TWI262962B - Surface treated galvanized steel sheet excellent in resistance to tape peeling, manufacturing method thereof and surface treating agent - Google Patents

Abstract

In the galvanized steel sheet, at least a surface modified layer and a topcoat layer are formed on a zinc-based plated layer. The surface modified layer contains 1 to 30 mg/m<2> of SiO2 being converted as Si, 0.5 to 15 mg/m<2> of P, and 0.4 to 10 mg/m<2> of Al. A non-chromate type surface treated galvanized steel sheet excellent particularly in the resistances to tape peeling and further to tape peeling after alkali degreasing can be provided.

Description

1262962 (1) 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 A galvanized steel sheet having a surface treatment layer excellent in resistance, a method for producing the same, and a surface treatment agent for surface treatment. [Prior Art] Regarding home appliances, building materials, and steel sheets for automobiles, galvanized steel sheets are usually used from the viewpoint of ί/L rotability. However, since zinc plating alone is not sufficient to achieve corrosion resistance (anti-whiteness) and it is difficult to ensure adhesion to the coating material when it is used as a primer layer, it is necessary to carry out acid treatment or chromium. The acid salt treatment is considered as a countermeasure. When the phosphate treatment is used as the undercoat layer treatment, the adhesion to the coating layer can be greatly improved, but the effect of suppressing white rust cannot be used for various purposes only when the treatment with the pity salt is used, although chromic acid is used. Salt treatment has an excellent effect on suppressing white recording, but the adhesion to the coating is insufficient when treated under such conditions. In order to improve adhesion while providing high corrosion resistance, fingerprint resistance and lubricity, a multi-functional product of about μμηι film coating is applied to the chromate-treated layer and is usually mainly used for electric power. Manufacturer of products. However, because chromate treatment uses harmful hexavalent chromium, it involves problems that cause public pollution and tends to bypass the environmentally friendly requirements of increased knuckle and avoid chromate treatment. Thus, many surface treatment methods (non-chromate methods) which do not use chromate treatment -5-(2) 1262962 have been proposed and put into practical use. For example, JP-A No. 8-3 2 5 7 6 0 discloses a surface treatment agent for a steel sheet coated with zinc metal, the surface treatment agent using a mixed composition of an aqueous resin and a polyhydric phenol carboxylic acid, and The surface treated steel sheet having excellent corrosion resistance is formed by roll coating the surface treating agent onto the surface of the plated metal. However, since the galvanized layer is directly coated with an organic layer while not being treated with chromate in this technique, the adhesion of the coating is not sufficient. Furthermore, the alkaline degreasing of the surface treated galvanized steel sheet may involve corrosion degradation after alkali degreasing by removing the surface during the pressing or during the cleaning of the grease applied during the improvement of the adhesion of the coating. The problem. For the improvement of such problems, JP-A No. 2000-1 44448 discloses coating an ion-exchanged two on a galvanized steel sheet directly or by an undercoat layer such as a lithium niobate or a lithium phosphate treatment layer. The organic layer of cerium oxide is formed to form a steel sheet coated with an organic material, thereby improving corrosion resistance, corrosion resistance after alkali degreasing, and adhesion of the coating. Further, JP-A No. 2 000-1 44444 discloses a surface-treated steel sheet excellent in corrosion resistance formed by a chemical conversion coating layer having a predetermined thickness, which utilizes a preferred ratio of cerium oxide or tantalum rubber, The phosphate compound, the acid treatment liquid of the specified metal oxide or hydroxide is treated by treating the zinc-zinc steel sheet and drying it by heating. However, since pinholes and the like are easily formed in the layer by coating an inorganic treatment agent such as silicone, phosphate or metal hydroxide to dry and leaving pinholes, the etching solution may be degreased in the alkali or such At the time of penetration through the pinhole, the corrosion resistance is insufficient. In view of the above problems, in the patent document, the chemical conversion layer is formed into a layer of -6 - 1262962 (3) to form an organic resin layer or an organic composite tantalate layer to improve corrosion resistance or coating after alkali degreasing. Adhesion. At the same time, .1 P - AN 〇. 2 0 0 0 - 1 2 9 4 6 0 reveals a surface treated steel sheet which improves the adhesion resistance and the adhesion of the coating by forming a zinc layer serving as the first layer a predominantly coating, an amorphous coating formed by coating and drying an aqueous mixture of phosphate and metal oxide colloids that serves as a second layer of polyvalent metal, and an organic coating that acts as a third layer. And a multilayer structure is formed. Further, JP-AN 〇. 2 0 0 1 - 1 1 6 4 5 discloses a steel sheet coated with an organic material which has improved corrosion resistance, corrosion resistance after alkali degreasing, and coating adhesion by the following steps: formation a composite oxide layer containing fine Si 〇 2 particles and a phosphate compound of a predetermined thickness as a first layer on the surface of the galvanized steel sheet; and an organic polymer having a predetermined thickness and having a 0H group or a COOH group formed thereon An organic material layer of a base resin. Further, JP-A No. 2 003 -2 93 1 5 1 discloses a non-chromate surface-treated galvanized steel sheet formed of a surface modifying layer containing AI, Si and P in respective predetermined ratios. Shows corrosion resistance comparable to chromate treated steel sheets. As explained above, various improvements have been proposed for non-chromate treatments for several purposes, and attempts have been made to improve the performance. However, according to recent experience of the present invention, it is apparent that even if a modified non-chromate treatment is applied to a galvanized steel sheet, there is a serious problem of insufficient tape peeling resistance. That is to say, the surface-treated steel sheet is conveyed in a state of being wound by an iron hoop and the user uses it in the form of a shear piece after unwinding the steel sheet. At this time, &gt;7-1262962 (4) The remaining steel coils are sometimes temporarily taped to the end of the steel coil. Further, the sheared sheet is made into an A V product box or part by steps of punching, oiling, pressing, and alkali degreasing. In this case, an adhesive label indicating the part number, size, grade, etc., which is temporarily fixed, is sometimes attached to the surface of the case or the surface of the part. The phenomenon of tape peeling is when the user peels off the tape or the adhesive label, the surface layer on the galvanized surface peels off from the mineralized surface together with the tape. This is an important issue in terms of the quality of the surface treated steel sheet and may cause serious defects in the product. The conventional chromate-treated surface-treated steel sheet to which the film coating is applied in the upper layer hardly peels off the tape. Therefore, the method of "improving the tape peeling" which prevents the peeling of the tape has not been found so far. Accordingly, in the course of the present inventors' research on the improvement of the non-chromate type galvanized steel sheet, it is apparent that the tape peeling resistance is good or the case of the non-chromate surface-treated steel sheet is not good. Specifically, it is apparent that tape peeling easily occurs in the case of long-term storage while the surface is attached with a tape or a label or in the case of storage under high temperature and high humidity conditions at the time of shipping. Next, "tape stripping resistance" will be recognized as an extremely important product property. However, since the problem of "tape peeling" has hardly been found in nature, the purpose of "modified tape peeling resistance" has not been observed. With regard to this countermeasure, the disclosed technology is still insufficient for the above-mentioned non-chromate-treated plated steel sheet: use 'and in fact no clear method has been developed [invention content] Winter 1262962 (5) Here In the case of the present invention, the present invention relates to a non-chromate surface-treated galvanized steel sheet and its object is to provide a surface-treated galvanized steel sheet excellent in tape peeling resistance and excellent in peeling resistance after alkali degreasing, Manufacturing method and surface treating agent which can be used in the manufacturing method. The present invention can solve the above problems in the form of surface-treated plating comprising at least a surface modifying layer and a surface layer formed on a zinc-based plating layer of a galvanized steel sheet. Zinc steel sheet, wherein the surface modification layer contains Si〇2 converted to S i of 30 mg/m 2 , P of 0.5 to 15 mg/m 2 , and AI 〇 of 〇·4 to 10 mg / m 2 Another aspect of the invention resides in a phosphate-type surface treatment agent containing Si 02, which can be used for producing a galvanized steel sheet excellent in tape peeling resistance, wherein the solid content concentration is 0 · 〇1 to 1 4 · 5 % ( In this and the following, it refers to the mass %), and the treatment Contained in S i, P], and the composition ratio of each of the A's (mass ratio) are in compliance with the following conditions:

