TW201138994A - Surface-treating composition and surface-treated steel sheet - Google Patents

Abstract

To provide a surface treatment composition for forming a surface treatment film superior in corrosion resistance, thermal discoloration resistance, blackening resistance, scratch resistance, adhesiveness with an organic resin layer which is formed on the treatment film as the upper layer, after forming, and adhesiveness in a high-temperature and humid environment. This surface treatment composition includes a titanium-containing aqueous liquid (A) which is obtained by mixing at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide, and a low condensate of titanium hydroxide, with hydrogen peroxide water, a zirconium carbonate compound (B), an organophosphate compound (C), a metal phosphate (D), silicon oxide (E), a water-soluble organic resin and/or a water-dispersible organic resin (F), and a silane coupling agent (G), at a predetermined ratio.

Description

201138994 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface treatment composition suitable for use in automobiles, home appliances, building materials, and a surface-treated steel sheet, in which the composition and the film are completely free of hexavalent chromium. An environmentally compatible surface treatment composition and a surface treated steel sheet using the same. [Prior Art] Steel sheets for home appliances, steel sheets for building materials, and steel sheets for automobiles are widely used on the surface of galvanized steel sheets or aluminum-plated steel sheets for the purpose of improving corrosion resistance (white rust resistance and red rust resistance). The main component is a chromate-treated steel sheet of a treatment liquid of chromic acid, dichromic acid or a salt thereof. The chromate treatment is an economical treatment method which is excellent in corrosion resistance and can be easily carried out. The chromate treatment is a method of using hexavalent chromium of a pollution-damping substance, but the hexavalent chromium is treated by a closed system in the treatment process, and the organic film formed by the upper layer can be hardly replaced by chromic acid by using a sealing effect. Since chromium is eluted from the salt film, substantially hexavalent chromium does not contaminate the human body and the environment. However, with the recent increase in interest in global environmental issues, we have paid attention not only to the previous operating environment and drainage treatment, but also to legislation, and we have begun to pay attention to environmental load and environmental regulation and regulations. Moreover, the background of the times has changed to assessing the manufacturer with environmental contribution, so the motivation for reducing the use of heavy metals containing hexavalent chromium has increased. In this context, white rust suppression technology (chromate-free technology) that does not use hexavalent chromium galvanized steel sheets has been proposed many times. For example, as disclosed in Patent Documents 1 and 2, a surface treatment agent and a metal material coated therewith are contained in an aluminum and a phosphoric acid compound and a cerium oxide and an aqueous organic resin emulsion. Further, Patent Document 3 proposes to apply a galvanized steel sheet in which an organic coating layer is formed by applying a mixed aqueous solution of a polyvalent metal monophosphate and a metal oxide sol to dry to form an amorphous coating. Further, in the patent documents 4 and 5, a composite oxide film layer containing oxide fine particles, phosphoric acid and/or a phosphoric acid compound and one or more metals selected from Mg, Μη, and A1 is used as a lower layer, and the upper layer is formed. A steel sheet forming an organic film. In the application to galvanized steel sheets, niobium is present in a temperature range (500 to 600 ° C) which is above the melting point of zinc. For example, in the heat exchanger in the outdoor unit of the refrigerator, when the copper tube and the aluminum evaporator are waxed, in order to prevent the aluminum from being dissolved by the use of the spray gun, a galvanized steel sheet is disposed between the copper tube and the evaporator. The flame is in direct contact with the aluminum. When the surface-treated steel sheet of the above-mentioned prior art is used for this purpose, since the film main body is an organic resin, it is discolored to yellow or brownish brown by thermal decomposition, and the appearance is poor. It is therefore almost impossible to use the surface treated steel sheets of the prior art. In order to solve such problems, a chromate-free technology having excellent heat discoloration resistance has been proposed. For example, as disclosed in Patent Documents 6 and 7, the main component is an inorganic saturated film of magnesium diphosphate and colloidal cerium oxide and a phosphonic acid compound. Further, Patent Document 8 proposes that the inorganic composition of the first component phosphate and colloidal cerium oxide is a lower layer, and the upper layer is provided with a double layer coating of acetinate film and/or bismuth resin. Further, Patent Document 9 discloses at least one titanium compound and hydrogen peroxide water selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium oxyhydroxide, and a low condensate of titanium hydroxide. A surface treatment composition of the obtained titanium-containing aqueous liquid and organic phosphoric acid, water-soluble or water-dispersible-6-(9) 201138994 organic resin, vanadic acid compound, fluorinated pin compound, and zirconium carbonate compound. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-129460 (Patent Document No. 2000-129460) [Patent Document 5] JP-A-2002-53 98 (Patent Document 6) JP-A-2000-7937 〇 公报 [Patent Document 7] Special Opening 2 0 (H Japanese Patent Publication No. 2004-9 1 826 [Patent Document 9] JP-A-2006-9 1 The problem to be solved is that the inorganic saturated film of Patent Documents 6 and 7 has an extremely low level of corrosion resistance, and is difficult to be applied as a chromate film substitute. Further, the double-layer film of Patent Document 8 has a chromate film instead. The corrosion resistance of the product, but the use of high-priced tantalate and tantalum resin, there are cost problems. Moreover, the coating of these technologies is prone to discoloration to black in a humid environment (blackening), so it is difficult to adapt The frosting heat exchanger, in addition, the storage environment in the product transportation 201138994 is also limited and useless. Further, Patent Document 9 Since the surface-treated composition contains a fluoride which is resistant to water adhesion and corrosion resistance after alkali degreasing, when the upper layer has a thick organic resin layer, the adhesion is lowered. Further, the coated steel sheet and the layer are coated. In the organic resin-coated steel sheet such as a steel plate, the adhesion of the organic resin layer is an important performance. However, the film obtained by the phosphate treatment previously performed as a low-layer treatment is crystalline, so that severe processing may destroy the crystal and easily reduce it. Adhesiveness of the organic resin layer In particular, when the thickness of the organic resin layer is 100 or more, the coated steel sheet and the laminated steel sheet are destroyed, and the phosphate film is destroyed when the steel sheet is processed, and the organic resin layer is easily peeled off from the starting point. In order to solve this problem, for example, in the above-mentioned Patent Documents 3 to 5, the plating metal on the substrate is reacted with the treatment liquid to form a poorly soluble phosphate of an extremely thin film to find corrosion resistance, paint adhesion, etc., but even The surface-treated steel sheet is used for the organic resin-coated steel sheet, and it is easy to reduce the adhesion and corrosion resistance during processing, especially the organic resin having a thickness of 100 Å or more. When the organic resin-coated steel sheet has a high film strength, the organic resin layer is easily peeled off due to the strong shearing force at the interface between the organic resin layer and the bottom layer during deformation. In view of the above-mentioned problems of the prior art, the present applicant has In the proposal of Japanese Patent Application No. 2 008 -3 3 53 87, excellent corrosion resistance, heat discoloration resistance and blackening resistance are obtained, and excellent adhesion to the organic resin layer formed on the upper layer of the surface treatment film is obtained, in particular, When the steel sheet of the organic resin layer having a thickness of 1 00 // m or more is deformed, a surface-treating composition having excellent adhesion can be obtained. The surface treatment composition is at least one selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound of -8-5 201138994, a low condensate of titanium hydroxide or titanium hydroxide. The titanium-containing aqueous solution obtained by mixing the titanium compound with hydrogen peroxide water, and a carbonic acid pin compound, an organic phosphoric acid compound, a metal phosphate, and cerium oxide. However, it has been found by the inventors of the present invention that the film formed by the surface treatment composition has a brittle nature. Therefore, when a surface-treated steel sheet is produced by a real machine, it is necessary to form a film and then contact the metal roll. The film is injured and it is easy to reduce the problem of corrosion resistance. Further, in a high-temperature and humid environment, there is a problem that the adhesion to the above-mentioned thick organic resin layer cannot be sufficiently ensured. In order to solve the above problems, it is an object of the present invention to provide excellent corrosion resistance, heat discoloration resistance, and blackening resistance which are excellent in corrosion resistance, heat discoloration resistance, and blackening resistance, and excellent contact resistance when contacting a metal roller after forming a surface treatment film. And excellent adhesion to the organic resin layer formed on the surface of the surface treatment film, in particular, forming a thick organic resin layer having a thickness of 100 μm or more, and excellent adhesion even when the processing is excessively performed. The surface treatment composition and the surface-treated steel sheet having excellent adhesion to the thick organic resin layer can be obtained under the harsh environment of a high-temperature wet environment. Further, another object of the present invention is to provide an organic resin-coated steel sheet using the surface-treated steel sheet. [Means for Solving the Problem] The inventors of the present invention have reviewed the composition of the film to solve the above-mentioned problems, and as a result, found that the surface of the metal material (preferably a galvanized steel sheet or an aluminum-plated steel sheet) is used on the surface -9 - 201138994, and the use is specific to the use. The aqueous solution of titanium is compounded with a specific proportion of a carbonic acid pin compound, an organic phosphoric acid compound, a metal phosphate, a cerium oxide, a water-soluble organic resin and/or a water-dispersible organic resin, and a surface treatment composition of a decane coupling agent to form a surface-treated film. When the corrosion resistance, the heat discoloration resistance, and the blackening resistance are obtained, the abrasion resistance when the metal film is contacted with the surface treatment film, and the organic resin layer is formed on the surface of the surface treatment film, in particular, lOO^ After the thickness of the organic resin layer having a thickness of m or more, excellent adhesion can be obtained even when the processing is excessively performed, and excellent adhesion to the thick organic resin layer can be obtained even in a severe environment such as a high-temperature humid environment. Sex. Based on this finding, the gist of the present invention is as follows. [1] A surface treatment composition comprising at least one selected from the group consisting of a low condensate of a hydrolyzable titanium compound, a hydrolyzable titanium compound, a titanium hydroxide, and a titanium hydroxide. The solid content of the titanium-containing aqueous liquid (A) obtained by mixing the titanium compound with hydrogen peroxide water is 100 parts by mass, 10 to 300 parts by mass of the carbonic acid cone compound (B), and 50 to 200 parts by mass organic. The phosphoric acid compound (C), which contains 2 to 20 mass% of the metal phosphate (D) in the total solid content of the surface treatment composition, is 20 to 4 in the total solid content of the surface treatment composition. 〇mass% of cerium oxide, the proportion of the total solid content of the surface treatment composition is 2 to 10 mass% of the water-soluble organic resin and/or the water-dispersible organic resin (F), and the surface treatment composition The proportion of the solid fraction is 〇.5 to 20 mass% of the sand compound coupling agent (G).

