TWI271445B - Rust preventive for magnesium and/or magnesium alloy - Google Patents

Abstract

The present invention provides a rust preventive for magnesium and/or magnesium alloy comprising at least one member selected from the compounds represented by formula (1)-(2) and salts thereof as the effect component, and the process for producing a part made of magnesium and/or magnesium alloy using such rust preventive. [Wherein, R1 represents hydrogen or C1-4alkyl group, R2 represents hydrogen, C1-4alkyl group, mercapto group or hydroxy group, R3 represents hydrogen, C1-4alkyl group or hydroxy group, A represents -N= or -C(R4)=, R4 represents hydrogen or amino group.]

Description

1271445 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明[Prior Art] Magnesium is the most lightweight metal for practical structural materials, and because of its high specific strength and easy machining, it is widely used for electrical products such as automotive parts, computers, and audio equipment, and aircraft parts. In addition, in general, the production of magnesium and magnesium alloy molded articles is based on die casting (diecasting, extrusion molding, and calendering). In recent years, since the use of injection molding machines, the so-called thixomolding type (thixomolding) Since the technology of the law has been green, the shape of the molded product has been greatly improved, and its application and physical properties have been greatly improved. As a result, the application range of the magnesium S practical structural material is the most noble metal. It has an advantage of being susceptible to oxidation, and thus rust prevention has become an important issue. It is generally known that a triazole compound can be used as a metal rust preventive agent, as disclosed in Japanese Patent Publication No. 52-1377, 4H-1, 2, 4-. Triazotized human 铷 炎 炎 炎 炎 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为The rust preventive agent. The inventor of the present invention has an aromatic carboxylic acid and a salt thereof for use as a rust inhibitor for magnesium or a magnesium alloy, and the aromatic (four) and blood one, and/or compound and/or ruthenium ratio. The compounds were combined and found to be improved:: olfactory fruit ( For example, refer to Patent Document 1)., 秀坆5 1271445 L搜刊又驮1] WO00/40777 However, when aromatic carboxylic acids and their salts are combined with triazole compounds and/or pyridinium compounds, It is clear that there is a problem that the coating adhesion is not full. In addition, the 4Η-1,2,4-three-seat compound disclosed in Japanese Patent No. 52-1377 has insufficient anti-rust effect on magnesium, and must be The specified triazole compound has sufficient anti-rust effect on magnesium and magnesium alloy. The purpose of this month is to provide a rust inhibitor which has excellent anti-rust and coating adhesion to magnesium and magnesium alloy, and uses A method for producing a magnesium and/or magnesium alloy machine of the rust preventive agent, and a method for producing a machine made of at least one selected from the group consisting of ruthenium 2 and salts thereof selected from the formulas (1) to (7) A rust inhibitor for towns and/or town alloys in which the group is an active ingredient.

3

3 R (2) [wherein, R] represents a hydrogen atom or a Ci4 alkyl group or a meridine group, R3 represents a hydrogen atom, c #m, c^ group C(R4)=, R4, 〆, ···4 Base or hydroxyl group, A--N= or 'R-table hydrogen atom or amine group>. Furthermore, the present invention relates to a magnesium and/or magnesium alloy machine manufactured by the manufacturer, and the magnesium and/or magnesium alloy machine is used (表面) for the surface #315238 6 1271445 After the treatment with a physicochemical agent, (c) a method for producing a treated magnesium and/or an alloyed alloy member treated with a rust inhibitor for magnesium, wherein the rust preventive agent uses the anti-recording agent described above. Furthermore, the present invention relates to a method for producing a processed magnesium and/or magnesium alloy machine member, which is characterized in that magnesium and an alloy machine are subjected to (eight) after treatment with a surface treatment agent (B) use of a rust preventive pretreatment agent After the treatment, (6) a method for producing a treated town and/or a magnesium alloy machine member treated with a magnesium anti-money agent, wherein the rust inhibitor is the above-mentioned rust inhibitor. Further, the present invention relates to a method for producing a magnesium and/or magnesium alloy machine member which has been subjected to the treatment of the rust inhibitor for magnesium twice or more. The present invention relates to a method for producing a town and a fine alloy machine member of the above (A), (B), (C; at least one step of each step: the next step of the step) plus a water washing step. Furthermore, the present invention relates to a method for manufacturing a town and/or a magnesium alloy machine member, which is to perform a hair removal process if necessary (1) if necessary, and (10) with a