TW531567B - Surface treated metal material and surface treating agent - Google Patents

Abstract

A surface treated metal material having a corrosion resistant coating layer comprising an oxoacid compound, a hydrogen oxoacid compound or a mixture thereof of a rate earth element as a main component, and a surface treating agent therefor.

Description

531567 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to a surface-treated metal material with a coating traceability, excellent corrosion resistance, and completely free of hexavalent chromium. Surface treatment agent used. In the past, cold-rolled pin plates, galvanized steel plates, galvanized bar alloy pin plates, and aluminum-plated screed plates used in automobiles, home appliances, and building materials have been used to provide rust prevention. They are generally covered with chromium on their surfaces. Salt coating. In addition to stern plates, wire rods such as steel pipes or cables such as petroleum pipelines are also widely used. In addition, the surface of aluminum and its alloys is covered with natural oxides that are corrosive to many environmental protection materials. However, structural materials such as aeroplanes that require more excellent corrosion resistance and coating film adhesion are treated with anodizing or chromium salts. 〇The chromium salts widely used in these gold tincture materials are electrolytic chromium salts or coating chromium salts. Electrolytic chromium salt is a solution of M chromic acid as the main component, and other solutions added with various anions such as sulfuric acid, phosphoric acid, boric acid, and halogen. In addition, the coating type chromium salt has a problem that chromium is eluted from the chromium salt-treated metal plate, and is added to a solution in which a part of hexavalent chromium is reduced to a trivalent solution in advance, or a solution in which hexavalent chromium and trivalent chromium are specified. The inorganic colloid or inorganic anion becomes a treatment agent, and the metal plate is immersed therein or sprayed into the treatment liquid metal plate. Among the chromium salt coatings, although the coating layer formed by electrolysis has little dissolution of hexavalent chromium, it is difficult to say that the corrosion resistance is sufficient. In particular, when the film is damaged during processing, its corrosion resistance is reduced. In addition, the metal plate covered with the coating-type chromium salt film has high corrosion resistance, and particularly has excellent corrosion resistance in the processed portion, but the dissolution of hexavalent chromium from the chromium salt film causes a great problem. If covered (Please read the notes on the back before filling in this page)

Equipment --- Xu ----

This paper size applies to Chinese National Standard (CNS) A4 specifications (210: < 297 mm) 4 531567 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2); although organic polymers can be suppressed The equivalent hexavalent chromium eluted, but it was still insufficient. Further, as disclosed in the method of resin chromium salt generally disclosed in Japanese Patent Application Laid-Open No. 5-230666, improvement in the elution inhibition of hexavalent chromium can be seen, but a small amount of elution cannot be avoided. A coating process for forming a coating film completely free of chromium ions having the same function as the conventional chromium salt coating film is known as follows: disclosed in Japanese Patent Publication No. Hei 2-502655. A method of generating hydrogen gas by immersing an A1 plate in an acidic aqueous solution and obtaining a corrosion-resistant coating layer of a cerium-containing hydroxide; shown in Japanese Patent Application Laid-Open No. 2-25579, which uses zirconium ions, phosphate ions, and fluoride ions on aluminum The produced double salt film is disclosed in Japanese Patent Application Laid-Open No. 5-331658. It is known that it is a zinc phosphate film formed by a treatment solution of M zinc ions, phosphate ions, and lanthanum compounds. It also has insufficient corrosion resistance. An object of the present invention is to provide a surface-treated metal plate which has excellent processability and corrosion resistance, and does not use a corrosion-resistant coating layer of hexavalent chromium at all, and relates to a novel technique therefor.搿 Mingxi 拫 is shown as a system design in which M is completely free of hexavalent chromium. It replaces the current general chemical treatment film of chromium salt treatment. The inventors and other researchers have determined the results to make the rare earth elements form oxyacid compounds. It is paste-like, imparts traceability to the process, suppresses corrosion by inhibiting effects, and suppresses the cathode reaction by rare earth element ions, thereby making the oxo acid excess, and the inertness of the oxoate film type. The non-dynamic M of the oxide film type suppresses the reaction of the anode, and each component functions independently. In this way, a novel and epoch-making inorganic strip formation treatment film can be obtained. (Please read the notes on the back before filling this page)

Packing --- i --- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 5 531567 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Inventory (3) The invention The gist is as follows. (1) A surface-treated metal material, which is particularly characterized by a corrosion-resistant coating layer having an oxo acid compound or an oxo acid hydride or a mixture thereof as a main component on the surface of a gold tincture material. (2) The surface-treated metal material according to the above (1), wherein the rare earth element is E, lanthanum, and / or cerium. (3) The surface-treated metal material according to the above (1) or (2), wherein the cationic species of the oxygen-containing acid compound and the oxygen-containing acid hydride are polyvalent oxygen-containing acid cations. (4) The surface-treated gold tincture material according to the above (3), wherein the cationic species are phosphate ions, tungstic acid cations, molybdic acid ions, and / or vanadate ions. (5) The surface-treated metal material according to (1) above, wherein the corrosion-resistant coating layer is mainly composed of a phosphoric acid compound or a hydride phosphate of yttrium, lanthanum, and / or cerium, or a mixture thereof. (6) The surface-treated metal material according to the above (5), wherein the phosphoric acid compound and the phosphoric acid hydride are orthophosphoric acid (hydrogen) compounds, metaphosphoric oxides, polyphosphoric acid (hydrogen) compounds, or a mixture thereof. (7) In the surface-treated metal material of (1), (2), (3), (4), (5) or (6), the corrosion-resistant coating layer further contains an oxide selected from a rare earth element, One or two compounds of hydroxides, halides and organic oxides are used as additive ingredients. (8) The surface-treated metal material according to the above (7), wherein the rare earth element of the aforementioned added component is a knot. (9) The surface-treated metal material described in (8) above, added as above (Please read the precautions on the back before filling this page)

Packing-— • The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210) < 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 531567 A7 B7 V. Description of invention (4) points The rare earth element is cerium tetravalent. (10) The surface-treated metal material according to any one of (1) to (9) above, wherein the corrosion-resistant coating layer further contains an organic strip corrosion inhibitor as an additional component. (11) The surface treatment according to (10) Metal material, the aforementioned organic strip corrosion inhibitor is selected from the group consisting of a methylated derivative of N-phenyl-dimethylpyrrolyl, and a weicyl acetate represented by MHS-CH2C00C „H2n (η is an integer from 1 to 25) And its derivatives, d-fluorenyl carbonic acid and its derivatives, quinoline and its derivatives represented by (: ^ 2 | 1 (51〇 (: 00 [1 (0 is an integer from 1 to 25), 1 of the group consisting of acridine dithiol and its derivatives, gallate and its derivatives, nicotinic acid and its derivatives, catechol and its derivatives, and / or conductive polymers (12) The surface-treated metal material according to any one of (1) to (11), wherein the corrosion-resistant coating layer further contains a material selected from the group consisting of Si02, Cr203, Cr (0H) 3, ai203 calcium hydroxide, calcium sulfonate, calcium oxide, zinc phosphate, zinc hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium silicate, zirconium silicate One or two types of M in the group consisting of aluminum phosphate, aluminum hydrogen phosphate, titanium oxide, zirconium phosphate, hydrogen phosphate, sulfuric acid, sodium sulfate, sodium hydrogen sulfate, phosphoric acid, sodium phosphate, and sodium hydrogen phosphate. (13) A kind of surface treatment agent for forming a corrosion-resistant coating layer on the surface of gold tincture material, which is characterized in that it is an oxo acid compound or oxo acid hydride or a mixture of oxo acid as a main component. The surface treatment agent according to the above (13), the aforementioned rare earth elements are E, lanthanum and / or cerium. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) 7 • Installation --- ( (Please read the notes on the back before filling out this page)

Order 531567 A7 B7 V. Description of the invention (Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (15) The surface treatment agent described in (13) or (14) above, the aforementioned anionic species of oxyacid compounds and oxyacid hydrides It is a polyvalent oxygen-containing acid anion 0 (16) The surface treatment agent according to the above (15), and the precursor species are a discic acid ion, a tungstic acid ion, a molybdic acid ion, and / or a vanadate rotor Q (17) The above ( 13) The surface treatment agent described in the above, the corrosion-resistant coating layer is mainly composed of a phosphoric acid compound or a hydride phosphate of ME, lanthanum, and / or cerium, or a mixture thereof. (18) The surface treatment agent described in (17) above, The former phosphoric acid compound and hydrogen phosphate are orthophosphoric acid (hydrogen) compounds, metaphosphoric acid compounds, polyphosphoric acid (hydrogen) compounds, or a mixture thereof. (19> The above (13), (14), (15), (16) ), (17) or (18), the corrosion-resistant coating layer further contains one or two or more selected from the group consisting of oxides, hydroxides, dentates, and organic acid compounds of rare earth elements. Compound as an additive. (20) The above 19) The surface treatment agent according to the above description, wherein the rare earth element of the additive component is cerium. (21) The surface treatment agent according to the above (20), wherein the rare earth element of the addition component is tetravalent cerium. (22> Shangyang (13) to the surface treatment agent of any one of (21), the corrosion-resistant coating layer further contains an organic strip corrosion inhibitor as an additional component (23) the surface treatment agent according to the above (22), and the organic strip corrosion suppression The agent is selected from N-phenyl-dimethylpyrrolyl formazanyl derivative, Μ This paper size is applicable to Chinese National Standard (CNS) Μ specification (210 × 297 mm) 8 (Please read the note on the back first Please fill in this page for more details.) -------- Order— 531567 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 —__ B7_ V. Description of Invention (6) HS-CH2COOCnH2n + i (n is an integer from 1 to 25 ) And acetyl acetates and their derivatives shown by (: ^ 2 «(51〇 (: 00 [1 (11 is an integer from 1 to 25)) 〇 (-methyl carbonate and its derivatives , Quinoline and its derivatives, triazine dithiol and its derivatives, gallate and its derivatives, nicotinic acid and its derivatives 1 or 2 of the group consisting of a substance, catechol and its derivatives, and / or a conductive polymer. (24) Surface treatment according to any one of the above (13) to (23) The aforementioned corrosion-resistant coating layer further contains a material selected from the group consisting of Si02, Cr203, Cr (OH) 3, and ai203 calcium hydroxide, calcium sulphate, calcium oxide, zinc phosphate, zinc hydrogen phosphate, potassium phosphate, Potassium hydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium silicate, zirconium silicate, aluminum phosphate, aluminum hydrogen phosphate, titanium oxide, chromium phosphate, zirconium phosphate, sulfuric acid, sodium sulfate, sodium hydrogen sulfate, phosphoric acid, sodium phosphate, One or two species of M in the group consisting of sodium hydrogen phosphate. (25) A surface treatment agent, which is particularly exciting in that it contains 0.05 to 4 mol / kg of rare earth compounds in terms of M rare earth elements and 1 mole M H3P (0.5 to 100 in U equivalent) Moore's phosphate compound and / or hydrogen phosphate compound. (26) The surface treatment agent according to the above (25), wherein the rare earth element compound is a lanthanum or cerium phosphate compound, a phosphate hydride, an oxide, a hydroxide, or the like (27) The surface treatment agent according to (25) or (26) above, the phosphoric acid is orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, or a mixture thereof. (28) The above (25), (26) Or (27) surface treatment agent, containing water or a mixture of water and a water-soluble organic solvent as a diluent. (Please read the precautions on the back before filling this page)