Si : 0.002 - 4.5 % P: 0.0005 - 1.5 % A1 : 0·000] - 〇 5% 1.5 " &lt; Si / P &lt; 60 ? 4.5 &lt; Si / Al &lt; 230 One aspect of the present invention resides in A method of producing a surface-treated galvanized steel sheet comprising forming a surface treatment agent layer on the surface of a galvanized steel sheet using a surface treatment agent in accordance with the conditions described above, rinsing with water, removing excess P from the surface treatment agent layer and/or Or A1, followed by drying to form a surface modifying layer - 9 - (.6) 1262962 [Embodiment] The surface-treated galvanized steel sheet according to the present invention is modified by a surface containing a non-chromate treating agent. The layer is premised. The galvanized steel sheets to which the present invention is applied may include steel sheets which are only galvanized, and steel sheets of all other galvanized alloys such as galvanized-nickel, zinc-iron, zinc-aluminum steel sheets. Further, the plating method is also applicable to any of the methods of the melt plating method, the electroplating method or the vapor deposition method. The most striking feature of the present invention is the incorporation of SiO 2 converted to Si in the surface modifying layer, P in the range of 0.5 to 15 mg/m 2 , and A1 in the range of 〇 4 to 1 〇 mg/m 2 . This serves as a means to improve the "tape peeling resistance" which is a new problem which is firstly solved by the present invention in the field of non-chromate galvanized steel sheets. In the present invention, "tape peeling resistance" means that the peeling resistance is added to the surface-treated galvanized steel sheet and peeled off without attaching the surface treatment layer and the adhesive to the additional adhesive label or tape. Strip the tape or tape together. The degree of tape peeling resistance differs depending on the type of the adhesive tape used in the tape peeling test. Specifically, it depends on the adhesion or the solvent and the kind of the plasticizer contained therein. The reason why the surface resin layer or the surface modifying layer is peeled off by the tape peeling effect is attributed to the fact that the solvent or plasticizer contained in the adhesive diffuses and penetrates into the zinc through the surface modifying layer and the surface layer formed thereon. The main plating surface accumulates at the bond boundary and reduces the bond strength, and the tape peeling resistance may vary greatly depending on the type and content of the solvent or plasticizer contained in the tape -10- (7) 1262962 Although the type and blending amount of the chemical agent blended as an adhesive for ordinary tape may be somewhat changed, it is considered that the content of the special S i 02, its diffusion or permeation rate does not have significant after the present invention will It was selected and used as a typical embodiment, and the ribbon "part number #95] 0" and Nichiban @^ cellophane tape manufactured by Suril Division acted as a standard evaluation tape peeling resistance shown in the examples described later. It serves as a main component in the surface modifying layer according to the present invention, 矽(S i 02 ), for example, cerium oxide which is incorporated by colloidal cerium oxide or cerium. Since the above-described ceria has a good affinity with an inorganic material and a zinc-based plating layer and serves as an undercoat layer under the surface layer, it is possible to provide an effect of enhancing the peeling resistance between zinc and the surface layer. As described above, it is considered that the diffusing component such as a solvent or a plasticizer contained in the adhesive such as one of the tape-peeling adhesives has a weakened bond strength at the interface or boundary between the layers. However, the solvent and the plasticizer which are the main components contained in the surface modification layer of the present invention are diffused and infiltrated by the surface layer, and the excellent resistance can provide inhibition of invasion to the galvanized surface or suppression of diffusion at the surface or surface. The function. Therefore, if the formation of an appropriate amount of the oxidation-treated layer is formed, the tape peeling resistance can be remarkably exhibited. Then, from the results of the quantitative relationship to effectively provide the effect of improving the resistance of cerium oxide, it was confirmed that the conversion of the dioxane in the surface treatment layer to Si was controlled to be 30 mg/m 2 ( 2.14 to M. 3 ). The solvent or the plastic is the difference. However, the technology company's preliminary evaluation of the dioxide-derived synthesis is intrinsically so that when the main coating is made by the movement of the tape, the effect of the salt is confirmed, and the surface layer is modified. The surface of the present invention provides excellent tape peeling resistance within the range of -11 - (8) 1262962 S i Ο 2 ) of the tape peeling yttrium content mg / m 2 . If the cerium oxide content is converted to Si less than &gt; mg/m2, the function of the barrier layer described above is insufficient and it is difficult to provide moderate tape peeling resistance. Therefore, the content of cerium oxide in the surface modifying layer is converted to S ! must have ] m g / m 2 or more. The lower limit of the cerium oxide content is preferably 2 m g / πι 2 and more preferably 2.5 m g / m 2 . Then, as the cerium oxide content increases, the function as a barrier layer increases, but when the cerium oxide content excessively increases, the tape peeling resistance tends to decrease slightly. That is to say, it is considered that the ceria in the surface treatment layer exists as a small amount of clots, but when the amount of ceria increases, the particles may become a multi-layered state. Since the bonding strength between the respective fine cerium oxide particle layers in a multi-layered state is not always strong, the tape peeling force acts on the peeling direction of the fine cerium oxide particle layer in the multi-layered state to cause the peeling direction. Interlayer peeling of the particulate cerium oxide particle layer. In order to substantially inhibit interlayer peeling caused by shear cracking of the surface modifying layer, the content of cerium oxide in the surface modifying layer is preferably kept at 30 mg/m2 or less in terms of Si. If the cerium oxide content in the surface modifying layer exceeds the upper limit 胶带, the tape peeling resistance will clearly show a tendency to decrease. Furthermore, from an economic point of view, excessively increasing the content of cerium oxide in the surface modifying layer may also cause waste. From the above point of view, the upper limit converted to S i is preferably 5 mg / , more Good for 〇mg / m 2 and best for 8 mg / m 2 . In the cerium oxide containing the surface modifier of the present invention, when the surface modifier is also prepared by p and A1, it is preferable to etch the surface of the zinc-based plating layer and the surface of the moderately roughened coating layer. -12 - (9) 1262962 fine cerium oxide particles derived from cerium oxide. Etching components useful herein are, for example, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid. Particularly preferred for use as a surface modifier, an acidic aqueous solution containing an aluminum salt, for example, a phosphate, a hydrogen phosphate, a phosphite or a hydrogen phosphite (hereinafter referred to as an aluminum phosphate compound) serving as an etching component, A suitable amount of colloidal cerium oxide is dispersed therein. Therefore, the final surface modifier contains P and A1. When an acidic aqueous solution containing colloidal cerium oxide and an aluminum phosphate compound is used as a surface treatment agent, the surface of the plating layer mainly etched with the acidic aqueous solution is mainly less soluble in aluminum phosphate (less soluble in water or alkaline). The reaction layer (surface modification layer) of aipo4 or Al2 (HP04) 3 of the aqueous solution is formed on the surface of the zinc-based plating layer. When the cerium oxide particles are deposited, the aluminum phosphate and the cerium oxide particles are combined and merged into one into the reaction layer. Further, the formation of a dense reaction layer is relatively roughened by etching and is dense and strong as the zinc-based plating layer which is formed on the surface of the reaction layer, so that the tape peeling resistance can be remarkably improved. Further, as will be described later, if an aqueous solution of an organic resin is incorporated into an acidic aqueous solution, the deposition state of the cerium oxide microparticles in the obtained surface modifier can be made stronger. Because the reaction layer mainly containing the less soluble AIP 04 or A] 2 ( Η P 0 4 ) 3 and the aluminum oxide of the cerium oxide particles, which is composited and integrated, has a ratio of, for example, nitric acid as an etchant. The surface modification layer is more excellent in alkali resistance, so it can provide excellent performance and tape peeling resistance after alkali degreasing. However, if the aluminum phosphate compound described above is used as the uranium engraving component to form the cerium oxide-containing surface modifying layer, it has been found that the anti-alkaline or alkaline degreasing after the -13-(10) 1262962 tape peeling resistance surface modification The content of each component of P and A 1 contained in the layer differs. Specifically, it is known that the tape peeling resistance tendency after alkali degreasing decreases as the thickness of the surface modifying layer increases and the aluminum phosphate content in the layer increases. If the surface modification layer is thin, since the surface modification layer and the zinc-based plating layer are close to each other, 'zinc is etched out by the zinc-based plating layer and the yttrium + in the treating agent is reduced to Η 2 gas, so The ρ 附近 near the surface modification layer near the zinc-based plating layer increases and tends to become alkaline. In the environment where ρ η is greatly increased, a large amount of αιρο4 or Α12(ΗΡ04) 3 is formed to form a reaction layer in which the insoluble aluminum phosphate and the cerium oxide particles are combined and combined to significantly improve the tape peeling resistance and Tape peeling resistance after alkali degreasing. However, when the thickness of the surface modification layer is increased, since the surface of the surface modification layer is being formed and the zinc-based plating layer is diluted with each other, the pH effect accompanying the zinc filtration does not function and the surface of the surface modification layer is nearby. The environment becomes acidic in nature for surface modifiers, making A1 ( Η 2 P 0 4 ) 3 (more susceptible to alkali attack), which is more soluble in water, tend to form A1P04 or Ah (HP) which is less soluble in water. 〇 4) 3 more. It is believed that if a larger amount of water-soluble A](Η 2 P 0 4 ) 3 is present on the surface of the surface modification layer, the water-soluble component will be filtered out from the surface modification layer under alkali attack, so the surface is modified. The alkali resistance of the agent may decline and the tape peeling resistance after alkali degreasing may be lowered. However, in the present invention, the thickness of the surface modifying layer is defined within a predetermined range and the amount of each of the layers and the amount of A1 in the layer is defined. Within a predetermined range, excellent tape peeling resistance and tape peeling after alkali degreasing can be obtained - 14 (1) 1262962 resistance. Therefore, in the present invention, it is necessary to control the P content in the surface modifying layer to 0.5 to 5 mg/m2 and the Al content to 0.4 to 〇 mg/m:. If the P content is less than 0.5 mg/m2 or the Al content is lower than 〇. At 4 mg/m2, the etching effect is insufficient and a dense dense reaction layer is formed. Further, sometimes it is impossible to effectively improve the peeling resistance of the tape by promoting the ceria particles. The lower limit of the P content is preferably 〇 · 6 m g / m 2 and the lower limit of A 1 is preferably Q.5 mg/m 2 . In contrast, if the P content and the A] content are excessively increased: the A1 (HaPO4) 3 added to the surface modifying layer as described above is insufficient in alkali resistance and tends to be attacked and filtered out from the surface modifying layer. The upper limit of the p content is preferably 9 mg/m2, and the upper limit is 7 2 (7) "plus 2, and the upper limit is 5 mg/m2. The upper limit of the A1 content is preferably 8 mg/m2 and more preferably. The upper limit is 6.3 mg/m2, and the optimum upper limit is 4.4 lllg/m2. Furthermore, if the content of Si, P and AI contained in the surface modification layer can be in accordance with the relationship (]) and (2): 0.5 &lt; Si/P &lt; 20 ( 1 ) 0-7 &lt; P/A1 &lt; 6 ( 2 ) It is possible to ensure more excellent tape peeling resistance and tape peeling resistance after alkali degreasing. Below 〇. 5, since the ratio of si 〇 2 in the surface modifying layer tends to be relatively insufficient, it tends to reduce the tape peeling resistance. On the other hand, if the ratio exceeds 20, because it is compared with the cerium oxide content Since the amount of aluminum phosphate is insufficient, the effect obtained by the less soluble A]P〇4 or ai2 (HP〇4) 3 will become less effective. According to the above explanation, the S i in the modified layer is modified. The lower limit of the /P ratio is better] and the upper limit is better than 1 5 and (12) 1262962. The upper limit is 0.

If Ρ/Α1 in the relation (2) is less than 0.7, the insufficient etching due to insufficient phosphoric acid tends to lower the tape peeling resistance. On the other hand, if the ratio is excessively increased to exceed 6, the amount of the less soluble AI Ρ 0 4 or A 12 ( Η Ρ 0 4 ) 3 formed after the etching treatment is lowered to be insufficient to form a dense reaction layer. The effect of improving the tape peeling resistance after alkali degreasing is lowered. Therefore, the less soluble aluminum phosphate can be formed while ensuring an appropriate etching effect, whereby P / A1 is controlled at 0.7 or higher and 6 or lower to form a sufficient amount of the reaction layer. A lower limit of P/AI is better than 1 and a higher limit is 4. By rinsing the cerium oxide, ceric acid salt, phosphoric acid component, and the A1 component in the surface treatment agent, or as described later, the water rinsing is performed in the order of forming the surface modifying layer and rinsing and removing excess phosphoric acid component or component A. , you can control Si / P or Ρ / A]. Further, the amounts of Si, P and A1 in the surface modifying layer can be separately identified by, for example, fluorescent X-ray analysis.