surface treatment agent, (2_ υ Washing, (3) pre-treatment with anti-money treatment, (3)) water washing, (4) anti-rust treatment with anti-scaling agent, (6)), (7) drying, (6) painting or electroplating, (7) assembly, etc. The treated magnesium and/or magnesium alloy machine-made flocculant uses the above-mentioned anti-money agent. The method of the above-mentioned money uses anti-f: 'The invention relates to the repeated magnesium rust inhibitor treatment step twice or more The manufacturer and the manufacturer of the magnesium and/or magnesium alloy parts just described. The inventors of the present invention used the above aromatic carboxylic acid and its _ and/or 吼 系 compounds in combination. The low-synergy original, 315238 7 1271445 because of the aromatic m acid and its salts. The present invention can be achieved by using the same or a rust-preventing effect of the aromatic (4) and the salt, and the rust inhibitor for the magnesium or magnesium alloy of the present invention is selected from the formula (7) at least one selected from the group consisting of a compound and a salt thereof as an active ingredient. A linear isopropyl group, and in the present specification, a Cw alkyl group means a carbon number i to 4 or a heterocyclic alkyl group. For example, a mercapto group, an ethyl group, a n-propyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. The compound represented by the formula (1) may, for example, be A->1== a triazole compound, A is a -C(R4) = pyrazole compound. The compound of the formula (2) can also be a 1,2,4-triazole compound. -^ - j 5 1 _ 十^ 巯-152 , 4_triazole, 3_mercaptomethyl^dicentric triazole, 3_巯gristyl^, 2,4-triazole, 3_mercapto-1-isopropyl-1,2,4-triazole, 4-Amino 4,2 triazole, etc. These triazole compounds may be used alone or in combination of two or more. Further, for the salts of the triazole compounds, various kinds of tests and inorganic bases may be used. Salts. ^Specific examples of organic bases Alkanolamines such as alkanolamine, diethanolamine, triethanolamine, early = propanolamine, diisopropanolamine, triisopropanolamine, methyl ethylamine, cyclohexylamine, I2-ethylenediamine, 1 , 3-bis(aminomethyl)cyclohexyl and other known aliphatic amines; aminopyrrolidine, morpholine, diaza- & [5·4·〇]-7-undecene), DBN ( A cyclic amine such as 1,5-diazabicyclo[4 3 oxime 5, decene]. 315238 8 1271445 The specific examples of the inorganic test may be exemplified by sodium hydride, potassium hydride, hydrogenation clock, etc., and the like. This test can be! Used alone, or

Kind of P is used in combination. In the tests, the 祛A in the double t 乂彳 bauxite is an alkanolamine, an alkali metal hydroquinone and hydrazine. The triazole compound used in the present invention is an acid scallop of about 3 angstroms, and the amount of these bases can be adjusted by adjusting the 中 门 正 马 大约 大约 大约 大约 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The triazole compound 铷 1C σ substance and a salt thereof which are particularly preferable in the present invention may, for example, be 3-mercapto-1,2,4-triazole and its alkanolamine salt, alkali metal salt or phosphonium salt. The pyrazole compound may, for example, be 3,5-dimethylpyrazole, diethylazole, 3-methyl-5-pyridylpyrazole, 3-ethylidene-based carbazole, and isopropyl hydroxypyridyl Azole, 4-aminopyrazole. These pyrazole compounds may be used alone or in combination of two or more. The rust inhibitor of the present invention can be used as it is, and it is generally preferred to use it in a form dissolved in a suitable solvent. The solvent may be water, methanol alcohol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, butanol, n-hexanol, ethylene glycol ethyl ether (ethylcell〇S() lve), Alcohols such as b (bUtylCellUS0lve), b-methoxy-2-pentanol, ethylene glycol propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol; vinegars such as ethyl acetate, vinegar, and butyl acetate; Petroleum, hexane, heptane and other lipids; benzene, toluene, xylene and other aromatic hydrocarbons; acetone, methyl ethyl methyl isopropyl ketone and other ketones; dimethyl ether, dibutyl ether, An ether such as tetrahydrogen dichloride or dioxane, an amine such as N,N-dimercaptosulfonate amine or a mixed solvent thereof, and k is considered in terms of a cost surface, a safety surface of an operator, a waste liquid treatment surface, etc. < 315238 9 1271445 It is particularly preferred to use it in the form of an aqueous solution. The compounding amount of the triazole compound or the pyrazole compound at this time may be appropriately set, and generally, the total amount thereof is 0.001 to 10% by weight of the solution, preferably 〇1 to 5% by weight, more preferably It is 5 to 1% by weight. The rust preventive agent of the present invention may be used by adding other kinds of rust inhibitors for magnesium. However, the use of aromatic carboxylic acids and salts thereof such as tributyl benzoic acid and nonyl benzoic acid may cause coating adhesion. Falling is not suitable. The magnesium or magnesium alloy of the rust inhibitor for magnesium or magnesium alloy of the present invention