 0.11 1 〇233 (No Na (Na 0.2%) 20 0.10 1 〇 234 30 0.09 Gelation 235 0 3.0 2 〇236 40 60 10 2.7 1 〇237 (Na0.55%) (Na 4.6%) 20 2.5 1 〇238 30 2.3 Gelation -55- 200912047 [Table η] Addition of element to compound concentration in plating solution (PPm) Content in plating layer (ppm) Pb PbS04 0.05 3.5 T1 T1S04 0.12 8.3 Ni NiS04.6H20 190 565 Fe2+ FeS04-7H20 1650 524 Fe3+ Fe2 (S〇4)3 ·ηΗ2〇350 524 Mo Na2Mo〇42H2〇135 72 Cr Cr2(S04)3 120 2.2 Cu CuS04 0.2 31 Co C0SO4 0.2 0.002 W w2so4 1.3 1 Sn SnS04 0.2 1.1 In In(OH)3 1.2 0.8 Ag AgN03 0.15 18 Ir IrBr3 4H2〇0.4 0.17 Cd CdS04 0.6 0.002 Si Si02 62 70 As shown in Table 1, 在, in this When adding Silane coupling agent out of the optimum range, compared with the case Silane coupling agent was not added, the above-described characteristics are improved. Further, in the example in which 30 parts by mass of the decane coupling agent was added, since the treatment liquid gelled and could not be applied to the plating layer, the appearance could not be evaluated. [Brief Description of the Drawings] Fig. 1 is a "photograph of the -56-200912047 stain evaluation" corresponding to the evaluation criteria 1 to 5 of the stain resistance of the present embodiment, and Fig. 1A to Fig. 1E correspond to evaluations, respectively. Benchmark 1 to 5. -57-

Claims (1)

200912047 X. Patent application scope 1. An electrogalvanized steel sheet is characterized in that a resin film containing substantially no Cr and containing Na 〇〇 5 〜 5 (% means mass%. The same applies hereinafter) is provided on the electrogalvanized layer. Pb and τΐ in the electrogalvanized layer are controlled to be Pb in an atomic conversion: 5 ppm (ppm means mass ppm, the same applies hereinafter) and T1: 10 ppm or less. 2. The electrogalvanized steel sheet according to claim 1, wherein the electrogalvanized layer contains a group selected from the group consisting of Ni, Fe, Cr, Mo, Sn, Cu, Cd, Ag, Si, Co' In, Ir, and W At least one of them, in atomic conversion, Ni: 60 to 6000 ppni, Fe: 60 to 6 〇〇 ppm, Cr: 0.5 to 5 ppm, Mo: 30 to 50 〇 ppm, 〇 _6 to 20 ppm, Cu: 8 to 3 000ppm, Cd: 0.000 1 ~ 〇. 〇 2ppm, Ag: io ~ 400ppm, Si: 30 ~ 2000ppm, Co: 〇0 003 ~ 〇 3pprn, In : 〇 _ 1 ~ 3 〇 PPm, Ir: 0.01 ~ lOppm, w : 0.1 to 50ppm range. 3 _ galvanized steel sheet according to claim 1 or 2, wherein the resin film contains a carboxyl group-containing resin and an "inorganic compound. 4. The electrogalvanized steel sheet according to item 3 of the patent application, wherein the resin film Further, a method for producing an electrogalvanized steel sheet is characterized in that the plating solution containing Pb and T1 in the plating solution is controlled to have an acid plating solution of Pb: 0.08 ppm or less and T1: 0.2 ppm or less. The step of zinc and the step of forming a resin film containing 0.05 to 5% by mass of Na. 6. The method for producing an electrogalvanized steel sheet according to claim 5, wherein the acidic plating solution contains a material selected from the group consisting of Ni: 20 to 2000 ppm, Fe2+ : -58- 200912047 50 ~ 5000ppm, Fe3+: 50 ~ 5000ppm, Cr: 5 ~ 2000ppm, Mo: 50 ~ 2000ppm, S n * 0.05 ~ 20ppm, Cu : 0_05 ~ 50ppm, Cd : 0.0 5 ~ 5 ppm, A g : 0.0 5 to 5 ppm, S i : 2 0 to 2000 ppm, Co: 0.05 to 50 ppm, In: 0.5 to 50 ppm, Ir: 0.05 to 5 ppm, and W: 0.5 to 50 ppm of at least one element in the group. Zinc plating bath characterized by Pb and T1 in the plating bath Pb: 0.08 ppm or less and Tl: 0.2 ppm or less. 8. A zinc electroplating bath according to claim 7 containing Ni: 20 to 2000 ppm, Fe2 + : 50 to 5000 ppm, Fe3 + 50 to 5000 ppm. , Cr : 5 to 2000 ppm, Mo: 50 to 2000 ppm, Sn: 0.05 to 20 ppm, Cu: 0.05 to 50 ppm, Cd: 0.05 to 5 ppm, A g : 0.05 to 5 ppm, Si: 20 to 2000 ppm, Co: 0.05 to 50 ppm, In • 0.5 ～50ppm, Ir: 0.05 ～5ppm and W: 0.5 ～50ppm At least one element in the group. -59- 200912047 The statement is not simple. It is issued as a map. The pattern represents the book without a set of two or two CC. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none