If the cerium oxide is added to the surface modifying layer, P and A1 are each added in a predetermined amount, and further, the contents of S i , P and A1 are controlled within an appropriate range, and the resulting surface modifying layer will be further produced. It is dense without pinhole defects and the like, and has outstanding tape peeling resistance in dry conditions, and tape peeling resistance after alkali degreasing. In the present invention, an organic resin may be further added to the surface modifying layer. This is because the organic resin has an effect of depositing the cerium oxide microparticles on the surface-reformed layer in accordance with the case where the surface-modified layer is formed, and further improves the tape peeling resistance, and further, the tape peeling after the alkali degreasing Resistance. The-16-(13) 1262962 organic resin is not particularly limited and may include, for example, an acrylic resin, a melamine resin, a phenol resin, an epoxy resin, a urethane resin, a polyester resin, an alkyd resin, and a polyolefin. A resin which may be used singly or in combination of two or more of them. Among the organic resins described above, a water-soluble organic resin is preferably used, and an organic resin composed of an organic acid is particularly preferably used. As the organic resin composed of an organic acid, poly(meth)acrylic acid is suitable and the acid group may be partially or completely neutralized with a base. As described above, if a surface modifying layer is formed, it is preferred to etch the galvanized layer with an acidic aqueous solution. Since the organic resin having the organic acid as a constituent component is almost all water-soluble and the aqueous solution containing the organic resin is acidic, the organic resin has excellent stability and processability when it is blended in an acidic aqueous solution. The poly(meth)acrylic acid preferably has an average molecular weight of 2,0 0 or more, more preferably 1 Å, 〇〇0 or more, and more preferably, 〇〇, 〇〇〇 when used. Or bigger. The base in the case of using an organic resin salt composed of an organic acid may include, for example, ammonia water or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. If, for example, FT "R observes the surface modification layer, the FT-1R peak derived from the organic resin structure (ester bond, carboxyl group, ketone, amine group, hydroxyl group, carbon-hydrogen bond, etc.) will appear in In the spectrum, it is possible to recognize whether or not there is an organic resin in the surface modifying layer. Then, in the present invention, it is preferred to have an organic resin such that the structure of the organic resin is derived from the FT-1R absorbance system. 5. The absorbance of FT -1 R means that the content of the organic resin in the surface modifying layer and the tape peeling resistance and the tape peeling resistance after the alkali degreasing can be controlled by controlling the absorbance of FT-]R to a predetermined range. -17 - 1262962 (14 j The present invention also includes a surface treating agent for forming a surface modifying layer. The surface treating agent is a phosphate in the form of a solution containing cerium oxide particles such as colloidal cerium oxide. The type of treating agent is preferably controllable so that the solid concentration is from 0. 0] to 1 4 „5 mass%, and the content of s], p and A j contained in the treating agent (% by mass, hereinafter referred to as short The %) and composition ratio (Morby:) can meet the following conditions:

Si: 0.002 to 4.5% P : 0.0 0 0 5 to 1. 5 %

A1 : 0.0001 to 0. 5% 1. 5 &lt; Si/P &lt; 60 ^ 4.5 &lt; Si/Al &lt; 230

If the solid concentration of the surface modifying layer is lower than 〇. 〇 %%, it will be difficult to treat the surface modifying layer of a suitable thickness once, and it must be treated a plurality of times to become inconsistuous. Relatively, if the concentration is too high above 14.5%, a tendency to form a solid 'e.g., at the gas/liquid boundary of the treating agent tends to cause product defects such as indentations or seed crystals. Looking at the above, the solid concentration is preferably 〇 · 〇 5 % or higher and 10 ° /. More or less 'more preferably 0.1% or more and 0.5% or less. Further, if the Si concentration in the surface treating agent is less than 0.002%, the cerium oxide content which is a main component of the barrier layer serving as the surface modifying layer tends to become insufficient, and it is difficult to obtain appropriate tape peeling resistance. On the other hand, if the concentration of S 1 exceeds 4.5 %, an excessive increase in the ratio of cerium oxide in the surface treating agent will cause an excessive amount of cerium oxide in the grading layer, which will slightly lower the tape peeling resistance. In view of the above-described tendency, the lower limit of the concentration of s ] in the surface treatment agent is more preferably 0. 〇 ] %, and more preferably 〇 〇 3 %. Further, the upper limit is preferably 4% ‘and more preferably 3%. Further, the concentration of s j (15) 1262962 in the surface treatment agent can be mainly controlled according to the blending amount of SiO 2 which is a mixture of colloidal cerium oxide, and the blending amount of bismuth citrate or the like. The colloidal cerium oxide which can be used as a source of cerium oxide in the surface treating agent preferably includes, for example, "SNOWTEX" series (colloidal silica dioxide, manufactured by N issan C hemica ] I ndustry) "OS", "0 L", "Ο XS" and "0 UP", and the niobate is preferably Na4Si〇4 or Na2Si〇3 °

On the other hand, the P concentration in the surface treatment agent depends on the amount of the phosphate compound blended in the form of phosphate, hydrophosphate, phosphite or hydro phosphite, and the amount of the phosphate compound mainly controls the etching effect. And important factors in the formation of dense reaction layers. If the P concentration is too low, since the etching effect is insufficient and the formation of the dense aluminum phosphate type reaction layer described above is also insufficient to reduce the effect of promoting the deposition of the ceria particles, the adhesion or alkali resistance of the surface modifying layer tends to be low. Become insufficient. Therefore, the P concentration in the treating agent is preferably 0.0005 % or more. A more preferred lower limit is 0.001% and a more preferred lower limit is (K 0 1%. However, if the P concentration in the surface treatment agent is excessively increased, since the apparent tendency of the product becomes unsuitable and from the viewpoint of practical operation It also causes a problem that the liquid tank of the surface treatment agent is easily eroded, so the P concentration is preferably 1.5% or less. The upper limit is preferably 1% and the upper limit is 0.5%. The concentration of A1 in the surface treatment agent is mainly determined by the amount of the aluminum salt such as phosphoric acid, and the amount of the hydroxide which can be selectively added, such as A 1 or the like, is specifically determined. Source of the week of the insoluble aluminum phosphate. The aluminum phosphate is formed in the form of dense reaction layer -19-(16) 1262962 in an etching step such as phosphoric acid to promote the deposition of cerium oxide to provide adhesion of the surface modifier. Or an important function of alkali resistance. In order to effectively provide the functions described above, it is desirable that the concentration of Al in the treatment agent is at least 0.00% or more, preferably 0.05%, more preferably 0.0 0 1 % or higher. However, if the A 1 concentration is too high, because in the processing solution At the gas-liquid boundary, solids tend to form. 5 ITD tends to cause defects such as indentations or seed crystals, so the A1 concentration is reduced to 0.5% or lower. The upper limit is 0.4%, and the upper limit is better. 2%. · Si/P and Si/Al in the surface treatment agent influence the formation amount of the dense aluminum oxide-containing dense reaction layer formed at the initial stage of the surface treatment and affect the deposition amount of the cerium oxide as described above. If the P content and the A1 content are insufficient for the .S i content, the etching will be relatively insufficient and not dense enough or the formation amount of the reaction layer mainly containing aluminum phosphate will be insufficient, and the effect of promoting the deposition of cerium oxide will also be lowered. Therefore, the tape peeling resistance and the tape peeling resistance after the alkali degreasing become insufficient. In contrast, if the P content and the A1 content excessively increase with respect to the Si content, the cerium oxide in the reaction layer described above is excessively increased. The concentration will tend to be insufficient and may cause insufficient tape peeling resistance. From the above-described point of view, the S i /P contained in the surface treating agent is preferably 1.5 or more and 60 or less, and more preferably, 1.8. Or bigger and 20 or Small. Si/Al is preferably 4.5 or more and 203 or less, more preferably, 6 or more and 〇0 or less. Si, P and in the surface treatment agent for the base layer The method of controlling the content of A] is not particularly limited, since the content of S i depends on the content of cerium oxide or cerium in the surface of the -20-(17:) 1262962 physiochemical agent, and the content of P depends on the amount of the treatment agent. Phosphoric acid or phosphate content, and the content of A 1 depends on the content of aluminum phosphate or aluminum hydroxide in the processing agent, respectively, and the elements can be controlled by appropriately controlling the content of the component as described above in the surface treating agent. Content c Further, if the surface treatment agent contains the above-described organic resin, the organic resin addition concentration in the surface treatment agent is preferably from 0.01 to 3 g/Torr in terms of the solid content of the organic resin. If the concentration is less than 0.0] g/Ι, the effect of adding the organic resin is hardly obtained. On the other hand, if the concentration exceeds 3 g/Ι, the peeling resistance of the tape after degreasing of the alkali may be deteriorated. In the present invention, a particularly preferred surface treatment agent is a colloidal cerium oxide; an aluminum salt compound such as an aluminum phosphate, a hydrophosphate, a phosphite or a hydrogen phosphite; and an organic resin (preferably a poly(A) An acidic aqueous solution of a base acid or a salt thereof. If a surface treatment agent is used, the zinc-based plating layer on the surface of the steel sheet is etched with an acidic aqueous solution, and a dense layer mainly containing less soluble aluminum phosphate is formed on the surface of the zinc-based plating layer, and the ruthenium dioxide is deposited on the reaction layer. And combined with the effect of the organic resin and reliably combined. Therefore, such effects can form a dense reaction layer associated with etching the filtered zinc, thereby producing a surface modifying layer which is not excellent in tape peeling resistance and tape peeling resistance after degreasing. More specifically, the surface treatment agent is preferably a phosphate (or hydroxyphosphate) containing aluminum having a solid content of from 0.02 2 to 5.0% (more preferably, from 0.0) to 1.0% by weight of each component. a phosphite or hydroquinone), 〇4 to 〇% (preferably, 〇·〇5 to 3%) of colloidal cerium oxide; and containing 〇.] to 3 g/j -21 - (18) 1262962 organic resin, and an acidic aqueous solution having a pH range of 5 to 4. The composition of the surface modifying layer can define the composition of the surface treating agent within the range described above, and is preferably controlled by the above-described range by applying water washing or the like.