can be suitably used, and the magnesium monomer or the gold or composite material composed of magnesium and other metals can be widely used. Other metals can be exemplified by aluminum, rhetoric, manganese, iron, recorded, copper, wrong, tin, and words! Kind or more than two. The rust preventive agent of the present invention is preferably a solid or a chelating solution, which is preferably dissolved in water or diluted to a predetermined concentration. The rust preventive agent of the present invention is prepared by applying the rust preventive agent in the form of a solution to the surface of a town or a town alloy ingot (ingQt), Mehip or various molded articles, by spraying (four) with a spray, or A method of immersing it in a solution. The use of rust inhibitors is in place. The enthalpy to 9 〇t, preferably 5 to 8 ϋ is the degree of scratching. In this step, an additive such as a surfactant may also be added to the anti-recording agent without damaging the effect. Ultrasonic processing is also available. As the general public, for example, a surfactant such as nonionic active material or the like can be used, and an interface or a cationic agent such as a cationic agent can also be used. Specifically, the nonionic surfactant is not particularly limited as long as it is 〇315238 1271445 3 Oxygen ethyl lauryl ether, polyepoxypyrene higher alcohol _ (tetra) oxyethyl bromide (4); polyepoxy base Phenyl poly(ethylene bromide), polyepoxy ethane glycol fatty acid such as polyethylene oxide monostearate, quotient sorbitol needle lauric acid vinegar, poly Epoxy sorbitan, liver lauric acid vinegar and other sorbitan fatty acid lys; ethylene glycol monostearic acid (tetra): alcohol fatty acid esters; fatty acid monoglycerides. Among them, it is preferably a poly(ethylene oxide) base (4), a polyepoxy(tetra)phenyl group, and the like, and the HLB (hydrophilic lipophilic balance) value is 丨3 to 1 $. The amphoteric surfactant is not particularly p-specific, and specifically, an alkylaminopropionic acid 4-based imidodipropionic acid; an amine-based acrylamide-based acid; a trimethylglycine and the like Test ('Μ) class, of which preferably is -5-aminopropionic acid, beet test. The cationic surfactant is not particularly limited, and specific examples thereof include an aliphatic amine amide salt, an alkyl pyridinium salt, a quaternary ammonium salt, and the like. Among them, an aliphatic amino acid halogen acid is preferred. Salt, quaternary ammonium salt. The above interface dopants may be used singly or in combination of two or more. Further, the amount of the surfactant may be usually from 全 to 5 〇 of the total amount of the composition. /. The degree 'is preferably about u1 GH%. The amount of the rust inhibitor to be used in the present invention is not particularly limited as long as the surface energy of the object to be treated is uniformly covered. When the surface of the molded article formed by the thixomolding method or the die casting method is treated by using the rust preventive agent of the present invention, the molded article can be circulated and stored for a long period of time before the coating, and the manufacturing steps are rationalized. It is very helpful. That is to say, it is formed by the thixoforming method or the town casting method (heat chamber 315238 11 1271445 _ Chamber die cast) and the cold room town transfer method (c〇id coffee::)) The bismuth molded article and the bismuth alloy molded article are directly coated by the surface rot* after the molding, and once the anti-money = is applied, the rust preventive agent or the like must be removed before the smear, and the rust preventive agent is removed by the present invention. In the case of surface treatment, the coating is not directly applied to the coating without the removal step of the previous method. θ After the treatment with the anti-throat agent of the present invention, the coated coating film obtained by coating is excellent in adhesion to the surface. It is extremely suitable for use on the surface of a magnesium or magnesium alloy molded article to be coated. When the anti-money agent of the present invention is used, in order to improve the anti-money effect, the surface of the lye can be degreased and washed before use. A conventional degreasing treatment step such as solvent degreasing, degreasing, emulsion degreasing, and acid degreasing may be applied, and one of them or a combination of one or more of them may be used. In the present invention, after the degreasing step, the surface treatment: the step of pre-rusting, the step of preventing pre-rusting, and the step of preventing the recording may be sequentially performed to prepare a processed part and/or a magnesium alloy machine. Although the rust-preventing treatment step may be performed once, it is preferable to obtain an excellent rust-preventing effect when performing two or more times. The method for producing magnesium and/or magnesium alloy treated by the rust inhibitor of the present invention is similar to the method disclosed. The rust inhibitor of the present invention is particularly suitable for the magnesium rust inhibitor. Sound, that is, magnesium and/or magnesium alloy parts are processed (A) after treatment with a surface treatment agent, (C) treated with magnesium with a rust preventive agent, and treated with magnesium and/or alloys as described above. In the method, the rust inhibitor of the present invention is used for the magnesium rust inhibitor of the step (c). 