TW201111552A - Metal surface treatment agent and application thereof - Google Patents

Abstract

A metal surface treatment agent of the invention comprises a metal compound and an organic phosphor containing compound. The metal compound is selected from a metal oxide, a metal hydroxide, metal acid salt or a combination thereof. The metal therein is selected from IIA group metal, transition metal, Al, In, Sn, Pb or a combination thereof. The organic phosphor containing compound contains at least one -OPOXY group, wherein X and Y individually represent H, OH, OR, OCI or OBr, and R is an alkyl radical of C.sub.1 to C.sub.4.

Description

201111552 VI. Description of the Invention: [Technical Field] The present invention relates to a metal surface treatment agent, in particular to a metal surface treatment agent for treating a metal material, and a surface treatment method for a metal material and A surface treated t metal material. [Prior Art] In recent years, chromium-free coatings for treating the surface of electromagnetic steel sheets are almost all organic-inorganic composite types in order to simultaneously satisfy insulation, contact resistance, annealing property and workability. Among them, the inorganic component is usually a metal disc acid salt or an inorganic colloid, and the organic component is a source of an organic resin (such as Mokley, etc.). The current coating formulation composition can be divided into three categories: (1) composed of organic resin and metal phosphate; (7) composed of organic resin and inorganic colloid; and (3) composed of organic resin, metal phosphate and inorganic colloid. However, since many organic resins are soluble in water, the organic secrets of the above three types of formulations are formulated into a coating with an inorganic component in the form of an emulsion or a dispersion. US 5,945,212 discloses a surface treatment agent for non-directional electromagnetic steel sheets, the formulation of which is composed of at least one inorganic metal acid salt and an organic resin emulsion resin which is dispersible in water, wherein The inorganic metal phosphate is selected from the group consisting of aluminum phosphate, calcium phosphate or zinc phosphate, and the corresponding molar number of Α1203/Η3Ρ〇4, 00&〇/3卩〇4 and ZnO/H3P〇4 The ratio is 〇.15~〇.2〇, 〇.4〇~〇.60 and 〇.4〇~〇.60, and the particle size of the latex resin emulsion in the organic resin emulsion is between 0.3" The cross-linking degree of m to between 'only 是 is between 4 and 1 且 and wherein the cross-linkable 201111552 is between 0.4m〇1% and 8〇1〇%. , special open 2 diagnosis 69657 also reveals an electromagnetic steel sheet with super (four) film properties and a method for preparing the same, the main component of the coating formulation used for preparing the film is organic resin and inorganic phosphate, which are used Surface potential (briTential, (a) an organic resin with an absolute value greater than 3 〇 mv to obtain a stable coating' and agglomeration of the lipid-suppressed milk The organic resin contains OH or S〇3H groups, so the S〇3NH4+ salt base can be used in the ammonia water to adjust the surface potential of the resin. ', In fact, the existing organic-inorganic composite metal surface treatment agent Coatings are all emulsification systems, which means that emulsifiers need to be added, and even in order to increase the stability of the emulsion and improve the performance of the coating, special additives such as polymers and surfactants must be added. In addition, because of emulsion polymerization. Reaction (4) as a condition material, at the time, it will affect the compatibility of the organic resin with the inorganic component, and cause the coating to be unstable, which in turn leads to poor film properties. Therefore, in the process of preparing the coating liquid of the prior art, The operating parameters of the organic tree sorghum ritual agent, the amount of each formula component and the pH value need to be strictly selected and regulated. Moreover, due to the coating solution containing the metal phosphate, the 3 And the salinity is higher, so in the selection of organic resin, it is also necessary to pay attention to the stability of the resin under strong acid, its compatibility with high ionic strength aqueous solution: low foaming and fast defoaming Such problems make the coating formulation more complex. Therefore, the prior art has the problems of high formulation complexity, strict preparation conditions and high cost, so there is still a need to develop a simple process, low cost and obtained. In view of the above, the inventor of the present invention skipped the previous use of two compounds of organic resin and phosphate to prepare the coating (four) concept, and the organic-containing compound 4 to replace the organic The tree vinegar and the dish acid salt are prepared by mixing a metal compound and an organic Wei compound to prepare a metal surface treatment agent having excellent water solubility or dispersibility.