Packing --- ordering-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 9 531567 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___ _B7__ V. Description of the invention (7) (29) ) The surface treatment agent of (25), (26), (27) or (28) above, the rare earth element compound is a lanthanum compound, and the molar ratio of cerium to lanthanum cerium is 1.0 to 0.001 cerium The compound and / or the molar ratio to lanthanum contain 2 to 0.001 organic strip corrosion inhibitors. (30) In the surface treating agent of (25), (26), (27) or (28> above, the rare earth element compound is a cerium compound, and its ear ratio is 1.0 to 0.001 in terms of cerium lanthanum. The lanthanum compound and / or the molar ratio to lanthanum contain an organic strip corrosion inhibitor of 2 to 0.001. Brief description of the drawing The first figure is a schematic diagram showing the relationship between the lanthanum / phosphoric acid mixing ratio and the corrosion-resistant coating structure. Figures 2 to 3 are anodic current and potential curves of zinc metal adjusted to 0.1 fflol / liter of NaCl solution of pH 8.4. The best mode for carrying out the invention using M is described in detail below. The present invention The film is made of rare earth elements as oxyacid compounds (including oxyacid hydrides, the same under M), forming a paste, which has sufficient processing traceability. Its blocking effect can inhibit corrosion, and at the same time, it inhibits the formation of rare earths. The cathodic reaction caused by the group element ions causes excess phosphoric acid, and it is planned to suppress the anode reaction caused by the oxo acid film type non-dynamic and oxide film type non-dynamic. Extreme reaction inhibition, and other rare earth element compounds, especially cerium compounds can also be added. The oxo acid compounds of rare earth elements refer to the oxo acid anions such as phosphate ion, tungstic acid ion, molybdic acid ion, and vanadate ion. The paper scales with rare earth elements are subject to the Chinese National Standard (CNS) A4 specification (210X 297 public holidays)-1〇- (Please read the precautions on the back before filling this page) 4 Pack--, 1Τ sm & gt tLUV ml 1 i · 531567 V. Description of the invention (8 A7 B7 compounds printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The so-called oxyacid hydrides refer to compounds containing hydrogen as part of the cations. In addition, rare earth elements contain 17 elements of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dg, Ho, Er, Tib, Yb, Lu. For example, the phosphorous compounds of lanthanum include LaPCU, etc., corresponding to this The lanthanum phosphate hydride includes La (H2PCU) 3, La2 (HPCU> 3. The oxyacid compound and / or oxyacid hydride of the rare earth element forming the main component of the corrosion-resistant coating layer of the present invention should not be theoretically limited , But in the form of a paste, I am afraid Forms an amorphous (amorphous) inorganic polymer, and also has processing traceability to form a certain thickness. The inorganic coating layer with processing traceability can act as a corrosion resistance barrier. Even if an inorganic polymer is formed in it, The same effect can be obtained by dispersing crystalline or amorphous particles. Fig. 1 shows that when the mixing ratio (La / P) is changed on the pin plate 1 of the zinc plating 2 and the lanthanum / phosphoric acid mixture is coated, An example of a preferred coating layer. When La / P is very small, it becomes a crystalline and hard coating substantially the same as zinc phosphate coating. 3, the processability is low (Figure 1 / A >, but if the U / P ratio In the shape of an inorganic polymer, La (H2P04): and U (HP0) 4 as the main body can be coated with an inorganic polymer (Figure 1 / B). However, even if the La / P ratio is too large, many crystalline LaPtU particles 5 'will be precipitated, and the matrix portion 4' will be reduced, thereby reducing film-forming properties and processability (Figure 1 / C). However, Fig. 1 schematically shows an example of a certain method (manufacturing method). Depending on the type of the rare-earth element compound and the oxyacid (hydrogen) compound or the manufacturing method, the specific mixing ratio and the properties of the coating The relationship is a paper size applicable to the Chinese National Standard (CNTS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

11 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 531567 A7 _B7__ V. No description of invention (9). The rare-earth element ions and oxo-acid ions in the film of the rare-earth element oxo-acid compound or oxo-acid hydride or mixtures thereof (in the case of oxo-acid hydride, or a mixture containing them are converted into Oxygen ion) The styling ratio (oxygen ion / rare earth element ion) is generally 0.5 ~ 100, preferably 2 ~ 50, more preferably 5 ~ 10. When it is less than 0.5, the processability is insufficient, and when it exceeds 100, the film forming property is reduced. The source of the rare-earth element is not particularly limited, but examples thereof include rare-earth element compounds such as oxides, acetates, sulfonates, chlorides, and chlorides, and M oxides are preferred. Also, like cerium-lanthanum alloy or its precursor, even if other rare earth element compounds are mixed together as impurities, there is no particularly bad influence on the corrosion resistance. The so-called "precursor" here refers to a general term for substances such as lanthanum, cerium, and other raw materials, such as monazite (phosphate), etc., to the compounds obtained in the process of making and refining the chain. The amount of rare earth elements contained in the film is only required to be 1 mg / ®2M. If it is less than 1 mg / m2, the independence will be insufficient. In addition, even if it exceeds 10 g / a2, the corrosion resistance cannot be improved any more, and considering economic efficiency, S / ®2 is sufficient. The film thickness is preferably 0.001 or more, and more preferably 0.001 or more. Below 0.01 μ®, the corrosion resistance may be insufficient. However, if the film thickness exceeds 5 μm, the corrosion resistance is no longer improved, and 5 μm is sufficient in consideration of economy. Particularly suitable oxyacid compounds are phosphorus oxides and / or hydride phosphates, and phosphoric acid species include orthophosphoric acid, metaphosphoric acid, and polyphosphoric acid. Polyphosphate phosphoric acid is suitable. The rare earth element may be a mixture of one or two kinds of M. However, lanthanum, zinc, and yttrium are preferred, and lanthanum is particularly preferred. The suppression of the cathode reaction by cerium should be effective. For example, this paper size applies Chinese National Standard (CNS) Α4 size (2Ι0 × 297 mm) 12 (Please read the precautions on the back before filling this page)

Installation ---- 1-• Order-531567 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (ίο) The most suitable compounds, namely, lanthanum phosphate and hydride phosphate, can be easily determined by It is obtained by chemical reaction of water-soluble inorganic salts such as lanthanum chloride or lanthanum nitrate, hafnium oxides such as hafnium oxide or lanthanum hydroxide oxides and phosphates such as orthophosphoric acid, polyphosphoric acid, or sodium hydrogen phosphate. Here, M is water-soluble, such as chloride or nitrate, and ammonium compounds that are active acids are used as raw materials. Anions other than phosphate ion M are easily removed by heating, but it is preferable for water such as molybdate or tungstate. In order to be insoluble and non-volatile, a lanthanum compound composed of a corrosion-resistant anion can be reacted with phosphoric acid. The most preferred is the reaction of M oxide or hydroxide with phosphoric acid to obtain phosphorus oxide or hydride phosphate of lanthanum. It is also possible to use a mixture of lanthanum oxide or lanthanum hydroxide particles and phosphoric acid on the surface layer obtained by reacting only phosphoric acid compounds under relatively stable conditions. Here, in the coexisting state of the lanthanum compound and phosphoric acid, the stable phosphoric acid compound, lanthanum phosphate LaPCU, can exist alone, but the oxides and hydroxides of lanthanum cannot exist alone, and the surface of the particles of the oxides and hydroxides is phosphorus oxidation. It is inevitable that the compound or hydride phosphate is a mixture. It can also be a natural phosphate compound produced from minerals. The corrosion resistance coating of the present invention may further add rare earth elements, especially cerium oxides, hydroxides, halides, sulfonic acid compounds, sulfuric acid compounds, nitric acid compounds, organic acid compounds, and the like as additional components. These compounds, especially tetravalent cerium ions and cerium compounds, are said to have the effect of enhancing the inhibitory effect of the cathode reaction. The amount of the added component is preferably 50 times the molar ratio of the rare earth element of the added component to the molar number of the rare earth element of the oxyacid compound and / or oxyacid hydride. It is 10 times M, more preferably 5 times M. If there are too many added ingredients, (Please read the precautions on the back before filling this page)

Packing----- • The size of the paper is in accordance with the Chinese National Standard (CNS) A4 (210 × 297 mm). 13 Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs. Cooperatives. 531567 A7 B7 V. Description of the invention (11) The film-forming property is lowered, and sufficient processability of the film cannot be obtained. The cerium compound is an oxo acid compound or an oxo acid hydride, which is added to the oxo acid compound or oxo acid hydride matrix of other rare earth elements to enhance the inhibitory effect of the cathodic reaction. Other rare earth elements are still suitable to add a certain ear ratio at 50 times K. The organic strip corrosion inhibitor has the adsorption property to the metal surface. When the metal ions dissolve, it traps and forms dislocations, so it can further inhibit ionization. The organic strip corrosion inhibitor can use a functional group (= 0, -NH2, = NH, = N-, = S, -0H, etc.) necessary for the formation of metal complexes in the molecular structure, and can be used with metals Compounds with functional groups (-0H, = NH, -SH, -CH0, -C00H, etc.) that form covalent bonds on the surface. Further, the organic strip corrosion inhibitor contained in the film is preferably a poorly water-soluble compound. The reason is that the corrosion inhibition effect is through the water that passes through the film, and the organic strip corrosion inhibitor will dissolve. If it is soluble, when water passes through the film, it will easily dissolve completely, fail to exert its function, or have insufficient persistence, so it is not good. . Specific examples of corrosion inhibitors of poorly water-soluble organic strips that have the above functional groups are: formazanyl derivatives of N-phenyl-dimethylpyrrole, M HS-CH2C00CnH2 «+1 (η is 1 to 25 Integers shown in integers> and fluorenyl acetate and their derivatives, (-*-sulfonic acid and its derivatives shown by (: * ^ 2 «(51〇 (: 0011 (11 is an integer from 1 to 25)) Derivatives, quinoline and its derivatives, triazine H-dithiol and its derivatives, gallate and its derivatives, nicotinic acid and its derivatives, catechol and its derivatives, etc. Electronic conductive polymers can be used as corrosion inhibitors for organic strips with different anti-corrosion mechanisms. This is a 7T electronic conjugate bond in the whole molecule. The paper size is applicable to China National Standard (CNS) M specifications (210X 297) Mm) 14 (Please read the notes on the back before filling this page)

531567 A7 B7 V. Description of the invention (12) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, a single molecule with repeated units, known as polyacetylene, polyaniline, poly_pan, polypyrrole, etc. Among them, electron conductivity can be imparted by adding, for example, barium sulfate as a donor. The details of the anti-corrosion effect of this conductive polymer are not clear, but it is speculated that the electron current exhibits a corrosive current rectification effect and an oxygen reduction suppression effect at the interface, and functions as a cathodic corrosion inhibitor. In addition, one or two kinds of organic strip corrosion inhibitors are mixed, and the amount of addition is based on the ratio of rare earth element ions to the organic strip corrosion inhibitor (organic strip corrosion inhibitor / rare earth ion). It is (K001 ~ 2, preferably 0.01 ~ 1, more preferably 0.02 ~ 0.5. Its ear ratio is less than 0.001, the addition effect is insufficient, and if it exceeds 2, the adhesion is insufficient. Also, these organic strips in the film are inhibited from corrosion. The form of the agent is not particularly limited. For example, it can be directly added and mixed in the treatment liquid, or it can be dissolved in phosphoric acid beforehand and added to the treatment liquid, or completely dissolved in alcohol such as ethanol, isopropanol, and the like. A method of adding water to a fine colloid and adding it to a treatment liquid, thereby allowing it to be contained in the film. In addition to the rare earth element compound M such as a cerium compound, M strengthens the corrosion resistance or the barrier properties of the coating layer and suppresses the added components In addition, in order to enhance the anti-cathode corrosion performance or the anode anti-corrosion performance, Si 02, Cr2 03, Cr (0H) 3, AU〇3, calcium hydroxide, calcium carbonate, calcium oxide, phosphoric acid can be further added. Zinc, zinc hydrogen phosphate Potassium phosphate, potassium hydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium silicate, zirconium silicate, aluminum phosphate, aluminum hydrogen phosphate, titanium oxide, zirconium phosphate, zirconium hydrogen phosphate, sulfuric acid, sodium sulfate, sodium hydrogen sulfate, phosphoric acid, Sodium phosphate, sodium hydrogen phosphate, etc. The metal material that is the subject of this invention is not particularly limited, but it is applicable (please read the precautions on the back before filling in this page)

Install -------- Order——

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 15 531567 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 1 --_ _------------ ----V. Description of the invention (13) such as molten galvanized steel sheet, molten galvanized-iron alloy steel sheet, molten galvanized-aluminum-magnesium alloy steel sheet, molten aluminum-silicon pin plate, molten lead-tin Melt-plated pin plates such as alloy pin plates, or surface-treated steel plates such as electrical galvanized steel plates, electrical galvanized-rhenium alloy copper plates, electrical galvanized-alloy plated steel plates, electrical galvanized-chrome alloy plates, etc. , Cold-rolled steel plate or zinc or aluminum, etc. In addition, not only metal plates, but also other types of materials such as metal wires and metal pipes. The representative manufacturing method of the surface-treated metal material film of the present invention is that the olefinic earth element compound and the oxo acid are thoroughly mixed and heat-treated (100-200¾, 0.5 ~ 24 hours). Add organic strip corrosion inhibitor and mix well. Further, as required, an additive component such as a cerium compound and an appropriate amount of water can be added. Addition of ingredients and water can improve corrosion resistance and film formation, respectively. This treatment liquid is applied to a metal material, and dried and heat-treated (for example, the temperature of the metal material is 100 to 200 C for 30 seconds to 1 hour) to obtain the intended surface-treated metal material. The present invention provides in one aspect: a rare earth compound containing M lanthanum, cerium, etc., which is converted into a rare earth compound of 0.05 to 4 aol / kg, and 1 mole KH3P (equivalent to 0.5 to 100 in U conversion) relative to the ene earth element. Surface treatment agent for phosphoric acid compound and / or hydride phosphate of the ear. The rust-proof coating layer containing no hexavalent chromium and its manufacturing method are disclosed in International Patent Application No. W088 / 06639. The trivalent cerium ion is passed through the cathode. The reaction precipitates on the surface of the metal material as a hydroxide, and then is oxidized to tetravalent by hydrogen peroxide to obtain an excellent anti-rust property (^ 02 layer. The coating layer obtained in this way lacks the same as the metal material). Adhesion, lack of corrosion resistance (please read the precautions on the back before filling this page)

