TW200416300A - Treating solution for surface treatment of metal and a method for surface treatment - Google Patents

Abstract

This invention provides an aqueous fluid for surface treatment for use in surface-treating one metal material selected from iron based materials, zinc based materials, aluminum based materials and magnesium based materials, or surface-treating, at the same time, two or more of the above metal materials, characterized in that it comprises one or more compounds selected from zirconium compounds and titanium compounds in an mount of 5 to 5000 ppm in terms of the metal and 0.1 to 100 ppm of a free fluoride ion and has a pH of 2 to 6; and a method for the surface treatment of the metal material, which comprises contacting the metal material with the aqueous fluid or subjecting the metal material to an electrolytic treatment in the aqueous fluid, to form a coating film. The fluid may further comprise a calcium compound, a magnesium compound or a strontium compound, a phosphate residue, an oxygen acid and/or a salt thereof , a polymer and a surfactant. The aqueous fluid is free of a component harmful to the environment and the method allows the precipitation, on the surface of a metal, of a surface treatment coating film being excellent in the corrosion resistance after coating, without generating a sludge resulting in a waste.

Description

200416300 Description of the invention: [Technical field to which the invention belongs] This: Ming is about the surface treatment liquid and the surface treatment of iron-based materials represented by car bodies, magnesium-based materials, rough materials, etc. ^ 、 Aluminum alloy materials and materials Two, early one, or two or four kinds of metal structures: = each individually or two kinds ... After simultaneous coating, it can precipitate the strange surface of the famous insect II Handle the film. [Previous technology] Technique 7 for precipitating a surface-treated film with excellent recording resistance after coating a metal surface. At present, the oncite treatment method or chromate treatment method is generally used. The zinc scalate treatment method can deposit a film with excellent neodymium resistance on the surface of steel such as cold rolled steel, galvanized steel, and some aluminum alloys. However, when the phase zinc treatment method is performed, generation of sludge by reaction side is unavoidable ', and depending on the type of aluminum alloy, the rust resistance after coating is sometimes not diminished. For aluminum alloys, chromate treatment can fully ensure the performance after coating. However, according to the current environmental protection regulations, the chromate treatment method that contains the harmful component hexavalent chromium in the treatment liquid is kept away. Therefore, the invention shown below proposes a surface treatment method that does not contain harmful components in the treatment liquid. For example, a non-chrome coating agent for a metal surface containing a compound having a non-shared electron-to-nitrogen atom and a non-chrome coating agent for a metal surface containing the above compound and a compound are proposed (see Japanese Patent Application Laid-Open No. 2000-204485). In this method, by coating the composition described above, it is possible to obtain a surface treatment film that does not contain a hexavalent complex of harmful components and has excellent corrosion resistance and adhesion after coating. But 200416300 = Γ; Γ is limited to Shao alloy, and because the surface τ 'is formed by coating and drying, it is applied to complex structures such as automobile bodies.

, Surface Γ, there are various methods for depositing adhesiveness by chemical reaction after coating and Qing Youli's surface treatment coating. U 1 ^! RQ7Q V ^ (see Japanese Patent Application Laid-Open No. Sho 56-material 404). However, the object of the Ren-Method gold = two is limited to the material itself, the excellent alloy, and it is impossible to deposit a surface treatment film on the surface of the iron ', plutonium material. You Mingming proposed that the surface treatment group consisting of metal acetoacetone and water-soluble titanium-soluble compound = = a surface treatment film technology (够 照 特) capable of precipitating coatings and excellent adhesion after coating. Open _-Bribery Bulletin No. 7). After using this method, the applicable metal materials are expanded to magnesium, ballast, zinc, and plating other than Shao alloy. However, it is impossible to deposit a surface treatment layer on the surface of an iron-based material such as a cold-rolled steel sheet, and the iron-based material cannot be simultaneously processed. Another invention proposes a "metal surface treatment method using a chromium-free coating-type acidic composition", for example, after coating an aqueous solution that can form a film with excellent resistance to recording t on the metal surface, a water washing step is performed to fix the film by baking and drying. Chemical surface treatment method (refer to Japanese Patent Application Laid-Open No. 5-1195244) This method is capable of performing coating treatment on metal surfaces such as galvanized steel sheets, cold-rolled steel sheets, and alloys, because the formation of coatings does not involve chemical reactions. As the invention proposed in the aforementioned Japanese Patent Application Laid-Open No. 2000-204485, it is difficult to implement uniform coating treatment on complex structures such as automobile bodies because coatings are formed by coating.