[2] The surface treatment composition according to [1] above, wherein the cerium oxide (E -10- 5 201138994) is a gas phase cerium oxide produced by a dry method. [3] The surface treatment composition according to the above [2], wherein the gas phase cerium oxide has a bulk specific gravity of 40 g/L or less. [4] The surface treatment composition according to any one of the above [1] to [3] wherein the decane coupling agent (G) has a glycidyl group. [5] The surface treatment composition according to any one of the above [1] to [4], which has a pH of from 7 to 12. [6] A surface-treated steel sheet characterized by coating the surface treatment composition of any one of the above [1] to [5] on the surface of a galvanized steel sheet or an aluminum-plated steel sheet to have The surface-treated film having a film deposition amount after drying of from 0.3 to 0.5 g/m 2 was used. [7] An organic resin-coated steel sheet characterized in that the surface-treated coating of the surface-treated steel sheet according to the above [6] has an organic resin layer. [Effect of the Invention] The surface treatment film formed by the surface treatment composition of the present invention has a high barrier property by being composed of a specific inorganic component, and therefore has excellent corrosion resistance and blackening resistance comparable to a chromate film. Moreover, it has excellent heat-resistant discoloration which is not easily colored or discolored by heating. Further, when the surface treatment film is formed, contact with a metal roller or the like can provide excellent scratch resistance, and the surface of the surface treatment film can form an organic resin layer, particularly a thick organic resin layer having a thickness of 100 or more, even if it is too strict. Excellent adhesion is also obtained during processing, and excellent adhesion to the thick organic resin layer can be obtained even in a severe environment such as a high-temperature wet environment. -11 - 201138994 Further, the surface-treated steel sheet and the organic resin-coated steel sheet of the present invention have excellent corrosion resistance, blackening resistance, heat discoloration resistance, and scratch resistance, and are in close contact with the organic resin layer, and particularly have l〇 The adhesion of the thick organic resin layer having a thickness of m#m or more and excellent adhesion in a severe environment like a high-temperature wet environment. BEST MODE FOR CARRYING OUT THE INVENTION The surface treatment composition of the present invention contains an aqueous liquid (A) containing titanium, a zirconium carbonate compound (B), an organic phosphoric acid compound (C), a metal phosphate (D), and oxidation.矽 (E), a water-soluble organic resin and/or a water-dispersible organic resin (F), and a decane coupling agent (G). The surface treatment composition does not contain hexavalent chromium (except for the unclean 6-valent chromium). The titanium-containing aqueous liquid (A) is a titanium compound selected from at least one selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide, and a low condensate of titanium hydroxide. The aqueous solution containing titanium obtained by mixing hydrogen peroxide water. The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and is formed by reacting with water such as water or steam to form titanium hydroxide. Further, the hydrolyzable titanium compound may be one in which all of the hydrolyzable groups are bonded to the titanium, or the hydrolyzable group bonded to the base of the titanium. The hydrolyzable group may be one which is formed by reacting with water to form titanium hydroxide as described above, and is not particularly limited, for example, a lower alkoxy group or a salt forming a salt with titanium (for example, a halogen atom such as chlorine or a hydrogen atom, a sulfate ion, or the like). )Wait. -12- 8 201138994 The hydrolyzable titanium compound containing a hydrolyzable group which is a lower alkoxy group is particularly preferably 'general formula Ti(OR) 4 (wherein R is the same or different carbon number of 1 to 5) Titanium tetraalkoxide represented by the group). The alkyl group having 1 to 5 carbon atoms is, for example, methyl, ethyl, η-propyl, iso-propyl, η-butyl, iso-butyl, sec-butyl, tert-butyl or the like. The water-decomposable group to be contained is a hydrolyzable titanium compound which forms a salt with titanium, such as titanium chloride or titanium sulfate. Further, the low condensate of the hydrolyzable titanium compound is a low condensate between the hydrolyzable titanium compounds. The low condensate may be one in which all of the groups bonded to the titanium are hydrolyzable groups, or the base group bonded to the titanium is a hydrolyzable group. The hydrolyzable group is a hydrolyzable titanium compound (for example, titanium chloride or titanium sulfate) which forms a salt with titanium, and the orthotitanic acid obtained by reacting an aqueous solution of the hydrolyzable titanium compound with an alkali solution such as ammonia or caustic soda ( Titanium hydroxide gel) can also be used as a low condensate. As the low condensate of the hydrolyzable titanium compound and the low condensate of the titanium hydroxide, a compound having a degree of condensation of 2 to 30 can be used, and a compound having a degree of condensation of 2 to 10 is particularly preferably used. When the degree of condensation is 30 or less, a stable aqueous solution containing titanium can be obtained by mixing with hydrogen peroxide. The hydrolyzable titanium compound, the low condensate of the hydrolyzable titanium compound, the low condensate of the titanium hydroxide or the titanium hydroxide may be used alone or in combination of two or more kinds thereof, and the hydrolyzability represented by the above general formula. Titanium compound titanium tetraalkoxide. The reason is that the alcohol formed by the tetraalkoxy titanium during the hydrolysis can be volatilized during the process of drying the surface-treated composition, so that the film properties such as resistance to corrosion resistance of -13 to 201138994 are not affected, and in particular, an excellent film can be obtained. The aqueous liquid (A) containing titanium may be an aqueous liquid containing titanium obtained by mixing the above hydrogenated hydrogen water, and may be used first. The li body is, for example, the following. (i) a titanium hydroxide-containing gel or a sol-added titanium oxide ion hydrogen peroxide complex or titanic acid (peroxide titanium liquid (refer to Japanese Laid-Open Patent Publication No. 63-3 54 119 (ii) The liquid for forming a film is formed by a solution of titanium chloride or titanium sulfate and an alkali titanium hydroxide gel by hydrogen peroxide water (refer to Japanese Patent Laid-Open Publication No. Hei 9-7141 No. 8-10-675 In the production of the titanium dioxide forming liquid, a titanium hydroxide gel called orthotitanic acid is precipitated by an aqueous solution of titanium chloride or titanium sulfate having a base or caustic reaction. The titanium hydroxide gel is separated by an analytical method, and the water is sufficiently washed with water to decompose and remove excess cerium peroxide. The above-mentioned ortho-titanic acid obtained by yellow dialysis is obtained by using a ruthenium bond to form a gel state of macromolecularization. It is used directly as a liquid. The addition of hydrogen peroxide to the gel causes the state of the ruthenium to become a sol state in which the peroxotitanate ion is dissolved or the polymer molecule, and the excess hydrogen peroxide water can be used as the inorganic film. Forming a titanium-containing aqueous liquid using the sol in addition to titanium atoms Containing only oxygen atoms and gas energy. The hydrate of the compound and the substance before peroxidation without special hydrogen peroxide water. The titanium dioxide prepared by the solution of the water soluble solution 224220 has an alkali solution such as sodium salt formed with titanium. Use a hydrogen peroxide to add a viscous liquid. The polymerization between hydrogen or hydrogen is a titanium-containing water component, and the peroxide chain is interrupted to be low-decomposed into water and oxygen argon atoms. Therefore, when it is changed to titanium oxide by drying or baking, only water and oxygen are generated. Therefore, it is not necessary to remove the carbon component and the halogen component which are necessary for thermal decomposition of a sol-gel method or a sulfate, etc., and a titanium oxide film having a high density can be formed even at a low temperature. (i Π) adding an aqueous solution of hydrogen peroxide to an aqueous solution of an inorganic titanium compound of titanium chloride or titanium sulfate to form a perovskite hydrate, and adding a basic substance, the resulting solution is placed to be heated to form a precipitate of the titanium perotate hydrate polymer. And a solution for forming a titanate which is obtained by the action of a hydrogen peroxide, and a solution for forming a titanate, which is obtained by the action of a hydrogen peroxide, and a solution for forming a titanate, which is obtained by the use of a solution of the titanium-containing raw material solution (refer to Japanese Laid-Open Patent Publication No. 2000-24763, No. 2000-247639) . The titanium-containing aqueous liquid (A) in which the titanium compound to be used is a hydrolyzable titanium compound and/or its low condensate (hereinafter referred to as "hydrolyzable titanium compound a" for convenience of explanation) can be made of a hydrolyzable titanium compound a is obtained by reacting hydrogen peroxide with water at a reaction temperature of 1 to 70 ° C for 10 minutes to 20 hours. The titanium-containing aqueous liquid (A) of the hydrolyzable titanium compound a is presumed to be a reaction between the hydrolyzable titanium compound a and hydrogen peroxide water, and the hydrolyzable titanium compound a is hydrolyzed with water to form a hydroxyl group-containing titanium compound, followed by Hydrogen peroxide is located in the titanium compound containing a hydroxyl group, so that the hydrolysis reaction and the coordination of hydrogen peroxide are generated at the same time, so that the stability at room temperature is extremely high, and long-term storage can be formed. Chelating solution. The titanium hydroxide gel used in the previous method is partially ternary by the Ti-0-Ti bond, so the composition and stability are substantially different from the titanium containing the reaction of the gel with hydrogen peroxide water. Aqueous liquid (A). Further, when the aqueous solution (A) containing titanium of the hydrolyzable titanium compound a is used for heat treatment at 80 ° C or higher or autoclave treatment, a titanium oxide dispersion containing ultrafine particles of crystallized oxygen-15-201138994 titanium can be obtained. . The above-mentioned heat treatment or autoclave treatment is carried out at 80 ° C or higher to sufficiently crystallize the titanium oxide. The titanium oxide ultrafine particles of the thus-produced titanium oxide dispersion preferably have an average particle diameter of 10 nm or less, more preferably 1 to 6 nm. When the average particle diameter of the titanium oxide ultrafine particles is 1 nm or less, the film forming property is excellent (when the film is formed by drying after coating, the film thickness is not more than #m and no crack occurs). Further, when the average particle diameter of the titanium oxide ultrafine particles is 1 nm or more, the surface treatment composition can be maintained in a state in which the viscosity is not high. The titanium oxide dispersion has a translucent appearance. The titanium oxide dispersion liquid can also be applied to a surface of a gold-plated steel sheet by using a surface treatment composition (Η) containing an aqueous liquid (A) containing titanium using a hydrolyzable titanium compound a as an aqueous liquid (A) containing titanium. After drying (for example, drying at a low temperature), a dense titanium oxide-containing film (surface treatment film) having excellent adhesion thereto can be formed. The heating temperature of the steel sheet after coating the surface treatment composition (Η) is, for example, 200 ° C or less, particularly preferably 150 ° C or less, and by heating and drying at this temperature, an amorphous form containing a plurality of hydroxyl groups can be formed. A film containing titanium oxide. Further, when the titanium oxide dispersion obtained by the heat treatment at 80 ° C or higher or the autoclave treatment is used as the