Outfit —

This paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) 1 16 1 531567 A7 B7 V. Description of the invention (14) Permanent performance printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. In addition, in this way (^ 〇2 film cannot fully expect processing traceability, its use is obviously limited. In Japanese Patent Application Laid-Open No. 5-331658, a plating coating suitable for metal surfaces is advocated to form a coating film close Surface treatment method of zinc phosphate film with excellent resistance and corrosion resistance, and surface treatment liquid and zinc phosphate treatment method with M zinc ion, phosphate ion, osmium compound and film formation promoter as main components, but the main purpose of such promotion is to Zinc phosphate treatment as the premise of coating, therefore, the concentration of lanthanum metal contained in the proposed solution is 0.001 ~ 3 g / liter, that is, if the ear concentration is expressed, it is 7X 10_s ~ 0.22 mol / e, which is very small. Even if a lanthanum compound is contained in the zinc phosphate-treated film, the high corrosion resistance of the separate film of the conventional chromium salt film cannot be obtained. In addition, the surface treatment of aluminum or its alloy is proposed in Japanese Patent Application Laid-Open No. 2-25579. Agents and treatment liquids contain cerium ions, zirconium ions, phosphate ions, and fluoride ions. Aluminum is attacked by fluoride ions and exists in the liquid together with cerium, zirconium, phosphoric acid, and fluoride ions. M forms corrosion resistance. Excellent film, but the material is limited to the solution composition of aluminum and its alloys accompanied by erosion, and the effect can be obtained in a low concentration range of 10 ~ 1000 PPin for cerium ions and 10 ~ 500 ppm for phosphate ions. Adding trivalent cerium ions to the aqueous solution to suppress the anodic dissolution of mild steel, has been described in Jour · Electrochemical Soc · 1991, 138, p. 390, and has no industrial applicability, in Corrosion Sci. 1993, 34 , Page 1774 revealed in the stainless steel ion-implanted tetravalent cerium ions under vacuum, which can significantly inhibit the reduction of oxygen in solution (please read the precautions on the back before filling this page)

Install-

1T This paper is again applicable to China National Standards (CNS) Α4 specifications (2i0x 297 mm) 17 531567 Α7 Β7 V. Description of invention (15) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. As exemplified by such conventional technology, it is known that cerium can effectively improve the corrosion resistance of metal materials, but the suggestion of a surface treatment agent that has general versatility for metal materials and has industrial mass production properties has been sought. In order to solve such a problem, the present inventors have earnestly researched a surface treatment agent for forming a corrosion-resistant coating layer containing no hexavalent chromium, and as a result, have found a rare earth element such as M lanthanum, cerium, and phosphoric acid as main components. The above surface treatment agent. Under M, for the convenience of explanation, the rare earth elements refer specifically to lanthanum; the special feature of this surface treatment agent is that it is mainly composed of lanthanum compounds, phosphoric acid and diluent, and rhenium compounds are M phosphate compounds, hydrogen phosphate compounds, oxides, Hydroxide or its mixture exists, and contains other rare earth element compounds, especially cerium compounds and organic strip corrosion inhibitors as additives. The concentration of lanthanum compounds contained in this surface treatment agent is per 1 kg of surface treatment. Molar number of lanthanum contained in the agent. Here, the number of lanthanum moles per 1 liter of the surface treatment agent is not used as the concentration, because the amount of lanthanum compound and phosphoric acid contained in the treatment agent is large, and the proportion of the treatment agent is large, so the M capacity concentration is specified difficult. The phosphoric acid in this treatment agent forms a general term for phosphoric acid ions and hydrogen phosphate ions of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and phosphoric acid compounds, and its concentration is expressed in terms of a molar ratio relative to H3P04t4. Part of the main component of this treatment agent is the phosphoric acid compound and argon phosphate compound of lanthanum lanthanum, which can be easily obtained from: inorganic salts such as lanthanum chloride or lanthanum nitrate, or lanthanum compounds such as lanthanum oxide or lanthanum hydroxide oxides. Chemical reaction of phosphates such as phosphoric acid, polyphosphoric acid, metaphosphoric acid or sodium hydrogen phosphate. Here, M can be used as a raw material with lanthanum compounds such as chlorides or nitrates of volatile acids (please read the precautions on the back before filling out this page) --packing, one, and Chinese paper standards apply ( CNS) A4 specification (210X297 mm) 18 531567 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs i. Invention Description (16), because anions are easy to remove by heating, so it is good, but, for example, copper salts or lanthanates The non-volatile nature of the salt also allows the hydrazone compound composed of corrosion-resistant anions to react with phosphoric acid. The most preferable is the reaction of M oxide or hydroxide with phosphoric acid to obtain lanthanum phosphate compound or hydrogen phosphate compound. It is also possible to use a mixture of lanthanum oxide or lanthanum hydroxide particles and phosphoric acid in a relatively mild condition to obtain only a phosphoric compound on the surface layer. The mineral may be a natural phosphate compound. This surface treatment agent is a lanthanum compound and phosphoric acid as a main component, and more specifically is a phosphoric acid compound, a hydrogen phosphate compound, an oxide, a hydride, or a mixture thereof with a phosphoric acid as a main component, and may further have a dilution It is composed of water or a water-soluble organic solvent. Here, the purpose of selecting the organic solvent is to mainly reduce the viscosity of the surface treatment agent such as methanol and ethanol and improve the effect of promoting drying. The lanthanum compound used as a raw material of the surface treatment agent sometimes contains many other rare earth elements from the production and refining process of rare earth ore, such as yttrium, thorium, and cerium compounds, but their existence is not a problem. The phosphoric acid used is orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, or a mixture thereof. Here, the polyphosphoric acid having an average molecular formula of 5P4O13 is the 4th volume of 3P04, that is, if the polyphosphoric acid 1 haem is converted to 3P04, it is 4 moles. The concentration of the lanthanum compound contained in this surface treatment agent is characterized in particular by: M lanthanum conversion is 0.05 ~ 4 mol / kg. The lower limit of the concentration of the lanthanum compound 0.05 a01 / kg is the lower limit concentration required for coating the gold tincture material with a lanthanum compound-phosphate strip coating having the same excellent corrosion resistance as the chromate film, and preferably at 0.1 moI / kgM. In addition, the upper limit concentration of 4 πω 1 / kg is given by lanthanum compounds (please read the precautions on the back before filling this page)

-The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 19 531567 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, i, Invention Description (Π), Phosphoric Acid, and a certain amount of dilution It is a relatively hard paste-like treatment agent composed of an agent, and can form a coating layer uniformly on the surface of a metal material. The preferred concentration of the lanthanum compound is 2 mol / kgM. In addition, the main components of this surface treatment agent are lanthanum compounds and phosphoric acid. The special feature is that M lanthanum conversion is 0.5 to 100 moles of phosphoric acid relative to M H3P04 conversion. The lower limit of the molar ratio of phosphoric acid to lanthanum is 0.5, which is the lower limit of phosphoric acid necessary for coating the surface of metal materials with lanthanum compounds. Furthermore, by reducing the phosphoric acid ratio, for example, the reaction of phosphoric acid ions on the surface of particles with lanthanum oxide or hydroxide is consumed, etc., the phosphoric acid ions related to the adhesion of the surface of the gold tincture material are insufficient, and the corrosion resistance is reduced, In particular, the processing traceability of the film will be significantly insufficient and the corrosion resistance of the processed portion will be reduced. In order to obtain a film with excellent corrosion resistance, the molar ratio of phosphoric acid to lanthanum is 0.5M, and in particular, to obtain a film with excellent corrosion resistance in the processed portion, it is 2M, and more preferably 5 or more. Such excess phosphoric acid is very effective in forming lanthanum phosphate hydride. At the same time, it reacts with metal elements such as zinc on the surface of gold tincture to form a zinc phosphate compound, which improves the adhesion of the coating layer and also enhances the Mil compound and phosphoric acid as the main Corrosion resistance effect of the coating of the component. The purpose of the surface treatment agent for the metallic material of the present invention is to improve the rust prevention effect of the resulting coating layer, and it may also contain other rare earth compounds, such as a cerium compound and an organic strip corrosion inhibitor. The cerium compound to be added is one or two or more compounds selected from the group consisting of phosphoric acid compounds, hydrogen phosphate compounds, oxides, hydroxides, halides, carbonic acid compounds, sulfuric acid compounds, nitric acid compounds, and organic acid compounds. The selected valence of cerium is trivalent, tetravalent, or a mixture thereof. The amount of cerium compound added, relative to the size of this paper, is applicable to the Chinese National Standard (CNS) A4 gauge (210X297 mm) 20 (Please read the precautions on the back before filling this page) • Installation * • Order km 531567 A7 B7 V. Description of the invention (18) The molar ratio of cerium conversion printed on lanthanum printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is 1 to 0.001. High ear ratio relative to cerium of lanthanum, for example 1 ~ 0.1, lanthanum compound and phosphoric acid also constitute the main component of the coating layer. It is suitable to choose phosphoric acid compounds, hydrogen phosphate compounds, oxides, hydroxides or their mixtures with low solubility. Cerium compound. The molar ratio is 0] to 0.001. In addition to compounds having a small solubility, they are also preferably selected from soluble cerium compounds such as the above-mentioned halides. As the organic strip corrosion inhibitor, a compound as described above can be used. The amount of the organic strip corrosion inhibitor added is 2 to 0.001 relative to the molting ratio of lanthanum, and the added molar ratio is not only the effect of the corrosion inhibitor is strong, but also depends on the composition of the surface treatment agent and the coating layer. Methods. For example, organic bar corrosion inhibitors that strongly bind metal ions that are dissolved and dissolved from gold tincture materials, such as a combination with a quinoline derivative, can have an effect at a thin concentration of 0.01 to 0.001 with respect to the molar ratio of lanthanum to lanthanum. A type of corrosion inhibitor that adsorbs on the surface of gold tincture and inhibits anodic reaction, such as the methyl fluorenyl derivative of N-phenyl-dimethylpyrrole, especially the metal dissolution and hydrogen generation that are inhibited during the formation of the coating layer When it is added for the purpose, it is advantageous that the molar ratio is as high as 0.01M. In addition, when the molar ratio to lanthanum is 0.1 or more, and the organic strip corrosion inhibitor also forms the main component of the coating layer, for example, by adding a conductive polymer, polyaniline, to provide a corrosion inhibitory function When it is conductive with the coating layer. The ratio of the ear to ear is less than 0.001, and the effect of the organic strip corrosion inhibitor will be insufficient. If it exceeds 2, the adhesion of the coating layer will be insufficient, which will damage the processability. Also, compared to the lanthanum organic strip corrosion inhibitor, Morbi, also can be installed according to (Please read the precautions on the back before filling in this page) ---- 、 trIn 11 -...- km This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇 Χ 297mm) 21 531567 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _B7__ V. Description of Invention (19) The thickness of the coating layer is selected as the purpose. When the molar ratio of lanthanum is as small as 0.001, the absolute amount of the organic strip corrosion inhibitor contained in the coating layer will be large, so sufficient effects can also be obtained. In addition, for the purpose of forming a thin coating layer corresponding to a weakly corrosive environment, when using a diluted treatment agent with a small lanthanum concentration, it is desirable to contain an organic strip with a high morin ratio of 0.1 to 2 for lanthanum Corrosion inhibitor. On M, it is explained that lanthanum is selected as the rare earth element, and rhenium is replaced with other rare earth elements such as cerium. The treatment agent of the present invention is also effective. When replacing lanthanum, other rare earth element compounds used together are preferably lanthanum compounds. The surface treatment agent is characterized in that the rare earth element compound and phosphoric acid are used as main components, and water or a mixture of water and a water-soluble organic solvent is a dilution medium. The dilution medium is water and organic solvents contained in the raw materials used in the process of manufacturing the surface treatment agent, water or organic solvents used to dissolve the raw materials, and the original treatment agent dilution. Based on the relative amounts of rare earth compound, phosphoric acid, other olefinic earth compound, organic strip corrosion inhibitor, and the diluent contained, the surface treatment agent presents a hard paste, soft paste, gelatinous, Or the solid solution is rarely in the form of a solution. The dilution range can also be determined by the degree of corrosion resistance sought by the M film and the method by which the M film covers the surface of the metal material. For example, a surface treatment agent in which the molar ratio of phosphoric acid to rare earth elements is small and the concentration of rare earth elements is high can effectively form a highly corrosion-resistant film with a thickness of 1 to 10 μ® according to the coating method. If M water or water-soluble organic solvents are added to increase the degree of dilution, the surface can be coated with 0.1 ~ 1 μm skin by spraying method (please read the precautions on the back before filling this page)