2UU410JUU Therefore, to deal with zinc-based materials and actinide-based materials such as cold-rolled steel plates of automobile bodies without harmful environmental components and house physiological fluids at the same time ... Knowing the technology and concentrating on the contents [Content of the invention] Ben = Guangxi aims at the problems that cannot be achieved by the conventional technology, and 2 surface treatment fluid, which * contains environmentally-friendly components, not producing materials; 2 'in iron-based materials, words Series materials, samarium materials and I-series batches in February "precipitated a surface treatment film with excellent corrosion resistance after coating; and a type of surface treatment treatment fluid, such as the car body assembly iron series material surface: 系 材 # ㉟ 系 and magnesium 2 to 4 types of materials in the materials table. With the same composition and the same conditions, the surface treatment film with excellent button resistance after coating can be simultaneously precipitated, and a surface treatment method using this surface treatment treatment liquid is also provided. The inventors and others carefully reviewed the results of the solutions ^ &, +, ^ 0S ^ < Xie Fu described the method of class delivery, and completed the surface treatment method of the surface treatment treatment liquid which is not known in the art. Mingzhi metal surface treatment The liquid is characterized in that it is a water-based surface treatment liquid that is selected from iron-based materials, ^ eight fresh 糸 materials 枓, aluminum 镁 materials, and magnesium-based materials to perform surface treatment separately or simultaneously. 'It contains 1 or more compounds selected from a rhenium compound and a titanium compound t. The metal element I is 5 to 5 ppm, and contains free gas ions 0.1 to 100 ppm, and the pH is 2 to 6. 200416300 This surface treatment treatment liquid may be It also contains more than i kinds of compounds selected from the group consisting of calcium compounds, magnesium compounds, and compound compounds. At this time, the concentration of these compounds is converted into metal elements, and the calcium compound is 5 to 100 ppm, the magnesium compound or the compound 1G. ~ 5_ppm is better. The treatment solution preferably contains nitrate 10000 ~ 50,000 ppm. It also preferably contains hci〇3, HBr03, HN02, HN〇3, HMn04, HVCU, η nu Wn nu 4 U3 , Ί ^ 04, H2Mo〇4 and at least one of the salts containing hydrogen / +, ^ ® 3 milk S and / or oxo acid salt. The surface treatment liquid may further contain optional Water-soluble Bayi dry compound r Wang homomolecular compounds and water dispersion At least one of the South molecular compounds] Lugu 2/1 kinds of molecular compounds, and may further contain one selected from non-ionic samarium surfactants, anti-hybrid Umbrella U-ion samarium surfactants and cationic surfactants. At least i kinds of surfactants. Furthermore, the metal surface treatment method of the present invention is characterized in that it is selected from iron-based materials, zinc Materials' contact with the above-mentioned surface treatment treatment liquid individually or simultaneously. Μ Main species or more. In this surface treatment method, @ β, after the metal material is in contact with the surface treatment liquid, washed or removed, It can be washed with two fires, and can be contacted with an acidic aqueous solution containing -H ^ ^, a compound of one element selected from the group consisting of cobalt, nickel-copper, titanium and rhenium. Cen w \ Monoaqueous molecular compounds and water-knife release are still among the sub-compounds. A treatment solution for one kind of molecular compound, and the present invention is a self-correcting method of surface treatment, which is characterized in that it is to be released from iron-based materials, lexical materials, materials, π, 1 糸, and magnesium. The metal compound in the series material is alone or at the same time 2 at the above surface, and the metal material is used as the cathode, and the electrolytic solution is treated with 4 π Tianlili. In this surface treatment method 200416300 'The metal material is electrolytically treated in a treatment liquid for surface treatment, and after being washed with water or without water, it can be further composed with selenium, nickel, tin, copper, titanium, and copper_ 中 至v An acidic aqueous solution of a compound of 1 element can be contacted with a treatment liquid containing at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound. In addition, the method of the present invention is to select two or more kinds of metal materials that have not been degreased or purified from iron-based materials, lexicon-based materials, 1 Lu-based materials, and lock-based materials. The surface treatment liquid selected from non-ionic surfactants, anionic surfactants, and cationic surfactants is contacted with a surface treatment liquid, and the surface of the metal can be degreased and coated at the same time. The metal material of the present invention is characterized in that, on the surface of the metal material selected from the iron series materials θ ^ 卞 及 and magnesium 糸 materials, 有, there is a ground knife formed by the surface treatment method described above, and contains The surface treatment is less than one kind from titanium and the wrong metal element, and the adhesion amount of the surface treatment film is changed: when it is a metal element, it is 30_2 or more on the iron-based metal surface: the surface is 20, and the metal surface is 10 mg / m2 or more: The town metal surface is 10 mg / m2 or more. [Embodiment] In the related technology of the present invention, # 蒋 系 will be selected from the metal species in iron-based materials, zinc-based materials, aluminum alloys, and magnesium-based materials. The surface treatment of the lamp is carried out at the same time or at the same time, and the surface of the surface with excellent corrosion resistance after coating is broken in batches. The so-called iron-based materials are cold-rolled steel plates and hot-rolled steel plates. 10 200416300 Iron-based zinc die-casting materials such as steel plates, cast iron and sintered iron materials, and zinc-containing layers. This material contains materials that refer to at least one of the metals (such as nickel, iron, inscription, turtle, and other species of zinc saccharum), and at least one of the genus of cobalt, lead, antimony, etc.) There are no restrictions on the plating, plating, vapor deposition, etc. of alloys and unavoidable impurities. And ... again / 〇 ',,, Han plating, Ren a Shaoqi materials, such as 5000 series inscription ", 6_ series Shao alloy, Ming alloy plate or alloy alloy die-casting materials, etc., and' magnesium series materials, Refers to the use of ballasting: = or die-casting material. Missing. I. The material of the invention is applicable to: a single metal, +, i "< 八 9 # 月" said metal material is a component of the structure ', species to 4 The aforementioned metal material is a structure constituting a member. Furthermore, 'is applicable to a structure in which two to four kinds of the aforementioned metal materials are structural members, and the surface of the two to four kinds of metallic materials can be simultaneously placed on the surface. Here, when two or four kinds of metal materials are surface-treated at the same time, different metals may be in a non-contact state, or a contact state in which different metals are joined to each other by a joining method such as flashing, bonding, or riveting. . The treatment liquid for surface treatment of the present invention contains 5 to 50000 claws of metal element equivalent to one or more compounds selected from the group consisting of an erroneous compound and a titanium compound, and contains free fluoride ions Oi-MOppm, and the pH is 2 to 6 的 treatment fluid. Here, the zirconium compound used in the present invention may be, for example, ZrCl4, ZrCl2,

Zr (S04) 2, Zr0S04, Zr (N03) 4, Zr0 (N03) 2, H2ZrF6, salt of H2ZrF6, Zr02 'ZrOBr2, ZrF4, etc. Also titanium compounds can be exemplified by Ti