aqueous liquid (A ) containing titanium, the surface-treated composition (Η) can be coated to form crystallinity. The coating of titanium is suitable as a coating agent for materials without heat treatment. Further, an aqueous liquid (A) containing titanium may be used, and an aqueous liquid (A 1 ) containing titanium -16- 5 201138994 obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide in a titanium oxide sol. The titanium oxide sol is a sol obtained by dispersing water in an amorphous titanium dioxide fine particle or/and anatase-based titanium oxide fine particle (if necessary, an aqueous organic solvent such as an alcohol-based or alcohol ether-based solvent). The titanium oxide sol can be obtained by hydrolyzing an organic titanium compound such as (i) titanium oxide solution obtained by hydrolysis of a titanium-containing solution such as titanium sulfate or titanyl sulfate, or (ii) an alkali titanium compound such as titanium alkoxide. An amorphous titanium dioxide sol obtained by dispersing a titanium oxide agglomerate such as a titanium oxide aggregate or (iii) a titanium halide solution such as titanium tetrachloride or a titanium oxide agglomerate obtained by dispersing the titanium oxide aggregate in water, or the above titanium oxide agglomerate is calcined After the anatase type titanium fine particles are obtained, the substance is dispersed in a sol obtained by water. When the amorphous titanium dioxide is calcined, the amorphous titanium oxide can be converted into anatase type titanium dioxide by baking at a temperature higher than the crystallization temperature of the anatase, for example, at a temperature of 400 ° C to 50 (TC or higher). An aqueous sol of titanium dioxide, for example, TKS - 2 0 1 (trade name, manufactured by Tieka Co., anatase crystal form, average particle size 6 nm), ΤΑ-1 5 (trade name, manufactured by Nissan Chemical Co., Ltd., anatase type Crystalline), STS-1 1 (trade name, manufactured by Ishihara Sangyo Co., Ltd., anatase crystal form), etc. In the aqueous solution containing titanium (Α1), the above titanium oxide sol X and titanium hydrogen peroxide reactant y ( The mass ratio χ/y of the reaction product of the hydrolyzable titanium compound a and hydrogen peroxide water may be from 1/99 to 99/1, preferably from about 10/90 to 90/10. The mass ratio x/y is 1. When it is at least 99, the effect of sufficiently adding a titanium oxide sol can be obtained from the viewpoints of stability and photoreactivity, and it is preferable that an excellent film forming property is obtained at 99/1 or less. 17-201138994 Aqueous liquid containing titanium ( A 1 ) can be obtained by the presence of a hydrolyzable titanium compound a under titanium oxide sol and peroxidation The water is obtained by reacting at a reaction temperature of 1 to 7 ° C for 1 to 20 minutes. The form and characteristics of the aqueous solution containing titanium (A 1 ) and the aqueous solution containing titanium containing the hydrolyzable titanium compound a (A) In the same manner, in particular, when a titanium oxide sol is used, it is possible to suppress partial condensation reaction during the synthesis and to increase the viscosity. The reason for this is that the surface of the titanium oxide sol adsorbs a condensation reaction product, thereby suppressing macromolecularization in a solution state. When the aqueous solution (A 1 ) containing titanium is treated by heat treatment at 80 ° C or higher, or autoclave, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide can be obtained. The temperature conditions and crystallization of the titanium oxide dispersion are produced. The particle diameter of the titanium oxide ultrafine particles, the appearance of the dispersion liquid, and the like are also the same as those of the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a. The titanium oxide dispersion liquid can also be used as an aqueous liquid containing titanium (A1). And 'the same as the above-mentioned titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a', the surface treatment composition (Η) containing the titanium-containing aqueous liquid (a 1 ) is applied to the plated steel sheet On top, drying (for example, drying at a low temperature) can form a dense titanium oxide-containing film (surface-treated film) which has excellent adhesion to itself. The heating temperature of the steel sheet after coating the surface treatment composition (Η) is, for example, 200 eC or less, particularly preferably 150 Å: The film containing titanium oxide containing an anatase type having a plurality of hydroxyl groups can be formed by heating and drying at this temperature. Hydrolyzable property is used in the aqueous liquid (A) containing titanium as described above. The titanium compound a contains an aqueous liquid (A) and an aqueous liquid containing titanium (ai -18- 5 201138994), and has excellent storage stability, corrosion resistance and the like. Therefore, the present invention is particularly preferably used. The titanium compound having at least one selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium oxyhydroxide, and a low condensate of titanium hydroxide, is preferably added in a ratio of hydrogen peroxide water. It is 0.1 to 100 parts by mass, more preferably 1 to 20 parts by mass, based on 10 parts by mass of the titanium compound in terms of hydrogen peroxide. When the ratio of addition of hydrogen peroxide is 0.1 parts by mass or more in terms of hydrogen peroxide, it can be sufficiently chelated to form a white turbid precipitate, and no unreacted hydrogen peroxide remains in 100 parts by weight or less, during storage. It is better not to release active oxygen. The hydrogen peroxide concentration of the hydrogen peroxide water is not particularly limited, but it is easy to handle, and the solid content of the coating liquid for the coating workability is preferably from 3 to 30 m as s %. The aqueous liquid (A) containing titanium may be added to disperse other solvates and pigments as necessary. The additive may be one or more selected from the group consisting of commercially available titanium oxide sol and titanium oxide powder, mica, talc, xenon, and clay. The surface treatment composition contains the content of the aqueous liquid (A) of titanium, and the solid content is preferably from 1 to 10 g/L, more preferably from 5 to 50 g/L, from the viewpoint of stability of the treatment liquid and the like. The surface treatment composition of the present invention is characterized in that the aqueous solution containing titanium (A) is added with a zirconium carbonate compound (B) to further improve the corrosion resistance and even the organic resin coating layer (the organic resin layer formed by lamination or coating) The anti-rust can be used to lift the corrosion resistance of the coated organic resin layer. Further, the organic phosphoric acid compound (C) can improve the reactivity with the steel sheet to improve the corrosion resistance -19-201138994, and obtain the storage stability of the good surface treatment composition. Further, the addition of the metal phosphate (D) and the cerium oxide (E) can enhance the organic resin layer formed by the upper layer, particularly a thick organic resin layer having a thickness of more than 10 μm (for example, an organic resin formed by lamination) The adhesion of the layer to the deformation of the steel sheet and the addition of the decane coupling agent (G) can also improve the adhesion under the harsh environment like the high temperature and humidity environment (adhesion to the above-mentioned thick organic resin layer) . Further, the addition of the water-soluble organic resin and/or the water-dispersible organic resin (F) can improve the scratch resistance of the surface-treated film, and the excellent corrosion resistance can be found even when the surface-treated film is formed and contacted with the roll. The compound (B) is preferably an ammonium carbonate or an oxycarbonate or the like, and the corrosion resistance can be improved by using one or more of these compounds. The addition S of the zirconium carbonate compound (B) is 10 to 300 parts by mass, preferably 50 to 100 parts by mass, based on 100 parts by mass of the solid content of the aqueous liquid (a) containing titanium. When the amount of the cerium of the zirconium carbonate compound (B) is less than 1 part by mass based on 100 parts by mass of the solid content of the aqueous liquid (A) containing titanium, the effect of improving the corrosion resistance is reduced, and when it exceeds 300 parts by mass, the tendency is increased. The adhesion is deteriorated. The organic phosphoric acid compound (C) is preferably, for example, 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid '1-hydroxypropane-1,1-diphosphonic acid, etc. a hydroxyl group-containing organic phosphorous acid; a 2-hydroxyphosphonaki acetic acid; a 2-phosphonium butane-1,2,4-tricarboxylic acid-containing carboxyl group-containing organic phosphorous acid, and the like; One or two or more of these may be used. The organic phosphoric acid compound (C) has an effect of improving corrosion resistance and storage stability of an aqueous liquid containing titanium (Α), wherein 1-hydroxyethyl

-20- (D 201138994 alkane-ι, ι-phosphonic acid has a particularly large effect, so it is particularly preferable to use it. The amount of the organic phosphoric acid compound (C) added is 100% relative to the aqueous solution containing titanium (A). The amount of the component is preferably from 50 to 200 parts by mass, and is particularly preferably from 70 to 150 parts by mass in terms of water resistance, etc. The amount of the organic phosphoric acid compound (C) added is not more than 100 parts by mass relative to the solid content of the aqueous liquid (A) containing titanium. When the amount is 50 parts by mass, the storage stability of the surface treatment composition is deteriorated, and the corrosion resistance is also lowered. Further, when it exceeds 200 parts by mass, the water-resistant adhesion is deteriorated. Metal phosphate (D) and cerium oxide ( E) is an addition of an organic resin layer formed on the upper layer by lamination or the like, in particular, a thick organic resin layer having a thickness of 100 μm or more. The ruthenium oxide (E) is reacted in a liquid phase. The liquid phase cerium oxide produced by the method, the amorphous cerium oxide such as the gas phase cerium oxide produced by the dry method, one or more of these may be used. The specific liquid phase cerium oxide may be used in Nissan. Snowy (registered trademark) 化学, N, manufactured by the chemical industry (shares) 20, 30, 40, C, S, gas phase cerium oxide can be used in Japan Ai Luoji (shares) AERO SIL (Dengyan trademark) 130, 200, 200V, 200CF, 300, 300CF, etc. From the viewpoint of the adhesion of the resin layer, the gas phase cerium oxide is excellent, and good performance can be obtained. Further, the type of the metal phosphate (D) is not particularly limited, and among them, an aluminum salt, a magnesium salt, and a manganese salt are effective, particularly aluminum. The salt has the advantage of lowering the solubility of the phosphate and the effect of the continuous wet environment. The metal phosphate may be used alone or in combination of two or more. Further, the metal phosphate (D) is preferably a phosphoric acid which can be present in an aqueous solution. The metal cation component has previously been sold as an aqueous solution of the city of Phosphate-rich rock - 201138994. It is preferred to add the metal phosphate (D) and cerium oxide (E) to the surface treatment composition, premixing the metal phosphate (D) with Cerium oxide (E) is added in the form of the mixture. When added in a premixed state, better adhesion and resistance can be obtained when compared with each other. Touch. Although the reason is not clear, it is estimated that the effect of using a phosphoric acid component can increase the cohesive force of the film obtained by the surface treatment composition. Further, mixing by this method can enhance the storage stability of the surface treatment composition. Further, when the cerium oxide (E) is produced by a dry method of cerium oxide (gas phase cerium oxide), the gas phase cerium oxide can be added to the metal phosphate aqueous solution to be dispersed in a metal phosphate aqueous solution by strong stirring. The cerium oxide dispersion obtained from the gas phase cerium oxide is mixed with other components. At the same time, the surface treatment composition can be prepared by vigorously stirring the gas phase cerium oxide and the metal phosphate aqueous solution with other added components