Internal C The method for treating a galvanized steel sheet by a surface treating agent can be applied to a conventional coating method such as dip coating, spray coating or roll coating. In the dip coating method, the steel sheet is preferably immersed for about 1 to 10 seconds. The spraying method promotes a better reaction with a zinc-based coating, and is preferably sprayed; the coating pressure is in the range of 20 to 500 kPa (about 0.2 to 5.0 kgf/cm2) and the preferred spraying time is zero. Within the range of 1 to 10 seconds. After the galvanized steel sheet is surface-treated with the above surface treating agent to form a surface treating agent layer (a layer for forming a surface modifying layer after water rinsing-drying), the soluble component is preferably removed by a suitable water rinse. Next, it is dried by heat, for example, at about 30 to 550 ° C to remove water, thereby preparing a surface modifying layer. In this step, water rinsing is an important processing step, particularly for improving alkali resistance, and therefore, the tape peeling resistance of the surface modifying layer after alkali degreasing can be finally obtained. That is, according to different experiments conducted by the present inventors, it was confirmed that in the case where the surface modifying layer was dried after being treated with the above surface treating agent, or in the case of the dried surface modifying layer, the surface was modified. The P content or the A1 content in the layer may sometimes be excessive, and the content exceeds the preferred content of P of the surface modifying layer 〇. 5 to]. 5 nig/m2 or the preferred content of A1 is 0.4 to I 〇 mg/m2. It is difficult to ensure tape peeling resistance after alkali degreasing. That is, as previously described in the prior art, it has been known to treat the surface of a galvanized steel sheet with a treatment agent containing cerium oxide (19) 1262962 cerium particles and aluminum phosphate to improve the corrosion resistance of the galvanized steel sheet after alkali degreasing, At the same time, it has been confirmed that the surface treatment can effectively serve as an undercoat treatment to improve the adhesion of the organic surface layer. However, the inventors have confirmed that a surface modifying layer is formed from a surface treating agent containing cerium oxide microparticles and aluminum phosphate (which also includes those disclosed in the above-mentioned patent documents), and the surface modifying layer contains a considerable amount of phosphoric acid. The aluminum component and sometimes a total of about 30 mg/m2 or more converted to P and about 15 mg/m2 or more converted to A1. Thus, the inventors have found that if the content of P or 厶1 is large, a small but useless effect is not obtained, particularly resistance to tape peeling after alkali degreasing, and it is found to be convenient and desirable to be applied after surface treatment for the base layer. Water rinsing, thereby pre-filtering out and removing the water-soluble component of the aluminum phosphate (mainly AI ( Η 2 P 0 4 ) 3 ) contained in the surface treatment layer to reduce the content of lanthanum and A1 to the above A good range forms a dense surface modifying layer which is less soluble (excellent in alkali resistance). As for the water rinsing method, a dip coating method or a spray coating method can be considered, and the amount of the water-soluble component in the aluminum phosphate component contained in the surface treatment agent layer can be appropriately changed to the conditions of the water rinsing. Since the water-soluble component can be removed more effectively, in the case of dip coating, it is preferred to control the water rinse time to about 0.5 to 15 seconds, and in the case of spraying, it is preferable to control the water rinse time to Approximately 0.5 to 5 seconds and the spray pressure is controlled to between about 20 and 500 kPa (about 0.2 to 5 kgf/cm2). The lower limit of the deposition amount of the surface modifying layer on the galvanized steel sheet is not particularly limited, and is preferably 4.2 m g / m 2 or more in the dry coating after the water rinsing treatment. If the amount of deposition is insufficient, it is difficult to uniformly cover the zinc as -23* 1262962 (20)

The main plating surface, so tape peeling resistance tends to be insufficient. The lower limit of the deposition amount is more preferably 7 mg/m2, still more preferably 8 mg/m2. In contrast, if excessive, the aluminum phosphate formed in the surface treatment layer is converted into a water-soluble A 1 ( Η 2 Ρ 〇 4 ) 3 by the less soluble A 1 P 0 4 or A 12 ( Η Ο Ο 4 ) 3 . At the same time, the compactness of the reaction layer tends to decrease due to insufficient etching of the zinc-based plating surface. These tend to degrade the tape peeling resistance after degreasing the alkali. Therefore, the total deposition amount of the surface modifying layer is preferably 1300 m g / m 2 or less. The upper limit of the deposition amount is preferably 65 mg/m2, more preferably 50 mg/m2, and most preferably 37 mg/ni2. The total deposition amount of the surface modification layer is a enthalpy obtained by quantitatively measuring Si, P, and A1 in the surface modification layer, for example, by fluorescent X-ray analysis and assuming that SiO 2 is formed in the modified layer, The deposition amounts of A1P04, Zn3 (P〇4) 2 and ai2o3 were calculated. If the layer thickness is large, the deposition amount of the surface modified layer is preferably a range, and the deposition amount of the surface modified layer will be 0.0021 to 0.0657 μni assuming a specific gravity of 2.

In the surface-treated galvanized steel sheet according to the present invention, there is formed a surface modifying layer inherent to the present invention as described above. In addition, in order to provide properties such as corrosion resistance, anti-fingerprint 'workability and adhesion of the coating layer or its improvement, epoxy resin, acrylic resin, polyamide resin, polyester resin, alkyd resin will be included. The surface layers of different organic materials such as urethane resin, polyethylene resin, eucalyptus, fluorene fej, and fe:based plastic resin are stacked directly or through other layers on the surface modifying layer. Preferably, it is a galvanized steel sheet comprising a surface-back treated layer of a lanolin layer formed from a specified emulsified composition serving as a surface layer. The emulsified composition for forming a resin layer (surface layer) contains an ethylene-unsaturated carboxylic acid as a main component, a total of -24,262,962 (21 j polymer (speed including a neutralized state); and one mole of the ethylene-unsaturated) The carboxyl group of the carboxylic acid copolymer is based on the amine, and the amine having a boiling point of 1 〇〇t or lower corresponding to 〇. 2 to 〇·8 mol (20 to 80 mol%); The carboxyl group of the unsaturated carboxylic acid copolymer is based on the content of 一. 〇2 to 〇. 4 mol (2 to 4 G mol%) of the monovalent metal compound; and the solid content of the emulsified composition is 100 mass. % is a cross-linking agent having a content of 0.5 to 2% by mass of a functional group containing two or more reactive groups which can react with the residue. The emulsified composition is substantially free of ammonia water. The resin layer obtained by the material is superior to various properties such as coating property, lubricating power, workability, and electrical conductivity (grounding property), and is also superior to corrosion resistance and tape peeling resistance after degreasing, and the inventors have found that It has been proposed as Japanese Patent Application No. 2 〇〇 4 _ 3 〇 2 3 1 . The unsaturated carboxylic acid copolymer is a copolymer of ethylene and (meth)acrylic acid, such as non-running and residual acid. The copolymer can be obtained by a polymerization method such as a known high-temperature high-pressure polymerization method, etc. The copolymer is preferably a random copolymer. Or a graft copolymer of a block copolymer or an unsaturated carboxylic acid. A hydrocarbon monomer such as propylene or ]-butyl can be used as a part of ethylene. Further, other conventional oxime The base monomer may be partially copolymerized (about 0% by mass or less) within a range that does not impair the object of the present invention. The total monomer amount is 1% by mass based on the unsaturated carboxylic acid to ethylene. The copolymerization ratio is preferably from 10 to 4% by mass of the unsaturated carboxylic acid. Since the ethylene-unsaturated carboxylic acid copolymer contains a carboxyl group, it can be emulsified by neutralization with an organic or metal ion (becomes an aqueous dispersion) In this case, the amine with a boiling point of 〇 or lower is used as the organic base. When the resin coating is dried -25 - 1262962 (22:) to increase the water absorption of the surface layer, the boiling point is higher than 1 〇〇 °c. The amines will tend to remain on the steel sheet, thus reducing corrosion resistance Or tape peeling resistance. Therefore, the emulsified composition for forming the surface layer does not contain an amine having a boiling point higher than 100 ° C. Further, since the effect of adding ammonia water is not clear, the composition does not contain ammonia water. The boiling point under the action of the chamber pressure. Specific examples of the amine having a boiling point of 100 ° C or lower (hereinafter referred to as an amine) may include, for example, triethylamine, N:N dimethyl butyl a tertiary amine such as an amine, N 5 N -dimethylallylamine, N-methylpyrrolidine, tetramethyldiaminomethane or trimethylamine; N-methylethylamine, diisopropylamine and diethylamine And other secondary amines; and primary amines such as propylamine, tert-butylamine, second butylamine, isobutylamine, hydrazine 2-dibutylpropylamine and 3-pentylamine. You can mix one or more months of women. Among them, tertiary amines are preferred and secondary amines are preferred. The amine content is from 0.2 to 0.8 moles (20 to 80 mole %) based on the carboxyl group of the saturated ethylene carboxylic acid copolymer of one mole of the ethylene. This is because corrosion resistance or tape peeling resistance is preferable within the range described above. If the amine content is less than 〇 2 mol, the particle diameter of the resin particles in the emulsion is increased and the above effects are not provided. On the other hand, if it exceeds 0.8 m, the viscosity of the emulsified composition will increase, and sometimes gelation will occur. This is not preferable. The upper limit of the amine content is more preferably 0. 6 moles and more preferably 0.5 moles. The lower limit of the amine content is preferably 0.3 mole. In order to prepare the emulsified composition, a monovalent metal ion can also be used. This is effective for improvement in solvent resistance or film hardness. The monovalent metal compound preferably comprises a metal selected from one or more selected from the group consisting of sodium, potassium and indium and is preferably a hydroxide, carbonate or oxide of the metal. Among the 'better' - 26 - 1262962