Accordingly, a first object of the present invention is to provide a metal surface treatment agent which is simple in process, low in cost, and excellent in coating film properties. In the present invention, the metal surface treatment agent of the present invention comprises a metal compound and an organic phosphorus compound (QrganGphGsphate) selected from the group consisting of metal oxides, metal hydroxides, metal acid salts, and the like. And the metal therein is selected from the group IIA metal 'transition metal, october,

Pb or a combination thereof, wherein the organic scaly compound contains at least an -OPOXY group, wherein each of χ and γ is independently a fluorene group of Η, ◦, (10) or ’, and a ruthenium. A second object of the present invention is to provide a surface treatment method for treating a metal material by using the above metal surface treatment agent in the United States. The surface treatment method for forming a metal material according to the present invention as described above comprises the step of applying a metal surface treatment agent to the surface of a metal material. — ^ (7> - a surface-treated metal material of a layer (ie, a coating film). The surface-treated metal material of the present invention comprises a metal material body and a protective layer, the protective layer being formed on the metal material body and It is composed of a metal surface treatment agent as described above in 201111552. The effect of the present invention is that the metal surface treatment agent of the present invention firstly uses an organic filler-containing compound to firstly derivatize an organic group with a hydroxy acid group-derived group. The problem of compatibility between the conventional mixed-organic resin and the monophosphate is solved by combining with the same compound, and since the emulsifier is not required, the metal surface treating agent of the present invention may be in the form of an aqueous solution. Compared with the previous process, the complexity of the process is greatly reduced, and the present invention has the advantages of high formulation flexibility, low foaming property, simple process and low cost, and further, the metal surface treatment of the present invention. The coating film formed by the agent also has good insulation and corrosion resistance, and has better lubricity than the conventional film, that is, protection of the surface treated metal material. The surface property of the present invention can be achieved by the surface properties of the present invention. [Embodiment] The metal surface treatment agent of the present invention comprises a metal compound and an organic phosphorus compound selected from the group consisting of metal oxides and metal hydroxides. a metal salt, or a combination thereof, and wherein the metal is selected from the group consisting of a Group IIA metal, a transition metal, a, In, Sn, Pb, or a combination thereof; and the organic phosphorus compound contains at least a mono-[gamma] gamma group, wherein each of ruthenium and osmium is independently Η, OH, OR, 〇ci or 〇Br, and R is a thiol group of (^~〇:4. Preferably The metal compound is selected from the group consisting of oxidative locks, oxidative locks, magnesium carbonate, magnesium sulfate, magnesium sulfite, magnesium phosphate, magnesium dihydrogen phosphate, magnesium phosphite, magnesium hypophosphite, magnesium nitrate, magnesium nitrite, and magnesium salt of organic acid. , Oxidation, aluminum hydroxide, aluminum carbonate, aluminum sulfate, aluminum sulfite, dish acid, the organic acid salt of the dish contains formate, acetate