Packing---- Order — 4 This paper size applies to the Chinese National Standard (CNS) A4 specification (210: < 297 mm) 22 531567 A7 B7 V. Description of the invention (2) Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed film. Furthermore, by increasing the degree of dilution, a film having a thickness of 0.1 μm or less can be coated by the dipping method. Although this treatment agent exhibits strong acidity, the hydrogen ion concentration (pH) can be arbitrarily adjusted depending on the purpose or the type of metal material to be surface-treated. In addition, M rare earth element compounds and phosphoric acid are used as main components, and other rare earth element compounds and organic strip corrosion inhibitors are added; for the purpose of supplementing the rust preventive effect of the coating layer, it may be further added to 5 or 02 or 6012. The said additive component is disperse | distributed to a processing agent. The method for applying the present invention to these metal materials is not particularly limited, but a conventionally known method such as a dipping method, a spray method, and a coating method may be used, and the drying method is in a temperature range from room temperature to 300t: It is appropriately determined according to the properties sought for the coating layer, the composition of the treating agent, and the method for forming the coating layer. EXAMPLES [Examples 1 to 6] (Preparation method of treatment liquid) Example 1 ① 32.6 g of lanthanum oxide and 69 · 2 g, 115.3 g, and 173.0 g of phosphoric acid (85%) were thoroughly mixed, and the temperature was 100 to 200 ° C. After heating for 0.5 ~ 24 hours, the paste product obtained by Μ is used as the treatment liquid (sample No. 1 ~ 3 in Table 1). In the treatment solution of N0.2, the molar ratio of cerium and lanthanum is 1:10. Lanthanum hydroxide, cerium oxide, cerium hydroxide, cerium chloride, and cerium acetate M become the treatment liquid (No. 4 ~ 8 in Table 1). This paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) ) 23 ， installed-(Please read the precautions on the back before filling this page), tr 531567 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) ② In the above ①, phosphoric acid is not used Then, 261.0 g of an aqueous solution of ammonium tungstate (") 5 (ΝΗ4) 2〇 · 12W03 · 5Η20 and 176.6 g of an aqueous solution of ammonium molybdate (28%) (NH4) 6 · M〇07〇24 · 4Η20 were respectively added and mixed. And 117.0 g of an ammonium vanadate aqueous solution (5%> NH4 ♦ V03) in a paste-like product (samples no.9, 15, 21 in Table 1) are mixed in the same manner as in (1) above. Lanthanum hydroxide, thorium oxide, cerium hydroxide, cerium chloride, and cerium acetate (in Tables 1 and 2, sample Nos. 10 to 14, 16 to 20, and 22 to 26). Example 2 In Example 1, no oxidation was used. 23.5 g of cerium phosphate was used for lanthanum, and the treatment solution was adjusted in the same way (sample No. 27 to 52 of Table 2). Μ_3. In Example 1, lanthanum oxide was used instead of yttrium chloride 6 water and 30.3 g. The treatment solution was adjusted in the same manner as in other samples (Sample Nos. 53 to 58 in Table 3). 0 Example 4 In Example 1, lanthanum oxide was used instead of 39.6 g of thallium chloride 6 water, and other samples were adjusted in the same manner. Treatment liquid (Sample Nck 79 ~ 104 in Table 4) ° Also, all the test reagents of Examples 1 to 4 are commercially available. (Please read the precautions on the back before filling this page

f:-1 · Order— This paper size applies Chinese National Standard (CMS) A4 specification (210: < 29, mm) 24 531567 A7 B7 V. Description of the invention (22) Table 1 Sample No. Rare earth elements Oxy-acid additive lanthanum hydroxide cerium hydroxide cerium hydroxide cerium chloride cerium nitrate lanthanum oxide lanthanum oxide lanthanum oxide lanthanum oxide lanthanum oxide lanthanum oxide lanthanum oxide 32.6g 32.6g 32.6g 32.6g 32.6g 32.6g 32.6g phosphorus phosphorus Phosphorus Phosphorus Phosphorus Phosphoric Acid Acid Acid Acid Acid Acid Acid 62.9g 115.3g 173.0Og 115.3g 115.3g 115.3g 115.3g 115.3g 3.8g 3.4g 4.2g 7.5g 6_7g (Please read the precautions on the back before filling in this Page) 10 11 12 13 14 Rhenium oxide 32.6g Lanthanum oxide 32-6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution Ammonium tungstate solution Ammonium tungstate aqueous solution Ammonium tungstate Aqueous solution of ammonium tungstate 261.0g 261.0g 261.Og 261.0g 261.Og 261.0g 3.8g 3.4g 4.2g 7.5g 6.7g 15 16 17 18 19 20 Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6 g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution 176.6g 176.6g 176.6g 176.6g 176.6g 176.6g 3.8g 3.4g 4.2g 7.5g 6.7g Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 21 22 23 24 25 26 Lanthanum oxide 32.6g Lanthanum oxide 32-6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Lanthanum oxide 32.6g Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Aqueous ammonium acid solution 117.0Og 117.Og 117.Og 117.Og 117.Og 117.Og 3.8g 3.4g 4.2g 7.5g 6.7g This paper size applies to Chinese National Standard (CNS) Α · 4 specifications (210X 297) 25) 531567 A7 B7 V. Description of the invention (23) Table 2 Sample No. Rare earth element oxo acid additive lanthanum hydroxide cerium oxide cerium hydroxide cerium chloride cerium nitrate 27 28 29 30 31 32 33 34 cerium phosphate cerium phosphate Cerium phosphate cerium phosphate cerium phosphate cerium phosphate cerium phosphate cerium phosphate cerium phosphate cerium phosphate 23.5g 23.5g 23.5g 23.5g 23.5g 23.5g 23.5g 23.5g g 115.3g 115.3g 115.3g 115.3g 3.8g 3.4g 4.2g 7 .5g 6.7g (Please read the notes on the back before filling out this page) 35 36 37 38 39 40 Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Ammonium tungstate Aqueous solution of ammonium tungstate Aqueous solution of ammonium tungstate Aqueous solution of ammonium tungstate Aqueous solution of ammonium tungstate Aqueous solution of ammonium tungstate Aqueous solution of ammonium tungstate 261.0g 261.0g 261.0g 261.0g 261.0O 261.0g 3.8g 3.4g 4.2g 7.5g 6.7g 41 42 43 44 45 46 Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23-5g Lanthanum oxide 23.5g Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution 176.6g 176.6g 176.6g 17 & .6g 176.6g 176.6g 3.8g 3.4g 4.2g 7.5g 6.7g Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 47 48 49 50 51 52 Lanthanum oxide 23.5g Lanthanum oxide 23.5g Lanthanum oxide 23.5g Rhenium oxide 23.5g Lanthanum oxide 23-5g Lanthanum oxide 23.5g Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution 117 · Og 117.Og 117.Og 117.Og 117.Og 117 .Og 3.8g 3.4g 4.2g 7.5g 6.7g China National Standard (CNS) A4 specification (210X 297 mm) 26 531567 A7 B7 V. Description of invention (24) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Table 3 Sample No. Rare Earth Oxygen Additive Hydroxide _ Cerium oxide cerium hydroxide cerium chloride cerium nitrate 53 yttrium chloride 30.3g phosphoric acid 57.7g mono----54 yttrium chloride 30.3g phosphoric acid 115.3g-----55 yttrium chloride 30.3g phosphoric acid 230.6g--- --56 Yttrium chloride 30.3g Phosphoric acid 115_3g 3.8g----57 57 Yttrium chloride 30.3g Phosphoric acid 115.3g-3.4g---58 Yttrium chloride 30-3g Phosphoric acid 115.3g--4.2g--59 Chlorine E 30.3g 115.3g phosphoric acid---7.5g-60 Yttrium chloride 30.3g 115.3g phosphoric acid---6.7g 61 Lanthanum oxide 30-3g Ammonium tungstate aqueous solution 261.0Og----62 Lanthanum oxide 30.3g Tungsten Aqueous ammonium acid solution 261.0Og 3.8g----63 Lanthanum oxide 30.3g Aqueous ammonium tungstate solution 261.0g-3.4g---64 mm 30.3g Aqueous ammonium tungstate solution 261.0Og--4.2g —-65 Lanthanum oxide 30-3g aqueous ammonium tungstate solution 261.0g---7.5g-66 lanthanum oxide 30.3g aqueous ammonium tungstate solution 261.0g----6.7g 67 lanthanum oxide 30.3g 176.6g ammonium molybdate aqueous solution---68 lanthanum oxide 30.3g 176.6g ammonium molybdate aqueous solution 3.8g-mono--69 30.3g ammonium molybdate aqueous solution 176.6g-3.4g---70 lanthanum oxide 30.3g Aqueous ammonium molybdate 176.6g--4.2g--71 Lanthanum oxide 30.3g Ammonium molybdate aqueous solution 176.6g---7.5g-72 Lanthanum oxide 30.3g Ammonium molybdate aqueous solution 176.6g----6.7g 73 Lanthanum oxide 30 -3g aqueous solution of ammonium vanadate 117.0Og-----74 Lanthanum oxide 30.3g aqueous solution of ammonium vanadate 117.0Og 3.8g----75 Lanthanum oxide 30.3g aqueous solution of ammonium vanadate 117.0Og-3.4g--- 76 Lanthanum oxide 30.3g ammonium vanadate aqueous solution 11.7.0g--4.2g--77 Lanthanum oxide 30.3g ammonium vanadate aqueous solution 117.0Og---7_5g-78 Lanthanum oxide 30.3g ammonium vanadate aqueous solution 117.0Og--- -6.7g (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297mm) -27-531567 A7 B7 V. Description of Invention (25) Table 4 Samples No. Rare earth element oxo acid additive lanthanum hydroxide cerium oxide cerium hydroxide cerium chloride cerium nitrate 79 80 81 82 83 84 85 86 niobium chloride Niobium chloride Niobium chloride Niobium chloride Niobium chloride Niobium chloride Niobium chloride Niobium chloride 39.6g 39.6g 39.6g 39.6g 39.6g 39.6g 39.6g 39.6g Phosphorus phosphorus phosphorous phosphorus phosphorous phosphorous phosphoric acid acid acid acid acid Acid 57.7g 115.3g 230.6g 115.3g 115.3g 115.3g 115.3g 115.3g 3.8g 3.4g 4.2g 7_5g 6.7g (Please read the notes on the back before filling this page) 87 88 89 90 91 92 Lanthanum oxide 39.6g Oxidation Lanthanum 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution Ammonium tungstate aqueous solution 261.0g 261.0g 261.0g 261.0 g 261.〇δ 261.0G 3.8g 3.4g 4.2g 7.5g 6.7g 93 94 95 96 97 98 Lanthanum oxide 39.6g Hafnium oxide 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Molybdic acid Ammonium aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution Ammonium molybdate aqueous solution 176.6g 176.6g 176.6g mM 176.6g 176.6g 3.8g 3.4g 4.2g 7.5g 6.7g Printed 99 100 101 102 103 104 Lanthanum Oxide 39.6g Lanthanum Oxide 39.6g Oxidation 39.6g Lanthanum oxide 39-6g Lanthanum oxide 39.6g Lanthanum oxide 39.6g Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution Ammonium vanadate aqueous solution 117.0g 117.0g 117.0g 117.0g 117.Og 117 .Og 3.8g 3.4g 4.2g 7.5δ 6.7g This paper size applies to China National Standard (CNS) A4 (210: < 297 mm) 28 531567 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (26) m 5 As shown in Table 13, 32.6 g of lanthanum oxide and 115.3 g of phosphoric acid (85%) were thoroughly mixed, and heated at 150 M for 12 hours, and organic strips were added to the obtained paste to corrode 1 g of inhibitor was used as a treatment liquid (Nos. 151 to 165 in Table 13). In addition, in the treatment liquid of No. 161, a molar ratio of 1:10 and lanthanum cerium and lanthanum was respectively added and mixed as a treatment liquid (No. 166 to 173 of Table 14). In 6, in addition to α-weilyl lauric acid and N-phenyl-3-methynyl-2,5-dimethylpyrrole-based synthesizers, other commercially available reagents were used. Example ft As shown in Table 15, after 23.5 g of cerium phosphate and 115.3 g of phosphoric acid (85%) were sufficiently mixed, respectively, M 150t: heated for 12 hours. 1 g of an organic strip inhibitor was added to the obtained paste-like products as a treatment liquid (No. 174 to 188 in Table 15). In addition, each of the treatment liquids of No. 184 was added with a mixed additive 侔, and the ratio of cerium to cerium compound contained in the ear was 1:10 as a treatment liquid (No. 189 to 195 of Table 16). (Film formation method) The treatment liquid is applied to a metal plate using a rod roller, and the film thickness after drying is 1 μ®, and the plate is heat-treated at a plate temperature of 100 to 200C for 30 seconds to 1 hour. The metal plates used are Gl (melting galvanized pin plate, plating adhesion: 90 g / πι2), EG (galvanized galvanized plate, plating adhesion · 20 g / a2), AL (melting aluminum plating-silicon composite) This paper size applies to China National Standard (CNS) A4 (210x297 mm) 29 --------- clothing-(Please read the precautions on the back before filling this page)