and water. Further, when the gas phase cerium oxide is dispersed in the surface treatment composition by a sand mixer or the like, aggregation occurs in one week to several weeks to form a precipitate. Although the detailed mechanism is not clear, it is judged that the coagulation is less likely to occur when the gas phase cerium oxide having a lower specific gravity is used, and the storage stability (solution stability) can be effectively improved. Specifically, it is preferred to use a gas phase cerium oxide having a bulk specific gravity of 40 g/L or less. The volume specific gravity of the gas phase cerium oxide can be adjusted by controlling the degassing conditions after the dry process, whereby a gas phase sulphur dioxide having a small specific gravity can be obtained. The reason for adding the adhesion between the metal phosphate (D) and the cerium oxide (E) to the organic resin layer is that the addition of cerium oxide to the metal phosphate (# -22-201138994 salt can change the surface polarity of the surface treated film). The effect of the adhesion to the resin layer and the adhesive layer is improved when the organic resin layer is directly applied to the upper layer and the adhesive is adhered to the organic resin film. However, when the polarity is too high, it is easy to inhale moisture and swell in a humid environment, so it is disadvantageous. Relatively adding non-polar phosphoric acid (metal phosphate) can make the adhesion and the stability during wetting stand up to a moderate degree. In addition, when the cerium oxide is secondarily agglomerated, surface unevenness at the submicron order level is formed, and the surface unevenness is formed to increase the effective area of the adhesion interface, so that it is effective to obtain an effective effect with respect to the adhesion. Although the influence on the surface properties cannot be fully understood, it is inferred that the secondary coagulation of yttrium oxide affects the surface properties. The addition of metal phosphate (D) to the surface The ratio of the total solid content of the treatment composition is 2 to 20 mass%, preferably 2 to 8 mass%, and the ratio of the amount of cerium oxide (E) added to the total solid content of the surface treatment composition is 20 to 40 mass%. When the ratio of the addition amount of the metal phosphate (D) to the total solid content of the surface treatment composition is less than 2 maSS%, the effect will not be exhibited, and the adhesion to the steel sheet will be insufficient. Further, when the excess amount exceeds 20 maSS% In addition, when the amount of the metal phosphate (D) is more than 8 maSS%, the liquid stability during storage is lowered, and the stability of the metal phosphate (D) is less than 8 maSS%. When the ratio of the addition amount to the total solid content of the surface treatment composition is less than 20 masS%, the unevenness of the submicron size formed will be insufficient, and the organic resin layer of the upper layer will not be sufficiently adhered when the processing is excessively performed - 23- 201138994. In addition, when it exceeds 40 mass %, the good adhesion will cause the film to be damaged by contact with the surface of the film due to the embrittlement of the surface treatment film. Therefore, it is not necessary to say that the corrosion resistance is good, and even the organic resin is coated. After the injury Corrosion at the starting point. The water-soluble organic resin and/or water-dispersible organic resin (F) is an organic resin which can be dissolved or dispersed in water, and the method of water-soluble or water-dispersing the organic resin in water is applied to a previously known method. Specifically, an organic resin can be used, and a functional group (for example, a hydroxyl group, a polyepoxyalkyl group, a carboxyl group, an amine (imine) group, a sulfide group, a phosphino group, etc.) which can be separately water-soluble or water-dispersed can be used. And if necessary, part or all of the functional groups may be an amine resin such as an ethanol resin or a triethylamine such as an acidic resin (a carboxyl group-containing resin); chlorine water; lithium hydroxide, sodium hydroxide, or hydroxide A substance neutralized with an alkali metal oxide such as potassium, or a fatty acid such as acetic acid or lactic acid of a basic resin (an amine group-containing resin) or the like, and a neutralized product of a mineral acid such as phosphoric acid. Water-soluble or water-dispersible organic resin such as epoxy resin, phenol resin, acrylic resin, urethane resin, olefin-carboxylic acid resin, nylon resin, resin having polyalkylene oxide chain , polyvinyl alcohol, polyglycerin, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and the like. One type or two or more types of the above organic resins can be used. Among these, it is particularly preferable in terms of storage stability of the surface treatment composition, and at least one selected from the group consisting of water-soluble or water-dispersible acrylic resin, urethane resin, and epoxy resin. The organic resin, in addition, is particularly preferable in terms of the balance between the storage stability of the surface treatment composition and the film coating property, and the water-soluble or water-dispersible acrylic resin or the amine group A-24- 5 201138994. Resin is the main component. The water-soluble or water-dispersible acrylic resin can be synthesized by solution polymerization by, for example, an emulsion polymerization method, a suspension polymerization method, or a hydrophilic substance, and if necessary, it can be obtained by neutralization, a method, or the like. The polymer having a hydrophilic group may be, for example, a hydrophilic saturated monomer such as a carboxyl group, an amine group, a hydroxyl group or a polyepoxyalkyl group, and if necessary, another unsaturated monomer may be polymerized to be water-soluble. Or the water-dispersible acrylic resin is obtained by copolymerizing styrene in terms of corrosion resistance, etc., and the amount of the wholly unsaturated monomer is preferably from 10 to 60 mass%, particularly preferably from 15 to 50 mass%. The Tg (glass transition point) is preferably from 30 to 80 ° C, particularly preferably from 35 to 70 ° C, in terms of toughness and the like. The above carboxyl group-containing unsaturated monomer is, for example, acrylic acid, methyl maleic acid, maleic anhydride, crotonic acid, itaconic acid or the like. The above nitrogen-containing unsaturated N,N-dimethylaminoethyl (meth) acrylate, n, N-diethyl (meth) acrylate, Nt-butyl group containing an amino group-containing unsaturated monomer or the like Aminoalkyl (meth) acrylate such as formate or the like; acrylamide amide, N-methyl (meth) acrylamide, N-ethyl (formamide, N-methylol (meth) acrylamide, N-methoxymethyl) acrylamide, N-butoxymethyl (meth) acrylamide, benzyl (meth) acrylamide, N, N-dimethylaminopropyl (formamide, N,N-dimethylaminoethyl (meth) acrylamide, etc., the polymerization method based on the polymerization of the base has no basis. Polymerization of a strong acryl-based monomer such as a copolymerized film such as ethylamino) propylene or methylpropyl) propylene (methyl N,N-dimethyl) propylene. 25- 201138994 Anthracene; an aromatic nitrogen-containing monomer such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone or 4-vinylpyridine; allylamine or the like. The above hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth) acrylate vinegar, propyl propyl (meth) propylene oleate, 2, 3-dibutyl butyl (methyl) a polyvalent alcohol such as a propyl acrylate, a 4-butylidene (meth) acrylate, a polyethylene glycol mono (meth) acrylate, a polypropylene glycol mono(methyl) propylene vinegar, and the like. a monoesterified product of a acrylic acid; a compound obtained by ring-opening polymerization of ε-butyrolactone with a monoester of a polyvalent alcohol and a silicic acid or methyl propyl acid. Other unsaturated monomers such as 'methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isopropyl (meth) acrylate, η-butyl Base (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl acrylate ' η - octyl (meth) acrylate, lauryl Alkyl groups having 1 to 24 carbon atoms such as (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl hydrazine (meth) acrylate ( Methyl) acrylate; vinyl acetate, and the like. The above-exemplified unsaturated monomers may be used alone or in combination of two or more. "(Meth)acrylate" as used in this application means "acrylate or methacrylate". The urethane-based resin is preferably a polyurethane formed from a polyol such as a polyester polyol or a polyether polyol and a diisocyanate, and if necessary, a diol, a diamine or the like is present. Under the chain extender of a low molecular weight compound of two or more active hydrogens, the stability obtained by chain elongation can be dispersed or dissolved in the water, and the previously known substances can be widely used (for example, refer to Japanese Patent Publication No. 42-241 92). Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Sho 53-29 No. 75 (75). The method of dispersing or dissolving a polyurethane in water is, for example, the following method. (1) A method in which an ionic group such as a hydroxyl group, an amine group or a carboxyl group is introduced into a branch or a terminal of a polyurethane polymer to impart hydrophilicity, and is dispersed or dissolved in water by self-emulsification. (2) using an emulsifier or a mechanical shearing force, the end of the polyurethane polymer obtained by the reaction or the block agent of hydrazine, alcohol, phenol, thiol, amine, bisulfite, etc. A method in which a polyurethane polymer obtained from an isocyanate group block is forcibly dispersed in water. Further, a method in which a urethane polymer having a terminal isocyanate group and water, an emulsifier, and a chain extender are mixed and dispersed by a mechanical shearing force is used. (3) The polyol of the polyurethane main raw material is a method of dispersing or dissolving in water in the form of a water-soluble polyurethane using a polyethylene glycol-like water-soluble polyol. The polyurethane resin may be used in combination with a method different from the above dispersion or dissolution methods. A diisocyanate such as an aromatic, alicyclic or aliphatic diisocyanate which can be used for the synthesis of the above polyurethane resin, specifically, for example, hexamethylene diisocyanate, tetramethylammonium diisocyanate, 3,3 '-Dimethoxy-27- 201138994 ke - 4,4'-stretched phenyl diisocyanate, p-xylylene diisocyanate, m-extended xylylene diisocyanate, 1,3_(two Isoflavone methyl) cyclohexanone, 1,4-(diisocyanatomethyl)cyclohexanone, 4,4,-diisocyanatocyclohexanone, 4,4'-methyl Bis(cyclohexyl isocyanate), isophorone diisocyanate, 2,4-streptyl diisocyanate, 2,6-exotolyl diisodecanoate, P-phenylene diisocyanate, diphenyl Methane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-linked phenyl diisocyanate, 4,4'-stretched benzene Diyl isophthalate and the like. Among them, particularly preferred are 2,4-xyl-tolyl diisocyanate, 2,6-methyl-tolyl diisophthalate, hexamethylene diisocyanate, and isophorone diisocyanate. Commercial products such as Hydralan (registered trademark) HW-3 3 0, HW-3 40, HW-3 5 0 (all are trade names, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) ), Superbend (registered trademark) 1〇〇, 〗 50, E-2500, F-3438D (all trade names, manufactured by Daiichi Kogyo Co., Ltd.), etc. 前述 The epoxy resin is obtained by applying an epoxy resin to an amine. A cationic epoxy resin; a modified epoxy resin modified with an acrylic acid modified with a urethane or the like. a cationic epoxy resin such as an adduct of an epoxy compound with a primary mono- or polyamine, a 2-stage mono- or polyamine, a 1,2-stage mixed polyamine (for example, refer to US Pat. No. 3,984,299); an epoxy compound An adduct of a ketone-imidized grade 2 mono- or polyamine having a grade 1 amine group (for example, refer to the specification of U.S. Patent No. 40 1 743 8); an epoxy compound and a ketone imidized grade 1 An etherification reaction product of an amino group-containing hydroxy compound (for example, see JP-A-59-4301-3). 