201111552 酉文一一铝铝, aluminum phosphite, aluminum hypophosphite, aluminum nitrate, aluminum nitrite, organic salt 'zinc oxide, barium hydroxide, zinc carbonate, zinc sulfate, sulfite octate & Zinc, sub-acidic acid, zinc hypochlorite, acid-breaking acid, zinc nitrite, organic acid salt, or a combination of these. Workers -- -- J s salt citrate, oxalate, sulphate, tartrate, benzoate, salicylate and organic acid salt. More preferably, the metal compound is selected from the group consisting of oxidative locks, magnesium hydroxide, hydroxyacetic acid, magnesium formate, magnesium acetate, magnesium propionate, magnesium butyrate, magnesium magnesium succinate, magnesium succinate, tartaric acid Magnesium, magnesium benzoate, magnesium laurate, formazan acid lock, magnesium ethate, barium benzoate, oxidized sulphate, IL oxidized, hydrogen oxyacetate, formic acid, acetic acid, propionate, Butyric acid, sputum, sour, oxalic acid, sorrel, tartaric acid, tartaric acid, benzoic acid, sulphuric acid, sulphuric acid, sulphuric acid, oxidized, oxidized Zinc acetate, zinc formate, acetic acid, propionic acid, zinc butyrate, citric acid, zinc oxalate, zinc sulphate, zinc tartrate, benzoic acid, salicylic acid, zinc citrate, B, Benzene __, or such a - Jihe. More preferably, the metal compound is selected from the group consisting of magnesium hydroxide: magnesium sulfate, squaraine, magnesium dihydrogen hydride, magnesium nitrate, magnesium acetate, gas oxidized chain, aluminum sulphate, aluminum phosphate, diargon aluminum phosphate , aluminum sulphate, aluminum acetate, zinc sulphate, zinc phosphate, zinc dihydrogen phosphate, zinc nitrate, acetic acid: one level ^ In the present embodiment, the metal compound is sulphur magnesium sulfate. Sigh station 4 Preferably, the weight average molecular weight of the far organic filler compound is between 201111552 140 and 300,000. Preferably, the organic phosphorus-containing compound further contains at least one _CH2(〇H) group or a -CH(OH)- group. Preferably, the organic phosphorus-containing compound is obtained by reacting an alcohol having a weight average molecular weight of 50 to 1 Torr and 〇〇0 with a phosphorus-containing inorganic acid. Selected from phosphonic acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, etc. a halogen derivative, or a combination of these. The polypolyacid acid described above contains triphosphoric acid or a polycarboxylate having a higher molecular weight. Preferably, the phosphorus-containing inorganic acid is selected from the group consisting of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, or a combination thereof. Preferably, the organic phosphorus-containing compound is selected from the group consisting of ethylene glycol monophosphate, ethylene glycol diphosphate, propylene glycol monophosphate, propylene glycol diphosphate, glycerol monophosphate, and glycerol two-fill Acid ester, glycerol three-filled acid vinegar, butanediol monophosphate, butyl diphosphate diphosphate, butyl tetraol monophosphate, butyl tetrahydrofuran, butyl tetraacetate, butyl Alcoholic acid from daily, pentaerythritol monophosphate, pentaerythritol diphosphate, pentaerythritol triphosphate vinegar, pentaerythritol tetraphosphate, pentaerythritol pentaphosphate, hexanediol monophosphate, Diol dicarboxylate, sorbitol monophosphate, sorbitol diphosphate vinegar, sorbitol triphosphate, sorbitol tetraphosphate, sorbitol pentaphosphate, sorbitol hexaphosphate, or One of these combinations. 201111552 More preferably, the organic phosphorus-containing compound is selected from the group consisting of ethylene glycol diphosphate, propanol diphosphate, glycerol triphosphate, butanediol diphosphate, pentaerythritol pentaphosphate, sorbus A sugar alcohol hexaphosphate, or a combination of these. Optionally, the organic phosphorus-containing compound is selected from the group consisting of ethylene glycol diphosphate, propylene glycol tri-salt, sorbitol hexaphosphate, or a combination thereof. The amount of the metal compound is between wt2〇% and 40% by weight based on the total weight of the metal surface treatment agent. Better yet, it’s between