•-, -IT 531567 A7 B7 V. Description of the invention (27) Printed on gold screens and plating deposits: 120 g / m2, AL / Si = 90/10) by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In addition, for comparison with chromate-treated pin plates, the chromate-treatment solution is composed of 30 g / 1 of chromic acid (MCr03 conversion) partially reduced by starch, 40 g / l of Si02, and 20 g / 1 of phosphoric acid. Then, the pin plate is coated, dried, and hardened to form a film (the amount of Cr in the film is converted to 100 mg / m2 of metal Cr) ° (performance evaluation method of film) U) processing traceability test Rickson (Erichsen> 7 m® after processing, SEM observation, evaluation of debt processing traceability. Comment: ◎: no cracks 0. · micro cracks △: micro peeling X: large cracks, large area peeling (b) The corrosion resistance test of the flat plate M was sprayed on the sample to evaluate the corrosion resistance of the area where the rust occurred after the 351C salt water was sprayed. The GI and EG were 10 days during spraying, and the AL was 15%. Both were measured by the incidence of white rust. In addition, the salt spray time of the cold-rolled pin board was 2 hours. The red rust occurrence rate was measured. The aluminum plate was immersed in 100t: boiling water for 30 minutes and the K black rust occurrence rate was measured. Comment 0: The rust occurrence rate is 0% 〇: Rust occurrence rate under 5% M △: Above rust occurrence rate, X at 20% M ·· Rust occurrence rate (Please read the note on the back first (Please fill in this page if you have any questions)

The paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 30 531567 A7 B7 V. Description of the invention (28: (c > Processing corrosion resistance test M) After processing the sample Eriksson 7㈣, The area where rust occurred after spraying 5%, 35t: salt water was used to evaluate the corrosion resistance of the processed part. The spray period was GI, EG was 10 days, AL was 15 days, and any white rust occurrence rate was measured. Evaluation points ◎ : Rust occurrence rate 0¾ 〇: Below rust occurrence rate △: Above rust occurrence rate, under 20% M X: Above rust occurrence rate 20% M Results The evaluation results of Examples 1 to 6 are shown in Tables 5 to 6. From here on The table clearly shows that the surface-treated metal sheet of the present invention is excellent in processing traceability and shows corrosion resistance of a flat plate and a processed portion equivalent to that of chromate treatment. Therefore, a chemical treatment film completely free of hexavalent chromium has an excellent environment Suitability, and the corrosion-resistant film can exert its effect. (Please read the precautions on the back before filling this page)

: Ordered by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 31 The paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 531567 A7 B7 V. Description of the Invention (29) Table 5 Staff Consumption of the Central Bureau of Standards of the Ministry of Economic Affairs Cooperative printed Να metal 加工 Counter-attack flat plate corrosion resistance Processing section corrosion resistance 1 BG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ 〇 〇2 EG ◎ 〇〇Ci ◎ 〇0 AL ◎ 〇〇3 EG 〇〇〇GI 〇〇〇AL 〇ο 〇4 EG ◎ ◎ — ◎ G (◎ ο 〇AL ◎ ◎ ◎ 5 BG ◎ ◎ ◎ GI 〇ο 〇Al 〇〇〇6 EG ◎ ◎ ◎ GI ◎ ο 〇AL ◎ ◎ 〇7 EG 0 〇0 GI Ό 〇ο AL 〇Γ 0 〇8 EG ◎ 〇 · CI 〇ο 〇AL ◎ 0 〇9 EG 〇 〇〇GI 〇〇ο AL 〇〇〇10 EG ◎ ◎ ◎ GI © 〇ο AL ◎. ◎ 11 EG ◎-◎ ο Gf 〇ο 〇AL ◎ ό 0 12 BG ◎ ◎ ο GI 0 〇〇AL ◎ 〇〇13 EG ◎ ◎ GI ◎ © ◎ AL ◎ ◎ ◎ 14 EG ◎ ◎ Gi ο 〇〇〇〇AL ◎ Ό ο Comparative Example EG 〇— Δ Δ Gi Δ Δ X AL 〇Δ Δ (Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) Α · 4 specifications (210X: 97 mm) 32 531567 A7 B7 V. Invention Explanation (30) Table 6 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

No. Sheet metal processing traceability Flat plate corrosion resistance Corrosion resistance 15 EG 〇〇0 G1 〇〇〇AL 0 0 〇16 EG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ ◎ ◎ 17 EG ◎ ◎ 0 GI 〇〇〇AL ◎ ο ο 18 EG ◎ ◎ GI 0 〇〇AL ◎ 0 〇19 EG ◎ ◎ GI ◎ ◎ AL ◎ ◎ ◎ 20 EG ◎ ◎ GI 〇〇〇AL ◎ 0 〇21 EG 〇 ◎ '· ◦ GI 0 〇 〇 〇AL 0 ο 〇22 EG ◎ ◎ ◎ GI ◎ 〇0 AL ◎ ◎ ◎ 23 BG ◎ ◎ 〇GI O " 〇〇AL ◎ .〇〇24 EG ◎ 〇GI 〇〇〇AL ◎ 0 〇25 EG ◎ ◎ ◎ GI ◎ ◎ ◎ AL ◎ ◎ ◎ 26 EG ◎ ◎ ◎ GI 〇〇〇AL ◎ 〇0 (Please read the notes on the back before filling this page)

丨 *, the size of the paper used in the edition is subject to the Chinese National Standard (CNS) Α · 4 specification (210X297 mm) 33 531567 A7 B7 V. Description of the invention (31) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 7 Sheets Να Metal sheet processing Trace flat plate corrosion resistance 27 EG ◎ GI 〇ο AL ◎ Γ ο 0 28 EG ◎ 〇1 ο GI ◎ 〇〇AL © 广 ο 〇29 EG 〇〇〇GI 〇〇ό AL 〇0 ο 30 I EG ◎ ◎ ◎ GI ◎ 〇0 AL ◎ ◎ ◎ 31 EG ◎ ◎ GI 〇〇 ◎ AL 〇〇〇32 EG ◎ ◎ GI ◎ 0 〇AL ◎ ◎ 33 33 EG 0 〇〇GI 〇0 • 〇AL 〇 〇〇34 EG ◎ ◎ ο 1 GI 〇〇ο AL ◎ 0 ο 35 EG 〇0 0 I GI O 〇0 AL 〇〇〇36 EG ◎ ◎ GI ◎ 〇AL AL ◎ ◎ ◎ I 37 EG ◎ ◎ GI 〇 0 〇AL ◎ 〇0 38 EG ◎ GI 〇〇ο AL ◎ 〇0 39 EG ◎ ◎ GI ◎ ◎ ◎ AL ◎ ◎ ◎ 40 EG ◎ ◎ GI 0 ο 〇AL ◎ 〇〇 This paper size applies to China Standard (CNS) A4 specification (210X29 " / PCT) (Please read the notes on the back of this page and then fill in) ---- installed - Revising ---- 531567 A7 B7 V. description of the invention (32) Ministry of Economic Affairs Bureau of Standards staff printed consumer cooperatives

No. Gold plate processing traceability Flat plate corrosion resistance Processing section corrosion resistance 41 EG 〇 ο 〇GI ο 〇〇AL 〇〇〇42 EG ◎ ◎ GI ◎ 〇〇AL ◎ ◎ ◎ 43 EG ◎ ◎ GI 〇〇〇〇AL ◎ 〇〇44 EG ◎ ◎ GI GI 〇〇〇〇AL ◎ 〇〇45 EG ◎ ◎ ◎ GI ◎ ◎ ◎ AL ◎ ◎ ◎ 46 EG ◎ ◎ ◎ GI 0.〇0 AL ◎ 〇ο 47 EG 0 '© ^ ο GI 0 〇 • 〇AL 〇〇〇48 EG ◎ ◎ ◎ GI ◎ 〇0 AL ◎ ◎ 49 EG ◎ ◎ GI ο-〇〇AL ◎ 0 ο 50 EG ◎ ◎ — 0 GI 〇0 〇AL ◎ 0 〇 〇 51 EG ◎ © GI ◎ ◎ ◎ AL ◎ ◎ ◎ 52 EG ◎ ◎ ◎ GI 〇0 0 AL 1 ◎ 〇I 〇 (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 35 531567 A7 B7 V. Description of the invention (33) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 9 No. Metal Embedding Process «Corrosion resistance of processed parts 53 EG ◎ ◎ GI ◎ 〇〇AL ◎ 〇〇54 EG ◎ 〇ο GI ◎ 〇〇AL ◎ 〇〇55 BG 〇ο 〇GI 〇〇Γ ο AL 0 〇〇56 EG ◎ ◎ GI ◎ 0 0 AL ◎ ◎ ◎ 57 BG ◎ ◎ ◎ GI 〇0 〇AL 0 0 〇58 EG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ ◎ 59 BG 〇ο GI 〇Γ 0 • 〇AL 〇〇〇〇〇 60 BG ◎ ◎ GI 〇〇〇〇AL ◎ ο 〇 61 BG 〇〇〇GI 〇〇〇AL 〇〇〇62 BG ®. ◎ — ◎ GI ◎ 〇〇AL ◎ ◎ ◎ 63 BG ◎ ◎ 〇GI 〇〇0 AL ◎ 0 〇64 EG ◎ 〇GI 0 〇〇AL ◎ 〇〇65 EG ◎ ◎ ◎ G—I ◎ ◎ ◎ AL ◎ ◎ ◎ 66 EG — ◎ ◎ GI 0 〇ο AL 〇1 〇 (Please read the back first (Please note this page before filling in this page) Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 36 531567 A7 B7 V. Description of invention (34) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 10 Printed sheet Να Metal sheet processing traceability flat plate corrosion resistance processing department Resistant to 67 BG 〇〇0 GI 〇t〇〇AL 〇Ό Γ ο 68 EG ◎ ◎ ◎ GI ◎ 0 δ AL ◎ ◎ ◎ 69 EG ◎ 1 ◎ GI 〇〇0 AL 〇ο 70 EG ◎ ο GI 〇〇 〇AL ◎ ο 〇71 EG ◎ ◎ GI ◎ 「◎ ◎ AL ◎ ◎ 72 EG ◎ ◎ GI 0 〇〇AL ◎ 〇〇73 EG o ◎ GI 0 〇.〇AL 0 .〇〇74 EG ◎ ◎ ◎ GI ◎ 〇0 AL ◎ ◎ ◎ 75 EG ◎ ◎ 〇GI 〇 · 〇0 AL ◎ 〇ο 76 EG ◎. ◎ GI ό 〇〇AL ◎ 〇〇77 EG ◎ ◎ ◎ GI © ◎ ◎ AL ◎ ◎ ◎ 78 EG ◎ ◎ ◎ GI 0 〇〇AL ◎ 〇0 (Please read the precautions on the back before filling in this page)