(23J is Na〇H, KOH, and the best is Na〇H with good performance. Moreover, because the additive effect is not clear, the compound of one or more valence metals is not used. The carboxyl group of the ethylene-unsaturated carboxylic acid copolymer is based on the carboxyl group, and the amount of the monovalent metal compound is from 〇.02 to 〇.4 mol (2 to 40 mol%. If the amount of the metal compound is less than 〇. 02 Moer's emulsion stability is not enough. On the other hand, if it exceeds 0.4 mol, the last resin layer's masturbation (especially for alkaline solution) will increase and the anti-corrosion and anti-corrosion tape peeling resistance Sexual recession' is not so good. The lower limit of the metal compound content is preferably 0.03 mol, and more preferably 0.1 mol, and the upper limit of the metal compound content is preferably 0.5 m, and more Preferably, the amine and monovalent metal compound described above are used in a preferred range of the above contents and are used to neutralize the carboxyl group of the ethylene·unsaturated carboxylic acid copolymer to emulsify. (The amount used for neutralization) is preferably not excessive 'because the viscosity of the emulsified composition will suddenly rise High, sometimes causing solidification, and excessive alkali content will cause corrosion resistance to decay and require huge amounts of energy to evaporate. However, the amount of neutralization week is not good enough, because it will degrade the emulsifying properties. Based on the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer, the total amount of the amine and the monovalent metal compound used is preferably in the range of 0.3 to 1.0 mol. In the ethylene-unsaturated carboxylic acid copolymer In the step of neutralizing the amine and the monovalent metal ion (emulsification step), it is preferred that the amine having a boiling point lower than 0 0 ° C. and the monovalent metal compound are simultaneously added to the copolymer or the boiling point is lower than previously added] 0 0 t; the amine. Although the cause is not obvious, if the subsequent addition of the amine boiling point below -27 - 1262962 (24:) ] 〇〇t: 'improvement of corrosion resistance and tape peeling resistance sometimes is not enough In the emulsified composition, a crosslinking agent containing two or more functional groups reactive with a carboxyl group is incorporated, and the layer is modified in order to chemically crosslink the ethylene-unsaturated carboxylic acid copolymer. Strength. The solid content of the emulsified composition When the amount is 10% by mass, the amount of the crosslinking agent is 2% by mass (more preferably, 5 to 10% by mass). If it is less than 1% by mass, the crosslinking of the chemical bond is insufficient, and it is difficult to provide The effect of improving the corrosion resistance and the tape peeling resistance. On the other hand, if the blending amount exceeds 20% by mass, the crosslinking density of the resin layer is excessively increased to increase the hardness and the layer cannot be deformed by pressing. The crack is caused, and as a result, the corrosion resistance and the coating property are lowered, which is not preferable. The ratio of the amount of the crosslinking agent to the ethylidene-unsaturated residual acid copolymer is preferably moderately changed so as to be based on the amount of the carboxyl group in the copolymer. The amount of the crosslinking agent is changed. Usually, the crosslinking agent is preferably from 0.5 to 50 parts by mass (more preferably, from 5 to 20 parts by mass) based on 1 part by mass of the copolymer. The crosslinking agent having two or more functional groups in the molecule which is reactive with the carboxyl group is not particularly limited and preferred examples include, for example, a glycidyl group-containing crosslinking agent such as sorbitol glycidyl ether. Poly(condensation) of (poly)glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, and (poly)ethylene glycol diglycidyl ether Glycerol ethers and polyglycidylamines; and aziridine-containing crosslinkers, for example, 4,4:-bis(ethyleniminecarbonylamino)diphenylnonane' Ν-hexamethylene Bifunctional acridine compounds such as keto-K 6 -bis(]-acridinium carboxamide) and toluene bixayl carboxamide; and oxidized tris- 1 - 28-(25) 1262962 pyridine phosphine, oxidation Reference [I-(2-methyl)acridinyl]phosphine, trimethylolpropane-gin (β-acridine propionic acid), ginseng-2,4,6-(1-anridinyl)-1 A 3.5 or more functional acridine compound such as triazine or tetramethylpropane tetraacridylpropionic acid or a derivative thereof. Among them, one or more crosslinking agents can be used. Specifically, an acridine group-containing crosslinking agent is preferred. A polyfunctional acridine and a monofunctional acridine (acetamide, etc.) can be used together. The solid content of the cerium oxide particles converted into the emulsified composition may be 5 to 40% by mass (more preferably, 2 Å to 3 Å by mass). This is effective for improving corrosion resistance, coating property and crack resistance, and is also effective for improving corrosion resistance and tape peeling resistance after degreasing. If the amount of ruthenium dioxide particles is not enough, the effect is less likely to manifest. On the other hand, if excessive, the ratio of the cerium oxide particles becomes too high to cause the film forming property to deteriorate and the resin layer sometimes encounters cracks during the drying step, which may undesirably cause a decrease in corrosion resistance. Furthermore, 'using cerium oxide particles as cerium particles to increase the lubricity of the layer' reduces the coefficient of friction and causes mold wear during manufacturing to shorten the life of the mold. ° In order to obtain the maximum effect of cerium oxide particles, cerium oxide particles are preferred. The average particle size range is from > to 200 nm. If the particle size of the silica sand particles exceeds 200 nm, the surface of the resin layer becomes rough. 'The dense resin layer cannot be obtained'. Further, the silica sand particles are also used as honing agents to deteriorate the processability. . If the particle size of the silica sand particles is small, the corrosion resistance of the layer can be improved. However, since the effect described above is saturated if the particles are very fine, the lower limit of the particle diameter is preferably 1 n m. If the corrosion resistance after degreasing is particularly important, the average particle size of the silica sand particles is preferably from 4 to -29 to 1262962 (26) 20 nm. The cerium oxide particles are generally referred to as colloidal cerium oxide and are preferably used. For example, "S N 0 W T E X" is 歹1J (colloidal cerium oxide)

"XS", "SS" 40", "N" and "U P" manufactured by Nissan Chemical Industry. The emulsified composition of the present invention preferably contains a wax. If the wax is converted to a solid content of 〇. 5 to 20% by mass (more preferably, 0.5 to 1% by mass, and more preferably, 0.5 to 5% by mass), a suitable lubricating power can be obtained. Resistance to cracking, deep drawability, punching properties, and mold wear resistance required for die casting or punching, and side blackening resistance during the production of the obtained resin layer. However, it is preferable that the amount of the wax is not excessive because the wax may be softened to liquefaction or bloom and after coating, the boundary between the resin layer and the coating may be thickened or the boundary between the surface treated layer and the resin layer may be Thickening, so the corrosion resistance and the peeling resistance of the tape after degreasing are degraded. The wax is not particularly limited, and any conventional wax such as a microcrystalline wax and an amorphous wax; a synthetic wax such as a polyethylene wax; and a mixture thereof can be used. It is best to choose a softening point of 8 〇 to 1 4 〇 t. The most preferred wax-shaped spherical polyethylene wax has an average particle diameter of from 0 μm to 3 μm (more preferably, from 0.3 to 1 · ο μ rn ). This is because the lubricating force, punching properties, mold wear resistance and deep drawability can be remarkably improved. Regarding the spherical polyethylene articles that can be suitably used, for example, "D] j ETE - 7" (made by G 0 〇u C hemica 1 company), "KUE _ 1", "KUE _ 5" and KUE-8" (manufactured by Sanyo Kasei Industry), r 2 0 〇", "'V - 3 0 0