315238 12 1271445 And after the 'magnesium and / or magnesium alloy machine parts, (B) use anti-Ye old order (A) using surface treatment agent rust agent treatment, after the above 〆 ... receiver (c) For the use of magnesium, the manufacturing method of magnesium and/or magnesium alloy parts inclined to half is too much for the step (C); especially for the r ^ go , , , , , Use this anti-rust agent. The subsequent steps of at least one of the steps (A), (8), and (C) are described in April Τ ‘with an additional water washing step. In the present invention, the magnesium and/or magnesium alloy parts are subjected to (1) removal to two sides, (2) treatment with a surface treatment agent, (n) water washing, (y treatment with an anti-recording treatment agent, (3)). Washing, (4) manufacturing method of magnesium and/or magnesium alloy parts using magnesium rust inhibitors ( ―1) water washing, (5) drying, (6) painting, plating treatment, assembly, etc. In the case of the rust inhibitor according to the step (4), the rust inhibitor of the present invention is particularly preferably used. The surface treatment agent in the method described above may be, for example, a surface treatment agent containing phosphoric acid or an organic acid. The orthophosphoric acid and the condensed phosphoric acid ammonium salt and the alkanolamine salt are exemplified. The condensed phosphoric acid may, for example, be a metaphosphoric acid or a polyphosphoric acid. The metaphosphoric acid may be exemplified by three biases of Sman, tetrametaphosphoric acid, etc. Polyphosphoric acid may be exemplified by pyrophosphoric acid or the like. Phosphoric acid, tetraphosphoric acid, etc. Specifically, a first generation ammonium phosphate, a second ammonium phosphate, a third generation ammonium phosphate, a phosphoethanolamine, a diethanolamine phosphate, a triethanolamine phosphate, an isopropanol phosphate, a trimer <5 citric acid can be exemplified. Money salt, tetra-amyl ammonium salt, tetra-fold acid ethanolamine salt, triphosphorus Ammonium salt, tetraphosphate salt, etc. The above-mentioned acid salt can be used alone or in combination of two or more kinds. > Among them, the salt of the acid-filling salt and the alkaloid salt have a moderate effect and are washed. After the occurrence of smut, it is less common, and it has high safety, easy treatment of wastewater and better 'more due to: easy money: the surface of the town and magnesium alloy' and can prevent excessive engraving The condensed disk acid is particularly preferred. The condensed ammonium phosphate is generally known, and can be obtained, for example, by heating and condensing orthophosphoric acid with urea. In this case, orthophosphoric acid and urea are preferably orthophosphoric acid. ··Urea=1: 〇·5 to 丨:5. The surface treatment agent may contain unreacted raw materials, ie, orthophosphoric acid and urea, and the effect of the invention is used. There is no effect. The concentration of the phosphate is usually from 0.001 to 9% by weight, preferably from about 5 to 50% by weight, more preferably from i to 4% by weight. % by weight, the surface of the magnesium after washing is blackened, on the other hand If it is less than 0.5% by weight, the degreasing effect tends to be insufficient, and the degreasing effect tends to be insufficient. However, in the case where the concentration of the disc acid salt is less than 5% by weight, even if it is insufficient or degreased The effect is not sufficient, and if the treatment of the anti-rust pretreatment agent in the next step is carried out, the above-mentioned unsuitable condition can be supplemented. Further, even if the phosphate concentration is higher than 50% by weight, the magnesium surface has a shape of "," Such an unsuitable condition can be solved by performing the treatment of the pre-recording pretreatment agent in the next step. The organic acid can be exemplified by a ferulic acid such as gluconic acid, citric acid, malic acid or tartaric acid. The state is used while using 3) 5238 14 1271445