This paper size applies to China's National Standards (CNS) A4 specification (210X297 mm) 531567 Employees 'Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs print A7 _____B7 V. Description of the invention (35) Table 11 No.' Metal plate _ Processing traceable flat plate Corrosion resistance of Sifi ~ 79 EG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ 0 〇80 EG ◎ 〇〇GI ◎ 〇〇AL ◎ 〇o 81 BG 〇o 〇GI 〇〇〇AL 0 oo 82 EG ◎ GI ◎ 〇 '〇AL ◎ ◎ ◎ 83 EG © ◎ GI 〇1 0 o AL 〇0 〇. 84 BG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ ◎ 85 85 EG 〇〇'〇GI 0 〇Ό AL • 0 〇〇 86 BG ◎ ◎ 0 GI 〇〇〇AL ◎ 〇〇87 EG 〇0 o GI 0 〇〇AL 〇〇o 88 BG ◎ · ◎ ◎ GI © 〇〇AL ◎ ◎ ◎ 89 BG ◎ ◎ 1 0 GI 〇〇〇〇 AL © 〇〇90 EG ◎ ◎ 0 Gi 〇〇0 AL ◎ 0 0 91 BG ◎ ◎ ◎ GI ◎ ◎ ◎ AL ◎ ◎ ◎ 92 EG ◎ ◎ GI 〇. O 〇AL ◎ 0 〇 This paper size applies to Chinese national standards (CNS) A4 size (210X 297 mm) (Please read the precautions on the back before filling out this page) # --- • Order-531567 A7 B7 V. Description of Invention (36) Printed Form 12 No. 'Sheet Metal Processing Tracking by Employee Consumer Cooperatives of Central Standards Bureau, Ministry of Economic Affairs Flat plate corrosion resistance Corrosion resistance of processed part 93 EG 0 0 0 GI 〇〇〇AL 0 〇1 0 94 PG ◎ ◎ ◎ GI ◎ 〇〇AL ◎ ◎ 1 © 95 BG ◎ ◎ ο GI 0 〇〇AL ◎ 〇0 96 EG ◎ f ◎ GI 〇〇1 0 AL ◎ 〇ο 97 EG ◎ ◎ GI ◎ ◎ ◎ AL ◎ ◎ ◎ 98 EG ◎ ◎ GI 〇0 〇AL ◎ 〇〇99 EG 〇 ◎ • 〇GI 〇0 · 〇 AL 〇〇〇100 BG ◎ ◎ GI ◎ 〇〇AL ◎ ◎ ◎ 101 EG ◎ ◎ 〇GI 〇〇〇〇AL ◎ 〇〇102 EG ◎ ◎ 0 GI 〇ο 〇AL ◎ 〇 1 0 103 BG ◎ ◎ GI ◎ ◎ AL ◎ ◎ ◎ 104 BG ◎ ◎ GI 〇〇〇〇AL ◎ 0 0 (Please read the precautions on the back before filling out this page), and the size of the book-the paper size applies to China National Standards (CNS) A4 specifications (210X 297 mm) 39 531567 A7 B7 V. Invention (3?) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Table 13 Oxidation m / g 85 Top acid / g Gold price can evaluate Να Organic strip corrosion inhibitor belongs to the plate Λα traceability flat plate corrosion resistance processing department corrosion hydrogen and sulfur Butyl acetate 1.0 Og EG 〇 ◎ 〇151 * 32. 6 115.3 G [〇〇〇AL 〇 0 ο octyl hydrothioacetate 1. Og EG ύ ◎ 152 32, 6 115.3 GI ◎ 〇〇AL ◎ 〇〇Hydroxythio stearate 1.Og · EG ◎ ◎ ◎ 153 32 · S 115,3 Cl ◎ 0 〇AL ◎ 0 〇α-Weigyloctanoic acid l'〇g EG ◎ ◎ ο 154 32.6 Π5.3 GI ◎ 〇〇AL ◎ 0 0 8-fluorenyl quinoline l.Og EC @ ◎ 〇155 32.6 Π5.3 Cl 〇〇〇AL 〇〇〇〇〇- 8-hydroxyquinoline. L. Og EG ◎ ◎ ◎ 156 32.6 115.3 GI ◎ ◎ 〇AL ◎ ◎ ◎ 6- (N, N'-dibutylamino) EG ο ο ο 157 32 · 6 115.3 -1,3,5-triacyl-2,4 GI 〇〇〇〇- 二Thiol 1. 〇 avoid AL 〇ο 〇 lauryl gallate 1.0 O EG ◎ ◎ ◎ 153 32.6 115.3 GI 〇〇〇AL ◎ ◎ 〇1 ^ 5; Polyaniline aqueous solution EG 〇00〇153 32. 6 115.3 (dopamine: barium sulfate) G [ο 〇〇ί, 0 g AL 〇0 ό; N-phenyl-3-methylfluorenyl-2,5 EG ◎ ◎ ◎ 160 32. 6 115. 3-2 Methylpyrrole G [◎ ◎ ◎ 1 l.Og AL ◎ ◎ ◎ α-Mercaptolauric acid l.Og BG ◎ ◎ 161 32.6 115.3 GI ο ο ο AL ◎ ο ο : α-Mercaptolauric acid EG ◎ 〇ο 162 32.6 115.3 G [ο 〇〇U. 1 g At ® 〇ο a-peayl lauric acid 10. Og EG ◎ ◎ 163 32.6 115.3 GI ◎ 0 0 AL ◎ ◎ ο smoke Basic acid l.Og EG ◎ ◎ 164 32 · 6 115.3 G [◎ ◎ ◎ AL ◎ ◎ catechol l.Og EG ◎ ◎ 165 32. 6 115.3 Cl ◎ ◎ AL ◎ ◎ ◎ (Please read the precautions on the back first (Fill in this page again) _ -S-1- ......... —-1— ....... ^. Order-This paper size applies to China National Standard (CNS) A4 ( 210X297 mm) 531567 A7 B7 V. Description of the invention (38) Table 14 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Ναlanthanum oxide / g 85X phosphoric acid / g α-mercaptolauric acid / g Performance evaluation of metal sheet Processing tracking Corrosion resistance Flat processing section Corrosion resistance 166 32.6 115.3 1.0 Cerium oxide 3.4 g BG ◎ ◎ GI 0 0 〇AL ◎ ◎ 167 32 · 6 115 · 3 1.0 Nitrogen oxide joint 4 · 2g EG 〇〇〇GI 〇〇〇AL 〇0 0 168 32.6 115.3 L0 Cerium chloride: 7 water and 7.5g EG ◎ ◎ GI 0 ◎ ◎ AL ◎ ◎ 169 32,6 115.3 1.0 Cerium chloride 8 water and matter 6,0g EG — ◎ ◎ ◎ GI 0 ◎ ◎ AL 1 0 〇0 170 32 · 6 115.3 1.0 Cerium sulfate · 6 Water compound 14, 3 g BG ◎ ◎ GI 〇 ◎ AL 〇〇〇171 32 · 6 115.3 1.0 'Cerium nitrate 6 water compound-8,7g EG ◎ ◎ ◎ GI 〇〇〇AL 〇.α 〇172 32.6 115 · 3 1 · 0, cerium acetate 1 water compound 6.7g EG ◎ ◎ ◎ GI 〇〇 〇AL 〇〇〇〇173 32.6 115, 3 ho cerium phosphate EG ◎ ◎ ◎ GI 〇〇〇1 7.3 AL 〇〇〇 Comparative example coating type chromate film EG 0 Δ Δ GI Δ Δ Δ AL 〇Δ Δ ( (Please read the notes on the back before filling out this page)

This paper size applies Chinese National Standard (CNS) Α · 4 specification (210X297 mm) 41-531567 A7 B7 V. Description of invention (39) Evaluation of gold performance of Mα film composition printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Cerium phosphate / g 857M acid / g organic strip corrosion inhibitor belongs to plate processing traceability plate corrosion resistance processing section corrosion resistance 17 ^ 1 23. 5 115.3 hydrogen thioglyceryl butyl ester L 〇g BG ◎ ◎ ◎ CI ◎ 〇0 At ◎ 0 〇175 23. 5 115.3 Hydrogenyl octyl acetate LOg RG ◎ ◎ ◎ GI ◎ 〇〇ΛΙ ◎ 〇〇176 23. 5 115.3 Argonyl stearyl acetate U〇g EC 0 0 〇CI 0 〇〇ΛΙ 〇0 〇177 23.5 115.3 C (-Weigylic acid LOg BG ◎ ◎ ◎: GI ◎ δ 〇i AL ◎ 0 〇173 23.5 115.3 8-mercaptoquinoline LOg EG ◎ ◎ ◎ GI Ι 〇〇〇: AL 〇, 〇 〇179 23.5 115.3 8-Hydroxyquinoline LOg EG ◎ ◎ ◎ " GI 〇〇AL ◎ ◎ 180 180 23.5 115.3 6- (N, N'-dibutylamino) -1,3,5-triazine- 2,4-Dimethylol 1.'Og · EG 〇〇〇G [ο 〇. 〇AL 〇〇 · 〇131 23. 5 115.3 Lauryl gallate 1. 〇g EG ◎ ◎ 〇CI 〇〇〇AL © 〇0 132 23.5 115.3 1 Reset X polyaniline aqueous solution (dopamine: barium sulfate) 1.0 g EG • 〇〇〇GI 0 0 〇AL 〇0 〇183 23,5 N-phenyl-3-methylfluorenyl-2,5EG ◎ ◎ 〇1 115.3 -2 methylpyrrole i.〇S GI 〇〇〇I AL ◎ 〇- 134 23.5 115.3 ct- Weicyl lauric acid LOg EG ◎ ◎ G [〇〇0 AL ◎ 〇185 23.5 115,3 〇t-mercapto lauric acid 0.1 S EG ◎ — ◎ GI ◎ ◎ ◎ AL ◎ ◎ 186 23.5 115. 3 α-frontyl lauric acid_10.Og EG ◎ ◎ ◎ GI 〇-〇〇AL 〇〇187 23.5 115.3 Nicotinic acid i.〇S EG ◎ ◎ GI ◎ 1 ◎ ◎ ΛΙ ◎ ◎ 188 23 5 115.3 Catechol I. 0 g EG ◎ ◎ GI ◎ ◎ ◎ M ◎ ◎ ◎ (Please read the precautions on the back before filling this page) ^ 衣 I • Order 4 This paper size applies to Chinese national standard ( CNS) A4 specification (210X297 mm) 42 531567 A7 B7 V. Description of the invention (40) Table Να film composition printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Evaluation of properties of metal plates cerium phosphate / g 85¾ phosphoric acid /% α-vegetyl lauric acid / g Additives processing traceability flat plate corrosion resistance processing section corrosion resistance 189 23. 5 115.3 1 · 0 cerium oxide 3.4 g EG ◎ ◎ ◎ GI 〇0 〇AL ◎ 〇0 190 23.5 115.3 1.0 Cerium hydroxide 4,2g EG ◎ ◎ ◎ GI 〇〇〇AL ◎ 〇0 191 23.5 115.3 1.0 Cerium chloride 7 water compound 7.5g EG ◎ GI 0 ◎ 〇AL ◎ 〇 ◎ 192 23,5 115, 3 1.0 Cerium carbonate 8 water and 6.0g EG ◎ Γ ® ◎ GI 0 「0 0 AL [◎ ό ◎ 193 23.5 115, 3 1.0 cerium acetate 6 water and 14 3 g EG ◎ ◎ ◎ GI 〇〇0 AL ◎ 〇 194 23.5 115.3 1.0 Cerium nitrate 6 water compound-8,7 g BG ◎ ◎ GI 〇 ◎ · 0 AL ◎ ο ◎ 195 23.5 115.3 1.0 Cerium acetate 1 water and 6'7g EG ◎ ◎ ◎ GI ο ό 0 AL ◎ 〇 ◎ Compared to OOU Example Coating Chromate Film EG 〇Δ Δ GI Δ Δ X AL 〇Δ Δ (Please read the precautions on the back before filling this page) --I —I— · _ This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) 43 53156 7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (41) Example 7 Specifically shows an example of simplification of the basic function of the surface treatment agent of the present invention. The lanthanum phosphate obtained by the reaction between lanthanum oxide and orthophosphoric acid is used as a samarium compound, and the lanthanum molar ratio MH3PCU is converted into moore's orthophosphoric acid, and M water is used as a diluent and a surface treatment agent with a lanthanum concentration of 0.64 inol / kg. It is coated on high-purity zinc to obtain a coating layer with a thickness of about 5 μm. Figure 2 shows the anodic current-current curve in a solution adjusted to pH 8.4 of 0.1111〇1 / liter "(: 1 solution by using coated zinc and zinc without boron and sodium borate and boric acid and sodium borate, without zinc coating. Zinc with coating The anode current is significantly smaller than that of zinc without a coating, which proves the effect of anodic dissolution inhibition of zinc in the coating and the inhibition of the diffusion of the corrosion-promoting substance 卽 chloride ions to the zinc surface. Example 8 In Example 7 The anode current-current curve obtained by processing the same except that trivalent cerium oxide is used instead of lanthanum oxide M as the lanthanum compound is shown in Fig. 3. The same result as in Example 7 can be obtained. [Example 9 ~ Example 10] (Adjustment of surface treatment agent) Example 9 A surface treatment agent containing lanthanum as a main component, a phosphoric acid compound, a phosphate hydride, an oxide, a hydroxide, or a mixture thereof and phosphoric acid. Lanthanum oxide (a) The lanthanum compounds such as lanthanum hydroxide (b>, lanthanum chloride (c), and the like react with orthophosphoric acid (d) or polyphosphoric acid (e) to obtain lanthanum compounds as surface treatment agents. Furthermore, orthophosphoric acid, polyphosphoric acid, Phosphoric acid (f) Or its mixture, and / or ammonium phosphate (g) and other phosphates to adjust the cost. Paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -44-(Please read the precautions on the back before filling in this (Page) ——Order—— 531567 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (42) The predetermined H3p〇4 conversion to lanthanum mol ratio. The obtained lanthanum compound and phosphoric acid in the composition Water or a mixture of water and methanol (h) was added as a diluent to obtain a surface treatment agent with a predetermined lanthanum concentration. Sample Nos. 201 to 217 shown in Table 11 are based on the molar ratio of phosphoric acid to lanthanum. The adjustment method is represented by U) ~ (h). A mixture of water and methanol is used as the diluent of sample No.201 and N0.210, and the weight ratio of the two is added to 2: 1. In the case of corrosion inhibitors for organic strips, when phosphoric acids are added after adjustment of the lanthanum compound, or when they are added at the same time as the diluent. Among the samples No. 218 ~ 224 shown in Table 12, No. 218 ~ 221 is the same lanthanum compound as sample No. 7 and The structure of a phosphoric acid treatment agent, that is, a treatment agent specific to a concentration of lanthanum compound of 0.3 a01 / kg and an orthophosphoric acid to lanthanum contamination ratio of 5, and a cerium compound and / or an organic thorium corrosion inhibitor are added. Sample No. .222 ~ 224 is the same as the treatment agent of osmium compound and phosphoric acid of sample No.210, and is also specific for the treatment agent with a concentration of lanthanum compound of 0.5 mol / kg and polyphosphoric acid as 3P04, which is equivalent to lanthanum with an ear ratio of 10. Add cerium nitrate and / or organic inhibitor as the cerium compound. Example 10 Surface treatment agent for cerium phosphate compound, hydrogen phosphate compound, oxide, hydroxide or mixture of these with phosphoric acid as main component. Make trivalent cerium oxide Ce203 (i), tetravalent cerium oxide Ce02 (j),

