TW200837220A - Aqueous surface-treating agent for environmentally acceptable pre-coated metallic materials, and surface-treated metallic material and environmentally acceptable pre-coated metallic material - Google Patents

Abstract

A non-chromium based aqueous surface-treating agent is useful as a substrate-treating agent for forming pre-coated metal materials having excellent corrosion resistance, coating adhesiveness (coating primary adhesiveness and coating secondary adhesiveness in T-bending test) and coin scratch resistance. An aqueous surface-treating agent for environmental response type pre-coated metal materials containing a silane coupling agent and/or a condensate of silane coupling agent (A), a metal oxide sol (B), a metal compound (C) and a water dispersible silica (D), the metal compound (C) being at least one selected from the compounds of V, W, Mo, Al , Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn, the mass ratio of (B)/(A) being 1/50 to 10/1, the mass ratio of (C)/(A) being 1/1000 to 4/10, the mass ratio of (D)/(A) being 1/50 to 10/1; a metal material having a coating thereof; and a non-chromium based pre-coated metal material.

Description

200837220 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a non-chromium-based water-based surface which is suitable as a substrate treatment agent for preparing a precoated metal material excellent in coating adhesion, corrosion resistance and coin scratch resistance. Treatment agent, as well as surface-treated metal materials, pre-coated metal materials corresponding to the environment. [Prior Art] For parts such as home appliances, building materials, and automatic vehicles, there are many pre-treatments for post-processing (post) coated products, but in recent years, For the home appliance, instead of such pretreatment, a precoated metal plate coated with a colored organic film is used. Since the metal plate is coated with a metal plate treated with a substrate or coated with an organic film on a plated metal plate, it has an aesthetic appearance and a processability, and has excellent corrosion resistance. For example, Patent Document 1 discloses coating. The specific chromate treatment liquid is subjected to drying without pre-coating to improve the corrosion resistance of the end plate. Such as I; the precoated steel sheet treated with the chromium-containing substrate is corrosion-resistant by the combination of chromate treatment and organic film, and has processability and coating adhesion, and is omitted after processing. It is now widely used for the purpose of improving productivity or quality improvement. However, since the chromate treatment film and the organic film containing the chromium-based rust-preventing pigment have the possibility of elution, that is, the toxicity of hexavalent chromium, there has been a high expectation for non-chromium rust-proof treatment and non-chromium organic film. The first characteristic required for the substrate treatment of the precoated steel sheet is coating adhesion 200837220. It is necessary to prevent the skin from being applied to the bottom of the coating. The two interfaces of the base metal of the lower layer and the primer of the upper layer are required. Good contact. The coating adhesion is also priced after being immersed in boiling water for a predetermined period of time, and is particularly referred to as a coating secondary adhesion, which is distinguished from the one-time adhesion of the coating adhesion of boiling water immersion. These 1st and 2nd adhesions are the most important characteristics necessary for pre-coated steel sheets before being processed into complex shapes. The T bending test was used as an extremely rigorous test for the evaluation of the adhesion of precoated steel sheets. The second characteristic required for the substrate treatment of the precoated steel sheet is F' resistance to coin scratch resistance. It is not only the adhesion but also the characteristics of the film hardness which affects the substrate treatment. The third characteristic required for the substrate treatment of the precoated steel sheet is corrosion resistance. In the case of a precoated steel sheet, the substrate treatment, the primer coating treatment, and the topcoat coating treatment are usually carried out sequentially on the steel sheet. In the case of conventional chromate-treated precoated steel sheets, not only the substrate treatment layer but also the lacquer layer also contained chromate. In particular, a primer layer having a thickness of 3 to 1 Ομηη containing a large amount of a chromium component as a rust preventive pigment is a main task for imparting corrosion resistance to a precoated steel sheet, in comparison with a substrate treatment which does not usually use more than 0.5 μm. However, the primer of the pre-coated steel sheet containing no chromium is inferior to the primer containing the chromium-based rust pigment, and the actual condition is that it can only impart corrosion resistance. Therefore, in the non-chromate precoated steel sheet, the substrate treatment portion is rather a task of imparting the resistance to the touch of the conventional chromate system. As a non-chromium-based rust-preventing treatment method instead of chromate treatment, Patent Document 2 discloses that an aqueous solution containing tannic acid and a decane coupling agent is used for surface treatment of zinc and a zinc alloy to improve white rust resistance and paint adhesion. Sexual Technology 200837220 'But this method does not fully ensure the resistance to coin scratching and corrosion resistance required for precoated metal sheets. Patent Document 3 discloses that a chemical conversion film containing a binder such as vermiculite particles and polyacrylic acid is formed on the surface of a galvanized steel sheet. However, in this method, the coating adhesion and uranium resistance required for the precoated steel sheet are not as good as those for the chromate treatment.

Patent Document 4 discloses a technique in which a surface of a galvanized steel sheet is surface-treated with an aqueous solution containing sand fine particles, a sand chamber coupling agent, and a resin composition to impart primary rust resistance. However, when the treatment agent is transferred to a precoated steel sheet, the performance as a coating substrate is insufficient for a precoated steel sheet which requires strict adhesion. The adhesion achieved by the treatment liquid for imparting temporary rust resistance is the processing adhesion at the Erich sen extrusion level, and the processing adhesion at a level acceptable for the T bending test cannot be achieved. Similarly, when the fingerprint-resistant agent or the lubricant agent is transferred to the base treatment agent of the precoated steel sheet, the strict T-bend adhesion test is also incapable. Patent Document 5 discloses a substrate treatment technique for treating a precoated steel sheet having a surface of a plated steel sheet with an aqueous solution containing a water-dispersible vermiculite, a decane coupling agent, a ruthenium compound or a titanium compound, a sulfur-containing carbonyl compound, an acrylic resin, and phosphoric acid. The corrosion inhibitor of the sulfur-containing carbonyl compound or phosphoric acid is insufficient, and the corrosion resistance of the precoated copper plate, particularly the corrosion resistance of the end surface portion, is not as good as that of the precoated steel sheet treated with chromate. Patent Document 6 discloses that a steel sheet is not impregnated with a steel plate but is immersed in a treatment bath containing a decane coupling agent and ammonium molybdate, and then washed to form a reaction-treated base film, and an upper layer is subjected to an anti-corrosion coating treatment to produce A method of resisting coated steel. Since this technology requires a dipping and water washing step, 200837220 is not suitable for pre-coated steel sheets. Patent Document 7 discloses a surface of a plated steel sheet such as a galvanized steel sheet, which is an aluminum salt, a boron compound, a metal salt other than aluminum, and SiO 2 , SnO 2 , Fe 203 , Fe 3 04, MgO, Al 2 〇 3, Zr 02 and Sb 205. At least one of the sol or the powder is dissolved or dispersed in a liquid in water to be treated, and a technique for imparting corrosion resistance and coating adhesion is provided. However, even with this technique, the coating adhesion cannot be withstood in the case of precoated steel sheets. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. JP-A-2002-80979. JP-A-2001-164195 PATENT DOCUMENT 5: JP-A-2001 - 3 1 6 845 Patent Document 6: JP-A-2002-3 4 8 8 1 Patent Document 7: Special Opening 2 00 5 - 2 5 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a non-chromium type which is environmentally compatible, but when a coating substrate as a precoated steel sheet is used, coating of a coating film is provided. Water-based surface treatment agent excellent in adhesion, corrosion resistance and coin scratch resistance, and surface-treated metal material obtained by using the same, and environmentally-compatible precoated metal excellent in coating adhesion, corrosion resistance and coin scratch resistance material. The above problems are solved by the following: (1) An environmentally compatible pre-coated metal material water-based surface treatment agent containing a decane coupling agent (A), a metal oxide sol (B), a metal compound 200837220 (c) and water-dispersible vermiculite (D), the metal compound (C) is derived from a v compound, a W compound, a Mo compound, an A1 compound, a Sn compound, a Nb compound, an Hf compound, a Y compound, a Ho compound, At least one selected from the Bi compound, the La compound, the Ce compound, and the Zn compound, and the ratio of the component (A) to the component (B) is 1/50 to 1 in terms of the solid content ratio of (B)/(A). In the range of 〇/1, the ratio of the component (A) to the component (C) is in the range of 1/1000 to 4/10 by mass ratio of the solid component of (c) / (A), and the component (a) and the component The ratio of (D) is in the range of 1 / 5 0 to 1 0 /1 in terms of the solid content ratio of (D) / (A); (2) The aqueous surface treatment agent of the above (1), wherein the metal is oxidized The sol (B) is derived from cerium oxide sol, cerium oxide sol, alumina sol, tin oxide sol, cerium oxide sol, zinc oxide At least one selected from the group consisting of a gel, a cerium oxide sol, a cerium oxide sol, a cerium oxide sol, and a cerium oxide sol; (3) an aqueous surface treating agent according to (1) or (2) above, wherein the decane coupling agent (A) At least 5% by mass of a decane coupling agent having an amino functional group;