The time of the "Chen" is 0.01 to 50 willow 〇 / AJ. y, >> A Μ 里 里%, preferably 0" to 10%, to the extent of 5%. If less than 0^1. /士.,·01 /. %, there will be insufficient etching, and it is necessary to frequently add organic 4 to the treatment liquid. In the case where the right is more than 50 〇 / ’, it will be less than the result of excessive >1 insects. It is particularly preferable to use citric acid in consideration of the workability accompanying the generation of sludge in the surface treatment agent or in the treatment liquid. When the surface treatment agent is used, the occurrence of stains after the treatment can be reduced, and when the treatment of the pre-rust treatment agent of the second step is carried out, the stain can be easily removed. Although the temperature is usually sufficient to obtain an etching effect by selecting Pr7 tJJ and v曰 plate at a normal room temperature, it is preferably 30 to 50 C, preferably 4 〇〇c. The resulting stain is easily removed in the next step of the treatment. In the present month, an additive such as a surfactant is added to the extent that the effect of the dish acid or the organic acid in the surface treatment agent is not known. For the use of the rust-proof enamel treatment agent used in the above method, it is disclosed in WO01/838495. The anti-rust pretreatment agent may, for example, be ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, trisodium quinone/, alkanolamines of the inner drunk moon temple, mercaptoamine, ethylamine , such as cyclohexylamine, such as aliphatic peptides, such as 1,3-bis(aminomethyl) cyclohexane, 12-ethylenediamine and other aliphatic diamines, tetramethyl hydroxide Ammonium salts such as tetraethylammonium hydroxide and tetramethylammonium nitrate, ... dinitrogen heterocycle [5.4.〇] winter ten-lean (reward), ^•diazabicyclo[43 bucket 5_壬(DBN), amino-pyrrolidine, morpholine and other cyclic ammonium, ammonia, hydrazine, sodium hydroxide, potassium hydroxide and other alkali metal hydroxides, 'sodium sulphate, acid-cut clock, sodium sulphate, The metal salt of the stone acid of the sorrel and sorrel. Pre-money treatment 315238 15 1271445 1 can be used alone or in more than 2 types Λν U-inch. Among them, the alkali metal hydroxide such as 笱 仆 仆 sodium, potassium hydroxide, etc. The rust pretreatment agent has a twist of from 0.1 to 50% by weight. /. Preferably, the A ^ ^ weight is from Oj to 3 (% by weight), more preferably to the extent of % by weight. The anti-scaling agent is a method in which a treating agent is used before the anti-money agent is treated, and the treated object is sprayed or coated with a nozzle mist or a roll or impregnated into the solution. At the time of use, it is preferably used by heating the liquid agent, and it is preferably used in the range of 〇 to 9 (rc' is more preferably 40 to thief. The degree of the vehicle W8〇C can be improved after the table of the previous step. The rust effect is removed according to the rust pre-treatment agent, and the stain generated in the surface treatment step is removed and adhered to the coating. After the treatment with the anti-money agent of the present invention, the water washing step is added, and the step of adding the water washing step can be improved. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention is not limited to the examples by the examples and the test examples. Refers to parts by weight. Example 1 'Better is to apply the treated article to the coating. Therefore, it is particularly preferred. The present invention is described in detail, but the "parts" in the following units means that 5 parts of 3-mercapto-H4-triazole is put into deionized water to dissolve it to make 10M points. The anti-recording agent (1) was prepared by further diluting 1 〇 times with deionized water. Example 2 3 - thiol·1, 2, 4 - 3 was placed in 5 parts of water and dissolved to make 1 part. 3 parts of isopropanolamine was added to deionized and then diluted 10 times with deionized water to obtain rust inhibitor (2) from 315238 16 1271445. Example 3 3-hydroxy-1?2, 3 parts of triazole was dissolved in water to make 100 parts of the anti-money agent (3). Example 4 "4 parts of the lactamamine was deionized and then Deionized water is diluted 10 times and called (10) parts in only eight deionized water. Then deionized water is used to solve the problem of Example 5 and I pass the rust inhibitor (4). 5_ After taking 5 parts of the base and putting it into deionized water, it is made into 00 parts of solution. Then, it is removed from each agent (5). Diluted by 10 times to obtain anti-money. Example 6 3--based-ls2 , 4-three parts, Lavoru xA6〇/5〇 (manufactured by Li〇n, nonionic surfactant) 5 parts, Pavoning c (manufactured by Takemoto Oil Co., Ltd., amphoteric surfactant) 2.5份, 特特罗尼克 (4) is called Xingminghua company, defoamer) 5. 5 parts into deionized water 5 〇 parts, with gas; potassium adjusted to pH7.0 €, add deionized water to the original Then, the solution was diluted 5 times with deionized water to prepare a rust inhibitor 6. Example 7 2 parts of 4-amino-u〆-three wow was put into deionized water and dissolved to make 100 parts. And then diluted 1 to 10 times with deionized water to prevent Rust 7. Comparative Example 1 5 parts of the present diazole and 2 parts of isopropanolamine were placed in deionized water to dissolve 315238 17 1271445 to prepare a rust preventive agent (1). Comparative Example 2 100 wounds. Diluting i 〇 times with deionized water to make 5 parts of 3, yl-1,2,4-trisal, and p-t-butyl benzoic acid 5 t isopropyl 1 G of the mixture was poured into deionized water. It was dissolved to make 100 wounds, and then diluted 10 times with deionized water to prepare a comparative rust inhibitor (7). Comparative Example 3 was added to deionized water and released 10 times to obtain a ratio of 1,2,4-three. 