〇.2 Wt/° to 20 wt%. When the metal content is less than 0.02% by weight or more than 40% by weight, the corrosion resistance or mechanical properties of the protective layer may be deteriorated. Preferably, the content of the organic phosphorus-containing compound is between wt·2 wt% and 80 wt% based on the total weight of the metal surface treatment agent. More preferably, it is between 2.0 wt% and 4 wt%. Optionally, the metal surface treatment agent is in the form of a solution, emulsion or suspension. Preferably, the metal surface treatment agent is in the form of an aqueous solution. The surface treatment method of the metal material of the present invention comprises the step of applying a metal surface treatment agent as described above to the surface of a metal material to form a protective layer. In a specific embodiment of the present invention, the metallic material is between an electromagnetic steel sheet. And the bake preferably preferably 'the coating amount is between 〇1 g/m2 and g/m2. Preferably, the surface treatment method further comprises a drying treatment, the dry treatment temperature is between 100 ° C and 350 Between °C. 1 is a preferred embodiment of the surface treated metal material of the present invention comprising a metal material body and a protective layer formed on the body of the gold material and having a metal surface as described above The treatment agent is constructed in 201111552. Preferably, the body of the metal material is an electromagnetic steel sheet, the thickness of the protective layer being between 0 m and 1 G "m., more preferably between m and 2 m". Preferably, the filler content in the protective layer is between 0.2 Wt% and 70 wt%, more preferably between 24 and 35 Wt%, based on the total weight of the protective layer. When the content is less than 〇.2 or higher than 7〇wt%, the protective layer may have poor resistance to the surname. Preferably, the carbon content in the protective layer is based on the total weight of the protective layer. Between 0.2 Wt% and 70 wt%. More preferably, it is between 2 and 35 wt%. When the carbon content is less than 2.2 wt%, the friction coefficient of the protective layer will be biased as the carbon content. When the ratio is higher than 70 wt%, the durability of the protective layer may be poor. Preferably, the metal content in the protective layer is between 0.02 wt% and 30 wt% based on the total weight of the protective layer. Good ground is between wt·2 wt% and 15 wt%. When the metal content is lower than 〇〇2 or higher than % wt%, the corrosion resistance or mechanical properties of the protective layer may be deteriorated. Example 1 The present invention will be implemented as follows It is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting the implementation of the invention. Preparation of organic phosphorus-containing compounds <Preparation Example 1>Sorbitan hexaphosphate Preparation of the ester The preparation example is to firstly dispense 18.2 g (0.1 mol) of sorbitol in 10 201111552 in 100 ml of acetone, and then add 48 g (0.6 m〇1) of polyphosphoric acid (purchased from

Sigma-AldHch; model number 040101) was slowly added, and the reaction was searched for 2 hours at room temperature, and then the acetone in the reaction liquid was removed by a heating and concentrating machine to obtain 66 g of a light brown viscous liquid. A sugar alcohol hexaphosphate having the chemical formula of the following formula (el).

<Preparation Example 2> Preparation of ethylene glycol diphosphate

In this preparation example, 15·5 g (0.25 mol) of ethylene glycol was first combined with ίο. In the acetone of ml (acet 〇ne), the polyphosphoric acid (purchased from Sigma_Aldrich; model 〇4〇1〇1) of Dan (〇5〇〇1) was slowly added and the reaction was stirred for 2 hours at the temperature. 'After heating the concentrator, the propyl group in the reaction liquid was removed' to obtain 66 g of ethylene glycol diphosphate which was a light brown viscous liquid, and the chemical formula was as follows (e2). Ο