(4) The aqueous surface treatment agent according to (1) or (2) above, wherein the decane coupling agent (A) is a decane coupling agent containing an amino functional group and a decane having an epoxy group bonded to an adjacent carbon atom. a mixture of equivalent ratios of coupling agents of 50:1 to 1:50; (5) a metal material having a dry film of 0.01 to lg/m 2 on the surface, the dried film being from the above (1) a dry film of a water-based surface treatment agent according to any one of (4); and (6) an environmentally-compatible precoated steel sheet which is formed on the surface of the metal material as described in (5) above, and which is formed without chromium The upper layer of the membrane. 200837220 The invention relates to the metal material treated by the environment-based pre-coated metal material water-based surface treatment agent of the present invention, and the pre-coated metal material coated with the chromium-free upper layer is applied, although the coating layer does not contain chromium. However, the corrosion resistance, the coating adhesion (the primary adhesion after the T-bend test, the secondary adhesion after coating), and the coin scratch resistance are excellent. Therefore, the present invention is an extremely expensive industrial invention. The precoated metal material of the present invention is also excellent in moisture resistance and chemical resistance (alkali resistance and acid resistance). [Embodiment] The best shape bear for carrying out the invention The following δ sheep detail the invention. The aqueous surface treatment agent of the present invention is characterized by containing a decane coupling agent (Α), a metal oxide sol (Β), a V compound, a W compound, a Mo compound, a Α1 compound, a Sn compound, a Nb compound, H in a specific mutual ratio. At least one metal compound (c) selected from the group f compound, the Y compound, the anthraquinone compound, the Bi compound, the La compound, the Ce compound, and the Zn compound, and the water-dispersible sand (D). The oxirane coupling agent (A) has a high activity of -OH of the stanol group formed by hydrolysis, and is strongly chemically bonded to -S i - Ο - 经由 via the base metal ruthenium and oxygen atom of the base material. This chemical bonding is particularly helpful for good adhesion to the base metal. Further, by reacting with the organic functional group contained in the upper layer, it is also advantageous in improving the adhesion to the upper layer. When a polar group having a strong polar group such as ruthenium or osmium which is a functional group of a decane coupling agent is introduced as a constituent element, the adhesion to the upper layer can be further improved. -10- 200837220 The decane coupling agent to which the present invention is applicable may, for example, be Ν-β(aminoethyl)γ-aminopropyltrimethoxydecane or Ν-β(aminoethyl)γ-amino group. Propylmethyldimethoxydecane, Ν-β(aminoethyl)γ-aminopropyltriethoxydecane, Ν-β(aminoethyl)γ-aminopropylmethyldiethoxy矽, γ-aminopropyl triethoxy sand, γ-aminopropyl trimethoxy sand, Ν-phenyl-γ-aminopropyltrimethoxy decane, Ν-phenyl-γ- Aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, Ύ-methacryloxypropylmethyldimethoxydecane, γ-methylpropene oxime Propyltriethoxydecane, ί, γ-methacryloxypropylmethyldiethoxydecane, Ν·β-(Ν-vinylbenzylamineethyl)-γ-aminopropyl Glycosyloxydecane, Ν_β-.(Ν-vinylbenzylamineethyl)-γ-aminopropylmethyldimethoxydecane, Ν-β-(Ν-vinylbenzylamineethyl )-γ-aminopropyltriethoxydecane, Ν-β-(Ν-vinylbenzylamineethyl)-γ-aminopropylmethyl Ethoxy decane, "glycidoxypropyltrimethoxy sand", γ-glycidoxypropylmethyldimethoxy sand, γ,-glycidoxypropyl triethoxy Pyridinium, [glycidoxypropylmethyldiethoxylate, 2 - (3,4-epoxycyclohexyl)ethyltrimethoxy® 7 院' γ-ride 1 ij propyl Trimethoxy decane, γ-mercaptopropylmethyldimethoxy sand, γ-mercaptopropyltriethoxy decane, γ _ propyl propyl methyl diethoxy sand, methyl trimethyl Oxydecane, dimethyl dimethoxy chopping, methyl triethoxy shixi, dimethyl diethoxy sand, ethoxylated diethoxy ethoxylate, 丫-chloropropyl Trimethoxy decane, γ-chloropropylmethyldimethoxy sand, r chloropropyl triethoxy decane, γ-chloropropyl methyl diethoxy sand, hexamethyl 2 Nitrogen Institute, γ-anilinopropyltrimethoxy sand, γ-anilinopropylmethyl-methoxydecane, γ-anilinopropyltriethoxydecane, anilinopropylmethyldiethyl- 11- 200837220 Ox decane, vinyl trimethoxy decane, vinyl methyl Methoxy decane, vinyl triethoxy decane, vinyl methyl diethoxy decane, octadecyl dimethyl [3-(trimethoxy decyl) propyl] ammonium chloride, octadecyl Methyl [3-(methyldimethoxydecyl)propyl]ammonium chloride, octadecyldimethyl[3-(triethoxydecyl)propyl]ammonium chloride, octadecyl Methyl [3-(methyldiethoxydecyl)propyl]ammonium chloride, γ-chloropropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, A Trichlorodecane, dimethyldichloro-5, dimethyl chloride: & eve, etc. These may be used in combination of only one component or a combination of plural. When the amount of the substrate treatment agent is large, there is a certain degree of compatibility with the primer applied to the upper layer, and the combination does not appear to meet expectations in performance. Among the above coupling agents, those having an amino-based functional group are difficult to form a right-and-left compatibility with the upper layer. Therefore, in the aqueous surface treatment agent (base treatment agent) of the present invention, the decane coupling agent (Α) preferably contains at least one member having an amino group-based functional group. Here, the amino functional group of the present invention means at least one functional group selected from the primary amino group and the secondary amino group. The amine functional group has a relatively high reactivity in either of an acidic medium or an alkaline medium. That is to say, in the general organic functional group having active hydrogen, 'the acidity and alkalinity of the solution also depends on the substituent adjacent to the functional group', but the amino functional group has relatively high reactivity (nucleophilicity, Alkaline). A decane coupling agent having an amino-based functional group exhibits good coating performance by reacting with a functional group (ester group, oxy group) of a resin constituting the primer of the upper layer due to high reactivity of the amine-based functional group Adhesion. The effect of improving the adhesion of the coating is 'compared with other sanding coupling agents'. The composite effect of having a more tubular effect' -12- 200837220 also improves water resistance, chemical resistance (alkali, acid), moisture resistance Wait. Among the decane coupling agents having an amino functional group, it is preferred to have one amino-functional functional group in one molecule of the decane coupling agent. The amount of the decane coupling agent having an amino functional group for the entire decane coupling agent (A) is preferably 5 on a solid component basis from the viewpoint of exhibiting higher coating adhesion. The mass% or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. When two or more kinds of decane coupling agents (A) are used, it is preferred to use a decane coupling agent having a decyl-functional functional group, and a functional group having an amino-functional functional group, for example, having a bond adjacent thereto. A decane coupling agent for an epoxy group (glycidyl group, 3,4-epoxycyclohexyl group, etc.) of a carbon atom. The proportion of such decane coupling agents used is not necessarily such that the functional groups do not react excessively with each other, and the decane coupling agent having an amino functional group is equivalent to the functional group capable of reacting with the amino functional group. Preferably, it is in the range of 50:1 to 1:50, more preferably in the range of 10:1 to 1:10, using a decane coupling agent having an amino functional group and having an epoxy group. When the group is bonded to a decane coupling agent of an adjacent carbon atom, the corrosion resistance can be further improved in addition to the effect of the above-mentioned coating adhesion due to the decane coupling agent having an amino group functional group. Further, when a plurality of decane coupling agents are used, they may be mixed with other components after mixing the two. The aqueous surface treatment agent of the present invention contains a metal oxide sol (B). The metal oxide sol (B) contributes to the improvement of adhesion from the viewpoint of introduction of a polar group. However, excessive addition causes water to easily enter the interface, and the secondary adhesion of the coating is lowered. Further, the metal oxide sol (B) improves the hardness of the film of the substrate -13 - 200837220, and contributes to an improvement in the adhesion of the coating, and as a result, it also effectively acts to improve the scratch resistance of the coin. Further, the metal oxide sol (B) also acts effectively in improving the chemical resistance, and particularly plays an important role in improving the alkali resistance.