5 parts of hydrazine, 2 parts of isopropanolamine were dissolved to make 100 parts. Then use a deionized water to dilute the rust inhibitor (3). Comparative Example 4 5 parts of 1'2,3-azole was added, and isopropanolamine was added to deionized water to dissolve it to make 1 part. Dan was diluted 10 times with deionized water to prepare a rust inhibitor (4). Comparative Example 5 Dimethyl D is 2·5 parts of saliva, p-t-butylbenzoic acid:, 5 parts of propanolamine is put into deionized water, and dissolved to prepare a solution of 5 times diluted with chop water. Have to compare anti-recording agent (7). Cang Test Example 1 After mixing the normal acid and urea with a molar ratio of 1:2, the reaction was carried out for 2 hours to obtain a condensed ammonium phosphate. The condensed ammonium phosphate is / =, urea and normal acid. Deionized water is added to the obtained condensation; the second coat is about 16% - the condensed dish acid solution is used as the surface 丨 315238 18 1271445 Reference Example 2 is dissolved to make 100. 3 parts of citric acid is put into deionized water. 'As surface treatment agent 2. Test Example 1 A mold release agent was applied to the mold (Kashida Ace 225, the rice alloy AZ91D (containing 90% of magnesium, 9% of aluminum, 铉^ σ / 1% of zinc) was cast into a plate shape. Forming mouth (3x 15x 0.2cm) for use. In the ultrasonic generation at room temperature, the plate-shaped molded product is dipped in the surface treatment agent prepared in the reference example for 丨 minutes, and then blown at room temperature. Wash in medium water for 1 minute, then in the ultrasonic generation of 6 (TC), immersed in i〇% (w/w) aqueous solution of bismuth oxychloride for 10 minutes, then rinse at room temperature for 1 minute, then 6 (in the ultrasonic generation under TC) was immersed in the rust inhibitor 6 prepared in Example 6 for 10 minutes, and then washed with water at room temperature for 1 minute. Next at room temperature, in the example 丨After immersing in the obtained rust preventive agent (丨), it was washed with water at room temperature for 1 minute, and then dried at 150 ° C for 3 minutes to prepare a test piece (1). Further, the same treatment as described above was carried out. The anti-recording agent (1) in the foregoing operation was prepared by the anti-recording agent (2) prepared in Example 2, the rust-preventing agent (3) obtained in Example 3, and Comparative Example 1, respectively. Comparison of rust inhibitors (丨) The comparative rust inhibitor (2) prepared in Comparative Example 2, the comparative rust inhibitor (3) obtained in Comparative Example 3, and the comparative rust inhibitor (4) obtained in Comparative Example 4 were replaced, respectively. Test piece (2), test piece (3), comparative test piece (1), comparative test piece (2), comparative test piece (3), and comparative test piece (4). (Salt spray test) 19 315238 1271445 The prepared test pieces (1) to (3), and the comparative test pieces (1) to (4) were respectively rusted by spraying with 5% (w/w) of an aqueous solution of sodium chloride at 35 for 8 hours. Determination of the condition. Guarding 24 rust conditions are shown in proportion to the rust area per unit area

* One uses the contact resistance meter Rolita _Mp (Mitsubishi == Γ0), (2), (3), 'Results, two or two points (3 repetitions) to determine its resistance (coating compatibility test) The test piece (1), Ma (Magnum and 4), and the comparative test piece (2) are coated with Pu wipe a, 曰来伊玛-Gray-HB8655, Musashi paint public _Ί * ί: times , smear thickness... One place is followed by coating paint (d〇np, ^^20 points 1087 > ^ ^ ^ 4 e〇at) (Emmett Grinmetali 袼Ατ: manufactured by Wushang Coatings Co., Ltd.) Tu Chang (smear once, Apply thickness 13 315238 20 1271445 " m), bake at 160 ° C for 20 minutes, and test each test piece into a coating adhesion test. 仃 - and once coating adhesion test will be painted after the day Also, the s-type test piece is placed in a square of lmm size (1 〇〇 )), glued to the glass glue you ^,, ell〇Phane tape) Man's peeling the glass film to determine the number of residual cold main film And the first coating at 60 ° C

The secondary coating adhesion test was carried out by immersing the tested test water in warm water for 4 hours, and immediately after the water removal, the test for the compatibility was carried out. The results are shown in Table 2. It can be judged from the table that the plate is closed and the carboxylic acid is used in combination to make the coating adhesion insufficient. (Table 2) ------ Test piece (1) —------------ One-time adhesion test------____ '' '~~--- -- Packing test 100/100 100/100 test piece (2) 100/100 100/100 test piece (3) 100/100 100/100 comparative test piece (2) 100/100 70/100 test case 2 The plate-shaped molded article used in Test Example 1 was used. After the plate-shaped molded article was immersed in isopropanolamine, it was immersed in the surface treatment agent 1 prepared in Reference Example 1 at room temperature for ultrasonic generation for 10.5 