Cl4, Ti (S04) 2, TiSO4, Ti (N03) 4, Ti0 (N03) 2, Ti020C204, H2TiF6, H2TiF6 salt, Ti02, TiF4, etc. In the present invention, a complex compound is suitable. 11 200416300 The concentration of one or more compounds selected from the group consisting of an erroneous compound and a titanium compound used in the present invention, the conversion of the metal element (ie, zirconium and / or titanium) is preferably 5 to 5000 ppm, and more preferably 10 to 3000 ppm. Since the film obtained by using the surface treatment liquid and surface treatment method of the present invention is an oxide or hydroxide of hafnium or titanium, if the concentration of the above-mentioned compound selected from the zirconium compound and titanium compound is zirconium and / or When the calculated amount of titanium is less than 5 ppm, it is difficult to obtain a sufficient adhesion amount required for corrosion resistance in practical processing time due to a small concentration of the main component of the film. When the concentration is more than 5000 ppm, sufficient adhesion can be obtained, but the effect of further improving the corrosion resistance is not obtained, and it is only economically disadvantageous. The rhenium compound or titanium compound is more soluble in an acidic solution, but is unstable in an alkaline solution and easily precipitates into an oxide or a hydroxide. The pH of the treatment liquid for surface treatment according to the present invention is 2 to 6, and preferably Qi is 3 to 6. When the broken metal material is brought into contact with the surface treatment liquid of the present invention at this pH, a dissolution reaction of the metal material to be treated is caused. As a result, as a result of the dissolution of the processed metal material, a pH rise occurs at the interface of the processed metal material, so that the oxide or hydroxide of hafnium or titanium precipitates as a film on the surface of the processed metal material. Free fluoride ions are present in the surface treatment liquid of the present invention. In order to make free fluorine ions exist, a fluorine compound can be added to the surface treatment liquid. The supply source of this free fluoride ion can be, for example, hydrogen acid, H2ZrFe, I H2TiF6, H2TiF6 salt, H2SiF6, H2SiF6 salt, HBF4, HBF4 salt, NaHF2, KHF2, NH4hf2, NaF, KF, Li 4F Wait. Free fluoride ions have the effect of raising the compounds and titanium compounds in the surface treatment liquid. In addition, the free gas ions in the surface treatment material of the present invention include:-iron-based materials, zinc-based materials, Shao-based materials and town-based materials. Therefore, the branch has the effect of promoting the dissolution reaction in the acid solution. As a result of the existence of free fluoride ions by Nichihiro compounds, on the one hand, it improves the stability of the surface treatment liquid and the reactivity of the (surface treatment liquid) to the metal material to be treated. In the present invention, the applicant has previously proposed that, for treating at least iron-containing compounds, a surface treatment composition for surface treatment and a surface treatment treatment liquid, a dagger 5 compound, a zirconium compound, and a fluorine-containing compound, the surface treatment composition is proposed. When the total gas atoms in the metal sulfonium compound in the lili solution and the surface treatment are converted into hf: Moore A: -o-0-o- ^ o 〇2 / 1〇: 0: 0 :::: The result of prescribing the metal element concentration of the Chin compound or the wrong compound J At the concentration of the two rat ions' is outside the above-mentioned specific range, or it can be = do not alone or two or more simultaneous surface treatments are selected from iron-based materials, lexical materials, aluminum systems Materials and metallic materials in magnesium-based materials. The reactivity of materials, zinc materials, samarium materials and town materials is the same, so it is impossible to treat the surface of two or more of the above materials at the same time by conventional techniques. In the present invention, the result of adjusting the concentration of free gas ions can be obtained. Freely change the balance of stability and reactivity for surface treatment. Therefore, iron-based materials, word-based materials, inscription-based materials, and magnesium-based materials with different reactivity should be sufficient for two or more surface treatments simultaneously or separately. . The "free gas" refers to the degree of ion inertia, which means that the free fluorine ion in the surface treatment treatment liquid of the present invention is measured by a commercially available ion electrode. The concentration of the ion is preferably from 2004.1 to 100 ppm, and 2 to 70. ppm is better. Free fluorine ion wave is more than 100ppm. “Although it can promote the dissolution reaction of the treated metal material”, because the wrong compound and titanium compound in the surface treatment treatment liquid are very stable, the interface of the treated metal material Although ρίί rises, it is difficult to precipitate into a film. When it is lower than 0.1 ppm, it has a small effect on improving the stability and reactivity of the treatment liquid for surface treatment, making the meaning of free fluorine ions meaningless. Free fluorine ions in the present invention In addition to enhancing the health and reactivity of the virgin liquid used in surface treatment, it is also used to stably maintain the dissolved components dissolved in the treated metal material in the surface treatment liquid. It is known as ^ cattle fee zinc As an example, the iron ions and phosphoric acid eluted from iron-based metal materials produce insoluble salts of iron phosphate, so sludge occurs. The treatment liquid for surface treatment of the present invention may also contain Phosphate, but sludge may also occur if the phosphate concentration exceeds 1.0 Og / L. Another example is that the amount of treated metal material is significantly more than the capacity of the treatment bath. In order to dissolve the dissolved components, one kind can be added $ 2 or more inorganic acids such as sulfuric acid and hydrochloric acid, acetic acid, tartaric acid such as oxalic acid, organic acids such as citric acid, succinic acid, gluconic acid, and phthalic acid, and a coupler capable of mixing out dissolved components. The surface treatment liquid may contain at least one selected from the group consisting of a calcium compound, a compound, and a gill compound. According to the present invention, the specific concentration of the compound and the titanium compound in the aqueous solution is set to a certain range, It can make iron-based materials, word-based materials, and inscriptions 镇: town-based materials ... four or four kinds of surface genus at the same time or individually _ diaoguang gold K, magnesium contained in the above calcium compounds, magnesium compounds, or lithium compounds (Or record), in the aqueous solution to form a gaseous salt with fluorine, 14 and has the intention to make the aqueous solution φ; dazzle, lysine ion concentration is guaranteed to be certain. Because of this, at the same time, the role of the high U value is affected by its use ratio Influence, two When various metal materials are processed, no, so each product I often maintains a certain degree of free ion ionic inertia α < i gene material can obtain the most appropriate coating adhesion amount. Used in the present invention $ # AA, Zu M 3 compounds, magnesium compounds, and gill compounds can be ^, lice compounds, lice oxides, chlorides, sulfates, nitrates and carbonates, etc., and in addition to calcium compounds, magnesium compounds and barium

Anything other than “two substances” can be used in the present invention as long as it has the concentration of free fluorine ions in the fluorine-containing aqueous solution, whether it is inorganic or organic. 0 The concentration of the magnesium compound or thallium compound used in the present invention is converted into The metal element is preferably 10 to 5000 ppm, and more preferably 100 to 3000 ppm. Calcium compounds have very low solubility of europium fluoride, so they are converted to 5 ～ 100ppm #mother good, 5 ～ 50ρρπ is better. If the concentration of the compound is higher than the upper limit value, the stability of the surface-treating treatment liquid may be impaired, which may prevent continuous operation. If the concentration of the compound is less than the lower limit, the adhesion amount of the film of the present invention to the iron-based material may decrease. In addition, to the treatment liquid for surface treatment of the present invention, it is possible to add lignostearate from 1,000 to 50,000 ppm, and more preferably from 1,000 to 30,000 ppm. Lithosperate acts as an oxidizing agent, and has the effect of promoting the film precipitation reaction of the present invention, and increasing the solubility of the aforementioned compounds, magnesium compounds, and compounds in the surface treatment liquid. Therefore, a film with excellent corrosion resistance can be precipitated even when the concentration of zirconate is less than 1,000 ppm. However, when the concentration of the aforementioned calcium compound, magnesium compound, and samarium compound is high, the stability of the surface treatment treatment liquid may be affected. 15 200416300 Added more nitrate. In addition, a nitrate concentration of 50,000 ppm is sufficient, and is only economically disadvantageous. In addition, ‘3, _3, noodles 3, _4, _3, HA, and at least one of the constituent groups may be added to the treatment liquid for surface treatment of the present invention! An oxoacid and a salt of these oxoacids. The oxo acid or its salt 'acts as an oxidant on the material to be treated, and promotes the film formation reaction of the present invention. The above-mentioned oxo acids or salts of these oxo acids ^

The concentration is not particularly limited, but the effect of the oxidant can be fully exerted in an amount of about 10 to 5,000 milliseconds. Furthermore, at least i kinds of polymer compounds selected from water-soluble polymer compounds and water-dispersible polymer compounds may be added to the surface-treating treatment liquid of the present invention. The metal material surface-treated by using the surface-treatment treatment liquid of the present invention has sufficient corrosion resistance, but it is further improved if lubricity is required.

In the one-step function, the polymer compound can be added according to the desired function to improve the physical properties of the coating. As the water-soluble polymer compound and the water-dispersible polymer compound, for example, polyvinyl alcohol, poly (fluorenyl) acrylic acid, a copolymer of acrylic acid and methacrylic acid, ethylene and (fluorenyl) acrylic acid, or (fluorenyl acrylic acid) can be used. Copolymers of acrylic monomers, polymers of ethylene and vinyl acetate, polyurethanes, amine-denatured phenol resins, polyester resins, epoxy resins, etc. are polymer compounds used to treat metal surfaces. Surface treatment using the present invention When treating a metal surface with a treatment liquid, only after degreasing the metal surface with the ¥ method, the cleaned metal material to be treated may be contacted with the treatment liquid for co-surface treatment. Thereby, the surface of the metal material is selected from zirconium and titanium. Compositions of oxides and / or hydroxides of metallic elements 16