The metal oxide sol is preferably selected from the group consisting of a chromium oxide sol, a cerium oxide sol, an alumina sol, a tin oxide sol, a cerium oxide sol, a zinc oxide sol, a cerium oxide sol, a cerium oxide sol, a cerium oxide sol, and a cerium oxide. At least one kind of the sol, more specifically, Zr〇2 sol (zirconia sol), TiO 2 sol (titanium oxide sol), Ce02 sol, Al 2 〇 3 sol (alumina sol), Sn02 sol, NbO sol, ZnO sol , Sb205 sol, Bi203 sol, Y203 sol, Ho2〇3 sol, and the like. The particle size of the metal oxide sol particles used in the present invention is preferably from 1 to 100 nm, more preferably from 1 nm to 500 nm, even more preferably from 1 n m to 1 0 0 n m, in terms of primary particle diameter. These metal oxide particles may have a secondary particle diameter or a tertiary particle diameter in the case of secondary aggregation or tertiary aggregation, but may be stably dispersed in water even if aggregated. When the primary particle diameter is less than 1 nm, the stability of the treatment agent such as chattering deteriorates. Further, when it exceeds 1 〇〇〇 nm, the bending adhesion is deteriorated. The content of the metal oxide sol (B) must be in the range of 1/50 to 10/1, preferably 1 in terms of the solid content ratio of (B)/(A) for the decane coupling agent (A). / 3 0~4 /1 range, better in the range of 1 / 1 0 ~ 2 / 1. When the content is less than 1 /5, the chemical resistance and the corrosion resistance tend to be lowered, and if it exceeds 1 0/1, the chemical resistance tends to be lowered. As a commercially available product of the metal oxide sol (B) used in the present invention, a Nanouse ZR40BL, a Nanouse ZR30BS, a Nanouse ZR30, a Nanose ZR3 OAL, and a Nanouse, which are oxidized chromium sols, can be used. ZR30AH (Nissan Chemical Co., Ltd.), ZSL-20N, ZSL-10T, ZSL-10A (manufactured by Daisei Chemical Industry Co., Ltd.), YSL_10 as a bismuth sol (first Xi Elementary Chemical Industry Co., Ltd.) ), tin oxide sol as a tin sol (made by Daisei Element Chemical Industry Co., Ltd.), SBSL-50 (made by Daiichi Element Chemical Industry Co., Ltd.) as a ruthenium sol, CESL-15N as a ruthenium sol (Nippon Elemental Chemical Industry Co., Ltd.), Nanotek Bi203 (made by C. I. Chemicals Co., Ltd.), and Nanotek Ho203 (C·I·Chemical Co., Ltd.) Nanotek Ti02 (manufactured by C.I. Chemical Co., Ltd.) as a titanium oxide sol, Nanotek ZnO (manufactured by C.I. Chemical Co., Ltd.) as a zinc sol, alumina sol 100 as an alumina sol, oxidation Aluminum sol 200, alumina sol 5 20 (manufactured by Nissan Chemical Co., Ltd.), NanoTek A1203 (C·I. Chemical (share) system) and so on. The aqueous surface treatment agent of the present invention contains the metal compound (C). The metal compound (C) is selected from at least a V compound, a W compound, an anthraquinone compound, an A1 compound, a Sn compound, a Nb compound, an Hf compound, a Y compound, a Ho compound, a Bi compound, a La compound, a Ce compound, and a Zn compound. 1 species. The metal compound (C) functions as a corrosion inhibitor (corrosion inhibitor) to improve corrosion resistance. The mechanism for improving the corrosion resistance of the metal compound (C) is not clear, but a number of valence systems are available. Further, when there is no change in the valence, the presence of the heteropoly acid can be obtained by the change in pH. The doped polyacid also has a sand chamber coupling agent (A) or a metal oxide sol (in the surface treatment agent). B) The physical or chemical action of the former has been modified by -15-200837220. Therefore, in addition to improving corrosion resistance, chemical resistance, moisture resistance, and the like are also improved. Examples of the metal compound (C)' include a carbonate, an oxide, a hydroxide, a nitrate, a sulfate, a phosphate, a fluoride, a hydrofluoric acid or a salt thereof, an oxyacid salt, an organic acid salt, etc. of the above metal. . When the metal compound (C) is an oxide, the sol form is excluded. Specific examples of the V compound include vanadium pentoxide (V), vanadium (III) oxide, vanadium (IV) oxide, vanadium (II) hydroxide, vanadium (III) hydroxide, and vanadium sulfate (II). ), vanadium (III) sulfate, vanadium (IV) sulfate, vanadium (III) fluoride, vanadium (IV) fluoride, vanadium fluoride (V), vanadium oxychloride V0C13, vanadium trichloride VC13, hexafluoride Vanadic acid (III) or its salt (potassium salt, ammonium salt, etc.), metavanadic acid (V) or its salt (sodium salt, ammonium salt, etc.), oxyvanadin acetate (iv) vo (oc (= Ch2)ch2c 〇ch3)2, vanadium acetate acetate (iii)v(o -c( = ch2)ch2coch3)3, phosphovanadomolybdate ruthenium 15_χ[Ρν12_χΜο04〇]·ηΗ2〇(6<X<12,n<; 3 0) and so on.