minutes, and then blown at room temperature. The water was washed with water for 1 minute, and then impregnated in a 2% (w/w) aqueous potassium hydroxide solution at 6 〇t in ultrasonic generation! After 〇 minutes, again 21 315238 1271445 at room temperature, pain + t, in the implementation of:: =: minutes ' and then at 6 ° ° c ultrasonic generation under the temperature of the air in the water wash =: rust inhibitor 6 After immersing for 5 minutes, and then obtaining the rust inhibitor in the chamber (2, after 2 minutes from the knife 4 and then at room temperature, under the method of (2), the solution was dried for 1 minute, for 20 minutes, and the test was prepared. Sheet (4). The same treatment as described above was carried out, (7) Calculated in Comparative Example 4... ▲ ❿ will be described as a rust preventive test piece (5). ^Comparative rust preventive (4) replacement, and It is necessary to compare the test piece (4) and the comparative test (Table 3) material (Magede, Kuboxiao paint:=) on the r: the coating is applied to 15 to 2. 'Smear thickness double-coating adhesion test.', 'Li' will test each test piece""^7^7 - secondary coating!^Combination test 100/100 than the car test piece (5) 72/100 —---------1 Test Example 3 (Preparation of test piece 1) Release of mold release agent in mold (Kashida Ace 225, manufactured by Riemi Co., Ltd.) , the town alloy AZ91D (containing lock 90%, Ming 9〇 / 〇, zinc ι%) town into a board Molded product (3X 1 5χ 0.2cm) is reserved. 'Water side; to subsurface ultrasonic generation, the plate-shaped molded product is immersed in the surface treatment agent 1 manufactured by reference to Guardian! Minutes, and then at room temperature ^ Blowing in 315238 22 1271445 for 1 minute' followed by ultrasonic wave generation at 60 ° C, immersed in i〇% (w/w) potassium oxyhydroxide aqueous solution for 1 〇 minutes, and then blown at room temperature After washing for a few minutes, then in the ultrasonic generation at 60 ° C, the rust inhibitor 0 prepared in Example 6 was immersed for 10 minutes, and then washed with water at room temperature for 1 minute. Next at room temperature After immersing in the rust inhibitor prepared in Example 4 for a minute, the mixture was washed with water at room temperature for 1 minute, and then dried at 15 ° for 3 minutes to obtain a test piece (5). The same treatment as described above was carried out, and the rust preventive agent (4) in the above operation was replaced with the rust preventive agent (5) obtained in Example 5 and the comparative rust preventive agent (5) prepared in Comparative Example 5, respectively. Test pieces (6) and comparative test pieces (6) were separately prepared. % (Modulation of test piece 2) The plate-shaped molded article used in Test Example 1 was used. Ultrasonic generation was performed at 60 °C. The plate-shaped molded product was immersed in potassium oxide and 0.1% (w/w) No. SD_8 〇 (manufactured by Daiichi Kogyo Co., Ltd., nonionic surfactant) for 5 minutes, and then blown at room temperature. In the water wash for 1 minute 'at 3 (the surface treatment prepared in Reference Example 2 under TC; 2 in the dipping for 1 minute, then in the air at room temperature, the water is washed for a few minutes, then the ^60C under the super-wave generation] After immersing in a 5% (w/w) aqueous potassium hydroxide solution for 5 minutes, 'washing again at room temperature for 1 minute, then flying the ultrasonic wave to produce a towel, and the defense obtained in Example 7 (4) The 丨7 towel was dipped for 5 cm, and then washed with water for 1 minute at room temperature. Next, after immersion for 1 minute in the anti-(4) M obtained in Example 4, the mixture was washed with water at room temperature for 1 minute, and then dried at 150 t for 2 minutes to obtain a test piece 3 5238. 23 1271445 (7). The obtained test piece (saline τ test) (7) has an excellent metallic luster elbow/1 crack test ,μ, ^ j (5) to (7), and comparative test piece (6) respectively 5 〇 / 〇 (w / W) of gasified sodium water dissolved in 35 C 唷 8 hours and 24 hours # 灯 rusting gold measurement (Table 4), rusting conditions per unit area of rust The proportion of the area is not. The results are shown in Table 4. ,

, Determination of resistance value) Using contact resistance meter Luo Lita _ Μ ρ (Mitsubishi Chemical Co., Ltd., old in the 夂 ^ plate needle method) on the test piece (5), (6), (7), comparative test piece (6 _ = ^ ^ The resistance value is determined by 3 points (2 repetitions). _ • The resistance value below ZU. (Coating adhesion test) Genna 2): (:, Comparative test piece (6) coated with Pleyim times ,=?8: Μ55, made by Musashi Paint Co., Ltd.) (Smear-Daichi, Deyixin)' for baking for 20 minutes at 16 °C, dope coat (Aima lacquered 袼林美塔利Grid 315238 24 1271445 1087, made by Musashi Paint Co., Ltd.) (smear once, smear thickness 1 3 to 1 5 // m), bake at 160 ° C for 20 minutes, each test, ▼ double film And secondary coating adhesion test. - The coating adhesion test is carried out by placing the test piece after the day of painting into a square of size (100 cells), and after adhering