5 -28 - 201138994 The epoxy resin is preferably a number average molecular weight of 400 to 4,000, particularly preferably 800 to 2000' epoxy equivalent of 19 Å to 2 Å, and particularly preferably 400 to 1,000. Such an epoxy resin can be obtained, for example, by reacting a polyphenol compound with epichlorohydrin, such as bis(4-hydroxyphenyl)-2,2-propane or 4,4-dihydroxybenzophenone. Ketone, bis(4-hydroxyphenyl)-i,i-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl)-2 , 2-propane, bis(2-hydroxynaphthyl)methane, anthracene, 5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)-1,1,2 , 2-ethane, 4,4-dihydroxydiphenylphosphonium, phenol novolac, cresol novolac, and the like. The water-soluble organic resin and/or the water-dispersible organic resin (F) is added in an amount of from 2 to 10% by mass in the total solid content of the surface-treated composition. The amount of the water-soluble organic resin and/or the water-dispersible organic resin (F) is such that the ratio of the total solid content of the surface treatment composition is less than 2 mass%, the brittleness of the surface treatment film cannot be improved, and the surface treatment film is formed. Since the rear contact roller or the like brings the flaw into the film, it is not necessary to mention the bare corrosion resistance, and the organic resin is coated and the corrosion is started from the wound portion. Further, when it exceeds 10 m a s s %, heat discoloration resistance and adhesion after processing are lowered. Decane coupling agent (G) such as vinyl methoxy decane, vinyl ethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane ' θ - ( 3, 4 ring Oxycyclohexyl)ethyltrimethoxydecane, r-glycidoxypropyltrimethoxydecane, r-glycidoxypropylmethyldiethoxydecane, r-glycidoxypropane Triethoxy decane, :(aminoethyl)r-aminopropylmethyldimethoxydecane, N-callo(aminoethyl)r-aminopropyltrimethoxydecane, N- /3 (Amino-29-201138994 ethyl) r-Aminopropyltriethoxydecane, r-Aminopropyltrimethoxydecane, r-Aminopropyltriethoxydecane, Methylpropene Oxypropyl propyl dimethoxy decane, r-methyl propylene methoxy propyl trimethoxy decane, methacryloxypropyl methyl diethoxy decane, r- methacryloxy propyl Triethoxy decane, r-mercaptopropylmethyldimethoxydecane, r-mercaptopropyltrimethoxydecane, P-styryltrimethoxydecane, r-propyleneoxypropyltrimethyl Oxydecane, N-phenyl-r-aminopropyl Trimethoxydecane, r-ureidopropyltriethoxydecane, 7-chloropropyltrimethoxydecane, bis(triethoxydecylpropyl)tetrasulfide, τ-isocyanatepropyltriethoxy Baseline, r-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, >1-(vinylbenzylamine)-; 3-aminoethyl- One or two or more kinds of these may be used, for example, r-aminopropyltrimethoxydecane. Among them, the viewpoint of improving corrosion resistance is preferably a glycidyl-based decane coupling agent, particularly preferably r-glycidoxypropyltrimethoxydecane, r-glycidoxypropylmethyldiethoxylate. Decane, r-glycidoxypropyltriethoxydecane. As a result of review by the present inventors, as a result of the surface-resistance of the film, it is impossible to obtain a composite effect of only metal phosphate (D) and cerium oxide (E) at the concentration of cerium oxide (E). In order to solve the above problems and improve the adhesion in a high temperature and humidity environment, it is judged that the addition of a decane coupling agent has an effect in order to solve the above problems in order to solve the above problems and to improve the adhesion under a high temperature and humidity environment. . However, when the organic resin and cerium oxide are used in the decane coupling agent, the liquid stability during storage tends to be lowered, and by suppressing the concentration of the metal phosphate (D), the problem does not occur, and when the processing is performed 5 - 30 - 201138994 The non-destructive adhesion is judged to improve the adhesion in a high-temperature wet environment (especially the adhesion to a thick organic resin layer). The amount of the decane coupling agent (G) is such that the ratio of the total solid content of the surface treatment composition is 0. 5 to 20 maSS%, preferably 0. 5 to lOmass %. The amount of the decane coupling agent (G) is such that the ratio of the total solid content of the surface treatment composition is less than 0. At 5 mass%, the adhesion under high temperature and humidity conditions cannot be sufficiently improved. - When it exceeds 20 mass%, the liquid stability is lowered and the cost is increased. The pH of the surface treatment composition is preferably adjusted to 7 to 12. When the pH is less than 7 and exceeds I2, the surface treatment composition aggregates and the film cannot be formed. The surface treatment composition of the present invention may contain, for example, an etchant such as resin fine particles or an inorganic phosphate compound, and a heavy metal compound, a tackifier, a surfactant, and a lubricity imparting agent (polyethylene) other than the components specified in the present invention. Wax, fluorine-based wax, carnauba wax, etc.), rust inhibitors, coloring pigments, extender pigments, rust-preventive pigments, dyes, and the like. Further, the surface treatment composition of the present invention may be diluted, for example, with a hydrophilic solvent such as methanol, ethanol 'isopropyl alcohol, a glycol solvent or a propylene glycol solvent. The surface treatment composition of the present invention preferably has a solid content of 2 to 10 mass% from the viewpoints of storage stability and stability at the time of coating. The surface treatment composition of the present invention can be used as a surface treatment agent for various metal materials. However, it is particularly preferably used as a surface treatment agent for a galvanized steel sheet or a shovel aluminum-based steel sheet which will be described later. -31 - 201138994 The surface-treated steel sheet of the present invention is formed by coating the surface treatment composition described above on the surface of a galvanized steel sheet or an aluminum-plated steel sheet, that is, an aqueous liquid solution containing titanium (A) and a carbonated product (B). After the surface treatment composition of the organic phosphoric acid compound (C), the metal phosphate (D), the cerium oxide (E), the water-soluble organic resin or/and the water-dispersible organic resin (F), and the decane coupling agent (G) And drying the formed surface treatment film having a certain amount of film adhesion. The surface treated film does not contain hexavalent chromium (except for hexavalent chromium which is unavoidable). Further, the aqueous liquid (A) containing titanium and the surface treatment composition may contain other additives listed above as necessary. The galvanized steel sheet of the substrate of the surface-treated steel sheet of the present invention may be, for example, a galvanized steel sheet, a Zn-Ni alloy plated steel plate, a Zn-Fe alloy plated steel plate (a plated steel plate, a plated alloyed molten zinc plate), or a Zn-Cr alloy plated. Steel plate, Zn-Mn alloy plate, Zn-Co alloy plate, Zn-Co-Cr alloy plate, Zn-Cr-Ni alloy plate, Zn-Cr-Fe alloy plate, or Zn-Al alloy plate For example, a Zn-5 mass% Al alloy steel plate, a Zn-55 mass% A1 alloy steel plate, a Zn-Mg alloy steel plate, a Zn-Al-Mg alloy steel plate, and a gold-plated film of such a gold-plated steel plate are dispersed in a metal oxide. A galvanized composite steel sheet such as a polymer (for example, a Zn-SiO 2 plated steel plate). Further, in the above gold plating, a two-layer or more multi-layered ore-gold steel plate of the same type or a different type may be used. Further, the aluminum-plated steel sheet of the substrate of the surface-treated steel sheet of the present invention may be used, ore-alloy steel sheet, Al-Si alloy-plated steel sheet or the like. Further, the gold-plated steel sheet may be such that the steel sheet surface is previously plated with a thin layer of Ni or the like, -32 - 5 201138994 The above various gold-plated objects are implemented on top of it. The gold plating method may be any method which can be carried out by electrolysis (electrolysis in an aqueous solution or electrolysis in a non-aqueous solvent), a melting method, or a gas phase method. Further, in order to form a surface-treated film on the surface of the gold-plated film, film defects and spots are not generated, and if necessary, alkali degreasing, solvent degreasing, and surface conditioning treatment (alkaline surface conditioning treatment or acid surface conditioning treatment) may be performed on the surface of the gold plating film in advance. ) and so on. In addition, in order to prevent blackening in the use environment (one of the gold plating surface oxidation phenomenon), it is possible to perform acidity using iron-containing metal ions (one or more of Ni ions, Co ions, and Fe ions) on the surface of the gold ore in advance, if necessary. Surface conditioning treatment of alkaline aqueous solution. When an galvanized steel sheet is used as the underlayer steel sheet, iron group metal ions (one or more of Ni ions, Co ions, and Fe ions) can be added to the plating bath to prevent blackening, and the gold plating film contains lmass ppm or more. Wait for the metal. The upper limit of the concentration of the iron group metal in the gold plating film at this time is not particularly limited. The surface treatment film formed by the surface treatment composition has an adhesion amount of 0. 03 to 0. 5g/m2. The amount of film adhesion is less than 0. When it is 03g/m2, the contact resistance will be deteriorated, and it will exceed 〇. When it is 5 g/m2, the film is easily broken, and the adhesion of the excessively processed after the organic resin is coated is lowered. In the case of producing the surface-treated steel sheet of the present invention, the above-mentioned surface treatment composition is used. That is, an aqueous liquid containing titanium (A) 'chromium carbonate compound (B), an organic phosphoric acid compound (C), a metal phosphate (D), cerium oxide (E), a water-soluble organic resin or/and a water-dispersible organic resin ( F) and 矽-33- 201138994 The surface treatment composition (treatment liquid) of the alkane coupling agent (G) is applied to the surface of a galvanized steel sheet or an aluminum-plated steel sheet, and is directly dried without washing with water. Further, the aqueous liquid (A) containing titanium and the surface treatment composition may contain other additives as listed above as necessary. The coating method of the surface treatment composition (treatment liquid) may be, for example, spray + roll extrusion, roll coating, or the like, and the drying method after coating may be, for example, a hot air method, a derivative heating method, or an electric furnace method. The drying temperature (steel plate temperature) of the surface treatment composition (treatment liquid) after application is preferably 60 to 200 °C. When the drying temperature is 60 °C or higher, it is possible to sufficiently form a film having excellent corrosion resistance and the like. Further, when the drying temperature is 2 〇〇 ° C or less, the film is not cracked by heat, so that the effect of sufficiently improving the corrosion resistance can be obtained. Further, the drying temperature is preferably 60 to 140 ° C, more preferably 60 to 100 ° C. Further, the organic resin-coated steel sheet according to the present invention is an article in which an organic resin layer is formed on the surface treatment film of the surface treated steel sheet. The method for forming the organic resin layer may be any method, for example, a method of applying a coating composition for re-drying or a method of laminating an organic resin film. Further, the surface-treated film of the present invention has excellent adhesion to a thick organic resin layer having a thickness of 100 < m or more, and therefore the organic resin-coated steel sheet of the present invention is particularly suitable for a thickness of 100 Ai m of the organic resin layer. Above. At this time, various additives including a non-chromium-based rust preventive additive, a solid lubricant, a coloring pigment, and the like can be added to the organic resin layer. 