ZUU ^ tlOJUU ′ forms a surface-treated coating layer having excellent affinity and corrosion resistance. This contact treatment can be applied by any of spraying treatment and / or flow coating treatment, and this contact method is not inconspicuous. It can be generated by +, person s ~ θ. It is chemically difficult to obtain aerobic oxides in the form of pure hydroxides. Generally, the state of adding above water to hydrated water is also included in the scope of hydroxides. Therefore, the gas oxide of = is heated and finally becomes an oxide. In the present invention, dry-welding Happi H "" After surface treatment at normal temperature or low temperature 'can be regarded as oxide and hydroxide treatment after the treatment with ionization, ionization, and surface conditions. "... 1 can be regarded as only oxides or even more oxides than the surface treatment of the present invention. The reactivity of the surface treatment liquid of the present invention, == other limited control. Therefore, the treatment temperature and == Γ concentration ... It can be changed arbitrarily. Λ treatment ㈣ can be made reactive with the treatment bath ^ 'The above-mentioned surface treatment treatment liquid can also be selected from non-ionics. The surface activity is uniform, the anionic interface agent is up to / 丨, 1 soil Han 丨 Interactive ion surface active surface treatment with 2 ', species boundary: active agent is used for surface treatment. Use this surface treatment, clean ... Surface treatment of metal materials, do not need to degrease the surface in advance? Treatment of metal materials can also A good film is formed. That is, the two treatment liquids can be used as a degreasing and surface treatment agent. When it is, the surface treatment liquid of the present invention can be used to treat a metal surface treatment liquid to treat a metal material as a cathode. In the surface treatment, the solution method is used. Here, when the treated metal material is treated as a cathode of 17 200416300, the pH rises. As the stability of the pH on the substrate decreases, the coating is treated. 'Hydrogen reduction reaction occurs at the cathode interface and it is raised' After the compound and / or titanium compound at the cathode interface is precipitated with oxide or aqueous hydroxide, the treated metal material comes into contact with the surface treatment treatment liquid, or two surfaces After electrolytic treatment in the treatment liquid for treatment, after being washed with water or not, it can be contacted with an acidic aqueous solution containing at least jade species = in the group consisting of starting, recording, tin, copper, titanium, and copper, or it can be contacted with The treatment liquid selected from at least one of the water-soluble protonated compound and the water-dispersible polymer compound is contacted to further enhance the effect of the present invention. The surface treatment coating layer obtained according to the present invention is a thin film and It has a good soiling property, but depending on the surface state of the metal material being treated, there may be fine defect parts in the surface treatment film layer. Then, contact with an alkaline aqueous solution containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium, and copper, or with a water-soluble polymer compound and water-dispersible As a result of contacting at least one of the i-type polymer compounds with the treatment liquid of the i-type polymer compounds, the above-mentioned fine defect portion is covered and resistant to recording, and the above-mentioned content is selected from the group consisting of lead, nickel, tin, copper, titanium, and thallium. The compound of at least one element is not particularly limited, and the oxides, monooxides, fluorides, complex fluorides, chlorides, nitrates, oxynitrates, and sulfates of the above-mentioned 70 elements that are easily available can be used. , Oxosulfate, carbonate, oxocarbonate, phosphate, oxophosphate, oxalate, oxooxalate, and organometallic compounds. It also contains two of the above-mentioned metal elements. 18 200416300 The pH of the aqueous solution is preferably 2 to 6. Acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, and organic acids, such as sodium hydroxide, potassium hydroxide, and hydrogen can be used. Lithium oxide, alkali metal salts, ammonium salts, and amines and other alkali adjustments. The above-mentioned choice is from at least one polymer compound among water-soluble polymer compounds and water-dispersible polymer compounds, such as polyvinyl alcohol, methyl) acrylic acid, acrylic acid, and fluorenyl acrylic acid. Copolymers of ethylene, copolymers of ethylene with (fluorenyl) acrylic acid or (fluorenyl) acrylic acid monomers, copolymers of ethylene and vinyl acetate, polyurethanes, amine-modified phenol resins, polyester resins, epoxy resins , Tannin, tannin and its salts, phytic acid, etc. According to the present invention, the formation of a surface treatment coating layer composed of oxides and / or hydroxides selected from rhenium and / or titanium to a metal element on the surface of a metal material to be treated can result in a significant improvement in the corrosion resistance of the metal material. Here, the oxides and hydroxides of the above-mentioned metal elements are difficult to be corroded by acid or alkali, and have chemically stable properties. In an actual metal corrosive environment, the pH of the anode where the metal is dissolved is reduced, and the pH of the cathode where the reduction reaction occurs is increased. Therefore, the surface treatment film having poor acid resistance and alkali resistance is dissolved in a corrosive environment and loses its effect. The main component of the surface-treated coating layer of the present invention is difficult to be corroded by acid or alkali, so it can maintain excellent effects under corrosive environment. In addition, since the oxides or hydroxides of the aforementioned elements form a network structure by transmitting metal and oxygen, a very good barrier film is formed. Corrosion of metal materials depends on the use environment. It is usually an oxygen-demanding type of corruption in the presence of water and oxygen, and the presence of components such as chloride will promote its corrosion rate. Since the surface-treated coating layer of the present invention has a barrier effect against water, oxygen, and rot 19 200416300, it is an excellent ingredient. Here, when using the above-mentioned p-early wall effect to improve the recording resistance of iron-based materials such as cold-rolled steel plates, hot-rolled steel plates, cast iron, and sintered iron materials, the adhesion amount needs to be 30 mg / m2 or more when converted into the aforementioned metal elements. It is better to attach more than _2, and it is better to attach more than 5Gmg / m2. In addition, in order to improve the surname resistance of zinc-based materials such as zinc or zinc-zinc steel plates and alloyed hot-dip zinc steel plates, it is necessary to convert the adhesion amount into the aforementioned metal S element by 2 Gmg / m2 or more, and 3, /: 2 The above adhesion amount is better. In addition, in order to increase the financial records of Shao series materials such as aluminum castings and aluminum alloy plates, it is necessary to convert the amount of time into the aforementioned metal element by 10 mg / m2 or more, and it is preferable that the adhesion amount is 20 mg / in2 or more. In order to improve the corrosion resistance of magnesium-based materials such as magnesium alloy plates and magnesium castings, it is necessary that the adhesion amount is 10 mg / m2 or more when converted to the aforementioned metal element, and the adhesion amount is preferably 20 mg / m2 or more. The upper limit of the adhesion amount is not particularly limited, but if it exceeds lg / m2 or more, cracks may easily occur on the surface treatment film layer, making it difficult to obtain a uniform film. Therefore, the upper limit of the total adhesion amount of iron-based materials, zinc-based materials, magnesium-based materials, and aluminum-based materials is lg / m2, and it is better not to "..." Examples Examples and comparative examples are listed below for specific explanation The effect of the surface indoor treatment liquid and surface treatment method of the present invention. In addition, the materials to be treated, degreasing agents, and coatings used in the examples are arbitrarily selected from commercially available materials. The surface treatment treatment liquid and surface treatment method of the present invention are only apricots, and only show application 20 200416300 [ Test plate] "For the test plates of the examples and comparative examples, cold-rolled steel plates, hot-dip ore steel plates, Ming alloy plates and rhenium alloy plates are used. The abbreviations and details of this test plate are as follows and the appearance after surface treatment For evaluation, three test materials such as spc GA and A1 were joined by spot welding. For the evaluation of the adhesion amount of the surface treatment film layer, ^, ⑶, and each of the test plates and spot welding were used. Test board with 3 kinds of metal materials such as SPC and A1. For evaluation of coating performance, test boards made by spot welding with 3 kinds of metal materials such as spc, GA, and M are used for surface treatment and coating. A series of tests from installation to evaluation of coating performance. Figure i is a top view of a test plate using three types of metal materials, namely spc, GA, and A1, and Figure 2 is a front view. 1 is a point welding joint. • SPC (cold-rolled steel sheet: jis- G- 3141) • GA (double-sided alloyed hot-dip galvanized steel sheet: plating amount of 45 g / m2) • Al (aluminum alloy: 6000 series aluminum alloy) • Mg (magnesium alloy: jIS-η- 4201) "Processing steps" Examples, The processing procedure of the comparative example is as follows. Examples 1 to 4, Example 7 and Comparative Examples 1 to 4: Alkali degreasing 4 Water washing film formation treatment-water washing-> Pure water washing and drying implementation Example 5 ·· Degreasing 4 water washing θ electrolytic generation treatment-water washing-pure Water washing-drying Example 6: Film formation treatment (degreasing and washing with water—pure water washing-drying 21 200416300) Example 8: alkali degreasing—water washing—film formation treatment—water washing—post-treatment— > pure water washing—drying implementation Example 9: Film formation treatment (degreasing and washing with water-post-treatment-pure water washing ~ drying) Comparative Example 5 · alkaline degreasing-water washing-surface adjustment-zinc linate-water washing-pure water washing-drying For the examples and comparative examples, F 丨 ne cleaner-L4460 (registered trademark: made by Japan Barka Lai Xing Co., Ltd.) was diluted with tap water to 2%, and sprayed on the treated board at 4 (rc 12 °). Seconds. Water washing and pure water washing after coating treatment, examples and comparative examples were sprayed on the plate to be treated at room temperature for 30 seconds. Example 1 Using a nitric acid oxygen hammer reagent and nitric acid, the radon concentration was adjusted to 2%. 〇ρ_'s aqueous solution After heating this aqueous solution to 45 ° C, adjust the pH to 3.0 with sodium hydroxide reagent and hydrofluoric acid, and adjust the free fluoride ion concentration under the measurement of a fluoride ion meter (IM-55G, manufactured by Toa Radio Industry Co., Ltd.). In order to obtain a treatment solution for surface treatment, the total fluorine concentration in the treatment solution for surface treatment after adjusting the concentration of free fluoride ions was 50 ppm.