the glass film (ceU〇phane tape), the glass film is peeled off and the residue is measured. The number of normal coating films is shown as 0. The secondary coating adhesion test is performed by immersing the coated test piece at a temperature of 6 〇t: for 4 hours, and immediately after the water removal, performing the aforementioned one-time application density. Synergy test. The results are shown in Table 5. From the standpoint, it was judged that the use of the aromatic carboxylic acid in combination would result in insufficient coating adhesion. (Table 5) One-coat adhesion test Secondary coating adhesion test piece (5) 100/100 100/100 Test piece (7) 100/100 100/100 Comparative test piece (6) 100/100 90/100 Industrial Applicability According to the present invention, it is possible to provide a rust preventive agent having excellent rust preventive effect on magnesium and/or magnesium alloy and having excellent coating adhesion, and magnesium using the rust preventive agent and / or the manufacturing method of the town alloy parts. 25 315238

Claims (1)

1271445 The scope of the patent scope revision (March 1995), the dish and the at least one selected from the group consisting of formulas (1) to (2) are effective. 3 3 R [Formula m hydrogen atom or Cl_4 courtyard group, r2 represents a hydrogen atom, c group, a sulfhydryl group or a meridine group, r3 represents a hydrogen atom, Ci4 _N= or □, r4 represents a hydrogen atom or an amine group]. 2. ^Protection of Magnesium and / or Magnesium Alloys in the first paragraph of the patent scope: Department: r...hydrogen atom, r2 system Weiyl-hydrogen... 3. : Patent application scope! The anti-recording agent for magnesium and/or magnesium alloy, the R1 hydrogen atom in the formula (1), the R2 alkyl group, the caliper 3 system c syllabic group, or the a#_c(r4)=, r4 hydrogen atom. 4. If you apply for a patent scope! Anti-rust agent for the town and/or magnesium alloy, the R1 hydrogen atom in the formula (1), r2^Ci_4 炫, r3#c alkyl, A-C(r4)=, r4 hydrogenogen 315238 (Revised) 1 1271445 5. The rust inhibitor for magnesium and/or magnesium alloy according to the first aspect of the patent application, wherein R2 in the formula (2) is a hydrogen atom or a hydrogen atom of R3. 6. If the rust inhibitor for magnesium and/or magnesium alloy is applied in the scope of the patent item i, wherein the compound represented by the formula (1) to (2) is 3-hydroxy-1,2,4-triazole, 3 · Mercapto-1,2,4-triazole, 4-aminotriazole, 3,5-dimethylcarbazole, 3-methyl-5-hydroxyu-butyrazole. 7. A method for producing a processed magnesium and/or magnesium alloy machine, wherein the magnesium and/or magnesium alloy parts are subjected to (A) treatment with a surface treatment agent, and (C) use of magnesium for rust prevention. A method for producing a treated magnesium and/or magnesium alloy machine member, wherein the rust inhibitor is a rust inhibitor according to claim 1 of the patent application. 8. The method for producing a processed magnesium and/or magnesium alloy machine, the magnesium and/or magnesium alloy machine parts (A) after treatment with a surface treatment agent, and (B) the use of a rust pretreatment agent The treatment and the second method (c) are a method for producing a treated magnesium and/or magnesium alloy machine treated with a magnesium anti-recording agent, and the rust preventive agent uses the rust inhibitor of the first application of the patent scope. 9. The method for producing a treated town and/or a magnesium coin according to the application of the patent _ 7 or the item 8, wherein the use of the magnesium-based anti-aging agent is repeated twice or more. !〇·If you apply for the patent scope of item 7 of the yue yiqi u ice system m and magnesium, or magnesium alloy machine parts η method, #中, (〇 step to the next step Additional washing step U. As in the manufacturing method of the article of claim 8 of the patent scope, A, (4), at least one of the steps of the M/Μ alloy machine, the middle (A), (B), and (C) 315238 (amendment) 2 1271445 The washing step is added in the next step. 12. If the application of the ninth paragraph of the patent application, ... the manufacturing method of the heart scale and / or magnesium alloy parts, wherein钺, ^ (A) (C) each step or (Α), (Β), (〇 at least one of the steps above and above) < additional steps in the human step. And / or magnesium alloy parts The manufacturing method is to carry out the town and/or Zhenkou gold parts (1) deburring if necessary, *, treatment, (2_1) washing, η, dry / (3) using anti-rust pretreatment agent , (3_η water washing, (4) use of rust inhibitor for magnesium male rust prevention treatment, (4-1) water washing, η ^ times electroplating treatment, (7) assembly Magnesium Φ ^ ^ - 乂 method for the treatment of magnesium and/or magnesium alloy parts, the above-mentioned rust inhibitor for magnesium is used for the rust preventive agent of claim 1 of the patent scope. Article 13 沬., the manufacture of magnesium and / or magnesium alloy parts. /, the use of the town rust inhibitor treatment step is repeated 2 times to 315238 (amendment) 3