10 - 34 - 201138994 [Examples] Examples The titanium-containing aqueous liquid (A) and the components (B) to (G) used for the surface treatment composition are shown below. [Production of titanium-containing aqueous liquid (A)] • Production Example 1 (aqueous liquid T 1 containing titanium) Aqueous ammonia (1:9 = ammonia: water mass ratio) was dropped into distilled water to make titanium tetrachloride 60 mass% solution In a solution obtained by 5 cc of 500 cc, a low condensate of titanium hydroxide was precipitated. After washing with distilled water, a solution of 1 〇 cc of hydrogen peroxide water 30 rnaSS% was added to obtain a yellow translucent titanium-containing aqueous liquid T 1 containing titanium. • Production Example 2 (aqueous liquid T2 containing titanium) 30 mass% peroxidation of a mixture of tetraiso-propoxy titanium and 1 part by mass of iS0-propanol at 20 ° C for 1 hour 10 parts by mass of hydrogen water and 1 part by mass of deionized water. Thereafter, the mixture was aged at 25 ° C for 2 hours to obtain a yellow transparent, slightly viscous aqueous liquid T 2 containing titanium. - Production Example 3 (aqueous liquid T3 containing titanium) The titanium-containing water was obtained in the same production conditions as in Production Example 2 except that the four iso-propoxy titanium used in Production Example 2 was replaced by tetra-n-butoxytitanium. Liquid T3 • Production Example 4 (aqueous liquid T4 containing titanium) -35- 201138994 In place of the production of the second iso-propoxy titanium terpolymer (four iso-propoxy titanium low condensate), the production example 2 was used. In the same manner as in Production Example 2 except for the iso-propoxytitanium, an aqueous liquid T4 containing titanium was obtained. • Production Example 5 (aqueous liquid T5 containing titanium) A three-fold amount of hydrogen peroxide water was used, and it was dripped at 50 ° C for 1 hour, and then cooked at 60 ° C for 3 hours. 2 The same manufacturing conditions include an aqueous liquid T5 containing titanium. - Production Example 6 (aqueous liquid T6 containing titanium) The aqueous liquid T3 containing titanium produced in Production Example 3 was further heat-treated at 95 t for 6 hours to obtain a titanium-containing semi-transparent aqueous liquid T6 containing titanium. - Production Example 7 (aqueous liquid T7 containing titanium) A mixture of 10 parts by mass of four iso-propoxy titanium and 10 parts by mass of iso-propanol was added to the stirring "TKS-203" at 〇 hours. (trade name, manufactured by Tieka Co., Ltd., titanium oxide sol) 5 parts by mass (solid content), 30 mass% of hydrogen peroxide water 10 parts by mass, and deionized water 1 part by mass. Thereafter, it was aged at 1 〇 ° C for 24 hours to obtain a yellow transparent, slightly viscous aqueous liquid T7 containing titanium. [pin compound (B)] B 1 : ammonium carbonate B2 : zirconium oxycarbonate 201138994 B 3 : zircon fluorinated hinge [organic phosphoric acid compound (C)] C1 : 1-hydroxymethane-1,1-diphosphonic acid C2 : 1-hydroxyethane-1,1-diphosphonic acid [mixture of metal phosphate (D) and cerium oxide (E)] Solids as shown in Table 3, Table 5, Table 7, Table 9, Table 11. A mixture of cerium oxide (E) and an aqueous solution of metal phosphate (D) is strongly added to obtain a mixture of a metal phosphate aqueous solution dispersed cerium oxide. Also, No. 9 and Table No. The comparative example of 92 contained only cerium oxide E4. • Metal Phosphate (D) D 1 : - Aluminum Phosphate D2 : - Magnesium Phosphate D3 : - Manganese Phosphate • Oxide Sand (E ) E1: Ai Luoji 300 (trade name, Japan Ai Luoji Co., Ltd.) , gas phase cerium dioxide 'volume specific gravity: 5 〇 g / L) E2: Ai Luoji 2 〇〇 (trade name, 曰本艾洛吉 (stock) system, gas phase cerium oxide, volume specific gravity: 35g / L E3: Snow shovel (trade name, Nissan Chemical Industry Co., Ltd., colloidal cerium oxide) -37- 201138994 E4: Ai Luoji 300CF (trade name, Japan Ai Luoji (share) system, gas phase Cerium oxide, bulk specific gravity: 35 g/L) [Water-soluble or water-dispersible organic resin (F)] In the water-soluble or water-dispersible organic resin, the water-dispersible acrylic resin of F1 to F5 is produced by the following Production Example 8 It is manufactured to 12, and F6 to F13 are commercially available. Further, the "parts" and "%" of the following manufacturing examples are the quality standards. • Production Example 8 (water-dispersible acrylic resin F 1 ) 665 parts of deionized water, 9 parts of Akulon RN-50 (Note 1), 8 parts of Akulon RN_2〇25 (Note 2), and forced emulsification 5% (28,9 parts) of the pre-latex obtained from the monomer mixture 1 (paragraph 1) of the composition plus 4 streams of 2 liters of @流冷器, stirrer, thermometer and dropping funnel In the flask, nitrogen was replaced and the temperature was raised. "Monomer Mix 1" Deionized Water 1 6 6. 5 copies Akuron RN - 5 0 6. 6 parts Akuron RN-2025 53 parts Styrene 35 parts Methyl methacrylate 163. 5 parts 2-ethylhexyl acrylate 105 parts 2-hydroxyethyl methacrylate 5 parts methacrylic acid 3 parts -38- 5 201138994 acrylonitrile 3 8. 5 parts of t-dodecyl mercaptan 1 part up to 55 t: above, add all-butyl hydrazine (Note 3) 5 parts dissolved in deionized water 83. 5% of the obtained oxidant aqueous solution (4. 43 parts) and sodium formaldehyde hyposulfite 2. 5 parts of the reducing agent aqueous solution dissolved in 8 3 · 5 parts of the deionized water (4. 3 parts), and then heat up to maintain the temperature of 60 °C. After joining for 15 minutes, 1 .  The pre-emulsion will remain in 5 hours to 3 .  5 hours will be the oxidant aqueous solution, and to 3 .  The reducing agent aqueous solution was dropped over 5 hours. The aqueous solution of the oxidizing agent and the aqueous solution of the reducing agent were continuously added dropwise, and the pre-emulsion drip of the first stage was completed for 1 hour, and then the monomer mixture 2 of the following composition was dropped into the mixture of the following composition (second stage). "Monomer Mix 2" Styrene 15 parts Methyl methacrylate 84. 5 parts 2-ethylhexyl acrylate 22. 5 parts 2-hydroxyethyl methacrylate 4. 25 parts methacrylic acid 6 parts acrylonitrile 15 parts 7-methyl propyl oxypropyl trimethoxy sand yard 2. 75 parts After the completion of all the drops, the temperature was maintained at 60 for 1 hour. (:, then reduce the temperature to below 40 °C, then add 25% ammonia. 35 copies, Slao ex (Note 4) 〇. 35 parts, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 83. 5 parts, -39- 201138994 Get pH 8. 0. A water-dispersible acrylic resin F1 having a nonvolatile content of 31%. (Note 1) Akulon RN-50, trade name 'First Industrial Pharmaceutical Co., Ltd., non-ionic emulsifier, solid content 60% (Note 2) Akulon RN-2025, trade name, first industry Pharmaceutical (share) system, non-ionic emulsifier, solid content 25% (Note 3) All-butyl hydrazine, trade name, Japanese fat (stock), t-butyl hydroxy peroxide, active ingredient 69% (Note) 4) Slavi EX, trade name, manufactured by Nba Bale, Japan, Preservatives • Manufacturing Examples 9 to 12 (Water-Dispersible Acrylic Resins F2 to F5) Except for the first paragraph and the second paragraph of Production Example 8. The monomer composition was as shown in Table 2. The water-dispersible acrylic resin F2 to F5 ° was obtained in the same manner as in Production Example 8. Table 2 shows the characteristics of each water-dispersible acrylic resin. F6: Ultra-thin E-2500 (trade name, first industrial pharmaceutical (share) system, water-based polyurethane resin) F7: Ultra-bend 150 (trade name 'First Industrial Pharmaceutical Co., Ltd. system, water-based polyamine Carbamate resin) F8: Ultrabend 420 (trade name, manufactured by Daiichi Kogyo Co., Ltd., waterborne polyurethane resin) F9. Ultra-bend 300 (trade name 'the first industrial pharmaceutical (share) system, water-based polyurethane resin) F 1 0 : Bailuona MD-1 1 00 (trade name, Toyo Textile Co., Ltd. -40- 5 201138994, water-based polyester resin) F11: Aidan EM-0718C trade name, ADEKA (share), water-based epoxy resin) F12: Modan leather 3 03 (trade name, Arakawa Chemical Industry Co., Ltd., Waterborne epoxy resin) F13: Odda left S-370 (trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd., waterborne epoxy resin) [Chane coupling agent (G)] G1 : KBM-403 (trade name , Shin-Etsu Chemical Co., Ltd., containing glycidyl type) G2 : KBE-403 (trade name, Shin-Etsu Chemical Co., Ltd., containing glycidyl type) G3 : KBE-402 (trade name, Shin-Etsu Chemical Industry) (share) system, containing glycidyl type) G4 : KBM-3 03 (trade name, Shin-Etsu Chemical Co., Ltd., containing glycidyl type) G5 : KBE-9 03 (trade name, Shin-Etsu Chemical Industry Co., Ltd. ), containing amine type) G6 : KBM- 8 03 (trade name, Shin-Etsu Chemical Co., Ltd., containing sulfhydryl type) G7 : KBE-5 8 5 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., containing urea-based type) G8 : KBM- 1 003 (trade name, Shin-Etsu Chemical Co., Ltd., -41 - 201138994 Contains vinyl type The base steel sheet of the surface-treated steel sheet is obtained by using the gold-plated steel sheet shown in Table 1 and mixing the components (B) to (G) and distilled water with respect to the titanium-containing aqueous liquid (A), and the solid content is 2 to The surface treatment composition of lOmass % and pH adjusted to 8 was applied to the surface of the gold-plated steel sheet, and after 5 seconds, it was dried to a certain drying temperature (up to the plate temperature) to prepare a surface-treated steel sheet. With respect to the obtained surface-treated steel sheet, a rubber roller (48 mm φ x 205 mm) was used to attach the photocopying paper, and the surface of the film was subjected to a scratch treatment with a load of 690 g (including the drum self-weight) without rotating the drum. . Moreover, the No. shown in Table 5 and Table 6.  Comparative Example of 58 The above-mentioned banding treatment was not performed. With respect to the test materials 1, the heat-resistant discoloration property, the water-resistant adhesion property, the corrosion resistance, and the blackening resistance were evaluated by the following test methods (1) to (4). Further, a general polyvinyl chloride film was applied to the test material 1 with an adhesive so that the dry film thickness was 3 v m and the furnace temperature was 1 Torr. (: Heating of the heating furnace) Secondly, a polyvinyl chloride film having a film thickness of 250 μm was pressed onto the surface of the test material by a roller, and the polyethylene film was bonded by heat-pressing the steel sheet at a temperature of 230 ° C (organic resin). (Layer), an organic resin-coated steel sheet (which is "test material 2") was produced. The test material 2 produced was evaluated for post-processing adhesion and boiling water by the following test methods (5) to (7). Adhesion and Corrosion Resistance The storage stability of the surface treatment -42 - 5 201138994 was evaluated by the following test methods (8) and (9). The above results are related to the surface treatment composition of each test material. The composition of the material and its coating conditions are shown in Tables 3 to 12. (1) Heat-resistant discoloration The test material is heated to a plate temperature of 50 in 30 seconds using an infrared ray oven, and after 30 seconds, it is naturally placed. The appearance of the surface was visually observed when it was cooled to room temperature. The evaluation criteria were as follows: 〇: no discoloration △: discoloration was pale yellow X: discoloration was yellow to brown (2) water resistance adhesion 1 mL of pure water was dropped on the test material i, visual observation using 1 〇 (r oven drying for 10 minutes) The appearance of the surface is as follows: ◎: No discoloration 〇: almost no discoloration △: only the contour of the drip portion is observed X: discoloration of the entire drip portion (3) Corrosion resistance 50 mm x 100 mm cut out from the material 5 of the type 5 The test piece, after sealing the end portion and the back surface of the S-type test piece, was subjected to a salt spray test of jIS_z_2371-200〇, and the test time for measuring the area ratio of white rust was 5%. The evaluation benchmark was as follows: -43-201138994 ◎ : 36 hours or more 〇: 24 hours or more, less than 36 hours △: 12 hours or more, less than 24 hours X: less than 12 hours (4) Blackening resistance to AL (L値 after test - Before the test, the whiteness (L値) of the test material 1 was placed in a constant temperature and humidity machine controlled at a temperature of 80 ° C and a relative humidity of 95% for 24 hours, and the evaluation criteria were as follows. 〇: -5. 0