The test plate washed with degreasing and water was immersed in the surface treatment for 120 seconds for surface treatment. Example 2 An aqueous solution of an acid and oxygen test reagent, an acid and acid test reagent, and a nitric acid test reagent was prepared, with an aqueous solution of zirconium concentration of 100 ppm, magnesium concentration of 5000 ppm, gill concentration of ⑽ 卯 ⑽ 卯, and nitrate of 28470 Ppm. This aqueous solution is heated to the temperature after 22 2004 16 300

'Using ammonia test reagent and hydrofluoric acid to adjust the pH to 3.0, and adjusting the free fluoride ion concentration measured by a fluoride ion meter (IM-55G, manufactured by Toa Radio Industry Co., Ltd.) to 80 ppm, to obtain a treatment solution for surface treatment . After adjusting the concentration of free fluoride ions, the total fluorine concentration in the treatment liquid for surface treatment was 2000 ppm. The test plate washed with degreasing and water was immersed in the above-mentioned treatment solution for surface treatment for 60 seconds to perform surface treatment. Example 3 An aqueous solution of hexafluoro acid (IV), an aqueous solution of titanium (IV) sulfate, a calcium sulfate peony, and nitric acid were used to prepare a thallium concentration of 1,000 ppm, a titanium concentration of 20000, and a calcium concentration of 5PPm, nitrate is an aqueous solution of 1 000ppffl. After the aqueous solution was heated to 40 C, the pH was adjusted to 5.0 with potassium hydroxide reagent and hydrofluoric acid, and the concentration of free fluoride ions under the measurement of a fluoride ion meter (IM-55G, manufactured by Toa Radio Industry Co., Ltd.) was measured. When adjusted to 25 ppm, a treatment liquid for surface treatment was obtained. The total fluorine level in the surface treatment liquid after the free fluoride ion concentration was adjusted was 2250 ppm. The surface was washed by degreasing and washed with water; ^ μ, +, master < 仏 忒, immersed in the above-mentioned surface-treatment treatment liquid for 90 seconds for surface treatment. Example 4 An aqueous solution of hexafluorotitanate (IV), a test reagent for sulfonic acid, and a test substance for sodium schistonic acid were used to prepare a titanium concentration of 5 _, a pin concentration of 5 _, and a stone sulphate was purchased from Qing, Ya Shi Xiao acid is an aqueous solution of Qing pm. After 3VC, use triethanolamine test reagent and hydrogen ... to, Yong /, go to 贶 龀 to adjust the pH to 4.0, and then the fluoride ion meter (IM-55G, East Asia Ray, ancient engineering day "" Baishi Iya " μ Industry & Co., Ltd.) 23 200416300 The free fluoride ion concentration under measurement was adjusted to i 0ppm to obtain a surface treatment liquid. The concentration of perfluorinated solution in the surface treatment liquid after adjusting the free fluoride ion concentration was 11900ppm 〇 The degreased test plate was washed with water, and the surface treatment solution was sprayed with a sprayer for 120 seconds to perform surface treatment. Example 5 Oxygen nitrate reagent, hexafluorotitanic acid (Iv ) Aqueous solution, reagent of magnesium sulfate, reagent of nitric acid and sodium chlorate, to prepare an aqueous solution of rhenium concentration of 5 ppm, titanium concentration of 5 ppm, magnesium concentration of 00 ppm, nitrate of 3050 μm, and chlorate of 100 ppm. After heating this aqueous solution to pH ^, adjust the pH to 6.0 with an ammonia test solution and hydrofluoric acid, and adjust the free fluoride ion concentration measured by a fluoride ion meter (IM — 55G, manufactured by Toa Radio Industry Co., Ltd.). .5ppm, to obtain the treatment solution for surface treatment. Adjust the free The total fluorine concentration in the surface treatment solution after the ion concentration was 12 ppm. The test plate washed with degreasing and water was used as the cathode, and a carbon electrode was used as the anode. The electrolysis conditions were 5A / dm2 in the surface treatment solution. Electrolysis was performed for 5 seconds to carry out surface treatment. Example 6 ^ Using the test reagent oxonate, oxidized oxidant, test shirnonic acid and nitrogen peroxide, the concentration was adjusted to 15 ppm, and the concentration of magnesium was 1 〇p_, nitrate is 5200ppm, hydrogen peroxide is 10ppm aqueous solution. After heating this aqueous solution to 50 ° C, adjust the pH to 50 with ammonia reagent and hydrofluoric acid, and then change the fluoride ion (I 5 5 G Toa Radio Industry Co., Ltd.) The free fluoride ion concentration under measurement was adjusted to 50 ppm, and a non-ionic surfactant was added. 24 200416300 Water-emulsified ethylene nonyl ether (ethylene oxide addition mole number: 12 mol is known as the surface treatment solution. The total fluorine concentration in the surface treatment solution after adjusting the concentration of free fluoride ions is 170 ppm. A test board that has been oiled without degreasing treatment will be used on the surface. Processing fluid Spray with a sprayer for 90 seconds for surface treatment. 7 Using & fee titanium (IV) solution, calcium nitrate reagent, magnesium nitrate reagent and potassium high acid reagent, adjust the titanium concentration to $ IGGppm, feed concentration A to 50 mg, magnesium A water / hydrate solution having a concentration of 5000 Ppm, a nitrate value of 2566 ppm, and a permanganic acid value of ι〇ρ_. This aqueous solution is further added with a water-soluble acrylic polymer compound (Trjulima AC-10L: manufactured by Japan Pure Medicine Co., Ltd. ) Make the solid content / degree of 1 /. After heating to 50 C, adjust the pH to 3.0 with sodium hydroxide reagent and hydrofluoric acid. 