Jj 〇H 0 (e2) Preparation of surface-treated electromagnetic steel sheet <Example 1> 201111552 This example is an 8 g system for 丨%%, g sorbitol hexaphosphate synthesized in Preparation Example 1 Vinegar, 2 g of aluminum sulfate and 3 g of water are formulated into a clear light brown solution and then coated with 3 layers of clean electromagnetic steel sheets of 10 cm X 30 cm in size (cutting steel self-made 50CS1300) Made of the substrate). On the surface of the crucible, it was dried at 30 °C for 6 sec to prepare a surface-treated electromagnetic steel sheet having a coating film (ie, a protective film) having a thickness of 7'7 " m. <Example 2~ 4> Example 2 to 4 X were prepared in the same manner as in Example 1 to prepare the surface-treated electromagnetic steel crucible of the present invention, and + ι ^ was different only in the kind of the reactant and the formulation ratio, and the operating conditions were The following table i is shown. <Comparative Example 1> This comparative example is to apply an appropriate amount of a commercial acid-filled resin coating to a surface of a clean electromagnetic steel sheet which is the same as that of Example 1 by a No. 3 coating roller. 'And dried at 3GGtT for 6G seconds to obtain a surface-treated electromagnetic steel sheet having a coating film having a thickness of G. 6. Performance test of coating and coating film The inventors of the present invention respectively applied to Examples 1 to 4 The metal surface treatment agent of the present invention and the surface-treated electromagnetic steel sheet, and the commercially available phosphate resin coating and the surface-treated electromagnetic steel sheet are subjected to the following test. Table 1 shows: (1) Foaming test: 1 〇〇 ml of each of the examples The surface treatment agent and the commercial phosphate resin coating of Comparative Example 1 were placed in different 250 ml measuring cylinders, and the flaps were shaken 1 time and shaken 1 time after shaking 10 201111552 respectively. After standing for a few minutes, and shaking 100 times and letting stand for 5 minutes, observe the scale on the measuring cylinder, more than 100 ml of 3: the amount of foam, for example: the scale is 1 〇 2 ml, the amount of foam is 2, the following table The recording method in 1 is (the amount of foam after shaking 1 time, the amount of foam after shaking 100 times and standing for 1 minute, the amount of foam after shaking (10) times and standing for 5 minutes). (2)

(3)

(4) Inter-layer impedance value (iaminar resistivity): This case is based on the still C255 standard method 'Using an inter-layer impedance meter (manufactured by Toei Industry Co., Ltd., Japan, model number JIS C 255〇) to measure the above surface. The resistance value of the coating between the processed electromagnetic steel sheets. The industry generally accepts a range of 10 or more in Ω·4_. U number. This case is measured by the standard B〇wden_Leben friction tester and converted by the following formula, wherein the load weight is 50g and no punching oil is applied, and the test piece s motion curve is recorded under the pit respectively. Then, the amplitude length L (unit 丄_) of the second vibration is taken, and then the friction coefficient of the surface of each surface-treated electromagnetic steel sheet is converted by the equation: friction coefficient (8)=G Q32 χ l . Sah spfay test: A δ-type piece with a size of 6.5 cm x 75 cm and a cm size is prepared, and the test piece is sealed with tape: Salt spray: Check the machine (the amount of air is 24~48 hearts (4)). After taking the test piece for $hours, the percentage of the rusted area is estimated. The lower the ratio of the recorded area, the better the rust prevention. 13 201111552 Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Formula composition ratio Sorbitol hexaphosphate 8 g Ethylene glycol di-package vinegar _8g__ Commercial phosphate resin coating aluminum sulfate 2.0 g Magnesium sulfate L_2g aluminum sulfate 2.0g magnesium sulfate 1.2g water 30.0g water 28.0g water 30.0g water 28.0g metal surface treatment agent type clarified light brown solution white emulsion foaming amount (2, 0, 0) (1, 〇, 〇 ) (2, 0, 0) (3, 0, 〇) (15, 5, 2) Coating film thickness (μηι) 0.7 0.7 0.7 0.7 0.6 Interlayer impedance (Ω · cm2/sheet) 20±10 20 ± 10 20 ±10 20士10 20±1〇Coefficient of friction 0·15 Soil 0.5 0.15±0.5 0.15 ± 0.5 0.15 ± 0.5 〇.25±〇.5 Salt spray test (%) 13±5 20 ± 10 23 soil 10 23±10 20±1〇 It can be seen from Table 1 that the amount of foaming of the metal surface treatment agents of Examples 1 to 4 is significantly smaller than that of the commercial phosphate resin coating, and is generated by shaking after standing for 1 minute. Most of the bubbles will disappear, in addition

From the friction coefficients of the surface-treated electromagnetic steel sheets of Examples 1 to 4 and Comparative Example 1, it can be inferred that the surface lubricity of the surface-treated electromagnetic steel sheets of the examples is higher than that of the surface-treated electromagnetic sheets of Comparative Example 1. The steel sheet is good. Further, from the results of the interlayer resistance and the salt spray test, it is understood that the surface-treated electromagnetic steel sheets of Examples 丨 to 4 have insulation and durability in accordance with industry standards.