Examples of the W compound include tungsten (IV) oxide, tungsten (V) oxide, tungsten (VI) oxide, tungsten (IV) fluoride, tungsten (VI) fluoride, and tungstic acid (VI) H2W04 or a salt thereof (ammonium). Salt, sodium salt, etc.), metatungstic acid (vi) h6[h2w12o4〇] or its salt (ammonium salt, sodium salt, etc.), paratungstic acid (VI) H1G [W12〇46H1()] or its salt (ammonium salt As a Mo compound, phosphorus pentamo molybdate H15_x [PV12_xMoO40] • nH20 (6 < X < 12, n < 30), molybdenum oxide, molybdic acid H2Mo〇4, ammonium molybdate, secondary Ammonium molybdate, sodium molybdate, phosphorus molybdenum oxide (for example, phosphomolybdic acid (ΝΗ4) 3[Ρ〇4Μ〇ΐ2〇36] · 3H2〇, merciful sodium Na3[P〇4M〇l2〇36] Η Η 20, etc.). -16- 200837220 Examples of the A1 compound include aluminum nitrate, aluminum sulfate aluminum sulfate, ammonium aluminum sulfate, aluminum phosphate, aluminum carbonate, and oxygen/aluminum; and examples of the Sn compound include tin (IV) oxide and tin. Tin (II) chloride, tin (IV) chloride, tin (II) nitrate, ammonium stannate (NH4) SnF6, etc.; as Nb compound, can be [Nb205), sodium citrate (NaNb03), cesium fluoride (NbF5), (NH4)NbF6, etc. Examples of the Hf compound, the Y compound, and the Ho compound La compound include oxidative, hexafluorohydrogen acid, cesium oxyhydroxide, cerium oxide, cerium oxide, cerium oxide, and the like. Examples of the Ce compound include cerium oxide, cerium acetate, cerium (III) nitrate or (IV), cerium ammonium nitrate, barium sulfate, and a chloro Zn compound, and examples thereof include zinc oxide, zinc hydroxide, zinc sulfate acetate, and chlorination. Zinc, sodium zincate, etc. The content of the metal compound (C) must be 1/1000 ^ . , preferably in the range of 1 / 3 00 to 2/10, more preferably in the solid content ratio of the decane coupling agent (C) / (A). For the range of 1. If the content is less than 1 / 1 0 0 0, no effect is obtained, and if it exceeds 4/1 0, depending on the coating of the upper layer, the secondary adhesion of the coating may be lowered. Further, in the case where the physical properties are deteriorated due to the addition of the metal compound (C), acetic acid, gluconic acid, tartaric acid, malic acid, ascorbic acid or dan can be appropriately added to improve the liquid stability. , potassium aluminum sulfate, aluminum, sodium hydroxide, Na2Sn03, tin (IV), hexafluoride, ruthenium pentoxide, ammonium hexafluoroantimonate, Bi compound, ruthenium, ruthenium-based Ce(CH3C02)3, etc.; As zinc, zinc nitrate, and (A), the type of the primer is improved in the range of ～4/1 0/100 to 1/10, and the liquid stabilizer, propionic acid, oxalic acid, etc. Carboxylic Acid-17- 200837220 The aqueous surface treatment agent of the present invention contains water-dispersible vermiculite (D). Water-dispersed vermiculite (D), from the point of introduction of a polar group, is a lifting cylinder that contributes to the adhesion. However, the excessive addition causes the water to easily enter the interface, and the adhesion of the coating is lowered twice. Further, the water-dispersible vermiculite (D) improves the hardness of the base film and contributes to the improvement of the coating adhesion. As a result, the coin scratch resistance is also effectively improved. In the water-dispersible vermiculite (D), the gas phase vermiculite formed by the gas phase reaction and the liquid phase meteorite formed by the liquid phase reaction in a water-dispersed state can be used together. The particle diameter of the water-dispersible vermiculite (D) used in the present invention is preferably from 1 to 1 0 0 n m ', more preferably from 2 n m to 5 0 n m in terms of primary particle diameter. These water-dispersible sandstones (D) may have a secondary particle diameter or a tertiary particle diameter in the case of secondary aggregation or tertiary aggregation, but may be stably dispersed in water even if aggregated. When the primary particle diameter is less than 1 n m, the stability of the treatment agent such as shake degeneration deteriorates. Further, if it exceeds 100 nm, the bending adhesion is deteriorated. The content of the water-dispersible vermiculite (D) is preferably in the range of 1/50 to 10/1 in terms of the solid content ratio of (D)/(A) for the decane coupling agent (A), and J is preferably. In the range of 1/3 0 to 4/1, more preferably in the range of 1/10 to 2/1. When the content is less than 1 / 5 0, the coating adhesion and the coin scratch resistance tend to be lowered, and if it exceeds 1 0/1, the chemical resistance tends to be lowered. As a commercially available product of the water-dispersible vermiculite (D) used in the present invention, Snowtex C, Snowtex 0, Snowtex N, Snowtex NXS, Snowtex OS, Snowtex OUP, Snowtex OL, which are liquid phase ceresite, may be mentioned. Snowtex PS-MO, Snowtex PS-S, Snowtex S, Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex 30 -18- 200837220, Snowtex 40 (all are Nissan Chemical Industry Co., Ltd.), etc. Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX80, Aerosil MOX170 (all manufactured by Japan Aerosil Co., Ltd.), etc., which are gas phase sandstones. Only one of these components may be used, or a plurality of them may be used in combination. In the water-dispersible vermiculite (D) used in the present invention, an acid or a base can be appropriately added from the viewpoint of dispersion stability. The acid may be any of an inorganic acid and an organic acid, and examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and acetic acid. Further, examples of the test include sodium hydroxide, potassium hydroxide, calcium hydroxide, and aluminum hydroxide. The water-based surface treatment agent of the present invention preferably has a p Η of from 3 to 10, more preferably from 5 to 9. In particular, when a decane coupling (fluorene) having an amino functional group is used, its ρ Η is preferably from 7 to 9. In the aqueous surface treatment agent of the present invention, in order to control the pH of the treatment agent, an appropriate acid (e.g., acetic acid 'phosphoric acid or the like) or a base (e.g., ammonia, organic amine, etc.) may be added. (# The aqueous surface treatment agent of the present invention may further contain a water-soluble resin for softening the treated film, and a surfactant and a tackifier called a wetting improver for obtaining a uniform film on the surface to be coated. 'The conductive material for improving the solderability, the coloring pigment for improving the pattern design, etc. The medium of the aqueous surface treatment agent of the present invention is water. The total solid content concentration of the aqueous surface treatment agent of the present invention is not particularly However, considering the film formability or handleability, the total solid content concentration is preferably about 1 to 20% by mass. -19- 200837220 The aqueous surface treatment agent of the present invention can be obtained by using a decane coupling agent (A). The metal oxide sol (B), the metal compound (C), the water-dispersible vermiculite (D), and other additives at the time of use are added to water and stirred to be produced, and the order of addition of each component is not particularly limited.