'The fluoride ion meter' (IM _ 55G, East Asia Radio Industry Co., Ltd. Co., Ltd.) The free fluoride ion concentration under measurement was adjusted to 95 p_, and a treatment liquid for surface treatment was obtained. The total fluorine concentration in the treatment liquid for surface treatment after adjusting the concentration of free fluoride ions was 2000 ppm. The test plate washed with degreasing and washed with water was immersed in the above-mentioned treatment solution for surface treatment for 60 seconds to perform surface treatment. Example 8 A water-soluble acrylic polymer compound (Julima Ac — 丨 L: manufactured by Japan Pure Pharmaceutical Co., Ltd.) was prepared with a solid content of 1%, and an aqueous solution of 2 g / L of phosphonium phosphate was used. This The aqueous solution was heated to 4 (Γ (:), and the pH was adjusted to 4_5 with an ammonia test solution to prepare a post-treatment solution. The test surface impregnated with the surface treatment described in Example 5 above to perform film formation and water washing 25 200416300 treatment The solution was post-processed for 30 seconds in the liquid. Example 9 A hexafluoropyric acid (m +, hexa &, UV) water-cooled liquid and a cobalt nitrate reagent were used to adjust the concentration to 50 ppm, and the syrup was 5 〇ppm aqueous solution, and then heating this aqueous solution to 40 ° C. Continue with ammonia, Suigang 敕 eight 糸 with a pH adjustment of 5.0, to make a post-treatment solution. The surface of Example 6 will be stepped --- The test board for film formation and water washing was immersed in it and immersed in the above-mentioned post-treatment solution for 30 seconds for post-treatment. Comparative Example 1 Using Sodium Acid Acid Milk Test Solution, Magnesium Acid Test Solution, and Nitric Acid An aqueous solution with a concentration of 500 ppm, a degree of 1000, and an acid radical of 6 zine. This water After the solution was heated to 45 ° C, the pH was adjusted to 4.0 'with peony hydroxide to prepare a surface treatment solution. Also, a commercially available fluoride ion meter (55G, manufactured by Toa Denpa Industry Co., Ltd.) was used to measure the surface treatment. The concentration of free fluorine ions in the treatment solution was 0ρ. The test plate washed with degreasing and water was subjected to surface treatment in the above-mentioned treatment solution for surface treatment > fork > for 120 seconds. Comparative Example 2 Titanium sulfate was used (IV) Aqueous solution prepared with a titanium concentration of 2_Q. The aqueous solution of Jc Ling was heated to 50 C, and then adjusted to 3.5 with ammonia reagent and hydrofluoric acid. The fluoride ion meter (IM_55G, East Asia Radio Industry Co., Ltd. The concentration of free fluoride ions under measurement was adjusted to 40 porcine eggs to obtain a treatment solution for surface treatment. The test plate washed with water after removing the moon was immersed in the treatment solution for surface treatment for 90 seconds. Surface treatment. 26 200416300 Comparative Example 3 A commercially available chromate treatment agent, Alchrome 713 (registered trademark: made by Japan Barkalaixing Co., Ltd.) was diluted with tap water to 3.6%, and then the total acidity and free acidity were adjusted to table of Contents Intermediate value. The test board washed with degreasing and washed with water was immersed in the above complex salt treatment solution for 60 seconds to perform chromate treatment. Comparative Example 4 A commercially available non-chromate treatment agent Kete 3756 (registered trademark of Benagalai Co., Ltd.) is diluted with tap water to find, and then the total acidity and free acidity are adjusted to the middle value of the catalog value. The test board washed with degreasing is heated to 4 (The above-mentioned non-chromate treatment solution was immersed in the non-chromate treatment solution for 60 seconds to perform non-chromate treatment. Comparative Example 5: For a test plate washed with degreasing and water, the surface adjustment treatment agent blebaline ZN (registered trademark) : Made by Japan Barkalaixing Co., Ltd.) Released into 2% dilution with tap water, sprayed with a sprayer at room temperature for 30 seconds, and then immersed and precipitated in 42 CW 酉 long zinc generation treatment solution Phosphoric acid coating; this zinc phosphate generation treatment solution is based on Barbond L3020 (registered trademark: Japan's Bagalex Co., Ltd.) diluted with tap water to 48%, and the sodium hydrogen fluoride reagent is added as 200ppm in terms of fluorine. After that, adjust the total acidity and free acidity to the directory The intermediate value. [Evaluation of Surface Treatment Film]

The test panels of Examples and Comparative Examples after surface treatment were visually evaluated. The results are shown in Table 丨. The adhesion amount of the surface-treated coating layer was measured with a fluorescent X 27 200416300 ray analyzer (System 3270; manufactured by Rigaku Electric Co., Ltd.). The results are shown in Tables 2 and 3. The amount of adhesion of the surface-treated coating layer was measured separately for each metal material that was not bonded and treated separately (unbonded) and those that were treated by spot welding (bonded). Table 1 Except after surface treatment 1 a Example on SPC GA on A1 Uniform interference color uniform gray black uniform white Example 2 Uniform interference color uniform gray black uniform white Example 3 Uniform interference color uniform gray black uniform white Example 4 Uniform interference color uniform gray black uniform white Example 5 Uniform interference color uniform gray black uniform white Example 6 Uniform interference color uniform gray black uniform white Example 7 Uniform interference color uniform gray black uniform white Comparative Example 1 No precipitated film Film uneven white Comparative example 2 Light yellow uneven gray uneven white Comparative example 3 Unprecipitated film slightly golden yellow Comparative example 4 Unprecipitated film Unprecipitated film Uniform white Comparative example 5 Substrate exposed uniform gray uneven white Table 1 is The appearance evaluation results of the surface-treated films obtained in the examples and comparative examples. The example can obtain a uniform coating for all kinds of metal materials of all test boards. In addition, it is possible to observe the precipitation of the surface-treated film at the point-welded joint portion of the test plate used in the examples. In contrast, the comparative example failed to precipitate a uniform film on all test plates. In particular, in Comparative Examples 3, 4, and 5, no film was deposited on the spot-welded joints. Comparative Example 5 is a zinc phosphate treatment liquid used when cold-rolled steel sheets, galvanized steel sheets, and aluminum alloys are simultaneously processed. However, according to the results of this test, the test pieces were joined by spot welding under cold-rolled steel sheets. The exposed portion of the metallic material substrate is called "through-air". 28 200416300