c Η E ]yi ] p £ a RL" series "W - ] 0 0 W - 4 0 0", "W - 5 0 0 -30- (27) 1262962 manufactured by Mitsui Chemical Co., Ltd.) and "ELEPON-20" (Manufactured by N ikka C hemica 1 company). The emulsified composition used in the present invention preferably comprises an ethylene-unsaturated carboxylic acid copolymer, an amine, a monovalent metal compound, and a crosslinking agent, for example, an acridine compound serving as a basic component, and a 'dioxide which is optionally used.矽 particles and wax. The amount of the acridine compound, the cerium oxide particles and the wax is preferably adjusted in the ethylene-unsaturated carboxylic acid copolymer so that the resin component is 50% by mass or more in terms of the solid content of the emulsified composition. The emulsified composition is prepared by first adding an ethylene-unsaturated carboxylic acid copolymer as an essential component to, for example, an aqueous medium, into a homogenizing apparatus, optionally heating at 7 Torr to 25 ° C. The amine and the monovalent metal compound (whether or not the amine or the amine is added substantially simultaneously with the monovalent metal compound) are added in the form of a suitable aqueous solution or the like, and then stirred under high shear. The cerium oxide particles, the wax and the crosslinking agent may be added at any stage, but it is preferred not to heat after the addition of the crosslinking agent to avoid crosslinking reaction and gelation. In the emulsified composition, a diluent, a surface protective agent, a leveling agent, an antifoaming agent, a penetrating agent, an emulsifier, a film forming aid, a coloring pigment may be appropriately added within a range that does not impair the object of the present invention. , viscosity modifiers, decane coupling agents and other resins. When a surface resin layer is formed using another resin composition, various additives which can be blended with the emulsified composition can also be used in a conventional drying method, that is, roll coating, spray coating or curtain coating. The emulsified composition described above may be coated with one or both sides of the -31 - (28) 1262962 metal foil under the action of heat to form a resin layer. The temperature of drying under the action of heat is preferably carried out at a temperature at which the cross-linking reaction between the cross-linking agent and the carboxyl group is used. Further, since the processing of the subsequent manufacturing step 1 is preferable if the spherical shape is maintained, the spherical polyethylene ray cloth Kfi is used as the lubricant, and the drying is preferably carried out in the range of 7 Torr to 300 °C. The deposition amount (thickness) of the resin layer after drying is preferably from 0.2 to 2.5 g/m2. If it is too thin, the metal foil is difficult to apply uniformly and it is difficult to obtain a well-balanced desired layer property such as workability, corrosion resistance and coating property. However, it is not good when the deposition amount exceeds 2.5 g/m2 because it is used for, for example, the computer's main ground conductivity, that is, the conductivity is degraded. Further, the amount of enthalpy of the resin layer increases the amount of peeling due to deposition due to compression, and the peeling layer accumulates on the mold bird to cause trouble in die-casting, which is wasteful in terms of manufacturing cost. The lower limit of the deposition amount of the resin layer is 〇 5 g / m 2 and the upper limit of the enthalpy is 2.0 g / ni 2 . The surface-treated galvanized steel sheet according to the most preferred embodiment of the present invention can be obtained by forming the resin layer described above on the surface of the sheet. The galvanized steel sheet subjected to this processing step && surface treatment can be used as it is, or in the deposition coating, powder coating or smear printing (about 130 to 160 °C) Use from $ 2 〇 to 30 minutes), depending on the application. According to the present invention, the surface-treated galvanized steel sheet is completely free of harmful hexa® and is excellent in tape peeling resistance and tape peeling resistance after alkali degreasing. The stomach was first published by the inventors for the purpose of the invention. Further, if the layer obtained by selecting the emulsified composition is used as the surface layer, it is possible to provide a surface-treated galvanized steel sheet which is formed into a layer excellent in basic properties, for example, -.32 - (29) 1262962 Applicability, lubricity, workability and corrosion resistance, as well as exceptionally excellent tape peeling resistance and tape peeling resistance after alkali degreasing. Therefore, this can be effectively used as a surface-treated galvanized steel sheet which can be applied to, for example, automobiles, home electric appliances, and building materials. The present invention will be more specifically described with reference to the embodiments, but the present invention is not limited to the following examples and the invention may be appropriately modified and described below, and all of them are within the scope of the above description. The amendments are all included in the technical scope of the present invention. In the following embodiments, "%" and "parts" indicate "% by mass" and "parts by mass" unless otherwise specified. Experimental Example 1 (No. 1 to 2 9 ) was each galvanized by electroplating on a surface of a steel sheet of 8 mm thick (part number: SECC) at a deposition amount of 20 g/m 2 , degreased and then washed with water. A dry zinc-free steel sheet is used as a raw material sheet. Surface treatment using each of hydrogen-containing phosphoric acid (manufactured by Nippon Chemical Industry Co., Ltd., 50% solid content), colloidal cerium oxide ("SN〇WTEX-〇"; manufactured by Nissan Chemical I nd ii Uy company), and water Agent. By changing the amount of aqueous solution of hydrogen pity acid I, colloidal cerium oxide and water, and adding phosphoric acid and aluminum metal as needed, as shown in Tables 1 and 2, the respective concentrations of S i , P and A1 in the treating agent are changed and Varying the content of each of S i, P and A1 in the surface modifying layer 〇 after degreasing, immersing each galvanized steel sheet in the surface treatment agent for 2 seconds and then pulling up 'to remove the excess solution by the twisting roller, at 50 The spray pressure of k P a '33 - (30) 1262962 was washed with water for 5 seconds and dried at 4 ° C to form a surface modification layer on the galvanized layer. In Table 2, the 5 Tiger 2 9 was not washed. Separately, epoxy type cross-linking by blending and stirring a solid content of 5% (hereafter, a solid content of a composition for forming a surface resin layer of 100% by weight) Agent ("RICA Β Ο NDAP 3 5 5 B"; manufactured by C h U 〇R ika I ndus 11· y), cerium oxide particles with a solid content of 30%] 〇 to 20 nm (" S Ν Ο WTEX 40"; manufactured by N issan C hemica 1 I ndustry) and spherical solid polyethylene containing 5% solid content followed by C "CHEMIPERAL W7"; manufactured by Mitsui Chemical Co., Ltd.) in polyolefin dispersion (" A composition for forming a surface resin layer was prepared by CHEMIPERAL (registered trademark) S] 00"; manufactured by Mitsui Chemical Co., Ltd.). The composition was applied to the surface modification layer of each galvanized steel sheet by bar coating, and dried by heating at a sheet temperature of 90 ° C for 1 minute to obtain a surface layer having a deposition amount of 1 g/m 2 . A surface treated galvanized steel sheet of a resin layer. For each of the test pieces thus prepared, an evaluation test was conducted for the Si, P, and A] concentrations (%) in the surface treatment solution, and the amounts of S丨, p, and A in the surface modification layer (mg / m 2 ) The total deposition amount of the surface modified layer (mg / m 2 ) and the tape peeling resistance and the tape peeling resistance after alkali degreasing, the results are as shown! Shown. [Evaluation Method j (1) The amounts of S i, P, and A 1 are respectively measured in a surface treatment solution by a CP emission spectroscopic device (manufactured by Seik 〇A d V a Π ce -34 - (31) 1262962) S i, P and A] respective concentrations were measured by S-rays, X-rays (registered name: "Μ IF · 2 1 0 0"; manufactured by Shim azu S eisakusho) The amount of AI (mg / m 2 ). The total deposition amount (mg / m 2 ) of the surface modification layer is the quantitative analysis result of Si, P and A1 measured by fluorescent X-ray spectrochemical analysis. According to the formation of SiO 2 , aipo 4 , Ζ η 3 in the modified layer ( Ρ Ο 4 ) 2 A 12 Ο 3 assumptions are calculated. (2) Tape peeling resistance A ribbon (#9 50, manufactured by Surion Tech) was attached to the surface of the test piece and the test piece was stored in 40 ° C X 90% RH for 24 hours and 48 hours, and the ribbon was peeled off to observe the residue. The area ratio of the surface layer was evaluated and the resistance was evaluated according to the following criteria. ◎: residual ratio, 100% 〇 to ◎: residual ratio, 9 5 % or more and less than 100% Ο : residual ratio, 90% or more and less than 9 5 % △: residual ratio 70% or more and less than 90% X: Residual ratio, less than 70% (3) Tape peeling resistance after degreasing The test piece is immersed in an alkali degreasing agent ("CL - N 3 6 4 S" After being adjusted to 20 g/1, 60 ° C degreasing solution, the test piece was pulled out, rinsed with water and dried, and attached with cellophane tape (manufactured by Nichiba η Co., Ltd.) The surface of the test piece was peeled off after 24 hours and 48 hours, and the residual ratio of the remaining surface layer was observed and evaluated according to the same standard of the tape peeling resistance in the normal state. -35- (32) 1262962 EMBODIMENT OF THE INVENTION Embodiments of the invention Embodiments of the invention Embodiments of the invention i Embodiments of the invention Embodiments of the invention EMBODIMENT OF THE INVENTION Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention ^ ¢1 inch 〇〇〇〇〇〇&lt;1 &lt;&lt;]〇〇〇&lt;]&lt;&lt;&lt;&lt;&lt;1 inch (N ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 tape peeling resistance 〇〇〇 &&lt;&lt;&lt;&lt;&lt; 〇〇〇〇 &lt;&lt;&lt;&lt;1 Ο ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ I ◎ 15 _ _ 驷 $ i 晅 晅 oo 00 rH 〇 CN CN CN CN CN CN CN CN CN CN CN CN CN CN ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 6 inch rH τ—Η Ό CN· r—H Ο Τ—Η I '&lt; 00 00' &lt;Ν r—H r—H m ri m inch cn m 〇(N m 114.3 Ratio (N r—1 m ί—Η rH rH ο r—Η m rH r—Η y—i Ο &lt;Ν rH &lt;Ν CN| rH mr—H Ον Ο r—ir—ι r—i rH 1—f rH Ο 00 Ο ^Τ) ϊ—i CO iri iri · t—H ^sf ▼—H (N &lt;N CN· cn ^Τ) Q\ tn 1—( ( to to to inch m In Ό iri Ό Ό· m vb (Ν _ uo rH r—1 00 rH , mil m1 _ ® S ugly 〇 j &lt; 00 ο 卜 o Ό 〇 IT) Ο &lt;N r — Η On r — H inch · τ - Η inch rH Ό Ο ο 00 o' M3 rH MD τ &quot;i 00 r-H 00 rH rH &lt;NG\ pH &lt;NT '&lt; ο rH oo o C\ o IT) Ο ΙΟ rH 〇(si 00 &lt;N ON (N 〇 〇 Q\ ο ο 00 r-H 卜 T-H 〇&gt; f-^ oo f (r-H r-H r-H 'iri vd inch m ON T—H r—Η rH &lt;N 00 00 rH T—H inch·inch·rH 〇in Ο inch r-Η inch mm 〇m H o &lt;N rH 〇m rH Ό r—1 r— (&lt;N water rinse application application application i application application application application 1 application ι application application application application application treatment method dip coating dip coating dip coating dip coating dip coating Dip coating, dip coating, dip coating, dip coating, dip coating, dip coating, dip coating, dip coating ratio, Si/Al, Bu-I (Η 〇1~~1 inch Τ'&quot;&lt; r-^ oor- H 卜o' r-Η 卜τ—Η Ο 00 \ό r—Η cK 卜o' CO mm tTi O y—^ 卜寸Γ-Η Ο ι 1 1 &lt;N Ο 〇\ § GO ^Τ) Ό · 〇'sd Ο inch · o inch · r-Η 卜 · 卜'sd Ο Ό* 〇 \ &lt;N ο (Ν ^sO r-Η 卜 &lt;Ν OT-H r-im 8 IT) Surface treatment agent The concentration in the middle (0/〇) S Ο s ο 0.007 , 0.002 0.0003 S ο ο iT) (Ν Ο inch d 0.012 0.015 0.009 soso 0.038 s ο SOO Ph y-^ Ο Ο S ο 0.005 0.0007 τ—^ Ο ΓΊ Ο Ο Ο m rH ο S ο S ο T~&lt; 〇r—* 〇mr—HO r—H Ο oo oo rn iy5 ιη Ο m O' 00 ο ο (N 〇o 0.005 ο r—ι' ο (Ν (Ν寸·00 m 00 ο ο 00 ο ο CX5 Ο Ο or—i 〇CN o inch inch &lt;N inch^T) inch number τ—Η (Ν inchΌ 00 00 C\ ο r—Η (Ν Γ —' m rH 寸 r—ir—ir—i. 卜r—1· 00 1—i

-36- (33) 1262962 Section Reference Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 鹚 鹚 48 48h &lt;&lt;] X &lt;] XXXX &lt;&lt; X 24h &lt;1 &lt;] &lt; 〇 &lt; XX &lt; Ο &lt; X tape peeling resistance 48h &lt; XXXX &lt;&lt;1&lt; X 〇24h Ο 1 ◎ XX &lt;] X 〇 〇〇1 ◎ 〇1 ◎ &lt; 〇_ _ € ^ i 嗽S 67.2 00 m 00 &lt;Ν 〇\ 00 卜 m 150.3 169.9 134.4 83.0 108.9 181.0 Ratio P/Al 〇〇m rH 〇(N un 00 卜rH rH T—H cn Si/P o 卜·cn 〇〇 〇〇 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N ' 〇m Ο (N Ο 10.2 10.0 〇&gt;· 11.5 ό 00 15.5 PH (N m ο ο Ο Ο 3 15.3 17.7 16.2 τ—Η mrTMH r—H On 20.1 ·ύ5 22.3 oc o ο 〇〇 〇00 ο 38.2 1 40.1 27.3 14.6 33.5 r—i inch ft application application application application application application application application application process dip coating dip coating dip coating dip coating dip coating Dip coating dip coating ratio Si/AI inch ο 20.0 0.03 500 11.7 21.0 00 00 m in 16.0 Ο inch · Si/P rn inch · Bu 1 -&lt; Bu ^0 0.01 1667 5 oc CN ON Ο oo (N Ο &lt;Ν Concentration in surface treatment agent (%) 〇〇o' 0.0002 0.00006 0.03 0.00006 卜ο inchΟ ο 〇〇 〇〇 0.15 PH 〇r—' 0.0006 (0.0002 rH 〇0.0002 ο &lt;Ν ο η rn Ο ( &gt;0 cn inch · 0.001 0.004 1 0.001 r—ί (Ν 00 inch 00 inch inch · br ot o oc Ό Ο number On (N (Ν Ό &lt;Ν CS 00 &lt;N θ', (Ν