A : -5.0>AL ^ -1 0.0 X : -1 0.0>AL (5) Adhesiveness after processing (peeling strength after processing) A test piece of 30 mm x 20 mm which was cut out from the test material 2 was used for the test. In the almost central portion of the longitudinal direction of the sheet, two lines of 50 mm intervals are drawn at right angles to the longitudinal direction, and the ends of the test piece are clamped by the clamp of the tensile tester, and the interval between the two lines is extended in the uniaxial direction. Up to 60mm. The test piece after the extension was used as a sample, and the organic resin layer between the two lines was set up after the augmentation, and the width was 20 mm and the depth reached the cut of the steel sheet. After forcibly peeling one end of the organic resin layer provided with the cut, the end of the peeled organic resin layer was sandwiched by a clip of one of the tensile testers, and the steel plate was clamped by the other clip of the tensile tester at a peeling speed of 50 mm. /Part condition -44- 5 201138994 Under the peel test. In the peeling test, the organic resin layer was peeled off from the surface of the steel sheet in the direction of 180 ° (opposite direction), and the maximum strength (= peel strength) at the time of peeling was measured. When the peel strength is large, it is indicated that the organic resin layer is hardly peeled off from the metal sheet, and the adhesion after bending and twisting processing is excellent. Based on the measured peel strength, the post-processing adhesion was evaluated on the basis of the following criteria 评 4 (point): peel strength was 50 N/2 〇 mm width or more 3 (point): peel strength was 4 〇 N / 20 mm width or more, not reached 50N/20mm Width 2 (Comment): Peeling strength is 30N/20mm or more, less than 40N/20mm Width 1 (Remarks): Peeling strength is less than 30N/20mm Width (6) Boiling water adhesion (Peeling after hot water immersion) Strength) A test piece of 30 mm x 20 mm was cut out from the test material 2, and the test piece was immersed in boiling water for 5 hours and taken out. The peel strength of the organic resin layer of the test piece from the steel sheet was measured in the same manner as in the above test (5). When the peel strength is large, the adhesion after hot water immersion, that is, the adhesion in a high-temperature wet environment is excellent. Based on the measured peel strength, the boiling water adhesion was evaluated on the basis of the following criteria. 4 (Comment): Peel strength is 50N/20mm wide or more 3 (comment): Peel strength is 40N/20mm or more, less than 50N/20mm Width 2 (point): Peel strength is 30N/20mm or more, not up to - 45- 201138994 40N/20mm Width 1 (Comment): Peeling strength is less than 30N/20mm Width (7) Corrosion resistance (scratch resistance) Test piece of 50mm x 100mm is cut out from the test material 2, and cut out on the surface of the test piece The 1000-hour salt spray test was carried out according to the regulations of the Cross, 依ίΙ3-Ζ-2371-2000. The unilateral corrosion width from the cross was measured. The evaluation criteria are as follows. ◎: The average corrosion width of the self-cutting portion is less than 5 mm. 〇: The average corrosion width of the self-cutting portion is 5 mm or more, less than 10 mm. X: The average corrosion width of the self-cutting portion is l〇mm or more. When the film is poor in scratch resistance, the film is cut off to form a wound that reaches most of the gold-plated surface. Since the wound has no coating film, it lacks adhesion to the organic resin, and water is easily invaded. Therefore, the salt water invaded from the cross will soak the wound for corrosion. As a result, when the resistance to damage is poor, the corrosion from the cross is wide. The tape damage resistance was evaluated by evaluating the one-sided average corrosion width from the cross. (8) Storage stability (I) The surface treatment composition of the solid fraction of 8 m ass% was subjected to visual observation of the precipitation state and viscosity of the solid fraction after 2 weeks at 4 °C. The evaluation criteria are as follows. ◎: The solid form is not precipitated and the viscosity is unchanged. -46- 201138994 〇: A small part of the solid form precipitates or the viscosity changes slightly △: The solid part precipitates more or the viscosity changes more X: The solid part precipitates more and sticks Sexual change was large (9) Storage stability (II) The surface treatment composition of the solid fraction of 8 maSS% was kept at 30 ° C, and the precipitation state of the solid fraction was visually evaluated every one week. The evaluation criteria are as follows. ◎ : No precipitation after 4 weeks 〇: Precipitation occurred after 4 weeks △ : Precipitation occurred after 2 weeks to 3 weeks X : Precipitation occurred after 1 week [Table 1]

No. Gold plated single-sided gold plating adhesion (g/m2) 1 Electrically plated steel plate 50 2 Hot-dip galvanized steel plate 120 3 Alloyed hot-dip galvanized steel sheet (Fe: 1 Omass%) 45 4 Zn-Ni alloy plated steel plate ( N: 12mass%) 20 5 Zn-Al alloy steel plate (A1: 55 mass%) by melt-plating 90 6 Zn-5mass%Al-0.5mass%Mg alloy steel plate 90 7 Melt-plated steel plate (Al-Si alloy, Si: 6mass%) 60 8 Zn-Al-Mg alloy plated steel plate (Al: 6mass%, Mg: 3mass0/〇) 120 9 Zn-Mg alloy plated steel plate (Mg: 0.5mass%) 150 -47- 201138994 Water-dispersible acrylic acid Resin 1 F5 (Production Example 12) Stage 2 CO 1 21.0 I CO a> ο Οί o <〇ο CO CO σ>>-· CO | 1st paragraph I 〇CO dr- ο <〇Ο o ο 〇F4 (Manufacturing Example 11) Section 2 CO 〇CO ο ο CM o <〇ο GO T- 00 00 σ> ο 1 paragraph 1 | Bu 40.0 II 21·4 1 ο «Μ <£» Ο o ο CO F3 (Manufacturing Example 10) Section 2 CO I 15·3 I o 〇> 0.9 eg Production o (Ο ο o 00 in a % CO Paragraph 1 in CQ r· ui CM ο r— ( Ο ο o ο OJ F2 (Manufacturing Example 9) | paragraph 2 1 CO 19.8 4.5 0.9 CM o <〇ο 45*8 o CO o I paragraph 1 | Bu 40.4 21 .0 ο I °·6 I o ο ;R (Manufacturing Example 8) Section 2 CO 16.8 in 0.9 CM CO CO ο 45.2 o CO |Paragraph 1 | Bu I 32 7 II 21.〇I Ο CO o ο Styrene methyl methacrylate 2-ethylhexyl acrylate 2-hydroxyethyl methacrylate methacrylic acid acrylonitrile m secret in m K m « mn IE m a- • Bu glassy temperature ΓΟ calculation値X a Particle size (nm) Nonvolatile matter (%) 酹丨sas mm %ssma : § ※ 5 201138994 The contents of *1 to *10 in Table 3, Table 5, Table 7, Table 9, and Table 11 are as follows. *1 The gold-plated steel sheet described in Table 1 〇.1 to 1^〇.9 *2 The titanium-containing aqueous liquids T1 to T7 described in the present specification * 3 The zirconium compounds B 1 to B 3 *4 described in the present specification The organic phosphate compounds C1 and C2*5 described in the present specification are metal phosphates D1 to D3*6 described in the present specification. The cerium oxides E1 to E4 described in the present specification are water-soluble or water-dispersible organic substances described in the present specification. Resin F1 to F13 *8 The decane coupling agent G1 to G8 *9 surface treatment composition (aqueous treatment liquid) described in the present specification, the solid content (g) in 1 liter * 10 surface treatment composition (aqueous treatment liquid) Proportion of total solids (mass % ) -49- 201138994 m Composition of surface treatment composition 1 decane coupling agent (G) Addition ratio (mass%) *10 C4 (SJ OJ CSJ C^J CM CJ Cs ( csi OJ CKJ eg o Ο Ο 5 S - CO 寸 u> S S S s CM Π 1 CSJ 1 L 1 j CJ L· CM 底 ▼ aa 〇5 σ 5 aa δ a δ 5 5 1 1 1 δ δ σ 5 δ δ a δ δ 5 aa δ Aqueous organic resin (F) Addition ratio (mass%) *10 CO CO CO CO CO CO C9 CQ : CO CO CO CO CO CO <〇CO CO CO Μ CO cc C0 CO Γ 1 CVJ inch in ι 1 〇d lZ I: u: cn ϋ: iL ϋ u; u: * yr^ ι: C ι: u: u; τ~ iu: u: ϋ: ί: JL i II 1 U: " a: oxidized ____ added ratio (mass%) *10 CO CO CO CO 5 KK 〇ίο oo Ο ο - o 〇Μ 5 δ W κ R n CO wo qing * ui tS ai UI LU Mr S 2 LU UJ 2 ω S m 2 2 ui ω LLI UJ UJ 2 ui 2i s Record phosphorus surface (D) Add proportion (moss%) *10 兮 inch 々兮Tf 兮 inch inch 令 inch Inch 郷aa Q a 5 Q oo OQQ aa Q ο Q 5 Q o DD a ο a QQQ s 5 5 Organic phosphorylation (6) Addition amount ♦9 m in m in in in in m in in IO in l〇to ΙΛ IA IA l〇ΙΛ in Ui ΙΑ ΙΟ u·) l〇in in IA ΙΛ S* eg s S cst 〇SS CSj 〇CM 〇ss eg S s S eg s ss CSJ ο eM 〇s S s wrong compound (8) (g/L) ♦9 Ui m in l〇mm in LO io iO l〇l〇IO u> ΙΟ ιη in in ΙΟ IA ΙΛ ΙΟ in u> io IO to in foot mmmmm ω 〇ω 〇ffl m ffi ω ω mmmmm ω ffi m ω ω mmm Mm Titanium-containing aqueous solution (A) Addition (g/L) O oooo T~ 〇oo 〇oooooo Ο oo ooo ο o Ο Ο oo Tj o T- o 〇or— qing p pj P p PPPPP! ρ Ρ p <s Η w pj w 1 CN HP; P gold plated steel plate *1 oi I CM _I Oi CM CM CsJ €M CM CSI CM CM OJ CM: 〇| CM OJ CM CM eg CN 04 : <s C4 CSI distinguish invention Example m 槪msm Inventive Example Inventive Example Comparative Example Comparative Example § 槪dm Inventive Example Comparative Example ϋ Comparative Example m 谥 a Inventive Example Inventive Example Inventive Example Inventive Example Inventive Example Inventive Example Comparative Example Inventive Example B Proud Invention Example Invention Example Τ-» CM ΙΛ I co GO a> 〇y^\ <〇T~ τ~ ΙΟ τ- Φ r^'1· 00 r— 〇T— s CM CM S 3 in CM s S g 50 - 5 201138994 inch inch

Characteristics of the surface treatment composition I Storage stability (1) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 安 ◎ ◎ 〇〇 Storage stability (1) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ @ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ @ ◎ 〇X ◎ ◎ 〇〇〇m Your class m 箄Μ Net corrosion resistance 〇 ◎ ◎ ◎ ◎ @ ◎ X ◎ ◎ ◎ ◎ ◎ @ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 0 ◎ ◎ ◎ ◎ boiling water I tightness inch inch inch inch inch inch inch CM CM CS| inch inch inch inch inch inch inch m processing time tightness CO CO C3 CO CO CM CSI CM 00 CO CNJ w CO C5 eo C0 CO <〇CO CO CO CO 00 C4 Csl Surface treatment of steel sheet characteristics 丨Resistance to blackening 〇〇〇〇〇〇〇〇< 〇〇〇0 〇〇0 ο 〇〇〇〇〇0 〇〇〇〇〇〇〇 〇〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Water resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ © ◎ Heat-resistant discoloration 丨〇〇〇〇〇〇〇〇〇〇〇〇ο oo 0 ο 〇〇〇〇〇〇〇 〇〇〇〇〇〇Is there any damage treatment W- 蚺m « 劁 adhesion amount (g/m2) I 0.05 II 0.08 i I 0.14 II 0.20 II -0.25 _J I 0.30 II 0.40 II 0.50 II 0-01 1 1 A00 1 I .0.14 I 丨0-14 II 0-14, II 0.08 II 0-14 II 025 | I 0·14 II 0.14 II 0-14 II 0-14 II 0-14 II 0-14. II 0.14 | 丨0-14 1 1 0.14 II 014 II on | I 0.14 II 0.14 | 0.14 I Drying temperature (°C) § S § SS g % S % % I 100 II 140 | § ss § S § % % gg % % § g S Division I Inventive Example II Inventive Example I Inventive Example I Inventive Example Inventive Example I Inventive Example II Inventive Example II Comparative Example "Comparative Example IL Inventive Example" Inventive Example "I Inventive Example" I Comparative Example I Comparative Example "I Comparative Example" 丨Comparative Example I m Representation Example" I Inventive Example I 丨Inventive Example | m 睇I Inventive Example I | Inventive Example 1 丨Comparative Example II invention example II invention example "I invention example" I invention example j invention example <N C5 inch m <〇布«0 〇> 〇T-CM •r- CO inch in (Ο GO GO 03 S aa S -51 - 201138994 矽 i i mixture (6) Addition ratio (mass%) *10 CM CNi o <Ν esj CM CM CM CM CN CM CNJ CM CM Csl CM CM CSJ CS) C^J CO ΙΟ IA LO Csl eg CN| CsJ CM S? σ 5 1 a δ y— o 5 5 δ τ — 〇δ σ δ o δ a Τ Ο ο τ α a 5 5 5 ao 5 Τ Ο t-· a 〇Τ Ο ±ϊ^〇l〇 chain c ^ 1* ms ▼·· CVJ CO 12 CO 5ϊ 卿 IC 1 to Cl o L: □El u: C cu: U: ί: ϋ I: c C iZ c 1 1 ϋ: ϋ Zero 5 Steps on is added tt (mass4 *10 r- 〇C7 CO 〇o ri s Γ-* CO 5; n ?; f; K CO f; Csl <〇CO r) sss ο ss 8 O 1A 5 CO <〇I m »&lt ;〇0 * S m LU S UJ ω UJ ui αί ai Si s ω Si LU uj ui ai ai 1 IS s U ω •Μ mg 8 * inch inch inch inch兮 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 ^ 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE OE Ξ 5 Ξ sg Addition amount (g/L) *»9 ΙΟ ΙΟ to i〇iO in IO f— 严 strict mr— m r- IO to to in wo IO ΙΟ u> ΙΟ in to IO i〇to LO to &gt ;- IP r- m T~ to ΙΟ 8? esj 〇ssss SU ss 3 s SS ss SS ssssss 3 CM Ο ω Addition amount (g/L) ♦9 wo l〇m W> IA in u> ΙΛ to m ΙΛ In ir ir> LA u> in ir>\f> m ir> IA in IO in U» in to u>u> appearance f S? 卿, m ffl mmmmmm ffl mmmm ω m ω ffl mm 〇mmm E ffl m £ Mm ω Aqueous liquid containing titanium (A) Addition amount (g/L) ★9 ooooooo Ο oo 〇oooo 〇〇〇oo 〇o 〇ooo 〇oo Ο τ— Qing wp Cj pi p Pi P pj Cj Pi Gold plated steel* 1 1__ CJ Cst cv eg CV CM cv CM CO CM CM cv CsJ CN CNJ CJ OJ eg CSJ CM CM CM CM CM CM CM CM Csl CM 匡匡匡匡匡m 匡m 匡匡m International s- 攞镒m £ a 鞠睇m 镟镞 bottle 豳睇m 睇擗睇 睇擗睇睇 睇 镞 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 0 〇 0 ◎ ◎ 1 Storage stability i (1)! ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ & & & U U U U U U U U U U 耐 耐 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ @ @ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ XX © ◎ ◎ boiling water tightness inch CNJ inch inch inch inch inch inch inch CO inch inch inch inch CO CO CO - inch inch U m processing tightness c-> CO CO CO CO CO CO CM csl csl CM CM C M C>i CM CO CO CO CO CO CO o CM oo CO οι Surface treatment of steel sheet characteristics Resistance to blackening ο 〇ο 〇oo 〇0 o 〇oo ο 〇o 〇o ο 〇〇oo 〇o 〇oo 0 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ @ ◎ ◎ © ◎ ◎ Heat-resistant discoloration ο < ο 0 0 o 0 0 o 〇0 0 ο 0 0 〇〇0 0 〇0 0 0 0 0 0 〇〇0 0 捶囲K顿mm w 擗擗擗w 聛W- 擗擗聛W- 擗wm sword attachment amount (g/m2) 1 〇·Η I 1 0-Η-Ι 1 〇·Η II OH II 0-14 II OH | I OH .II OH- II 0-H . II 0.14 I ί ou I 0-14 II 0.14 I 0.14 II 0.14 II 0.14 I 0.14 I 0-14 I 0.14 I ί 0.UII 0-14 II 0-14 II 0-14 I i 0-H | I 0-14 II 0-HI 1 0.14 I 0-UI 1-_αΐ4 ! 