201111552 Sex. It is noted that since the organic phosphorus compound in the metal surface treatment agent of the present invention has both organic money and a base or gamma pure group, there is no problem of compatibility when the organic resin and the lysate are mixed, and The use of an emulsifier greatly reduces the complexity of the process compared to the prior art, so that the metal surface treatment agent of the present invention has a formula bomb, a sputum, a low package, a simple process, and a low cost. Further, in addition, the surface-treated metal material of the present invention also has *wrong insulation and durability" and good lubricity, so that the object of the present invention can be achieved. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a surface-treated metal material of the present invention. 15 201111552 [Explanation of main component symbols] 1 ··...··...metal material body 2 ·.........protective layer

16

Claims (1)

201111552 VII. Applicable Patent Range: h A metal surface treatment agent comprising: - a metal compound selected from the group consisting of metal oxides, metal hydroxides, metal acid salts, or a combination thereof The metal is selected from the group consisting of a Group IIA metal, a transition metal, Abin, Sn, Pb' or a combination thereof; and an organic phosphorus-containing compound containing at least one 〇ρ〇χγ group, wherein X and Υ are respectively separated Independently Η, OH, OR, OC1 or 〇Br ' and R is a C- to C4 alkyl group. 2. The metal surface treatment agent according to the scope of the patent application, wherein the 'far metal compound is selected from the group consisting of magnesium oxide, hydrogen hydroxide reduction, acid-breaking town, magnesium sulfate, magnesium sulfite, magnesium phosphate, and phosphoric acid. Magnesium Hydroxide, Magnesium Phosphite, Magnesium Hydrate M, Magnesium Nitrite, Organic Acids (IV), Oxidation, Aluminum Hydroxide, Aluminum Carbonate, Aluminum Sulfate, Aluminum Sulfite, Aluminum Phosphate, Diclosan Phosphate, Phosphorous Acid Aluminum phosphate, aluminum nitrate, aluminum nitrite, organic bismuth aluminum salt, zinc oxide, i-zinc oxide, zinc carbonate, sulfuric acid, sulfite, zinc phosphate, dihydrogen, phosphorous acid, cyanoic acid, nitric acid Words, zinc nitrite, organic acid salt, or a combination of these. 3. The metal surface treatment agent according to claim 2, wherein the metal compound is selected from the group consisting of oxidized town, hydroxide town, hydrogen oxyacetate I magnesium, magnesium formate, magnesium acetate, magnesium propionate. , magnesium butyrate, magnesium citrate, magnesium S-magnesium magnesium succinate, magnesium tartrate, magnesium benzoate, magnesium laurate, A: acid town [saki g magnesium, benzene continued acid town, oxidation Ming 'ammonia oxidation, Aluminum hydroxyacetate, aluminum formate, aluminum acetate, aluminum propionate, aluminum butyrate, lemon 17 201111552 Sodium oxalate, oxalic acid, aluminium silicate, aluminum tartarate, aluminum benzene, aluminum sulfonate, B Aluminum sulfonate...& "" Lu, Salicylic acid Yin, warm aluminum, aluminum sulfonate, zinc oxide, zinc hydroxyacetate, f酴铉^ ^ fly zinc oxyhydroxide, acetic acid, propionic acid, Citric acid, oxalic acid, sincere 6 secret, Xin Zao acid Shuhu white zinc, tartaric acid, zinc sulphate, zinc methanesulfonate, B---Zinc-one combination. Zinc acid (tetra) zinc acid, or the metal surface treatment agent according to claim 3 of the patent application. The metal compound is selected from the group consisting of sulfuric acid, magnesium sulfate, or a combination thereof. 5. The metal surface treatment agent according to the scope of the invention, wherein the organic phosphorus compound has a weight average molecular weight of between 140 and 300,000. 