-37- (34) 1262962 An embodiment of the present invention is shown in Table 1. In each of the examples, the contents of si, P, and A1 and the Si/P and P/A1 in the surface modifying layer were all within an appropriate range. In each of the examples, the examples showed an excellent tape peeling resistance after drying and degreasing. Sex. Compared with the embodiment of the present invention, since P / A 1 is lower than the proper range of No. 1 of Table 2, the tape peeling resistance and the tape peeling resistance after degreasing are slightly inferior. No. 2 0 to 2 3 are embodiments in which the amount of addition of S i , P and A1 partially or completely does not reach a predetermined amount of the surface modifying layer because the concentration of S i , P and A1 of the surface modifying agent is partially Or it is completely insufficient, so the tape peeling resistance and the tape peeling resistance after alkali degreasing are worse than the embodiment of the present invention. Nos. 24 to 28: Since the Si, P, and A1 concentrations of the surface modifier are all partially or completely excessive, the S i , P , and A1 depositions of the surface modification layer are partially or completely exceeded a predetermined amount, and Both the tape peeling resistance and the tape peeling resistance after alkali degreasing were worse than the examples of the present invention. No. 2 9 ·· Since the water rinse is not performed, the deposition amount of p and AI of the surface modification layer exceeds a predetermined amount. Although the tape peeling resistance is suitable, the alkali resistance of the surface modifying layer is poor due to an excessive amount of P and A] and the tape peeling resistance after alkali degreasing is poor. Experimental Example 2 (No. 3 0 to 4 8 ) #回改层层 was prepared by spray coating without dip coating. That is, in the table. After each surface treatment agent which was not composed was sprayed at a spray pressure of 50 kPa for 2 seconds (preparation method is the same as Experimental Example), a -38 - (35) 1262962 excess solution was removed by a twisting roller. Then, it was further washed with water at a spray pressure of 50 kPa for 5 seconds and dried at 4 (TC) to form a surface modification layer on the galvanized layer. The same method as the experimental example was carried out except for the steps described above. A surface-treated galvanized steel sheet having a surface layer was formed. Each test piece thus obtained was evaluated in the same manner as in Experimental Example, and the results are shown in Table 3.

-39- (36)1262962 mmmm 编mm 习 习 习 习 习 习 四 四 四 四 四 ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ ⁄ n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n鎞 馏 馏 镒 镒 柃 柃 柃 A A A A A A A A A A A A & & & & & & & & & & & ◎ ◎ ◎ ◎ X X X X X X X X X X X X ο 〇ο 〇^ Μ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X &lt;&lt;]&lt;]&lt; inch Ο 〇Ο ο ο 〇1 〇i 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ &lt;3 X &lt;3 &lt;3 ◎ X.ill ^ 4π 〇I 〇1 〇1 Λ (Ν ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X &lt; ◎ ο _运蜮灵CS /-Tv ^νΊ ^The product of the surface layer (mg/i 127.( 106.: οο 窆m ΓΊ (Γ) 卜tn m 〇\ 〇&lt; (N r—1 oi (Ν inch CD* ΠΊ 00 ό· &lt;Ν τ—Η od ι—Η (N ΠΊ cn οο inch cn inch inch 134S 112.: 120.: &lt; Ρί r &quot;&lt; τ—Η r—ι (N ι—Η cn f &lt; mt—Η r—Η Γ ι ι &lt; (N rH r^H Ο · · τ—Η (Ν 卜—Η vo γ··Η tn r_H rH 卜〇 inchΌ·rH &lt;Ν rH AJ Ρη iy5 Ο (Ν卜?—Η寸·cn rH τ........( ^-Η rn r—Η Ο Γ\Ι CO 1 &lt; o On) πί ι ί ΟΟ τ—Η (Ν ^Γ) m (N (N ( (N 〇〇&lt;Ν ΓΝ| rH OO ο r- m * vq ο Η &lt; 〇\ 〇\ Ο 〇\ Ο 00 mr,· Ό· ΓΝ | yr) οο cn ΠΊ inch (N Ο ι—Η inch·rH (Ν ο omo rs rsi &lt;Ν ι &lt; rH OO mil 卜CN ο .丨1 &lt;&lt;Ν o η pLi inch' ι i ι ι—Η (Ν τ—Η (N Os· ΟΟ οο cn 寸 · ΟΟ cn ΓΝ ΓΝ 1 Ο · · Ο m Ο (Ν f—-( r &lt; C\ o inch · o' inch Ο Ό τ Η OO rH o IS Μ Ο ΠΊ m 〇 (Ν cn (N 嗽S On (Ν Ν CN · (N r*-H Ο cK οο οο οο Ό · (7) un ΓνΙ wn inch · OO cn o r4 OO o σ σ r 寸 f f f f f f f f f η η η η η η η η η ^ ^ ^ ^ ^ ^ ^ ^ ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' '剑剑剑剑剑剑剑劁剡剑剡剑剑剑 β β » β β ff β m Si/Al οο 00 Ο r—Η οο οο m od 卜 · »〇卜. smm «ΤΊ ΓΝΐ ο ΓΝ) m \o cn &lt;N inch τ-Η m »〇卜·τ—H cn οο rH 66 On 〇\ 卜〇〇卜Ο ΓΌ VO VO iy^ \Q (N 〇ΓνΙ ΓνΪ oi r^i -Η r4 卜· ο 1—Η ο ο rH rsi 寸 r—H o rH rsi 〇〇ri (Ν r—H r-' _ g * ο 寸 · Ο inch ο ΓΟ o (Ν Ο (N 〇r- ο ο ο ο ο 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 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 〇o inch ο ο OO ο P-, ι~Η I· * ψ—i. o ο 〇Ο Ο ο Ο ο O ooo ο r—ι r· ir—Η rv^ 脃^ inch inch · r—- inch · υη mm oi Ο r—Η yn ο inch· ο ο o’ o 0·00{ 0.00 ο ο *〇 寸 · ΓΝΙ r4 Ο 卜 · 赖 Ο rn Ψ —i, r^) ΓνΙ m m m , n m 卜 m ΟΟ Γ. θ', rn ο inch r ί rj

-40- 1262962 (37) Experimental Example 3 (No. 49 to 72) Table 4 (also Table 5) was prepared using aluminum hydrogen phosphate, colloidal cerium oxide ("SN0WTEX-0" described above), three polyacrylic acids and water. A surface treatment agent of the composition shown. First, a surface-treated galvanized steel sheet which was formed before the surface layer was formed by a spray coating method (under the same conditions as in Experimental Example 2). The surface layer was formed in the same manner as in Example 1 to constitute numbers 49 to 60. Then, an ethylene-acrylic acid copolymer emulsion was prepared by adding 626 parts of water and 1 60 parts of an ethylene-acrylic acid copolymer (20% by mass of acrylic acid, melt index (ΜI) 300) to an autoclave, respectively. , adding 40 mol% of triethylamine, 1 mol% of N a Ο 以 based on the carboxyl group of the mol-acrylic-acrylic copolymer, and at 150 ° C and 5 P a environment Stir in high speed. Next, the glycidyl group-containing cross which is used as a crosslinking agent and which is used as a crosslinking agent at a solid content of 5% (the enthalpy obtained by using the solid content of the emulsified composition is 〇〇%, used herein and hereinafter) Preparation of emulsified composition by "EPICL Ο NCR 5 L" (abbreviated as CR 5 L ); "e PICL Ο N" is a registered trademark; manufactured by D aini ρ ρ ο η I nk C hemica ] I ndustry And an acridine group-containing cross-linking agent having a solid content of 5% (^ 4,-bis(ethyleniminecarbonylamino)diphenylmethane; "CHEMITI D E-Z-22E"; (abbreviated to DZ-22E) " CHEMITITE" is a registered trademark; manufactured by Nipp〇n C ata ] yst), a particle size of 30% by weight, 二2 to 2 〇nm of cerium oxide particles ("SNOWTEX 40"; by Nissan Chemical] Nd υ s 11· y company made) and solid content 5. /. A spherical polyethylene crucible having a softening point of 1 2 〇 t and an average particle diameter μm. Applying -41 - (38) 1262962 to the surface modification layer of the surface-treated galvanized steel sheet before the surface layer is formed by bar coating, and heating at a foil temperature of 90 ° C] It was dried in minutes to form a surface resin layer (No. 6 to 72) having a deposition amount of g/m2.

Each of the test pieces thus obtained was evaluated in the same manner as in Experimental Example 1 and the results were out of Tables 4 and 5. In each table, PA1 is a weight average molecular weight (M wj is 10 〇, 〇〇〇 to 20,000, 0 〇〇 polyacrylic acid, p A 2 Mw is 2,000 to 30,000 polyacrylic acid, and ΡΑ 3 The polyacrylic acid having a Mw of 8,000. The absorbance of the resin of the surface modified layer is measured by FT·IR and the analysis conditions are as follows. (F TM R analysis method) Measurement method: high sensitivity reaction method (incident angle) 7 5. Irradiate the IR light in parallel polarized light.) Comparative material: Analytical ability of the mirror deposited by gold vapor deposition: 4 c ηΓ 1 Cumulative number of times: 5 0 0 times Device: JIR - 5 5 0 〇 type Fourier transform 1 R spectrometer, manufactured by N i ρ ρ ο η D enshi 1R · RS cll 〇 reflection measuring unit (angle variable type) 1R - S Ε 〇〇 1 〇〇 test piece scanning table to add polyacrylic acid steel sheet 1 The peak area of 4 9 6 cm 1 to 7 7 6 c rrT 1 minus the peak area of 4 9 6 c rrT 1 to 7 7 6 c ] of the steel sheet to which no polyacrylic acid is added, to multiply the remaining portion The absorption of polyacrylic acid, which is defined as the surface modification layer. Figures 1 to 3 are not shown in Table 3. No. -42 - (39) 1262962 3 8. The FT-IR spectrum measured under the above conditions, No. 5 2 and sodium polyacrylate (standard test piece) described in Table 4. No. 52 of the second drawing is surface treatment. a system containing 0.50 g/Ι of PA], wherein absorption was observed at 1346, 1421, ] 4 5 7 and ] 5 92, but was not observed in the test piece No. 3 8 surface treatment agent containing no polyacrylic acid. The peak is the same as the absorption of sodium polyacrylate shown in Figure 3.