0.U 1 Drying temperature (°C) s § ggs § sgss § ss § § ssss % sss % g is different from comparison example 1 Comparative Example 1 I Comparative Example II Inventive Example II Inventive Example II Inventive Example II Inventive Example I 莩m I Inventive Example II Inventive Example "Inventive Example" Inventive Example II Inventive Example I m 粼I Inventive Example "I Inventive Example丨Inventive Example j I Inventive Example I Inventive Example "Inventive Example" I Inventive Example II Inventive Example I Inventive Example" I Comparative Example I a I Comparative Example I 镒 ± 5 1 Inventive Example 1 丨 Inventive Example 1 CM C7 in <〇ί ss K 5 s (O l〇!nsss -53- 201138994 Composition of surface treatment composition 1 decane coupling agent <G) Addition ratio (mass%) *10 CM CM CS1 Csl 04 CO to C>J CM CNi CM CSI CW <M co in CM Csj esj CO CM CSI CJ 09 in CvJ Species «8 τ α α α α τ α α Τ Ο ί α aaaaa 5 Τ Ο a ΊΓ· Ο aa O 5 5 5 aa δ δ δ r- CD shift: t -Mum addition ratio (mass%) *10 ο C0 C3 CO C0 CO in CO O CO CO CO CO CO CO CO in CO o « CO CO CO O ¢0 CO CO in CO Silkworm s qing ί: ϋ Π; u: U: nc Π: 1 [ u: lL iZ cu; V— V— u; 1 C: u; ί: cdniu: ί: L: Ζ 矽 矽 ( (E) Add Proportion (mass%) *10 CO e? <〇ο s § ο s in jn CO CM <〇CO CO o 8 os CO in K CM C9 s (O CO Γ oss 1 跸 跸<〇«tmll Μ foot u} ω ω ίΰ u } mw ω CS| UJ <Si tu CM ω CM UJ CM UJ <SJ Mountain CM UJ eg UJ UJ CM UJ ss 〇UJ ΰ s CO UJ s e> UJ ss CO UJ Metal phosphate (D) Add I ratio (mess%) *10 _ 兮 inch inch order can be L_ 甘XT inch Gan 'T Ai A V 々•«r inch 郷 郷 r r r 郷 Q Q QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ QQ a D aao T" organic dish acidified bismuth (6) addition amount (£/L) *9 ΙΟ ιη ΙΟ in tn ΙΑ LA in to ir> ΙΛ tn in ΙΛ in in u> ΙΛ 1C ur> in ΙΛ IO u> in in tn IO IO IO foot fee s C4 S ss 〇S g 3 SS CM 〇S s eg s 3 sssssss Mismatched (8) Addition amount (g/L) *9 ΙΟ ΙΩ ιη ΙΟ ίο in in \nl〇l〇ID in lf&gt U> m in LO to tA u> IO IO mi〇in tA tn ΙΩ ww ffl ω ω ω ω mm ω ffl m 〇ω m ω ω mm ω ω mm ω m ω mm ω mm ω Aqueous liquid containing titanium (A) Addition amount (e/L) »9 ο ο Ο Ο Ο o 〇〇o 〇〇oooooo 〇〇o 〇o 〇o 〇〇ooot—o qing, Ρ Ρ PPH C4 P CJ P p Pi P P1 i P w P! PP gold plated steel*1 Οί _I CM CM _I OJ ΟΙ cx C«J CM CM OJ CM cs CM eg csi cs cm CM CM <M CS| j CSJ ΓΊ CSJ CM distinguishing invention example : 5: invention example invention 匡 s comparative example comparison example naming m B:邝m B 睇Inventive Example 1 睇匡 匡 匡 匡 匡 匡 a 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 m m m m m m m : m m m m m m m m m m : is (〇ο ~l p- Bu CO ω s 5 Π CM CO CO s "Ί 卜 1 ω % 3 § 54- 5 201138994 Characteristics of surface treatment composition Storage stability (1) ◎ ◎ ◎ ◎ ◎ ◎ ◎ oo ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Storage stability (I) © ◎ ◎ ◎ 〇 ◎ ◎ << ◎ ◎ ◎ ◎ ◎ ◎ o ◎ ◎ <3 < ◎ ◎ ◎ @ ◎ ◎ 〇 ◎ ◎ <J •N 游 箄 D Dm 1 Corrosion resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X boiling water 丨 cabin inch inch inch inch c-> inch inch inch inch inch inch inch co o inch inch inch inch inch inch ο CO inch inch m Adhesion during processing CO <〇CO CO CO CD CO CO CO <0 CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO ο 〇o ο oooooo 〇〇oooo ο o 〇o ο ο oo 4U 翳1 Corrosion resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ <1 η 闼 闼 m Water-resistant adhesion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Heat-resistant discoloration 〇〇0 〇〇〇 ο 〇〇ο 〇〇〇o 〇〇〇oo 〇〇o 〇〇oo ο 0 oo Is there any damage treatment W- 擗* wmm Sword attachment amount (g/m2) Γ 0.14Ί Γ 0-14^ 丨0.14 1 1 0-U 1 丨0.14 II ·Η II 0-14 1 I 0.14 II 0-14 II 0.14 II ou II 0-14 II 0-14 II 0.14 | 1 0.14 II 0-14 | I 0.14· II ou II 0-HI 丨0.14 II 0-UII 0-14 1 I 0.14 II Du I I- - 0-14 II 0-14 I 丨 0.14 II 0-UII 0-14 I 1 0.14 I Drying temperature (. 〇§ gggs § § § s § § § % s § ssss § si § § ggg distinguish I invention example I 丨 invention example I 1 invention example 1 invention example 1 丨 invention example II invention example I 1 invention example 1 l comparative I Comparative Example I Inventive Example II Inventive Example II Inventive Example I 豳1 Inventive Example _1 丨 Inventive Example I 莩5: 餹I Inventive Example I Inventive Example 1: 1: a L Comparative Example JI Inventive Example „J 1 Invention Example I Inventive Example I Inventive Example II Inventive Example II Inventive Example s: 睇 睇 I Inventive Example II Comparative Example I ύ 7Ξ 2 SZS <〇<〇CO s 2 o Bu ó Ο CO ιο (Ο co og 3 % CO s -55- 201138994 $ Composition of surface treatment composition 1 decane coupling agent (6) Addition ratio (mass%) This 10 CM CM CM Csl CM CM CM CM cs CJ Csl cw <N CJ CSJ CS CSI CM CM CJ CM CSJ CM CM CM csl Csl ο 〇δ δ δ δ aa δ δ δ δ 5 5 δ T·· a 〇δ δ 5 5 δ a δ a δ δ δ aa Addition ratio (mass%) I *10 Ο Λ CO CO ¢0 CO CO CO CO ο CO CO M CO C*5 to CO CO Λ CO CO n CO CO CO CO CO CO CO CO Qing 1 [ u L: c C u; [ u: n ί: u: u: T- C ·»— L: n iL L· u u: c I: u: T~* u: u: cu: 矽 ( (E) Addition ratio (mass%) *10 in ίο K c〇w CO CO c? R κ CO CO K CO Λ CO 〇r5 CO r* o CO s; 55 « K CO C9 UJ t2 s oi ui 2 ss iS s 2i ω ai m S ai 2 s Σ ui LU ω at mu Metal phosphate (D) Addition ratio (mass%) 410 ο cs I〇00 os Sj Ai V «r 々'«T 寸 inch xf inch τ~ Ο 1 〇▼-· oooa cs Q gat— QQ a OQQ a Ύ- o O ar* QOO a QE ^―· ο Acidification (C) 1 addition amount (g/L) *9 in ΙΩ in in in LA 1A in in LO oso S in 1Λ l〇lf> to LO U>l〇\e> Ύ-* in IO IO L〇in w> §* s CM 〇g S g eg s CSJ o 1 spss 04 s S ss csi 〇1 Mismatch (8) Add 丨 ("/〇1 «9 1___ ΙΟ in in ιο lO mm U3 l〇l 〇in lO in in 1» in IO in 〇〇o r> o WO CO in in IO IO LO u> S? mmmm ω ω m ffi m ω ma ω ma <Ni CQ CO CQ mm 1 ω m ω ω ω QQ ω CQ Contains titanium aqueous solution (A) Addition amount, (g/L) 1 +9 Ο ▼ — 〇oooo Ooooooooo 〇〇〇o O ooooooo 〇o O qing CM Η P ppp! PP! P OJ p cw p CS p P |2 |〇p 1 gold plated steel*1 eg Csf CM CSJ CM CN CM CM CSI <s CM Csl CM Csl CN CM eg C>J Csl «Μ cs OJ CM CS CM distinction 1 1 comparative example" I 1 invention example I 发明 invention example 1 m 镞 1 invention example 1 1 invention example " a proud 1 invention ®" 1 invention example 1 m 豳m 睇1 Comparative Example 1 a Invention Example 1 睇Comparative Example I 匡5: 豳1 invention example m 睇1 comparative example 镞1 invention example 豳m m 5: proud 1 invention example invention 匡a ▼— 〇 > Ol 05 O (O σ> Oi s ο δ gsggsgs 〇ir- CsJ CO LO CD 卜 CO O) s -56- 5 201138994

Characteristics of OS surface treatment composition 1 Storage stability (Π) 〇〇 ◎ ◎ ◎ ο 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ o ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Storage stability (I) < 〇〇 ◎ 〇〇〇 < ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇 1 1 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X boiling water tightness inch inch inch inch inch inch inch inch inch inch inch inch CO inch inch τ - inch inch inch inch Time-adhesiveness «〇-CO CO CO CO CO c〇CO CO 00 CO CO CO CO CO Osl CO CO cm CO C0 CO CO CO CO CO CO m N Huan resistance blackening 〇0 〇< ο ο ο 〇 0 0 〇0 〇〇o 0 〇ο 〇〇〇〇〇〇o 0 Corrosion resistance X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ <J ◎ ◎ <1 ◎ ◎ ◎ < 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ < mil w> m 晅 Water resistance adhesion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ heat resistant discoloration 〇〇〇〇〇0 〇〇ο 〇ο 0 〇〇0 ooo 0 0 〇〇〇0 〇〇0 〇〇X 廿Is there any damage treatment 擗聃ww 蚺m Μ 劁 adhesion amount (g/m2) 1 0-14 II 0.14 I 丨0.14” I 0.14 II 0-14 I 丨〇·14ι 1 0-14 I 丨0.14 II . ·〇,14_1 I 0-14.,,,1 1 〇·14___1 I 0-UII 0-14 I 1 0-U 1 I 0-UII 0-14 I 1 0-14 ...l 1 0-14 I 丨0.14 II 0-14 I 1 〇·Ί4 1 1 0-14 II 014 1 1 0-14.1 I 0-14 .1 I0.H1 丨0.14...| L 0.14 I 1 0.14 1 1 0.14 I Drying temperature (°C) SSS § S § ssssgggggs § § sg Distinguish i I Comparative Example I i Comparative Example IL Inventive Example 丨 Inventive Example II Inventive Example I 睇I Inventive Example | al Inventive Example匕Inventive Example "I Inventive Example" I Inventive Example "I Inventive Example JL Comparative Example" "Comparative Example" l Inventive Example IL Inventive Example 丨 Comparative Example 丨 Inventive Example I 1 Inventive Example 1 Inventive Example "I Comparative Example" 1 invention 1 invention example | 1 invention example 1 mmm 睇 1 invention example" 15 a SZ m σ > CO σ > 00 σ > ο ο 1p 〇 δ S Τ - 103 104 s 106 ο o 110 τ —· τ — yr^ CM CO Τ*" 114 ΙΟ (D ΓϊϊτΊ 00 Oi 1 120] -57- 201138994

Composition of Ilm surface treatment composition 1 decane coupling agent (G) Addition ratio (mass%) *10 CvJ CM CM cvi Csl CNj Cv4 csl <NC^J <N <S| es CM type*8 τ α δ 5 ο δ o δ a CM 〇CO as in 〇CO o 〇CO Ο Aqueous organic resin (F) Addition ratio (mass%) *10 ο CO CO CO CO CO CO CO CO CO CO CO CO CO CO ilwil ; c L: τ— u: u: u: u: c τ— JL c T— u: u: 矽 ( (E) Addition ratio (mass%) *10 CO o CO wo CO i; CO CO 55 Σ5 g? foot ss ui ui ω s ai at ω ω £ ω 2 metal phosphate (D) I addition ratio (mass%) *10 inch to inch inch inch inch inch inch-r- 5 ο Τ Ο O a τ- o 5 T— QQT— α τ—addition amount (g/L) *9 u> in m u> »— l〇to to IT> in l〇ΙΟ l〇ir> ΙΟ LO τ-· AW s C4 s CM 〇 C4 eg 〇己 eg CSJ Ο s Addition amount of knot (g/L) *0 l〇LA in in in in in mm to m ΙΩ in foot I mm ω mmmm OO m ω ω m Ζ m Contains water of titanium Liquid (A) Addition amount (g/L) *9 o 〇Ο 〇〇oooo Oooo Ο o lion ▼ P! CM HP p Cj pppp Ρ P gold plated steel *1 CO in < 〇 00 σ gt; OJ CM CM CM csi CSJ <M distinguishes msmm Lai I invention example 莩m 雔 擗莩 擗莩 擗莩睇丨Inventive Example I 擗I Inventive Example I 匡睇丨Inventive Example 琅yr—CsJ s 124j s <〇eg »— 127 128 〇> csl 130 *—· CO Csi CO r— CO <2 134 Ui CO ▼— 5 -58- 201138994 zs Characteristics of surface treatment composition Storage stability (1) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ 0 0 〇 ◎ Storage stability (I) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇0 0 ◎ m Μ 幽gm Corrosion resistance _ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ boiling water tightness inch inch inch inch inch inch inch inch inch 3S m mm Η<π 〇〇CO CO CO CO CO CO ο 07 〇CO CO CO Surface treatment steel sheet Characteristics Blackening resistance 〇〇〇〇〇ο oo ο 〇〇〇〇〇〇 Corrosion resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Water resistant Adhesion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Heat-resistant discoloration 〇〇〇〇〇ο 〇0 ο 〇〇0 〇〇0 liters with or without damage treatment m 劁 adhesion amount (g/m2) 10.14 1 1 0-14 1 1 〇 -«4 1 丨0.14 1 1 0-14 1 丨0.14 II 0-t4.| I 0.14 1 1 〇·14.._1 1 〇·>4 1 1 0-14...1 1 0.14 1 1 QU --...-1 1 〇·Η 1 0.14 1 Drying temperature I (. 〇§§§g §S gg S distinguishes the first invention example" 1 invention example" 1 invention" S: 鞔匡 镟 镟 every 5: 珐匡镞 1 invention example 丨 invention example | 匡 «5Κ 豳镞m 豳a CO CM 2: ID CSJ CO CNJ is s a> CSJ T-* CO CM « C0 〇〇-59-

Claims (1)

201138994 VII. Patent Application Range: 1. A surface treatment composition selected to be contained in a low condensate relative to a low condensate of a hydrolyzable titanium compound, a hydrolyzable titanium compound, titanium hydroxide or titanium hydroxide. 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A) obtained by mixing at least one kind of the titanium compound and hydrogen peroxide water, 10 to 300 parts by mass of the carbonic acid pin compound (B), 50 to 200 parts by mass The organic phosphate compound (C), the ratio of the total solid content of the surface treatment composition to the total solid content of the surface treatment composition is 2 to 20% by mass of the metal phosphate (D), and the ratio of the total solid content of the surface treatment composition is 20 to 40maSS % of cerium oxide (E ), a ratio of 2 to 10 mass % of the water-soluble organic resin and/or water-dispersible organic resin (F ) in the total solid content of the surface treatment composition, and the surface treatment composition The proportion of the total solids is 0.5 to 20 mass% of the decane coupling agent (G). 2. The surface treatment composition of claim 1, wherein the cerium oxide (E) is a gas phase cerium oxide produced by a dry method. 3. The surface treatment composition of claim 2, wherein the gas phase cerium oxide has a bulk specific gravity of 40 g/L or less. 4. The surface treatment composition according to any one of claims 1 to 3, wherein the decane coupling agent (G) has a glycidyl group. 5. The surface treatment group -60-5 201138994 of any one of claims 1 to 4, which has a pH of 7 to 12. 6. A surface-treated steel sheet characterized in that, on the surface of a galvanized steel sheet or an aluminum-plated steel sheet, a surface treatment composition as described in any one of claims 1 to 5 is coated with The surface-treated film having a film deposition amount after drying of 0.03 to 0.5 g/m2 was formed. 7. An organic resin-coated steel sheet characterized by having an organic resin layer on a surface-treated film of a surface-treated steel sheet according to item 6 of the patent application. -61 - 201138994 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201138994 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none