6. The metal surface treatment agent according to claim 1, wherein the organic phosphorus compound is obtained by using an alcohol having a weight average molecular weight of from 5 Å to 1 Torr. And reacting with a cerium-containing inorganic acid, the phosphorus-containing inorganic acid is selected from the group consisting of citric acid, poly (tetra) acid, (tetra) acid, and coke dish An acid, a phosphorous acid, a hypotrimic acid, such a self-derived derivative, or a combination thereof. 7. The metal surface treatment agent according to claim 6, wherein the organic phosphorus compound is selected from the group consisting of ethylene glycol monophosphate, ethylene glycol diphosphate, propylene glycol monophosphate, and propylene glycol diphosphate. Ester, glycerol monophosphate, glycerol diphosphate, glycerol triphosphate, butanediol monophosphate 'butanediol diphosphate, butyl tetraol monophosphate, butanol mono-acid Known, butanol diphosphate, butyl tetraacetate, pentanediol 18 201111552 monophosphate, pentaerythritol diester, pentaerythritol trioctate, pentaerythritol tetraphosphate, Pentaerythritol pentaphosphate, hexanediol monophosphate, hexanediol diphosphate, sorbitol monophosphate, sorbitol diphosphate, sorbitol tri-plate acid ester, sorbitol tetra-olate 'Sorbet five pots of acid, sorbitol hexanoic acid g, or a combination of these. 8. The metal surface treatment agent according to claim 7, wherein the organic phosphorus-containing compound is selected from the group consisting of ethylene glycol diphosphate, glycerol triphosphate, sorbitol hexaphosphate, or One of these combinations. The metal surface treatment agent according to claim 1, wherein the content of the metal compound is between 0.02 wt% and 40 wt% based on the total weight of the metal surface treatment agent. The metal surface treatment agent according to claim 1, wherein the content of the organic phosphorus compound is between 0.2 wt% and 80 wt% based on the total weight of the metal surface treatment agent. . 11. The metal surface treatment agent according to claim 1 of the patent application, which is in the form of a solution, an emulsion or a suspension. A surface treatment method for a metal material comprising the step of applying a metal surface treatment agent as described in claim 1 of the patent application to a surface of a metal material to form a protective layer. The surface treatment method of the metal material according to claim 12, wherein the metal material is an electromagnetic steel sheet. 14. The surface treatment method of a metal material according to claim 12, wherein the coating amount is between g/m2 and 2〇g/m2. 15. The surface treatment method of the metal material according to claim 12 of the patent application scope. The 2011-11552 method also includes a drying treatment, and the temperature of the drying treatment is between 100 ° C and 350 ° C. 16. A surface-treated metal material comprising: a metal material body, and a protective layer formed on the metal material body and having a metal surface as described in claim 1 The treatment agent is composed of. 1 7. The surface-treated metal material according to claim 16 of the patent application, wherein the body of the β-metal material is an electromagnetic steel sheet. 18. The surface treated metal material according to claim 16, wherein the thickness of the protective layer is between 〇.〇5; czm to l〇"m. 19. According to the patent application The surface treated metal material of the scope of item 6 wherein 'the' content of phosphorus in the protective layer is between 0.2 wt% and 7 wt%. 21. The surface treated metal material 'where' according to claim 17 of the patent application, wherein the carbon content in the protective layer is between 0.2 wt% and 7 wt% based on the total weight of the protective layer. 22. The surface-treated metal material according to claim 17 of the invention, wherein the metal content in the protective layer is between 0.02 wt% and 3 wt%, based on the total weight of the protective layer. 20