The trivalent cerium hydroxide (k) and trivalent cerium chloride (1) react with cerium compounds, such as cerium nitrate (®), orthophosphoric acid (η) or polyphosphoric acid (〇), to obtain cerium as a surface treatment agent. Compound. Furthermore, add orthophosphoric acid, polyphosphoric acid, and phosphoric acid (P This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 45 (Please read the precautions on the back before filling this page)

531567 A7 B7 V. Description of the invention (43) Phosphoric acid or its mixture printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives) and / or phosphates such as ammonium phosphate (g) and adjusted to the predetermined H3P04 conversion pair Cer Morby. Water or a mixture of water and methanol (U) was added to the obtained cerium compound and phosphoric acid as a diluent to obtain a surface treatment agent having a predetermined cerium concentration. The columns of the surface treatment agents of Sample Nos. 225 to 241 shown in Table 13 are the order of M phosphoric acid to cerium molar ratio, and MU) to (r) indicate the adjustment methods. In addition, in the sample cores .225 and ".234, only a mixture of water and methanol was used as a diluent, so that the weight ratio of the two was 2: 1. When adding a pro-compound and / or an organic strip corrosion inhibitor, it was tied to cerium. When the compound-adjusted phosphoric acid is added, or added at the same time as the diluent. Among the samples No. · 242 to 248 shown in Table 14, sample Nos. 242 to 245 are the same as those of sample No. 231 of the cerium compound and phosphoric acid. The composition of the treatment agent, that is, a treatment agent specific to a concentration of cerium compound of 0.3 inol / kg and a molar ratio of orthophosphoric acid to cerium mol ratio 5, and a lanthanum compound and / or an organic inhibitor are added. Sample No. 246 to 248 are the same as Sample No. 234 is composed of a cerium compound and a phosphoric acid treatment agent, that is, a treatment agent specific to a cerium compound concentration of 0.5 mol / kg and a polyphosphoric acid ^ H3P〇4 conversion to a cerium acetic acid ratio of 10, adding thorium chloride and / or Organic bar corrosion inhibitors are lanthanum compounds. The organic inhibitors used in Table 2 are indicated by the following symbols: PEDP: Ν-phenyl ♦ 3-methylfluorenyl · 2,5-dimethylpyrrole TG0: Hydroxythiooctyl acetate MLA: α -Zhenyllauric acid MBA: 0 -Weyl benzoic acid MNA: 〇 -Wei Nicotinic acid (please read the precautions on the back before filling this page) Adjusting clothes ---- Xu --- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 46 531567 A7 B7 V. Description of the invention (44 HOQ: 8-Hydroxyquinoline (film formation method) The method of film formation is low dilution. Therefore, the treatment agent with high viscosity is coated with a coating roller thickness after drying by a rod roller. In addition, The degree of dilution is high. As a result, the thickness of the coating agent after spray drying is 0.2 μm after spraying and drying. After coating or spreading, the metal material is subjected to heat treatment for 30 seconds to 1 hour. The coating is formed by the immersion method. The layer system keeps the metal material in the 801: processing bath for 30 seconds, and it is dried in the atmosphere. The metal material used is GI (melting galvanized pin plate, plating adhesion: 90 g / W), EG (electrical plating Zinc pin plate, plated adhesion amount: 20 g / m2), AL (melt aluminized-silicon alloy pin plate, plated adhesion amount: 120 g / m2, Al / Si = 90/10), plated mesh and cold-rolled mesh Sheet and aluminum sheet. In Comparative Example 201, it was compared with the surface treatment of zinc phosphate containing a lanthanum compound. The metal materials are GI and EG, and M 40¾ is immersed for 2 minutes in a treatment solution consisting of lanthanum nitrate converted to M lanthanum 0.01 0.01 / kg, orthophosphoric acid converted to lanthanum mol ratio 15 and MH3P04. After washing, M 100¾ is dried for 10 minutes to form a film. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Comparative Example 203, which is compared with the cerium compound precipitated from the cathode. It is EG. In a 0.1 mol / liter trivalent cerium chloride solution, the trivalent cerium hydroxide is precipitated on the surface through a cathode current at a current density of 100 mA / ciH2, and then reacted with orthophosphoric acid to obtain cerium phosphoric acid. Mixture of compound and hydroxide-film. Also, in Comparative Example 202, for comparison with the chromate treatment, the chromate treatment solution contains M starch for partial reduction of chromic acid K Cr 03 conversion. The paper size is applicable to the Chinese National Standard (CNS) A4 standard. (2 丨 0: < 297 mm) 47 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 531567 A7 B7 _ V. Description of the invention (45) 30 g / l, Si02 ^ 40 g / l, 20 g phosphoric acid Per liter of the treatment solution, coated, dried, and hardened on a screed plate to form a film (the amount of Cr in the film converted to metal is 120 mg / m2). Comparative Example 203 is compared with the cerium compound precipitated from the cathode. The metal material is EG, the current density of M100 inA / cin2 in a 0.1 mol / liter trivalent cerium chloride solution passes the cathode current to precipitate trivalent cerium hydroxide on the surface, and then reacts with orthophosphoric acid to obtain the cerium phosphate compound and K-coated film of hydroxide. In the columns of the metal materials and film formation methods in Tables 11 to 12, the plated pins used as metal materials are GI, EG, and AL, and M (P>, (S), and (D) are formed separately. Coating, spraying, and dipping coatings. (Performance evaluation method of coating layer) According to the same performance evaluation method as in Examples 1 to 6. The composition of the surface treatment agent and the evaluation results are shown in Tables 17 to 20. From Tables 17 and 19 clearly show that the surface treatment agent of the lanthanum compound or cerium compound and phosphoric acid-based metal material of the present invention can provide a processing traceability and corrosion resistance that are superior to those of conventional zinc phosphate treatment. Separate coating layer with anti-rust property, and provide a coating layer with corrosion resistance equivalent to chromate treatment of flat plate and processed part. Therefore, a method for forming a film can be provided, which is completely free of hexavalent chromium. The film is processed to have excellent environmental suitability, and it also exhibits its effect as a corrosion-resistant film. It is also clear from Tables 18 and 20 that lanthanum compounds, cerium compounds, and organic strip corrosion inhibitors have cerium compounds. The corrosion resistance of the coating layer formed by the surface treatment agent of lanthanum compound and phosphoric acid as the main component, especially complements the corrosion resistance of the processing part, and enhances the effect of the corrosion-resistant film completely free of hexavalent chromium. This paper scale is applicable to China Standard (CNS) Α4 specification (210 × 297 mm)-48 _ (Please read the precautions on the back before filling this page)

531567 A7 B7 V. Description of the invention (46) Table 17 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. kg) Flat section machining section 201 1.0 (d) 2.4 (a, h) GKP) 〇Γ ο 〇202 1.0 (d) 1.5 (a) GKP) 〇〇〇203 3.0 (d) L 05 (a) GKP ) 0 〇〇EG (P) 〇 ◎ 〇 AL (P) 〇〇204 204 3.0 (d) 0.5 (a) GKP) ◎ 〇〇EG (P) i) ◎ 〇AL (P) ◎ ο 〇205 4, 0 (e) 1. 0 (a) GKP) ◎ ◎ EG (P) ◎ One ◎ ◎ AL (P) ◎ ◎ '206 5.0 (d) 0.64 (a) GKP): ◎ ◎ 207 5.0 ( d) 0.3 (a) GKP) ◎ 0 BG (P) ◎ ◎ 〇AL (P) ◎ 〇〇 [Steel plate (P) — 〇 · A name plate (p) 〇k 208 5, 0 (d , f) 0.3 (a) GKP) 0 〇〇209 5-0 (d, g) 0.3 (a) EG (P) —〇〇 210 10 (e) 0.5 (a) GKP) ◎ ◎ 211 10 (e, f) 0.5 (b, c) BGCP) ◎ ◎ ο 212 10 (e, f) 0.5 (c) BG (P) ◎ ◎ 〇213 10 (e) 0.2 (c) GI (S) ◎ 〇〇214 10 (e, f) 0.2 (c, h) GI (S) ◎ 0 〇BG (S) ◎ 0 〇AL (S) ◎ 0 〇215 10 (e, f) 0.1 EI (S) ◎ 0 〇216 10 (e) 0, 06 (a) GI (D) 〇0 0 217 25 (d) 0.11 (c) GI (D) 〇〇Δ EG (D) 〇 Ί Δ Comparative Example 201 15 (d) 0.01 GI (D) Δ XX EG (D) Δ XX 202 Chromate-treated GKP) Δ 〇Δ EG (P) 〇〇 △ AL (P) 〇〇 Δ (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) Α · 4 specifications (210X 297 mm) 49 531567 A7 B7 V. Description of invention (47) Table 18 Sample No. Cerium compounds and countermeasures printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs u Mole ratio organic inhibitor and La Mole ratio metal material and film forming method processing portion corrosion resistance flat portion processing portion 218 CePO, 1.0 i without GKP) ◎ ◎ 〇CePfL 1 · 〇 • PFDP. 0.01 CKP) ◎ ◎ ◎ CeP04 1 · 〇TGO 0,01 GKP) ◎ ◎ 〇CePO ^ 1.0 MIA 0.01 GI (P) ◎ ◎ 0 CeP〇4 1.0 MBA 0.01 GKP) ◎ ◎ ◎ CeP〇4 1,0 MNA 0,01 GKP ) ◎ ◎ ◎ CePCh 1.0 HOQ 0.01 GKP) ◎ ◎ 〇219 PFDP 0.5 GKP) ◎ ◎ 220 Ce02 0.01 without GKP) ◎ © 〇221 Ce (0H) 3 0.01 No. GKP) ◎ ◎ 222 N0.3) 3 0,5 .No GKP) ◎ ◎ ◎ 'EG (P) ◎ ◎ ◎ AL (P) ◎ ◎ ◎ 223 Ce (N03) 3 0.3 PFDP 0.2 GKP) ◎ ◎ ◎ BG (P) ◎ ◎ ◎ AL (P) ◎ ◎ 224 Ce (N03) 3 0.3 MNA 0.2 GKP) ◎ ◎ EG (P) ◎ ◎ ◎ AL (P) '◎ ◎ (Please read the note on the back first Please fill in this page if you want to pay attention to the matter.) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 50 531567 A7 B7 V. Description of the invention (48) Table 19 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Treatment example 'Metal processing and film formation method Traceability test sample No. Mortar phosphate concentration (mol / kg) Flat section processing section 225 0 · 8 (η) 2. 4〇, r) GI (P) Δ ο Δ 226 1.0 · (η) 1, 5 (j) Gi (P) 〇〇ό 227 3,0 (η) L05 (j) GKP) 〇〇〇EG (P) 0 〇〇AL (P) 〇〇〇228 3.0 (η) 0.5 〇〇〇〇K0) 〇〇〇EG (P) 〇 ◎ 〇AL (P) 〇〇〇229 4.0 (〇) 〇α) GKP) 〇 ◎ 0 EG (P) 0 ◎ ο AL (P) 〇 ◎ 〇230 5.0 · (η) 〇.64 (j) GKP) 〇Γ ® 〇231 5. 0 (η) ◦. 3 (j) GKP) ο 〇 ο EG (P) 〇〇ο AL (P) 〇〇〇 "Cold-extended bracelet plate (p)-0 ..."-name plate (p)-0-232 5 · 0 (η, ρ) 0.3 (j ) GKP) 〇1 〇〇233 5. 0 (η, q) 0.3 (i) EG (P) 〇 0 0 234 10 (ο) 0.5 (k) GKP) ◎ ◎ 〇235 10 (ο) 0.5 (k, I) EG (F) ◎ ◎ 〇236 10 (ο) 0.5 (k, m) EG (P) ◎ ◎ 〇237 10 (ο) 0.2. (K) GI (S) © 0 ο 238 10 (ο) 0,2 (k, r) EG (S) 〇0 239 10 (ο) 〇 · l (j) GI (D) 〇I 〇〇240 10 (η) 0:06 (j) GKD) 〇〇Δ 241 25 (π) 0. ll (k) BG (D) 0 0 Δ Comparative Example 203 Cathode precipitation — EG χ Δ X (Please read the precautions on the back before filling this page)