Table 2 Surface coating layer adhesion amount (unbonded) (Total adhesion amount of zirconium and titanium: mg / m2) SPC GA on A1 and Mg on Example 1 122 67 48 45 Example 2 108 66 49 41 Example 3 61 58 42 38 Example 4 73 59 14 12 Example 5 41 52 38 26 Example 6 35 38 25 19 Example 7 31 29 24 18 Comparative Example 1 Trace Trace Trace Trace ^ Comparative Example 2 25 15 15 10 鬌 Comparative example 3 Trace Cr33 Cr95 Cr75 Comparative example 4 Trace trace 25 15 Comparative example 5 Film weight 2.5g / m2 Film weight 4.5g / m2 Film weight 1.2g / m2 Film weight 0.5g / m2 Table 3 Surface treatment coating layer adhesion amount (with bonding) (total adhesion amount of junction and titanium: mg / m2) on SPC GA on A1 Example 1 125 67 48 Example 2 118 66 49 Example 3 65 58 42 Example 4 72 59 14 Example 5 45 52 38 Example 6 38 38 25 Example 7 32 29 24 Comparative Example 1 Trace Trace Trace Comparative Example 2 28 17 12 Comparative Example 3 Trace Cr35 Cr85 Comparative Example 4 Trace Trace 21 Comparative Example 5 Film weight 2.8g / m2 Film weight 4.7g / m2 Film weight 0.7 g / m2 29 200416300

In the comparative example, the test results of Table 2 and Table 3 could not be uniformly precipitated for all test plates. Target attachments were obtained, and the amount of surface-treated film attachments were all apparent from the σ-level estimation results, and no film was found in the comparative example. [Evaluation of Coating Performance] (Preparation of Coating Performance Evaluation Board) In order to evaluate the coating performance of the surface-treated boards of Examples and Comparative Examples, coating was performed in the following steps. Baking ~ Upper Coating-Baking Cationic Electrodeposition Coating, Middle Coating, Upper Coating Details are as follows: Cationic Electrodeposition Coating-Pure Water Washing-Baking-Middle Coating-Cationic Electrodeposition Coating: Epoxy Resin Cationic electrolytic deposition coating (Yelleklun 9400: manufactured by Kansai Paint Co., Ltd.), voltage 20000, film thickness 20 // m, baking at 175 ° C for 20 minutes, intermediate coating, amino alkyd resin Coating (Amerlock Tp — 3 7 Gray ·· Made by Kansai Paint Co., Ltd.), spray coating, film thickness 35 # m, baking at 140 ° C for 20 minutes, top coating: amino alkyd resin coating (Amei Rocco TM — j 3 white · made by Kansai Paint Co., Ltd.), spray coating, film thickness 35 "claw, baking at 140 ° C for 20 minutes 200416300 (painting performance evaluation) The coating performances of the examples and comparative examples were evaluated. The results are shown in Tables 4 and 5. The evaluation items and abbreviations are as follows. In addition, the coating film when the electrolytic deposition coating is completed is called an electrolytic deposition coating film, and the coating film when the upper coating is completed is called a 3 coats coating. Film ① SST: saline spray Test (electrodeposition coated film) ② SDT: warm salt water test (electrodeposition coated film)

③ 1st ADH: primary adhesion (3 coats coating film) ④ 2nd ADH: water resistance secondary adhesion (3 coats coating film) SST · Electrolytic deposition coating board with a sharp cutting knife cross-cutting, Spray 5% saline for 840 hours (based on jIS — z — 2371). After spraying, the maximum expansion width at both ends of the cross-cutting portion was measured. SDT: The electrolytic deposition coating plate is immersed in a 5 wt% NaCl aqueous solution heated to 50 ° C for 840 hours. After immersion, the whole surface of the test piece was washed with tap water after drying at room temperature with a tape, and the peeling area of the coating film on each metal material was visually determined.

1 st ADH · Use a sharp knife too q ^ knife to draw 100 squares at 2f intervals on the 3 coats coating film. Use scotch tape to make miscellaneous ancient cases 4 kg 丄 f brake 雔 grid, calculate the number of grid peeling. 2nd ADH: immerse 3 coats of cold and cold-coated paint panels in 5 (TC deionization:

24 hours. After dipping, use a sharp cutting π six Q knife to draw 100 squares of 2 mm on the 3 coats coating film. Use transparent and * to identify the monthly grid to peel off the grid, and calculate the number of grid peeling. 0 1 31 200416300

Table 4 shows the evaluation results of the coating performance of the electrolytic deposition coating film. The examples show good corrosion resistance to all test panels. In comparison, in Comparative Example 丨, since the surface treatment liquid did not contain free fluorine ions at all, the surface treatment was not fully analyzed and the corrosion resistance was poor. Also in Comparative Example 2, the result was that the concentration of free fluorine ions in the treatment liquid for surface treatment was high, and in particular, the amount of the coating adhered to the SPC was small, resulting in poor corrosion resistance. Although Examples 5 and 6 performed well, the coating performance of the Comparative Example was slightly worse than that of the other Examples after electrolytic deposition. However, as shown in Examples 8 and 9, the corrosion resistance was significantly improved as a result of the post-treatment. Since Comparative Example 3 is a chromate treatment agent for aluminum alloys, and Comparative Example 4 is a non-chromate treatment agent for aluminum alloys, the corrosion resistance of A1 is excellent, but the corrosion resistance of other test plates is obviously inferior to that of the examples. Comparative Example 5 is the zinc phosphate treatment currently used in 2004 2004300 for cationic electrodeposition coating. However, in Comparative Example 5, the results of this test were inferior to those of the Examples under the condition that each test sheet was joined by spot welding. Table 5 Coating performance of coats