As the metal material for applying the water-based surface treatment agent of the present invention, cold-rolled steel sheets, hot-milk steel sheets, hot-dip galvanized steel sheets, electrogalvanized steel sheets, molten alloyed galvanized steel sheets, aluminized steel sheets, and aluminized-zinc alloys can be used. A metal material such as a steel plate such as a steel plate or a stainless steel plate, an aluminum plate, a copper plate, a titanium plate, a magnesium plate, or another plated metal plate, which is generally known as a metal plate. Before the aqueous surface treatment agent of the present invention is applied to a metal material, the metal material can be arbitrarily subjected to usual treatment such as hot water washing, alkali degreasing, and surface adjustment. The aqueous surface treatment agent of the present invention can be applied to a metal material by a usual coating method such as roll coating, curtain coating, air spray, airless spray, dipping, rod coating, brush coating or the like. The drying after application is not particularly limited in terms of drying method, drying temperature, and drying time, as long as it is the evaporation temperature and time of moisture. For example, in an oven, the highest reaching temperature of the metal material such as the coated metal plate can be made dry at 60 to 120 °C. The coating amount of the aqueous surface treatment agent of the present invention must be in the range of 0.01 to lg/m 2 , preferably in the range of 0.02 to 0.4 g/m 2 , more preferably 0.05 to 0.2 g/m 2 in terms of the dry film amount. range. When the amount of the film is less than 0.01 g/m2, the amount of the film is too small, and the unevenness of the film amount tends to occur in the portion (the adhesion to the metal material and the upper layer) tends to be insufficient. Further, if the amount of the film -20-200837220 exceeds 1 g / m 2 ', the coating adhesion tends to be insufficient, and the cost is unfavorable. The treatment of the aqueous surface treatment agent of the present invention is usually carried out as a substrate treatment of a precoated metal material as described below, and can also be carried out as a substrate treatment of a laminated steel sheet. The invention also relates to pre-coated metallic materials. The precoated metal material of the present invention can be obtained by applying the aqueous surface treatment agent of the present invention to a metal material and forming a coating layer which is formed by drying to form an upper layer coating layer which does not contain a complex layer. By the non-chromate primer layer and the topcoat layer formed thereon (the topcoat layer usually does not contain chromium), the upper film layer can be coated with the aqueous surface treatment agent of the present invention and The non-chromate primer is applied onto the dried film to form a non-chromate primer, and after drying, a top coat is applied thereon. Further, the upper film layer may be composed only of a top coat. In this case, the upper film layer may be coated with a top coat by applying the aqueous surface treatment agent of the present invention and drying the film. form. As the above non-chromate primer which can be used in the present invention, any primer can be used as long as the primer of the chromate-based anti-rust pigment is not used in the blending of the primer. The base resin of the non-chromate primer may be any one of a water system, a solvent system, and a powder system. The type of the resin is generally known. For example, a polyacrylic resin, a polyolefin resin, a polyurethane resin, an epoxy resin, a polyester resin, or a polybutyral resin may be used as they are or in combination. , melamine resin, and the like. The rust preventive pigment is generally known, and for example, (1) a phosphate-based rust preventive pigment such as zinc phosphate, iron phosphate or aluminum phosphate, or (2) a calcium molybdate, an ammonium molybdate or a bismuth molybdate-21 can be used. - 200837220 is a rust-preventive pigment, (3) vanadium-based rust-preventive pigment such as vanadium oxide, and (4) fine-particle vermiculite such as water-dispersed vermiculite or fumed silica. For all of the non-chromate primers, the blending amount of each component based on the solid content is preferably such that the blending amount of the rust preventive pigment on a solid content basis is good for the entire non-chromate primer. 1 to 40% by mass. When the amount of the rust preventive pigment is less than 1% by mass, the corrosion resistance is insufficient, and if it exceeds 4% by mass, the workability is lowered. The coating film thickness of the primer is preferably from 1 to 30 μm in terms of dry film thickness. If it is lower than 1 μm, the corrosion resistance is lowered, and if it is more than 30 μm, the adhesion during processing is lowered. The baking and drying strip of the above non-chromate primer is not particularly limited, and may be, for example, 1 to 30 ° C for 1 〇 5 minutes to 5 minutes. The top coat is not particularly limited, and any of the usual top coats for painting can be used. The base resin of the top coat may be in any form such as a water system, a solvent system or a powder system. The type of the resin is generally known. For example, a polyacrylic resin, a polyolefin resin, a polyurethane resin, an epoxy resin, a polyester resin, or a polybutyral can be used as it is or in combination. A resin, a melamine resin, or the like. The coloring pigment may be blended in the topcoat. As the coloring pigment, there is no particular limitation, and titanium white, zinc yellow, alumina white, carbon black, red iron oxide, yellow iron oxide, molybdenum orange, chromium oxide may be used. An inorganic pigment such as (1 V) or an organic pigment such as Hansa Yellow, pyrazolone orange or azo pigment. Further, the above-mentioned anti-rust pigment may be appropriately blended in the top coat, and an antifoaming agent, a leveling agent, a dispersing agent, a diluent for reducing the viscosity of the coating, and the like may be appropriately blended. -22- 200837220 The coating film thickness of the top coat is preferably 3 to 4 〇 μ m in terms of dry film thickness. If it is less than 3 μm, the uranium resistance is lowered, and if it exceeds 40 μm, the adhesion is lowered and the cost is high. The baking and drying conditions of the above top coat are not particularly limited, and may be, for example, from 160 to 350 ° C for 10 seconds to 20 minutes. The method for applying the above-mentioned non-base salt primer and top coat is not particularly limited, and a general dipping method, a spray method, a light coating method, an air spray method, an airless spray method, or the like can be used. ('Examples Hereinafter, the present invention will be specifically described by way of examples and comparative examples of the present invention. 1. Production of test plates 1.1 Test materials and electrogalvanized steel sheets (hereinafter: EG) Thickness of 0.6 mm, plating amount per side 20g/m2 (both sides plating) • Hot-dip galvanized steel sheet (symbol: GI)