This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 531567 A7 B7 V. Description of the invention (49)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Table 20 Samples Να lanthanum compounds and organic strip corrosion inhibitors for Ce and ear ratios. CeM ear ratios. Gold hurricane material and film formation method. Processing department. Corrosion resistance. Flat section processing department. 242 LaPO ^ 0.8 without GKP) ◎ ◎ 〇LaP04 0.8 PFDP 0.01 GKP) ◎ ◎ ◎ LaPCh 0 · 8 TG0 0.01 GKP) ◎ ◎ 0 LeP〇4 0.8 MLA 0,01 GKP) ◎ ◎ 〇LaPO ^ 〇. 8 | MBA (λ 01 GKP) ◎ ◎ ◎ LaP04 0.8 MNA 0,01 GKP) ◎ ◎ ◎ LaP〇4 0 · 8 HOQ 0,01 GKP) ◎ ◎ 243 m, PFDP (λ 5 GKP) 〇 ◎ 〇244 la2〇3 0.01 > ΠΤ- Μ GICP) 〇 ◎ 〇245 La (0H) 3 0 · 01 Ant GKP) 〇 ◎ 〇246 LaCl 3 0.5 No GKP) ◎ ◎ ◎ EGCP) ◎ ◎ ◎ ALCP) ◎ ◎ 247 LaCi 3 0. 3 PFDP (λ 2 GKP) ◎ ◎ EG (P) ◎ ◎ ALCP) ◎ ◎ 248 LaC 13 0.3 MN 0.2 GKP) ◎ ◎ EG (P) ◎ ◎ ◎ ALCP) ◎ ◎ (Please (Read the notes on the back before filling out this page)

This paper size applies to China National Standard (CNS) A4 (210X297 mm) 52

Claims (1)

531567 i \ ___ Announcement Members are kindly requested to indicate whether there is any change in the amendments proposed in the year g (January: τ, whether the substance of the amendment is permitted to be repaired? OEα 86101342 Patent Re-examination Case Application for Amendment of the Patent Scope Amendment Date: November 91 u 1 1. A surface treatment Metal materials are those that have a corrosion-resistant coating on the surface of the metal material, wherein the corrosion-resistant coating is essentially composed of an oxyacid compound or an oxyacid hydride of a rare earth element. 2. If the scope of patent application is the first The surface-treated metal material according to the item, the aforementioned rare earth cube element is in B, steel, and / or electricity. 3. If the surface-treated metal material in item i or 2 of the scope of patent application, the aforementioned oxyacid compound and oxygen The anion species of the acid hydride are polyvalent oxygen-containing acid cations. 4. If the surface-treated metal material of item 3 of the patent application scope, the foregoing anion species are phosphate ions, tungstic acid cations, molybdate ions, and / or vanadate ions 5. If the surface-treated metal material of item 1 of the patent application scope, the aforementioned corrosion-resistant coating layer is made of yttrium, lanthanum, and / or osmium phosphate compound or hydride phosphate or a mixture thereof 6. If the surface-treated metal material of item 5 of the patent application scope, the aforementioned phosphorus oxide and phosphoric acid hydride are orthophosphoric acid (hydrogen), metaphosphorous oxide, polyphosphoric acid (hydro), or the like. 7. If the surface-treated metal material according to item 1 of the scope of patent application, the aforementioned corrosion-resistant coating layer further contains one or two selected from the group consisting of oxides, hydroxides, halides and organic oxides of rare earth elements. The above compounds are used as an additive component. 8. If the surface-treated metal material of item 7 of the patent application scope, This paper size applies to CNM Standard A4 (21GX297 male f 531567 The rare earth element that forms the knife is thallium. For example, for the surface-treated metal material in the 8th patent scope, the aforementioned rare earth element added to the knife is a quadrivalent ornament. 10: If the surface-treated metal material according to item 1 of the patent application scope, the aforementioned resistance coating layer further contains an organic corrosion inhibitor as an additive. 11. If the surface-treated metal material of the scope of application for item 10, the aforementioned organic corrosion inhibitor is selected from the methylated derivative of N-phenyl-dimethylpyrrolyl, and HS-dCOOCnHh.〆! ! Is an integer from 1 to 25) ^ fluorenyl acetate and its derivatives, α_fluorenyl carbonic acid and its derivatives represented by CnH2n (SH) COOH (η is an integer from 1 to 25), Quinoline and its derivatives, diacridine dithiol and its derivatives, gallate and its derivatives, alkali acids and its derivatives, catechol and its derivatives, and / or conductive properties One or more of a group of molecules. I2. If the surface-treated metal material is the first item in the scope of patent application, the aforementioned corrosion-resistant coating layer further contains a material selected from the group consisting of Si02, Cr2O3, Cr (〇H) 3, α2〇3 calcium hydroxide, calcium carbonate, Calcium Oxide, Zinc Phosphate, Zinc Hydrogen Phosphate, Potassium Phosphate, Hydrogen Phosphate Bell, Phosphate Phosphate, Hydrogen Phosphate, Broken Sour Acid, Broken Sour Acid, Linthylates, Aluminum Hydrogen Phosphate, Titanium Oxide, Rhenium Phosphate, Zirconium Hydrogen Phosphate 1 or 2 or more of the group consisting of sulfuric acid, sodium sulfate, sodium hydrogen sulfate, phosphoric acid, sodium phosphate, and sodium hydrogen phosphate. 13-A surface treatment agent used to form a corrosion-resistant coating on the surface of a metal material, wherein the surface treatment agent is essentially composed of an oxygen-containing oxide or an oxy-acid hydride of a rare earth element. -2-This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇297297) ----- 531567 A8 B8 C8 D8 VI. Application scope of patent 14 · Such as surface treatment agent for item 13 of scope of patent application The aforementioned rare earth element is yttrium, lanthanum and / or rhenium. 15. If the surface treatment agent in the scope of patent application No. 13 or 14, the aforementioned anionic species of oxyacid compounds and oxyacid hydrides are multivalent oxyacid anions. In the treatment agent, the anionic species is a phosphate ion, a tungstic acid cation, a molybdic acid ion, and / or a vanadate ion. 17. If the surface treatment agent according to item 13 of the application, the aforementioned corrosion-resistant coating layer is mainly composed of a phosphoric acid compound or a hydride phosphate of yttrium, lanthanum, and / or osmium, or a mixture thereof. 18. If the surface treatment agent according to item 17 of the application, the aforementioned phosphoric acid compound and hydrogen hydride are orthophosphoric acid (hydrogen) compounds, metaphosphoric acid compounds, polyphosphoric acid (hydrogen) compounds, or a mixture thereof. 19. If the surface treatment agent of the scope of application for the item π, the aforementioned corrosion-resistant coating layer further contains i or two or more kinds selected from oxides, hydroxides, compounds, and organic acid compounds of rare earth elements. Compound as an additive. 20. If the surface treatment agent according to item 19 of the patent application scope, the rare earth element of the aforementioned added component is rhenium. 21 of the monthly added ingredients • Surface treatment agent such as the scope of patent application No. 20 The rare earth element is a quaternary ornament. Monthly Corrosion Resistance Coating Additive. The above-mentioned organic corrosion 22. If the surface treatment agent of item 13 of the patent application, the layer further contains an organic corrosion inhibitor as the surface treatment agent of item 22 of the patent application, 531567 AB c D Application Patent scope P formulation is selected from N-phenyl-dimethyl. Formylated derivatives of biloki, acetoacetates and their derivatives represented by HS-CH2COOCnH2n + 1 (n is an integer from 1 to 25), and CnH2n (SH) c〇H (n is Integer from 25 to 25) α-thiocarbonic acid and its derivatives, 4 Lin and its derivatives, trisigmaphine dithiol and its derivatives, gallate and its derivatives, nicotine One or two or more of the group consisting of acids and their derivatives, catechol and its derivatives, and / or conductive polymers. 24. If the surface treatment agent according to item 3 of the patent application scope, the aforementioned corrosion-resistant coating layer further contains a material selected from the group consisting of Si02, Cr203, Cr (OH) 3, A1203 calcium hydroxide, calcium carbonate, calcium oxide, and zinc phosphate. , Zinc hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, calcium phosphate, calcium hydrogen phosphate, calcium silicate, zirconium silicate, phosphate phosphate, aluminum hydrogen phosphate, titanium oxide, phosphate file, zirconium hydrogen phosphate, sulfuric acid, sodium sulfate, sulfuric acid One or two or more of the group consisting of sodium hydrogen phosphate, phosphoric acid, sodium phosphate, and sodium hydrogen phosphate. 25. A surface treatment agent, characterized in that it contains a rare earth compound in the range of 0.005 to 4 ml / kg in terms of rare earth element conversion, and contains 1 mole of the rare earth element in terms of H3P04 conversion. 0.5 ~ 100 mole of phosphoric acid compound and / or hydrogen phosphate compound. 26. The surface treating agent according to item 25 of the application, wherein the aforementioned rare earth element compound is a phosphoric acid compound of lanthanum or thorium, a hydrogen phosphate, an oxide, a hydroxide, or a mixture thereof. 27. If the surface treatment agent of the scope of application for patent No. 25 or 26, phosphoric acid is orthophosphoric acid, meta-disc acid, polyfill acid, or a mixture thereof. 28. If the surface treatment agent in the scope of application for the item No. 25 contains water or water and water -4- ^ Paper size applies to China National Standard (CNS A4 specification U10X297 public love) ------ 531567 A8 B8 C8 6. Scope of patent application: A mixture of synthetic organic solvents is used as a diluent. 29. If the surface treatment agent of item 25 of the application for a patent, the aforementioned rare earth element compound is a lanthanum compound, and further contains a molybdenum compound of 1.0 to 0.001 with respect to lanthanum, and / or molybdenum relative to lanthanum Ear ratio contains organic corrosion inhibitors from 2 to o.ooi. 30. As the surface treatment agent in the 25th area of the Shenyan patent, the aforementioned rare earth element compound is a rhenium compound, and further contains 1.0 to 0.001 lanthanum compounds and / or Morby contains organic corrosion inhibitors from 2 to 0.001.