The test panels were homogeneous and the adhesion evaluation results of the CoatS board. All added good = good performance adhesion. Regarding the reading of lst, the results are not correct, but at 2nd, it is like the extension of electrolytic deposition coating. Example 5 shows a good level of adhesion to all test plates. Also at t foul dragon. ^ 2 When phosphate treatment occurs in the treatment bath after the treatment, ^ ~ Example ^ No sludge occurred at any level. As a result of the liquid C, it was found that "the surface treatment SPC for the surface treatment using the product of the present invention, two treatments," and without changing the treatment bath and treatment conditions, the surface with excellent adhesion and corrosion resistance can be simultaneously and immediately deposited. In addition, using the surface Luguo 'Yueyue' which has excellent resistance to residues, it can be analyzed at the welded portion. As long as the treated metal material is used for surface treatment:, it is necessary to contact the cosmetics such as bag makeup and Zhiqi A drink. May be within. The part that has no agitation effect also treats the film ', and can be improved. "Should be used on the surface [Possibility of industrial use] According to the present invention, the treatment liquid for surface treatment and the surface treatment using the treatment liquid ▲ Method 'ϋA treatment bath containing no harmful environmental components will not cause Hair: / 5 The surface is composed of 2 to 4 types of iron-based materials, lexicon-based materials, aluminum-based materials, and magnesium-based materials or separate metal surfaces, which precipitates a surface with excellent surname after coating. In the conventional technology, it is impossible to process the metal film without the surface adjustment step, and the surface treatment film can be precipitated by the conventional technology. This can shorten the processing steps and save space. [Schematic description of the drawings] (一) Schematic part Fig. 1 is a top view of a test plate for the examples and comparative examples of the present invention. Fig. 2 is a front view of the test plate. (II) Symbol of component GA · Double-sided alloyed hot-dip galvanized steel plate SPC: Cold-rolled steel sheet A1 · Shao alloy sheet 1: Spot welding joint 34

Claims (1)

200416300 Scope of application for patents: "... A kind of treatment liquid for metal surface treatment, characterized in that it selects the metal materials of zinc-based materials, Ming-based materials and town-based materials separately, respectively. Separately or on the same day " More than one water-based surface treatment for surface treatment =, it contains one or more compounds selected from the rhenium compound and titanium compound, replaced by a 7G element of 5 to 5000 ppm, and contains free fluoride ions 〇1〜100〇PMm, and the pH is 2 ～ 6. · ~ 2 The treatment liquid for metal surface treatment according to item 1 of the patent application scope, which further contains one or more compounds selected from the group consisting of a calcium compound, a magnesium compound, and a scandium compound, and the concentration of the compound is converted into a metal The element 'calcium compound is 5 to 100 ppm, and the magnesium compound or gill compound is M to 5000 ρρπι. For example, the treatment liquid for metal surface treatment according to item 1 of the patent application scope further contains nitrate 1 to 50000 ppm. 4. The treatment liquid for metal surface treatment according to item 2 of the patent application scope, which further contains 1 000 to 50000 ppm of nitrate. 5. The treatment liquid for metal surface treatment according to item 1 of the patent application scope, which further contains salts selected from HC103, HBr03, ΗΝ02, legs 〇3, ΗΜη04, HV〇3, H202, h2W04, HzMoO4, and salts thereof. At least i species of oxo acid and / or oxo acid salt. 6. The treatment liquid for metal surface treatment according to item 2 of the scope of patent application, which further contains HC103, HBr03, Dragon 02, HN〇3, ΗΜη04, HVO3, Η " 2, H2W04, Η2Μ〇04 and others At least i of oxo acids and / or oxo salts in the salts. 35 200416300 7 As stated in the patent claim No. 3 of the metal surface treatment treatment liquid, its progress contains selected from HC103, HBr03, HN02, HN〇3, ΗΜη04, HVO3, HA, Η ^ 〇4, H2Mo〇4 and so on At least i of oxo acids and / or oxo salts in the salts. 8 · If the metal surface treatment treatment liquid for item 4 of the scope of patent application,, and progress 3 are selected from HCl〇3, HBr〇3, HN02, HN〇3, ΗΜη04,, M2, h2WG4, h2MoG4 and others At least one of the salts! An oxo acid and / or oxo acid salt. The metal surface treatment treatment solution of any one to eight items in the scope of the patent application 月, which further contains at least " heavy polymer compounds selected from water-soluble polymer compounds and water-soluble polymer compounds. The surface area of the patent: 专利 1 ~ 8 of any one of the metal surface treatment sub :: liquid, which further contains a non-ionic surfactant, anionic surfactant, and a cationic surfactant At least one of the interfaces u · If the scope of the patent application is No. 1, the metal surface treatment of Gan and a is used for surface treatment, and further contains a selective active agent and a cationic interface activity :: surfactant, anion boundary 1? ', / At least one surfactant c-based material in the sword: = Γ surface treatment method, characterized in that the metal material selected from each of 1 糸 糸 糸 and magnesium-based materials will be selected :: = the same: Two or more types' are in contact with the treatment liquid for surface treatment in the scope of patent application. For example, in the scope of the patent application, the metal surface treatment method of item α of octavo 'is used to contact the metal material with the surface treatment _ persimmon and the treatment liquid in 4 places, and then washed with water or 36 200416300 7: wash :, and then An acidic aqueous solution containing a compound of an element selected from the group consisting of cobalt, nickel, tin, copper, titanium, and thallium is contacted. 14. The metal surface treatment method according to item 12 of the patent application scope, wherein, after the metal material is brought into contact with the surface treatment treatment liquid, it is washed with water or is dispersed with water containing a polymer compound selected from water-soluble compounds. Sexual Polymerization is at least! A treatment solution of a polymer compound is brought into contact. Department:; = Surface treatment method ', which is characterized in that the metal material selected from the iron material and the town material is used as the cathode, and two or more kinds are used as the cathode, and the solution is applied for treatment. Electricity is carried out in the surface treatment liquid for the staff member: 6 · If the metal surface treatment material in the scope of patent application No. 15 is electrolytically treated in the surface treatment treatment liquid_; at least in a group! Shop_Main Titanium and the compound composed of vanillin are contacted with an acidic aqueous solution. The metal surface treatment method of m2 in item 15 is based on washing or dehydration, and electrolytic treatment in the surface treatment liquid before being treated with water, and then containing water-soluble polymer compounds and water. Bio-molecular compounds come into contact with each other. 乂 1 kind of south molecular compound treatment liquid for Ukiba :: a kind of metal surface treatment method 'characterized by selecting from iron-based materials #, zinc-based materials, and Duomo iron treatment For metal materials, contact each of the non-degreasing and purifying scope of item: and town materials with item 0 or item U == at the same time two or more kinds of which come into contact with the surface treatment treatment solution for the patent application page. 37 19 · A metal material characterized in that the surface is formed of at least 1 selected from titanium and zirconium metal elements in any of the items 12 to 18 of the scope of patent application, and the surface treatment film is converted into metal 2 ·· metal The material is characterized in that the surface is formed in any one of items 12 to 18 of the scope of application for a patent and contains at least one selected from titanium and hafnium metal elements, and the surface treatment film adhesion amount is converted into a metal-general material, It is characterized in that the surface contains at least 4 selected from titanium and metal elements in the range of patent applications No. 12 to 18, and the surface treatment film adhesion amount is converted to gold. W 22 · — a metal material, characterized in that the surface is The names in the 12th to 18th of the scope of the application for the patent contain at least one selected from titanium and mismatched metal elements, and the surface treatment film adhesion amount is converted to gold. "Pick one, drawing: See the next page. The surface treatment film element in the surface treatment method of the iron-based metal material item is 30mg / m2, and the surface treatment film element in the surface treatment method of the zinc-based metal material item is 20mg / m2, which is used in the Ming-based metal material. The surface treatment method of the item has a surface treatment film element of 10 mg / m2 to be used in the surface treatment method of the town-type metal material. The surface treatment film element of the item is 1 Omg / m2 to 38