The plate thickness is 0.6mm, and the galvanized adhesion amount is 50g/m2 on each side (both sides are plated). • Aluminized-zinc alloy steel plate (hereinafter: GL) The plate thickness is 0.6mm, and the coating adhesion amount is 50g/m2 per side (both sides are plated) (1) Pretreatment of CL-N3 64 S (manufactured by PAR本 PARKERIZING Co., Ltd.) with an alkali degreasing agent into an aqueous solution having a concentration of 20 g / L and a temperature of 60 ° C, and immersing the test material therein 1 After two seconds, it is washed with pure water and dried. 1.3 Surface treatment -23- 200837220 • Examples 1 to 3 3. Comparative Examples 1 to 1 8 On the surface (single side) of the pretreated material, select the materials shown in Tables 4 to 6. For the test material, a surface treatment agent having the composition shown in Tables 1 to 3 was applied in a hot air drying oven at a temperature of 80 ° C using a roll coater in such a manner that the dry film amount became 〇·1 g/m 2 . Dry under the conditions. • Coating-type chromate treatment (Comparative Examples 19 and 20) On the surface (sheet surface) of the test material after the pretreatment, a roll coater was used, and the coating amount of Cr was 40 mg/m 2 . ZM- 1 3 00AN (made by Japan PARKERIZING Co., Ltd.) of the cloth type chromate agent was dried in a hot air drying oven at a limit plate temperature of 80 °C. 1.4 Coating of the lower coating and the top coating The primer and the topcoat were applied in the following two combinations on the treated surface of each of the surface-treated sheets prepared in 1/3. <Upper layer A>: Coated a commercially available primer coating (manufactured by Dainippon Co., Ltd., V-knit #200) (dry film thickness: 5·5 μm), baked at 200 ° C, and then baked Further, a top coat (V-knit # U 5 00) (dry film thickness: 17 μm) was applied to the surface, and then baked at 220 ° C to prepare a test plate. <Upper B > : Coated commercially available primer paint (made by Japanese Paint Co., Ltd.)