-43- (40)1262962

EMBODIMENT OF THE INVENTION Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention Embodiments of the invention Implementation of the invention Example Reference Example 1 Reference Example ι S鹚龌 鹚龌 48h 〇Ο 1 ◎ 〇 1 ◎ 〇〇〇〇〇〇〇〇 &lt; 24h ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Tape peeling resistance 48h ◎ ◎ ◎ ◎ ◎ ◎ 〇 1 ◎ 〇 1 ◎ ◎ ◎ 〇〇 24hJ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 15 Μ Art $ biliary system S 21.2 23.9 24.7 27.9 28.3 28.3 23.9 19.5 I 20.8 17.5 24.2 53.8 Resin Absorption 〇〇 ο Ν Ν 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Τ—Η inch· 00 ^-Η Si/P Ο &lt;Ν 卜r-H inch (Ν r—ί &lt;Ν卜(Ν O cn Ο oi 寸&lt;N 卜r-H Π 1—Η rH &lt ;N r—H The amount in the surface treatment layer (Νr r—ί 00 r—&lt; r—H &lt;Ν Ο &lt; Oi 00 • Η 〇oi σ\r—H &lt;Ν (Ν On Oh &lt;Ν &lt;Ν Ό &lt;Ν Η m 00 (Ν卜&lt;N 卜&lt;Ν rH &lt;N Ό &lt;Ν VO (Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν & & 00 00 · · wn wn wn wn wn K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K K 1 Spray Spray 1__ 剡 Spray Spray 1 Spray Spray Spray Spray Organic Acid Concentration (g/1) 0.05 0.10 0.25 0.50 0.75 om 0.10 0.25 0.10 0.25 0.005 ο Category ΡΑ1 ΡΑ1 ΡΑ1 ΡΑ1 ΡΑ1 PA1 PA2 PA2 PA3 PA3 PA1 ΡΑ1 Ratio sTM &lt;N (Τ) (Ν (Ν &Ν;Ν &lt;N &lt;N cn &lt;N (N &lt;N &lt;N iT) (Ν cr) (N Si/P m 00 m 00 Γ^) 〇 〇· ro 00 ΓΓ) CO m 〇〇' cn 00 ΠΊ 00 m cc cn 00 ΓΛ 00 cn oc Concentration in the surface treatment agent (%) &lt; 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 ΰο 〇Ο Ο νη Ο oo 〇o ο ο ^Τ) Ο o No. Os (Ν IT) 00 S

EMBODIMENT OF THE INVENTION Embodiments of the invention The embodiments of the invention The embodiments of the invention The embodiments of the invention The examples of the invention The examples of the invention The invention of the invention EXAMPLES Reference Examples of the Present Invention Reference Examples Lions 〇 1 ◎ ◎ ◎ 〇 1 ◎ 〇 1 ◎ 〇 t ◎ 〇 I ◎ 〇 1 ◎ 〇 1 ◎ 〇 ◎ 〇 1 ◎ 〇Λ 寸 (Ν ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎嗽 嗽 £ (N y—i (N m (Ν 〇 〇 Ν Ν cn cn N N r r r r r 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 〇σ&gt; ο m (Ν卜寸^Τ) G\ 00 inch r-Η VT) &lt;Ν inch 1—Η ο cn 0.003 &lt;N t-1 1 Ρ; m ! &lt; 卜r-H inch r —Η inch&lt;N rH Γ—Η inch&lt;Ν inchΗ 00 GO 〇&lt;Ν· 卜r—( 寸&lt;Ν r—( &lt;Ν卜&lt;N 〇Ο &lt;N inch&lt;Ν Bu τ Η η τ—Η Γ-*Η &lt;Ν ΓΊ The amount in the surface treatment layer (Νr r 00 rH r—i &lt;N Ο CN rn (N CO r—l Ο csi On r—H (Ν &lt;Ν ΟΝ rH G\ m Ph csi C\ &lt;N \〇(Ν τ—H m 00 (Ν卜&lt;N 卜 oi rH oi Ό &lt;ΝΪ \ο (Ν卜(Ν &lt;N Γ- ' m τ—Η tn 00 寸&lt;Ν 'Ο Ό ···················································· Method Spray Spray Spray Spray Spray 1 Spray Spray Spray Spray Spray Spray Spray Spray Organic Acid Concentration (g/l) l S 〇ο rH Ο (Ν Ο ο ο 卜 〇Ο m O r-HO IT) (Ν Ο Ο ^ -Η Ο (Ν Ο 0_005 Ο type τ—( &lt; CL τ—Η &lt; Ρη r—ΐ &lt; r—Η &lt;ί r—^ &lt; r—Η &lt; Ρη (Ν &lt; Ρη Ρ- &lt; r—H &lt; Ρη wn &lt;N m (Ν (Ν &lt;Ν (Ν in (Ν &lt;N &lt;Ν cn (Ν &lt;Ν m (Ν &lt;Ν % GO m 00* m 00 m 00 00 cn 00 ΠΊ 00 m 00 Γ^) 00 00 00 cn GO m 00 gg _ B gs 〇S ο &lt;Ν Ο Ο S ο (Ν Ο ds ο SO ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ^Γ) Ο ό ο o ο Ο ο Ο ιη ο r—H Ό (Ν \〇m S Ό VO Ό 卜 00 \〇$ τ—&lt; r, (Ν

-45- (42) 1262962 mouth J* Sees tape stripping resistance and alkali degreasing of the system with added organic resin. The tape peeling resistance after Z is better than the conventional unadded type. Further, it can be seen that the embodiment of the surface layer of the emulsified composition neutralized by the S-finger neutralization method (as shown in Table 5) can exhibit exceptionally excellent tape peeling resistance and tape peeling after alkali degreasing. Resistance. Industrial Applicability Since the surface modification layer is formed on a zinc-based plating layer of a galvanized steel sheet with a surface treatment agent containing a specified amount of Si, ρ, and Α1 and, if necessary, an organic resin, the tape peeling resistance is also The tape peeling resistance after alkali degreasing is excellent. Further, by selecting a layer made of a specified emulsified composition serving as a surface layer, it is possible to provide a layer excellent in various properties such as coating property, lubricating property, workability, and corrosion resistance, and at the same time, after the degreasing step The protruding tape peels off the resistant surface treated galvanized steel sheet. The manufacturing method according to the present invention is suitable for producing a tape peeling resistance, particularly a surface-treated galvanized steel sheet excellent in tape peeling resistance after alkali degreasing. [Simple description of the map]

Figure 1 is an FT-IR spectrum of the surface modifying layer numbered 38 described above.

Figure 2 is an FT-IR spectrum of the surface modifying layer numbered 52 as explained above. Figure 3 shows the FTIR spectrum of sodium polyacrylate. -46-

Claims (1)

1262962 (1) Pick, patent application scope 1 * A surface-treated galvanized steel sheet 'forms at least a surface modification layer and a surface layer on the zinc-based plating layer of galvanized steel sheet 3 There are 8丨〇2'〇.5 to 15 mg/m2 P and Si1 to mg/m2 A1 converted to si to 30 mg / m2. 2. The surface-treated galvanized steel sheet of claim 1 wherein the content (mass ratio) of S, P and A1 contained in the surface modifying layer conforms to the following relationship (1) and ( 2): 0.5 &lt; Si/p &lt; 2〇( 1 ) 0.7 &lt; P/A] &lt; 6 ( 2 ). 3. The surface treated mineral zinc steel sheet of claim 1 wherein the surface modifier further comprises an organic resin. 4) The surface-treated galvanized steel sheet as described in claim 3, wherein the organic resin is contained such that the surface-modified layer is observed under FT-1, and the absorbance obtained from the structure of the organic resin Become 〇.] to I 5. 5 · For example, the surface-treated galvanized steel sheet of the scope of claim 1 wherein the amount of the surface modifier is in the range of 4. 2 to 3 〇 buckle. The surface-treated galvanized steel sheet of the above item, wherein the surface layer is a resin layer obtained from an emulsified composition of an ethylene-unsaturated carboxylic acid copolymer serving as a main component, in addition to the ethylene-unsaturated carboxylic acid In addition to the copolymer, the emulsified composition further comprises, based on the carboxyl group of the one mole of the ethylene-unsaturated carboxylic acid copolymer, the boiling point of 〇·2 to 〇.8 mol is 1 〇〇t or lower. An amine, and a monovalent metal compound having a content of from 〇2 to 0.4 mol based on the carboxyl group of the molar copolymer of the ethylene-unsaturated carboxy-47- 1262962 (2) acid; and the emulsified composition further comprises The emulsified composition has a solid content of 100% by mass as a reference, and a content of 1 to 20% by mass of a crosslinking agent containing two or more functional groups reactive with a carboxyl group. 7. A phosphate-containing phosphate surface a treating agent for forming a surface modifying layer on a 4 galvanized steel sheet, The solid concentration system 〇. 〇] to 1 4 · 5 % (herein referred to as mass %), and the composition ratio (mass ratio) of Si, P and A1 contained in the treating agent may satisfy the following conditions: Si : 0.0 02 to 4.5% P : 〇 · 〇〇〇 5 to 1. 5 % A1: 0.0001 to 0.5% 1 · 5 幺S i / P &lt; 6 0 , 4 · 5 SS i / A1 S 2 3 0 8. The surface treatment agent of claim 7, wherein the surface treatment agent further comprises an organic resin. 9. The surface treatment agent of claim 8, wherein the organic resin is water-soluble. The surface treatment agent of claim 8, wherein the organic resin contained in the surface treatment agent is an organic resin having a solid content of from 〇·〇丨 to 3 g/1. The method for producing a surface-treated galvanized steel sheet according to the scope of the patent application, comprising forming a surface treatment agent layer on the surface of the galvanized steel sheet by the surface treatment agent described in claim 7 of the patent application, and rinsing with water Removing excess P and/or AI from the surface treatment layer and drying the surface treatment agent The layer is formed by a spray coating method. The method of claim 1, wherein the surface treatment agent layer is formed by a spray coating method. -49 -