Flekicoat 600) (dry film thickness 5·0μιη), baked at 200 ° C, and then coated with a top coat on the baking surface (made by Nippon Paint Co., Ltd., Flekico at 5 0 3 0) (dry film thickness) After 15#111), at 22 5 ° (: baking, making test plate. 2. Evaluation test 2.1 Corrosion resistance on each test plate produced by the cutter, cutting into the metal substrate - 02372220 In the case of the flaw, the salt spray test specified in JIS-Z2 3 7.1 was carried out for 480 hours. The judgment criterion was to measure the width of the coating film from the cut portion (the maximum 値 on one side). Further, the end face corrosion resistance was measured from the coating film on the end surface. Bulging width (maximum 値) ° &lt;Evaluation criteria - cutting portion&gt; ◎: less than 2 mm 〇: 2 mm or more and less than 6 mm Δ : 6 mm or more and less than l 〇 mm X : 10 mm or more ^ &lt; Evaluation standard - end face &gt; ◎: less than 4 mm 〇: 4 mm or more and less than 6 mm □ : 6 mm or more and less than 8 mm △ : 8 mm or more and less than 12 mm χ : 1 2 mm or more 2.2 Bending adhesion test 2 · 2 · 1 - time Bending adhesion test (coating one-time adhesion) I, according to the test method of JIS-G33 12, for each test plate, at 20 ° C In the 2 T bending test in which the inner partition plate was used as the two sheets, the peeling state of the coating film after the tape peeling was observed with the naked eye, and the coating adhesion was evaluated in accordance with the following criteria. <Evaluation criteria> ◎ : No peeling flaw: peeling area is less than 10% □: peeling area is 10% or more and less than 50% -25- 200837220 △: peeling area is 50% or more and less than 8〇% X: peeling area is 80% or more 2 · 2.2 Secondary bending adhesion (coating secondary adhesion) After immersing the test plate in boiling water for 2 hours, it is placed for one day, and the test is performed in the same test as the one-time bending adhesion test. The criterion is as follows: Evaluation criteria> ◎: no peeling ^ 〇: peeling area is less than 10% □: peeling area is 10% or more and less than 50% △ ·· peeling area is 50% or more and less than 80% X: peeling area 80% or more 2.3 The coin-resistant scratch resistance is set at 45 degrees from the respective test plates, and the coating film is rubbed at a load of 3 Kg and a fixed speed. The degree of damage of the coating film is visually observed, and the coin is resistant according to the following criteria. Scratch evaluation. Again, In the following evaluation, the area where the primer was peeled off and the primer was exposed was not caused by the damage of the substrate-treated film, and the exposed area of the substrate was not included. <Evaluation criteria> ◎: The exposure of the substrate was 0. % (Including only the primer is exposed) 〇: The exposure of the substrate is less than 10% □: The exposure of the substrate is 10% or more and less than 50% △: The exposure of the substrate is 50% or more and low. 80% -26- 200837220 X : The exposure of the substrate is more than 80%. 2.4 Alkali resistance. The number of occurrences of foaming after immersing the test plate in a 5% aqueous sodium hydroxide solution at room temperature for 24 hours. The evaluation of the density occurred. The judgment criteria are as follows. — ◎: No blistering 〇: 1 blistering is less than 2 mm and the density is also F. □ : The size of one foaming is about 0.2mm~1mm and the density is F f , or the size of one foaming is about 2.2mm~0.4mm and the density is Μ 〇 △ : the size of one blistering The density is about 1 mm to 1.5 mm, and the density is F, or the size of one foaming is about 4 mm to 1 mm, and the density is Μ, or the size of one foaming is 0.2 mm or less and the density is MD. X: The size of one foaming is 1.5 mm or more, or the density of foaming is 0.2 mm or more, and the density is MD, or the density D is independent of the size of foaming. Further, in the evaluation test of the above alkali resistance and the following acid resistance, F, Μ, M D, and D mean the following meanings. F: The number of occurrences of foaming is extremely small. Μ: The number of blistering is small. MD: The number of blistering occurs. D: The number of blistering is very large. 2.5 Acid resistance After the test plate was immersed in a 5 % aqueous sulfuric acid solution at room temperature for 24 hours -27-200837220, the number of occurrences of foaming and the occurrence density were evaluated. The judgment criteria are as follows. ◎: no blistering 〇: 1 blistering is 〇. 2 mm or less and the density is also F. □ : The size of one foaming is about 2mm~1mm and the density is F, or the size of one foaming is about ~〇.4mm and the density is Μ. △ : The size of one foaming is about 1mm~1.5mm and the density is F, or the size of one foaming is about 4mm~lmm and the density is Μ, or the size of one foaming is 〇. 2 mm or less and the density is MD. X: The size of one foaming is 1.5 mm or more, or the density of foaming is 0.2 mm or more, and the density is MD, or the density is D regardless of the size of foaming. 2 _ 6 Moisture resistance The coating film of the test plate was cut into the scratches of the metal substrate by a cutter, and placed at a temperature of 9.8 ° C and a temperature of 4 〇 ° C for 1 hour. The judgment reference system shifts the coating film bulging width from the cutting portion (maximum 値 on one side). / @ : less than 2mm 〇: 2 mm or more and less than 4 mm 〇: 4 mm or more and less than 6 mm △ : 6 mm or more and less than l 〇 mm Meaning, · 1 0 mm or more 31 fM Jia results Table 4 to 6 shows the above evaluation test the result of. In the examples 1 to 3 of Tables 4 and 5, the aqueous surface treatment agent of the present invention (N〇. J to 2 9 in Table 1) was applied, and the metal material which was dried to form a film was applied. The performance of the coated plate (test plate), corrosion resistance (corrosion of the cut portion and end face), adhesion of the coating (after the τ bending test, once, twice), and the resistance to coin scratching are good, showing Compared with the case of the chromate treatment of Comparative Examples 1 and 20, the performance is equal to or higher than that of the case of the use of a terpene coupling agent having an epoxy group. The chemical resistance (testability and acid resistance) and the moisture resistance are excellent (comparison of Examples 2 and 5 with Examples 18 and 19). Further, the decane having an amino functional group is used. When the coupling agent and the decane coupling agent having an epoxy group are used, in comparison with the case where only the former is used, in particular, the coating adhesion and the coin scratch resistance are excellent (comparison between Example 6 and Examples 3 1 to 3 3 ). In one aspect, Table 3 and 32 of Table 3 outside the scope of the present invention are used (no metal oxide is used) Sol (Β) and metal compound (C)), No. 33 and 35 (without decane coupling agent (A) and metal oxide sol (B)), and No. 31 and 34 (no metal oxide sol ( In Comparative Examples 1 to 6 of Table 6 of the water-based surface treatment agent of B) and water-dispersible vermiculite (D), corrosion resistance (cutting portion and end surface corrosion resistance), and coating adhesion (after T bending test, once) , secondary), at least 3 of the coin scratch resistance, moisture resistance and chemical resistance (alkaline resistance and acid resistance). Use No. 36, 37 and 44~47 (metal compound (C) In the comparative examples 7, 8 and 15 to 18 of the water-based surface treatment agent of the present invention, the corrosion resistance (cutting portion and end surface corrosion resistance) and the coating adhesion (after the T bending test, once) At least 2 of the resistance to coin scratching and chemical resistance (alkaline resistance -29-200837220 and acid resistance). Also, use No. 3 8 (water dispersible vermiculite (D) In the comparative example 9 of the aqueous surface treatment agent according to the present invention, 'corrosion resistance (cutting portion and end surface corrosion resistance), moisture resistance and chemical resistance (alkaline resistance and In the comparative example 1 0 to 1 4 of the aqueous surface treatment agent using N 〇. 3 9 to 4 3 (the amount of the metal oxide sol (D) is used in the present invention), Corrosion resistance (corrosion of cutting part and end face) and chemical resistance (alkaline resistance and acid resistance) are poor. Γ -30- 200837220 Chain 枭 2 观 闼漱 « « « « « « « « « « « « « D) / (A) '-. cn m 1 &lt; cn r - Η rH in rH in rH mr - ^ IT) 1 - Η r - ^ 1 / 25 in T - Η water dispersion 彳 (D type 1 liquid phase矽石1 ....... liquid gangue liquid gangue liquid phase sandstone liquid gangue liquid phase Ϊ 石 stone liquid gangue liquid gangue liquid phase gangue liquid gangue liquid phase Vermiculite liquid phase vermiculite liquid phase vermiculite liquid phase 5 Xishi liquid phase sandstone liquid vermiculite liquid phase 5 stone compound: C) (C) / (A) 1/20 1/20 1/20 1 1 /20 1/20 1/20 1/500 20/100 1/500 20/100 1_ 1/500 :20/100 1 1/500 20/100 1/20 1/20 1/20 1/20 Metal (type &gt; Mo &lt;&lt;du&gt;&gt;&lt;&lt; υ 〇 &lt;DU &gt;&gt;&gt; : sol 0 (B) / (A) ^ Τ) i &quot;4 T--^ r —^ in —. f A ΙΟ mm rH r—^ r—( KD ▼•ή metal oxyhydroxide seven (B type i Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol Zr sol | Zr sol 1_ Zr sol Zr Sol Zr Sol Zr Sol Sn Solane Coupler (A) Ν-β (aminoethyl) γ-aminopropyltrimethoxydecane γ-aminopropyltriethoxydecane γ-aminopropyltriethyl Oxydecane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decylaminopropyl Triethoxy oxane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane! γ-aminopropyl triethoxy矽 γ γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane 1 γ-glycidoxypropyl trimethoxy decane 1 ' γ-aminopropyl triethoxy decane γ-Aminopropyltriethoxydecane γ-Aminopropyltriethoxydecane d 1 i (Ν寸'Ο Bu 〇〇ON 〇r—Η CN 寸卜00 —T—(cn- 200837220 Chain Comedy Mis漱味爷&lt; N(矽)矽石) (D)/(A) T—Η in ▼—Η rH τ-Η V · &lt; 1 4 y—i Water dispersion 1 (D type liquid phase sandstone liquid gangue liquid phase 矽矽 矽 矽 矽 矽/20 1/20 1/20 1/20 1/20 1/20 1/20 1/20 1/20 1/20 Metal (Type > &gt;&gt;&gt;&gt;&gt;&gt;&gt;&gt;&gt;&gt; : sol 0 (B) / (A) ^ - 4 ^ - 4 τ - Η 1 / 25 τ - Η Τ - Η ί i τ - Η rH rH ^ r \ τ - Η metal oxygen 彳 seven (B type Ce sol Ζ sol Y sol_1 Zr sol Zr sol Zr sol Ζ sol Bi sol Zr sol Zr sol "Zr sol decane coupling agent (A) 1 γ-aminopropyl triethoxy decane γ-amino group Propyltriethoxydecane γ-aminopropyltriethoxydecane 1 ——— _ ...______ 1 γ-Aminopropyltriethoxydecane γ-Aminopropyltriethoxydecane γ- Aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane E: .. secret _ fu silver 5 S w two in Ss s secret m ^ U ?&quot;7 — l丨丨秘_ E .. Secret Zheng Baker Secret “N3$ IH ^ Paste Hf- ^ IH 2 Lake··: You ler ikif City IW Secret KHn ηΐ Crane 6 (Ν (Ν m (N ( Ν 00 (N On) (D)/(A) m rH 〇ψ Ή ο &lt; Η r mai 20/1 in r-^ rH 5 to 1 &lt; in τ-Η r^H water dispersion&gt; (D type liquid phase vermiculite 1 liquid phase vermiculite liquid vermiculite 1 gas phase vermiculite liquid phase vermiculite liquid phase vermiculite liquid phase vermiculite liquid phase vermiculite 1_ liquid phase Vermiculite liquid phase vermiculite liquid phase vermiculite liquid phase vermiculite liquid phase vermiculite liquid vermiculite liquid phase vermiculite liquid phase vermiculite compound [C) (C)/(A) 〇1/20 〇1 1/20 1 50/100 1/2000 1/20 1/20 1/20 1 1/20 1/20 1/20 50/100 1/2000 50/100 1/2000 Metal 1 Category 1 Mo 1 1 Mo Mo Mo &gt;&gt;&gt;&gt;&gt;&gt;&gt;&gt; Mo Mo U (DU : sol) (B) / (A) 1 1 1 1 1 1 ^ Τ) τ - Η rH rH 1 20/1 〇 1 /100 1/100 20/1 ^Τ) rH JO rH to τ-Η rH metal oxidation (B type 1 1 1 1 1 1 Zr sol Zr sol Zr sol Zr sol 1 Zr sol! Y sol sol Zr sol Zr sol Zr sol Zr sol decane Mixture (A) γ-glycidoxypropyltrimethoxydecane Ν-β(aminoethyl)γ-aminopropyltrimethoxydecane γ-aminopropyltriethoxydecane 丨1 γ- Aminopropyl triethoxy decane 1 γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl three Ethoxy decane γ-aminopropyl triethoxy decane γ-aminopropyl triethoxy decane i γ-aminopropyl triethoxy decane 1 .......... γ -aminopropyltriethoxydecane γ-aminopropyltriethoxydecane γ-aminopropyltriethoxydecane γ-aminopropyltriethoxydecane γ-aminopropyltri Ethoxy decane d 2 (Ν mm in mm 00 m 〇\ cn 〇rH 丨ε£_ 200837220 Metal oxide sol (B) Zirconia sol: Nanouse ZR30AL (manufactured by Nissan Chemical Co., Ltd.) Y2〇3 Sol: Nanotek Y203 (CI Chemical Co., Ltd.)

Ce02 Sol: CESL-15N (manufactured by Daisei Element Chemical Industry Co., Ltd.) Sn02 Sol: Sigma Elemental Chemical Industry Co., Ltd. ZnO Sol: Nanotek ZnO (C.I. Chemical Co., Ltd.)

Bi203 Sol: Nanotek Bi203 (manufactured by C.I. Chemicals) Metal compound (C) W: ammonium metatungstate

Mo: molybdenum acid A1: Hydroxide

Ce: yttrium oxide V: oxy vanadium acetate acetate water-dispersible vermiculite (D) liquid gangue: SnowtexN (manufactured by 曰Chemical Industry Co., Ltd.) 矽 矽 :: Aerosil 200 (曰本 Aerosil (股))) -34- 200837220 c 煺^¥|缄.«}&amp;-_inch嗽ng 〇◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇辍κ s 纒〇◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 硬币 硬币 硬币 硬币 ◎ ◎ 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇^|S ^ mn 13 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇m TM in* ^ 1 ◎ 〇〇〇〇〇〇〇〇〇 □ 〇 〇 〇 〇 ◎ : 虫 〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X X cutting section 〇 ◎ ◎ ◎ ◎ 〇〇〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 上上层&lt;&lt;&lt;&lt; CQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;;&lt;&lt; Water-based surface treatment agent No.1 No.2 No.2 No.2 No.2 No.3 No.3 No.4 No.4 No.6 No.7 No.7 No.8 No.10 No.10 No. No.12 No.13 No.14 No.15 Test material 〇V-) 〇〇〇ω 〇Ο Ο GL 〇GL aa 〇〇aa GL GL Example 1 Example 2 Example 3 Example 4 Example 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment M Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 · ξί· 200837220 Hu Guan 5 〇〇〇〇 〇〇 〇 〇〇〇〇 〇〇〇〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ resistant to coin scratch 〇 □ ◎ ◎ ◎ ◎ OH ^ ^ rb 11 〇〇〇〇〇〇〇〇〇〇〇〇 ◎ ◎ ◎ 1 m ^ 匕 1 〇〇〇〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ 丨 性 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇 ◎ 〇 _ X cutting part 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 Upper layer PQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; 17 No.18 No.19 No.2 No.2 No.2 No.2 No.2 No.2 No.2 No.2 No.2 No.2 No. GL GL 〇 GL 〇〇 &gt; -1 〇 Example 19 Embodiment 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 丨9CO—200837220 EKfiisflMKs: i9^ Hu Jing 1^1 y -- &lt;] X □ &lt; □ &lt; □ □ □ □ □ &lt; □ □ □ □ □ ◎ ◎ ◎ m iS X □ &lt; □ &lt; □ □ □ □ □ &lt;&lt; 〇 □ □ □ □ ◎ ◎ 耐 Moisture resistance &lt;] □ &lt; □ &lt;] 〇〇 □ □ 〇〇〇〇〇〇〇〇 ◎ ◎ Resistance to coin scratching 〇 □ □ &lt;&lt;]&lt;] 〇〇 ◎ ◎ 〇〇〇 ◎ 〇 &lt; 〇 ◎ ◎ Sb 1丨 □ □ 〇 XX &lt; 〇〇〇〇〇〇〇 &lt;3 〇 &lt; 〇◎ ◎ γτ-[ m TM &quot;bi ◎ □ 〇X &lt;3 X &lt; 〇〇□ 〇〇〇〇&lt;] 〇&lt; 〇〇◎ worm end face&lt;3 &lt;&lt;&gt;&lt;〇&lt; □ □ □ □ □ □ 〇 &lt; 〇 &lt; ◎ ◎ 耐仓X切割部&lt;] &lt;&lt;&lt;&lt;&lt;&gt; ◎ &lt;] □ 〇 □ □ □ 〇 ◎ ◎ &lt; ◎ ◎ Upper layer &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; No.32 No.33 No.34 No.35 No.40 No.4 No.4 No.4 No.4 No.4 No.4 No.4 No. Salt i chromate test material α Ο Ο GL Ο GL GL Ο GL GL 〇〇〇〇〇 GL 〇 a GL Ο Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparison Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example π Comparative Example 18 Comparative Example 19 Comparative Example 20_Li — 200837220 [Simple description of the drawing] \ \\ [Main component symbol description] &amp; 〇J \\\ -38-

Claims (1)

200837220 X. Patent application scope: 1 · An environment-compatible pre-coated metal material water-based surface treatment agent, which has a decane coupling agent (A), a metal oxide sol (B), a metal compound (c) and water dispersibility Vermiculite (D), the metal compound (C) is derived from a v compound, a w compound, a Mo compound, an A1 compound, a Sn compound, a Nb compound, a Hf compound, a Y compound, an anthraquinone compound, a Bi compound, a la compound, At least one selected from the Ce compound and the Zn compound, and the ratio of the component 丨A)iSi component (B) is 1/5 〇 to f '' 1 0 / by the solid content ratio of (B) / (A) / In the range of 1, the ratio of the component (A) to the component (C) is in the range of 1/1000 to 4/10 in terms of the solid content ratio of (c) / (A), and the component (a) and the component (D) The ratio of the solid content of (D) / (A) is in the range of 1 / 5 〇 ~ 1 〇 / 1. 2) The aqueous surface treatment agent according to claim 1, wherein the metal oxide sol (B) is derived from zirconia sol, cerium oxide sol, alumina sol, tin oxide sol, cerium oxide sol, zinc oxide sol, oxidation At least one selected from the group consisting of cerium sol, cerium oxide sol, cerium oxide sol and cerium oxide sol. The aqueous surface treatment agent according to claim 1, wherein at least 5% by mass of the decane coupling agent (A) is a decane coupling agent having an amino functional group. 4. The aqueous surface treatment agent according to claim 1, wherein the decane coupling agent (A) is a decane coupling agent containing an amino functional group and a decane coupling agent having an epoxy group bonded to an adjacent carbon atom. Equivalent ratio 5 0 : 1~1 : 5 0 mixture. -39- 200837220 5. A metal material having a dry film having a thickness of 0.01 lg/m 2 on the surface. The dry film is dried from an aqueous surface treatment agent according to any one of claims 1 to 4. Membrane. 6. An environmentally-compatible pre-coated steel sheet which is formed on the surface of a metal material as in the fifth item of the patent application, and is formed with an upper layer film containing no chromium. -40- 200837220 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: