KR101534765B1 - Surface Treating Composition of Magnesium and Magnesium Alloy and Surface Treating Method Using The Same - Google Patents

Abstract

A surface treatment agent and a surface treatment method applied to surface treatment of magnesium and magnesium alloy materials are disclosed. The surface treatment agent has a composition comprising 1 to 10% by weight of a metal complex, 5 to 20% by weight of an inorganic metal sol, 0.05 to 1.0% by weight of an anticorrosive agent, and excess water. In the surface treatment method, the magnesium and magnesium alloy materials subjected to the degreasing process are prepared, and then the magnesium and magnesium alloy materials are surface-treated using the surface treatment agent having the composition described above to remove oxides present in the material, Can be formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for magnesium and magnesium alloys and a surface treatment method using the same.

The present invention relates to a surface treatment agent for magnesium and magnesium alloy materials and a surface treatment method using the same, and more particularly, to a surface treatment agent capable of securing a transparent coat while contributing to reduction of surface treatment processes of magnesium and magnesium alloy materials, And a surface treatment method using the same.

Magnesium (Mg) is the eighth in the crust and the third in the seawater. It can be extracted from ore and seawater. The magnesium alloy is lightweight, has excellent non-strength, excellent dimensional stability, And exhibits high heat, electric conductivity and vibration absorbing property and is excellent in electromagnetic wave shielding effect and is widely used in a variety of fields such as household appliances, automobile parts, computers, aviation parts, communication devices, office equipment, sports goods and the like. Particularly, interest in magnesium and magnesium alloys is increasing as a substitute for aluminum, which is poor in mechanical properties and low in recycling, and low in electromagnetic wave shielding property and poor in workability.

Magnesium and magnesium alloys are low in corrosion resistance and corrosion by water or chemicals. For this reason, magnesium and magnesium alloys are subjected to surface treatment such as chemical conversion treatment or anodic oxidation treatment for the purpose of preventing corrosion. However, such a surface treatment is effective for improving the corrosion resistance, but has a problem that the original luster of magnesium and magnesium alloy is significantly lowered, so that the magnesium or magnesium alloy material can not be used immediately. Therefore, additional coating process is required for securing the appearance and physical properties, and there is a problem that the surface treatment process time and the economic cost of the magnesium material are increased.

Also, Korean Patent Laid-Open Publication No. 2011-0056706 discloses a technique for preventing discoloration and corrosion resistance of magnesium and magnesium alloy materials. A step of washing the outer surface of the magnesium or magnesium alloy disclosed in the aforementioned patent with degreasing treatment, a step of washing the surface of the magnesium or magnesium alloy after the etching treatment to remove the oxide film on the outer surface of the magnesium or magnesium alloy, Removing the magnesium or magnesium alloy from the surface of the magnesium or magnesium alloy, and washing the surface of the magnesium or magnesium alloy after the formation of the chemical conversion coating film and the surface coating step.

The above-described method has a problem in that an oxide film removing process, a dismutting process, an additional process and a coating film forming process have to be performed after the degreasing process, and at the same time, the surface treatment composition at a temperature of about 40-60 캜 There is a problem that a water-overflow process must be performed. Further, the magnesium and magnesium alloy materials surface-treated by the above-described method have a problem that they are discolored when stored under high-temperature and high-humidity conditions, and are poor in storability.

An object of the present invention is to overcome such a problem, and it is applied to a surface treatment process of a magnesium or magnesium alloy material to reduce the surface treatment process of the material, to secure a transparent appearance and to prevent discoloration of the surface during storage And a surface treatment agent.

Another object of the present invention is to overcome such a problem, and it is an object of the present invention to provide a magnesium alloy product which is excellent in corrosion resistance and storage property even though an etching process and a dismutation process using an acid are omitted using a surface treatment agent And a method for processing the same.

In order to attain the above object, the surface treatment agent applied to the magnesium and magnesium alloy material of the present invention is 1 to 10 wt% of a metal complex, 5 to 20 wt% of an inorganic metal sol, 0.05 to 1.0 wt% of an anti- Lt; / RTI >

In one embodiment, the metal complex may include at least one selected from the group consisting of a silane-based coupling agent, a titanium-based chelating agent, and a zirconium-based coupling agent.

For example, the silane-based coupling agent in the metal complex may be a silane-based coupling agent (Vinyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldiethoxy, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-Mercaptopropyl trimethoxysilane, (3-ACRYLOXYPROPYL) TRIMETHOXYSILANE, etc. The titanium-based coupling agent is a titanium-containing 2-propanolato, tris isooctadecanoato-O , Titanium IV bis 2-methyl-2-propenoate-O, isooctadecanoato-O 2 -p 2-propanolato-O, methoxydiglycolylato, Titanium IV 2-propanolato, tris (dioctyl) phosphato-O, Titanium IV, tris (2-methyl) 2-propanolato, tris (dioctyl) pyrophosphato-O, Titanium IV, tris (2-propenoato-O), methoxydiglycolylato-O, Titanium IV bis (dioctyl) pyrophosphato-O, oxoethylenediolato, N, N-dimethylamino-2-methylpropanol, Titanium IV bis (butylmethyl) pyrophosphato-O, Hexafluoro titanic acid, Titanium IV 2,2 (bis 2-propenolatomethyl) butanolato, bis (2-propenolatomethyl) butanolato, tris (dioctyl) pyrophosphato-O, Titanium IV 2,2 (bis 2-propenolatomethyl) butanolato, tris (3-amino) phenylato, Titanium IV bis octanolato, cyclo (dioctyl) pyrophosphato-O, O, Titanium IV bis cyclo (dioctyl) pyrophosphato-O, The zirconium-based coupling agent is selected from the group consisting of Zirconium IV 2. 2-dimethyl 1,3 propanediolato, bis (dioctyl) pyrophosphato-O, adduct 2 moles N, N-dimethylamino-alkyl propenoamide, Zirconium IV 2-ethyl-2-propenolatomethyl) 1,3-propanediolato, cyclo bis 2-dimethylamino pyrophosphato-O, adduct with 2 moles of methanesulfonic acid, Zirconium IV tetrakis 2,2 (bis-2 propenolatomethyl) butanolato, adduct with 2 moles of di-tridecyl, hydrogen phosphite, Hexafluoro zirconic acid, Zirconium IV 2-ethyl, 2-propenolatomethyl 1,3-propanediolato, cyclo di 2,2-bis (2-propenolatomethyl) butanolato pyrophosphato- (bis-2-propenolatomethyl) butanolato, tris (dodecyl) benzenesulfonato-O, Zirconium IV, ethylhexanolato, cyclo (di 2-ethylhexyl) pyrophosphato, Zirconium IV 2,2 Etc. may be used.

In one embodiment, the inorganic metal sol may include at least one selected from the group consisting of silica sol, alumina sol, titania sol, and zirconia sol.

In one embodiment, silica sol (Ludox® HS-30, Ludox® HS-40, Ludox®, Ludox® SM, Ludox® AM, Ludox® AS, Ludox® LS, Ludox® CL- Ludox® FM, Ludox® HSA, SNOWTEX® ST-20L, SNOWTEX® ST-40 and SNOWTEX® from NISSAN CHEMICAL are trademarks of Ludox® CL, Ludox® CL-P, Ludox® CL, SN-ST-50, SNOWTEX® ST-C, SNOWTEX® ST-N, SNOWTEX® ST-O, SNOWTEX® ST-OL, SNOWTEX® ST- SS-SOL 30S, SS-SOL 30S, SS-SOL 30F, SS-SOL 100, SS of SS-SOL 30SG, SS-SOL 30E, SS-SOL 30E, SNOWTEX® ST- SS-SOL 30EM, SS-SOL 30OPAC, SS-SOL 20EG, SS-SOL 30EK, SS-SOL 30BK) can be used.

Alumina sol (ALUMINASOL ^占 AS-100, ALUMINASOL ^占 AS-200 by Nissan Chemical Co., Ultra-Sol 200A, Ultra-Sol 201A / 60, Ultra-Sol 201A / 280 by Gerard Kluyskens Co., Inc., Wesol A, Wesol C12 , Wesol D30) and the like can be used.

In one embodiment, the rust inhibitor may include at least one selected from the group consisting of a phosphoric acid-based rust inhibitor, an aluminum salt-based rust inhibitor, a molybdenum salt-based rust inhibitor, a fluorine-based rust inhibitor, a vanadium salt-based rust inhibitor, a cerium salt-based rust inhibitor and a selenium salt-based rust inhibitor.

Dequests ^® 2000, Dequest ^® 2010, Dequest ^® 2066A, Dequest ^® 2016, Dequest ^® 2046, Dequest ^® 2060, Dequest ^® 2066, Dequest ^® 2041, and Dequest ^® 2041 from Thermphos, ^{Dequest ® 2090, Dequest ® Dequest ®} 4066, Dequest ® 2054, Dequest ® 7000, CHErbsloh Corporation ^{CHE ® -COAT-CI L2, CHE} ® -COAT-CI L8AF, CHE ® -COAT-CI LAF 1, CHE ® -COAT- CI LNF 2 or the like may be used. The molybdenum compounds zero _{Na 2 [Mo 2 (CO)} 10], Mo (CO) 6, Na [C 6 H 6 Mo], MoCl 2, Na 3 [Mo (CN)] 6, MoS 2, MoCl 5, MoF ₆ , (NH ₄ ) ₂ (MoO ₄ ), MoSi ₂ , MoO ₃ , (NH ₄ ) ₆ Mo ₇ O ₂₄ , and H ₃ PMo ₁₂ O ₄₀ . V2O5, VO2, Lithium vanadium oxide, Bismuth vanadate, Ammonium metavanadate, Sodium decavanadate, Sodium orthovanadate, Sodium metavanadate, Yttrium orthovanadate and the like can be used as the vanadium compounds. As selenium compounds, selenium dioxide, selenium trioxide, anhydrous potassium selenate, tetraselenium tetranitride, selenium tetrachloride, selenocyanates, zinc selenide, copper diselenide, indium diselenide, gallium diselenide and the like can be used. Cerium (IV) oxide, Ce (OH) 3, CeF3, CeCl3, CeBr3, CeI3, Cerium (III) oxide, Cerium (IV) sulfate, Ammonium cerium Etc. may be used.

In one embodiment, the surface treatment agent for magnesium and magnesium alloy material further comprises 1 to 10% by weight of an alcohol-based or glycol-based organic solvent.

In one embodiment, the alcoholic or glycolic organic solvent is selected from the group consisting of methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentan- 2-Methylbutan-2-ol, 2-Methylbutan-2-ol, 1-Hexanol, 2-Methylbutan-1-ol, 2,2-Dimethylpropan-1-ol, Pentan-3-ol, Pentan- , 2-hexanol, 3-hexanol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,3-butanediol, 1,2-pentanediol, etohexadiol, -3,8-diol, 2-Methyl-2,4-pentanediol, 2-butoxyethanol and the like.

In one embodiment, the surface treatment agent desirably has a pH of 0.5 to 6.0 and more preferably a pH range of 1.5 to 4.5. This is because when the pH is less than 0.5, the reaction rate is too fast to form a uniform film, and when the pH is 6.0 or more, sufficient surface etching is not performed and the oxide removal on the surface is insufficient, Because.

According to another aspect of the present invention, there is provided a surface treatment method of a magnesium and magnesium alloy material, comprising: preparing a magnesium and magnesium alloy material subjected to a degreasing process; and applying the magnesium and magnesium alloy material to a surface Wherein the surface treatment agent comprises 1 to 10% by weight of a metal complex, 5 to 20% by weight of an inorganic metal sol, 0.05 to 1.0% by weight of an antirust agent, and an excess of water.

In one embodiment, the surface treatment of the workpiece may be performed by impregnating the workpiece with a cleaning bath containing a surface treating agent having a temperature of 5 to 30 DEG C for 5 to 60 seconds.

In one embodiment, the surface treatment agent may further comprise 1 to 10% by weight of an alcohol-based or glycol-based organic solvent.

The surface treatment agent of magnesium and its alloys according to the embodiment of the present invention is a surface treatment composition having both an etching and a coating function that can be applied after the degreasing process is performed from magnesium and its alloys. The surface treatment agent does not require alkaline washing or acid washing for removing oxides and musth, so that the process is simplified and the adhesion of the formed surface treated film and the high temperature and high humidity resistance are excellent.

In addition, the magnesium and magnesium alloy materials surface-treated with the surface treatment agent of the present invention are excellent in storage stability of the surface treatment agent which does not cause discoloration even when stored under a high-temperature and high-humidity condition of about 60 ° C or higher or a humidity of 90% It is possible to give a sex.

In addition, the surface treatment method using the surface treatment agent of the present invention has an advantage that after the surface treatment, the magnesium material can maintain excellent glossiness and a coating process for imparting another glossiness is not required.

FIG. 1 is a process flow diagram illustrating a surface treatment method of a magnesium and magnesium alloy material according to an embodiment of the present invention.

Hereinafter, a surface treating agent for a magnesium and magnesium alloy material according to an embodiment of the present invention and a surface treating method using the same will be described in detail. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are further described in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, the surface treating composition according to one embodiment of the present invention will be described in detail.

The surface treatment agent of the magnesium and magnesium alloy materials according to an embodiment of the present invention may have a composition including an organic metal complex compound, an inorganic metal sol, a polystyrene, and water. The surface treatment agent having the above composition is applied to the surface treatment process of magnesium and magnesium alloy materials to remove the oxide film present on the surface of the magnesium and magnesium alloy material and to form a coating film for securing corrosion resistance of the magnesium and magnesium alloy materials to be.

That is, even if the magnesium and magnesium alloy materials are immersed in the surface treatment agent of the present invention, the effect of etching and removing the oxides present on the surfaces of the magnesium and magnesium alloy materials and the effect of forming the corrosion- Functional surface treatment composition.

The metal complex compound applied to the surface treatment agent of the magnesium and magnesium alloy materials according to the present embodiment is formed by bonding the surface of the magnesium and magnesium alloy material and the coating material or after the oil / inorganic components contained in the coating material are dried after coating And is a metal complex compound having properties capable of forming an excellent film.

The metal complex may include a silane-based coupling agent, a titanium-based coupling agent, a zirconium-based coupling agent, etc. These may be used singly or in combination of two or more.

For example, the silane-based coupling agent in the metal complex may be a silane-based coupling agent (Vinyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane, 3-Glycidoxypropyl-trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Methacryloxypropyl triethoxysilane, 3-Methacryloxypropyl triethoxysilane, 3-Methacryloxypropyl methyldimethoxysilane, 3-Methacryloxypropyl methyldiethoxy, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyl triethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyldimethoxysilane, N- 3-aminopropyltriethoxy silane, 3-Mercaptopropyl trimethoxysilane, (3-ACRYLOXYPROPYL) TRIMETHOXYSILANE, etc. The titanium-based coupling agent is a titanium-containing metal compound, IV 2-propanolato, tris isooctadecanoato-O, Titanium IV bis 2-methyl-2-propenoate-O, isooctadeca (2-methyl) -2-propenoate-O, 2-propanolate, 2-propanolate, tris (dodecyl) benzenesulfanato-O, Titanium IV 2-propanolato, , methoxydiglycolylato, Titanium IV 2-propanolato, tris (dioctyl) pyrophosphato-O, Titanium IV, tris (2-propenoato-O), methoxydiglycolylato-O, Titanium IV bis (dioctyl) pyrophosphato-O, oxoethylenediolato, (2-propenolatomethyl) butanolato, tris (dioctyl) phosphato-O, Titanium IV bis (butylmethyl) pyrophosphato-O, hexafluoro titanic acid, IV bis 2,2 (bis 2-propenolatomethyl) butanolato, tris (dioctyl) pyrophosphato-O, O, Titanium IV bis cyclo (dioctyl) pyrophosphato-O, O, and the like can be used. The zirconium-based coupling agent is selected from the group consisting of Zirconium IV 2. 2-dimethyl 1,3 propanediolato, bis (dioctyl) pyrophosphato-O, adduct 2 moles N, N-dimethylamino-alkyl propenoamide, Zirconium IV 2-ethyl-2-propenolatomethyl) 1,3-propanediolato, cyclo bis 2-dimethylamino pyrophosphato-O, adduct with 2 moles of methanesulfonic acid, Zirconium IV tetrakis 2,2 (bis-2 propenolatomethyl) butanolato, adduct with 2 moles of di-tridecyl, hydrogen phosphite, Hexafluoro zirconic acid, Zirconium IV 2-ethyl, 2-propenolatomethyl 1,3-propanediolato, cyclo di 2,2-bis (2-propenolatomethyl) butanolato pyrophosphato- ethylhexanolato, cyclo (di 2-ethylhexyl) pyrophosphato, Zirconium IV 2,2 bis (2-propenolatomethyl) butanolato, tris neodecanolato-O, Zirconium IV 2.2, bis (2-propenolatomethyl) butanolato, tris (dodecyl) benzenesulfonato- Can be used.

If the amount of the metal complex compound is less than 1.0% by weight based on the total amount of the surface treatment agent, it is not preferable because the metal complex compound applied to the surface treatment agent of the magnesium and magnesium alloy has a problem of adhering to the material. If it is more than 10% by weight, it is not preferable because the solution has poor storage stability, poor performance, and poor appearance. Accordingly, the amount of the metal complex compound to be applied to the surface treatment agent of the magnesium and magnesium alloy is preferably in the range of 1.0 to 10 wt%, and more preferably in the range of 2.0 to 8 wt%.

The inorganic metal sol used for the surface treatment agent of the magnesium and magnesium alloy materials according to the present embodiment is formed by coupling an organic metal complex contained in the surface treatment agent to the surface thereof after the oxide present on the surface of the alloy material is etched, Is used to form a coated film.

The inorganic metal sol may include silica sol, alumina sol, titania sol, zirconia sol. These may be used singly or in a mixture of two or more.

As one example, a silica sol GRACE Corp. Among the inorganic metal sol ^{Ludox ® HS-30, Ludox ®} HS-40, Ludox ® TM, Ludox ® SM, Ludox ® AM, Ludox ® AS, Ludox ® LS, Ludox ® CL- X, Ludox ^® SK, Ludox ^® TMA, Ludox ^® PG, Ludox ^® CL, Ludox ^® CL - P, Ludox ^® DF, Ludox ^® FM, Ludox ^® HSA, SNOWTEX ^® ST - 20L and SNOWTEX ^® ST - 40 from NISSAN CHEMICAL ^{, SNOWTEX ® ST-50, SNOWTEX} ® ST-C, SNOWTEX ® ST-N, SNOWTEX ® ST-O, SNOWTEX ® ST-OL, SNOWTEX ® ST-ZL, SNOWTEX ® ST-PS-M, SNOWTEX ® ST-PS ^{-S, SNOWTEX ® ST-PS-} SO, SNOWTEX ® ST-OUP, SNOWTEX ® ST-UP, S-CHEMTECH 's SS-SOL 30SG, SS-SOL 30E, SS-SOL 30, SS-SOL 30F, SS-SOL SS-SOL 30E, SS-SOL 30OEAC, SS-SOL 30OMAC, SS-SOL 30OPAC, SS-SOL 20EG, SS-SOL 30EK and SS-SOL 30BK). In the alumina sol (NISSAN CHEMICAL's ^{ALUMINASOL TM AS-100, ALUMINASOL TM} AS-200, GerardKluyskens Co., Inc 's Ultra-Sol 200A, Ultra-Sol 201A / 60, Ultra-Sol 201A / 280, WESBOND 's Wesol A, Wesol C12, Wesol D30) and the like can be used.

The inorganic metal sol used for the surface treatment agent of the magnesium and magnesium alloy materials according to the present embodiment is not preferable because it can not form a sufficient film when the amount of the inorganic metal salt used is 5.0% by weight or less based on the total amount of the surface treatment agent, If the amount is more than 20% by weight, a disadvantage that the coating film is easily broken due to excessive coating film formation is not preferable. Therefore, it is preferably used in the range of 5.0 to 20 wt%, and more preferably 10 to 17 wt%, of the inorganic metal sol used for the surface treatment agent of the magnesium and magnesium alloy materials.

A rust preventive containing a metal is applied to the surface treatment agent of the magnesium and magnesium alloy materials according to the present embodiment. This is used for improving the weathering resistance and corrosion resistance of the coating film formed on the surfaces of the magnesium and magnesium alloy materials.

The rust inhibitor may include a phosphoric acid compound, a molybdenum compound, a vanadium compound, a cerium compound, a selenium compound, and the like. These may be used singly or in a mixture of two or more.

Dequests ^® 2000, Dequest ^® 2010, Dequest ^® 2066A, Dequest ^® 2016, Dequest ^® 2046, Dequest ^® 2060, Dequest ^® 2066, and Dequest ^® 2066 of Phosphoric Acid, ^{Dequest ® 2041, Dequest ® 2090,} Dequest ® Dequest ® 4066, Dequest ® 2054, Dequest ® 7000, CHErbsloh Corporation ^{CHE ® -COAT-CI L2, CHE} ® -COAT-CI L8AF, CHE ® -COAT-CI LAF 1, CHE ^® -COAT-CI LNF may be used 2 or the like. The molybdenum compounds zero _{Na 2 [Mo 2 (CO)} 10], Mo (CO) 6, Na [C 6 H 6 Mo], MoCl 2, Na 3 [Mo (CN)] 6, MoS 2, MoCl 5, MoF ₆ , (NH ₄ ) ₂ (MoO ₄ ), MoSi ₂ , MoO ₃ , (NH ₄ ) ₆ Mo ₇ O ₂₄ , and H ₃ PMo ₁₂ O ₄₀ . V2O5, VO2, Lithium vanadium oxide, Bismuth vanadate, Ammonium metavanadate, Sodium decavanadate, Sodium orthovanadate, Sodium metavanadate, Yttrium orthovanadate and the like can be used as the vanadium compounds. As selenium compounds, selenium dioxide, selenium trioxide, anhydrous potassium selenate, tetraselenium tetranitride, selenium tetrachloride, selenocyanates, zinc selenide, copper diselenide, indium diselenide, gallium diselenide and the like can be used. Cerium (IV) oxide, Ce (OH) 3, CeF3, CeCl3, CeBr3, CeI3, Cerium (III) oxide, Cerium (IV) sulfate, Ammonium cerium Etc. may be used.

The rust inhibitor applied to the surface treatment agent of the magnesium and magnesium alloy materials according to this embodiment is not preferable because the surface discoloration due to moisture occurs when the amount of the surface treatment agent is less than 0.05% by weight based on the total amount of the surface treatment agent, If the amount is more than 1.0% by weight, it is not preferable because it reduces the corrosion resistance. Therefore, the rust preventive applied to the surface treatment agent of the magnesium and magnesium alloy materials is preferably used in the range of 0.05 to 1.0 wt%, more preferably 0.1 to 0.5 wt%.

The water used for the surface treatment agent of the magnesium and magnesium alloy materials according to the present embodiment is used as a solvent for setting the concentration of each component constituting the surface treatment agent, It is preferable that the spare is used.

The surface treatment agent of magnesium and magnesium alloy according to another embodiment of the present invention may have a composition including a metal complex compound, an inorganic metal sol, a rust inhibitor, an organic solvent and water, preferably 1 to 10% by weight of a metal complex compound, 5 to 20% by weight of a sol, 0.05 to 1.0% by weight of an antirust agent, 1 to 10% by weight of an organic solvent, and excess water. The detailed description of the metal complex compound, the inorganic metal sol, and the black body applied to the surface treatment agent of this embodiment is disclosed in the detailed description of the present invention and is omitted in order to avoid duplication.

 The organic solvent used in this embodiment is an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentan-1-ol, 3-methylbutan- 2-ol, 2-methylbutan-2-ol, 1-hexanol, 2-hexanol-2- , 3-hexanol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,3-butanediol, 1,2-pentanediol, etohexadiol, diol, 2-methyl-2,4-pentanediol, 2-butoxyethanol and the like, which may be used alone or in admixture of two or more. The organic solvent applied in this embodiment is applied to uniformly apply the surface treating agent to the workpiece and to improve the drying speed of the coated film.

When the amount of the organic solvent is more than 10% by weight based on the total amount of the surface treating agent, the drying speed is too high, which is not preferable because a uniform film thickness can not be secured during the operation. Accordingly, the organic solvent to be used for the surface treatment agent of the magnesium and magnesium alloy materials is preferably used in the range of 1 to 10 wt%, and more preferably 2 to 8 wt%.

The pH of the surface treatment agent of the magnesium and magnesium alloy materials is preferably in the range of 0.5 to 6.0, more preferably in the range of 1.5 to 4.5. This is because when the pH is less than 0.5, the reaction rate is too fast to form a uniform film, and when the pH is 6.0 or more, sufficient surface etching is not performed and the oxide removal on the surface is insufficient, Because.

Hereinafter, a method of surface-treating magnesium and magnesium alloy materials using a surface treatment agent according to an embodiment of the present invention will be described.

The surface treatment process of general magnesium and magnesium alloy materials is carried out by preparing a magnesium and magnesium alloy material, followed by degreasing using the alkaline cleaning liquid, a first washing step of cleaning the alkali cleaning liquid applied in the degreasing step, A desmutting step of removing the smut generated on the surface of the workpiece due to the etching step; a second washing step of washing the cleaning liquid applied to the desmutting step; A chemical treatment step of forming a protective coating film of rustproofing property, a third water washing step of cleaning the surface treatment solution applied in the lyophilization treatment step, and a coating step of applying a luster after the sequential treatment.

However, in the present invention, it is possible to obtain the effect of performing the surface treatment process using the surface treatment agent of the present invention without treating the etching step, the desmutting step and the second washing step.

FIG. 1 is a process flow diagram illustrating a surface treatment method of a magnesium and magnesium alloy material according to an embodiment of the present invention.

1, a surface treatment method of magnesium and a magnesium alloy material will be described in detail. First, a magnesium and magnesium alloy material having a surface glossyened by a physical treatment method is prepared (S110)

Next, a conventional degreasing process is performed to remove the grease existing on the surfaces of the magnesium and magnesium alloy materials (S120)

Subsequently, a first washing step using water is performed to remove the cleaning liquid applied in the degreasing step (S 130)

In step S130, the first washing may be performed by a method such as dipping, spraying, or submerging, and may be performed using all kinds of water including deionized water, distilled water, pure water, and the like. However, it may be preferably carried out at a temperature range of 25 to 80 캜. This is because, when hot water is used, the water is washed more efficiently and the composition of dehydration drying is improved, so that the inflow of water into the next processing tank is minimized and the treatment liquid can be easily managed.

In addition, ultrasonic vibration may be applied to enhance the cleaning effect during the washing step.

Next, a surface treatment agent for magnesium and magnesium alloy of the present invention is prepared (S140)

In the step S140, the surface treatment agent of the present invention may have a composition comprising 1 to 5% by weight of an organic metal complex compound, 5 to 15% by weight of an inorganic metal sol, 0.1 to 2% by weight of an anticorrosive agent and extra water. As another example, the surface treatment agent of the present invention may contain a composition comprising 1 to 5% by weight of an organometallic complex, 5 to 15% by weight of an inorganic metal sol, 0.1 to 2% by weight of an antirust agent, 1 to 10% by weight of an organic solvent, Lt; / RTI > A detailed description of the surface treatment agent is given in the detailed description of the present invention and is omitted in order to avoid duplication.

Subsequently, a chemical conversion treatment is performed using the surface treatment agent to form a coating thin film (S150)

In step S150, the chemical conversion treatment using the surface treatment agent of the present embodiment removes oxides present on the surfaces of the magnesium and magnesium alloy materials, and simultaneously forms a coating thin film having excellent adhesion to the surface of the oxide- The etching process, the dismut process, and the like are not required in the process.

The surface treatment process of this embodiment can be performed by impregnating a magnesium and magnesium alloy material into a cleaning tank containing the surface treatment agent for about 5 to 30 seconds. At this time, the surface treatment agent effectively removes the oxides present in the material even at a normal temperature, and a coating thin film having excellent rustproofing property can be formed on the surface.

Subsequently, the second water washing step is performed to remove the surface treatment agent remaining on the work surface (S160)

Subsequently, the surface-treated material is subjected to a heat treatment process as required (S170)

In step S170, the heat treatment process is performed to improve the gloss of the magnesium and magnesium alloy materials that have been chemically treated using the surface treatment agent of the above embodiment. The condition of the heat treatment process can be maximized when the material is left at a temperature of 100 to 300 DEG C for 30 to 600 seconds.

 Hereinafter, the present invention will be described in detail with reference to the following examples.

However, the scope of the present invention is not limited by the examples given below, and the amounts used refer to weight% unless otherwise stated.

≪ Example 1 >

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 3.50 Hexafluorotitanic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.10 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 74.30 Deionized water

The surface treatment compositions of magnesium and magnesium alloy materials were prepared with the ingredients and contents as shown in Table 1, and the pH of the surface treatment composition was adjusted to 1.7.

≪ Example 2 >

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 3.50 Hexafluorozirconic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.10 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 74.30 Deionized water

The surface treatment compositions of magnesium and magnesium alloys were prepared with the components and contents shown in Table 2, and the pH of the surface treatment composition was adjusted to 1.7.

≪ Example 3 >

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 3.50 Hexafluorotitanic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.20 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 74.20 Deionized water

The surface treatment composition of the magnesium and magnesium alloy materials was prepared by the ingredients and the contents as shown in Table 3, and the pH of the surface treatment composition was adjusted to 1.7.

<Example 4>

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 3.50 Hexafluorozirconic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.20 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 74.20 Deionized water

The surface treatment compositions of magnesium and magnesium alloy materials were prepared by the ingredients and contents as shown in Table 4, and the pH of the surface treatment composition was adjusted to 1.7.

&Lt; Comparative Example 1 &

Magnesium and magnesium alloys were prepared on the surfaces of the magnesium and magnesium alloys without any surface treatment.

&Lt; Comparative Example 2 &

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 0 Hexafluorozirconic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.10 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 77.80 Deionized water

The surface treatment compositions of magnesium and magnesium alloys were prepared with the components and contents as shown in Table 5, and the pH of the surface treatment composition was adjusted to 1.7.

&Lt; Comparative Example 3 &

Surface treatment agent Composition component Content (% by weight) Raw material name Metal complexes 1 3.50 3-Methacryloxypropyltrimethoxysilane Metal complex compound 2 8.50 Hexafluorotitanic acid solution (50 wt.% In H2O) Inorganic metal sol 15.00 SNOWTEX ^® ST-O Rust inhibitor 1 0.10 Cerium (IV) oxide Rust inhibitor 2 0.10 Mo (CO) ₆ Organic solvent 3.50 Ethyl alcohol water 69.3 Deionized water

The surface treatment compositions of magnesium and magnesium alloys were prepared by the ingredients and the contents shown in Table 6, and then the pH of the surface treatment composition was adjusted to 1.7.

Salt spray test of chemical treated material

AZ31 material (POSCO, 1.0T), a magnesium alloy material, was immersed in water for 5 seconds, dried, and heat-treated at 300 ° C for 1 minute using a surface treatment agent prepared by the blending of the examples and comparative examples. Spray test was carried out. After the chemical treatment, the oil-based acrylic paint was coated by a spray method to a thickness of 20 μm, dried at 130 ° C. for 30 minutes, and then subjected to a salt spray test for 120 hours. In order to measure the rust resistance of the coating film, the degree of rust formation was measured after salt spray test according to KS D 9502, and the degree of rust development was evaluated in accordance with ASTM D610. The results are shown in Table 7.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Chemically treated material
SST 24h 6 8 7 8 0 0 2 Spray material
SST 120h 10 10 10 10 One 2 7

In Table 7, SST 24h represents the salt spray test and Salt Spray Test 24 hours, and SST 120h represents the salt spray test and Salt Spray Test 120 hours.

The results shown in Table 7 show that Examples 1, 2, 3, and 4 have good corrosion resistance as compared with Comparative Examples, and particularly excellent corrosion resistance as compared with Comparative Example 1 in which no conversion treatment is performed. Also, it can be confirmed that the material subjected to the spray coating did not generate rubbing on the surface even after 120 hours of the salt spray test.

Appearance test of chemically treated material

AZ31 as a magnesium alloy material (POSCO, manufactured by POSCO, 1.0T) was immersed for 5 seconds, washed with water, dried at 300 ° C for 1 minute, and then subjected to heat treatment at a temperature of 300 ° C for 1 minute using a surface treatment agent prepared by mixing the above- Were compared. The gloss of the treated material was measured using a micro-TRI-gloss gloss meter BYK-Gardner GmbH and the whiteness (L) and yellowness (a) were measured using a ColorEyeⓡ XTH colorimeter from gretagmacbeth. The higher the gloss, the higher the whiteness, and the lower the yellowness, the better the color of the material.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Gloss (60 [deg.]) 411 417 388 310 378 305 330 Whiteness (L) 86.70 87.96 86.26 88.96 85.83 70.65 81.76 Yellowness (a) 0.97 0.93 3.27 -0.86 7.28 8.34 9.28

From the results shown in Table 8, it can be confirmed that the appearance evaluation results of Examples 1 and 2 are superior to those of other samples.

Constant temperature and humidity test of harmful material

Magnesium and magnesium alloy materials are exposed to high temperature and high humidity conditions for a long time to check the discoloration and corrosion of the material. They are put into a chamber where the temperature can be maintained at 60 ℃ and humidity can be maintained at 90% An experiment was conducted to confirm the color difference (? E) by comparing with the color before injection. The results are shown in Table 9.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 ΔE 3.93 1.22 3.06 2.97 15.45 12.05 11.30

From the results shown in Table 9, it can be confirmed that the converted magnesium alloy materials of Examples 2 and 4 have a good color difference (DELTA E) as compared with the comparative example. Compared with Comparative Example 1, which was not treated with a chemical conversion treatment, it was confirmed that a very excellent high temperature and high humidity resistance was secured.

As described above, when the magnesium and magnesium alloy materials are chemically treated using the surface treatment agent prepared using the formulation of the above-mentioned embodiment, the chemical treatment film having excellent physical properties without performing the conventional degreasing, etching and desmutting processes Can be secured.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.

Claims (10)

In the surface treatment agent applied to the surface treatment of magnesium and magnesium alloy materials,
1 to 10% by weight of two kinds of metal complex compounds containing a silane-based coupling agent and a titanium-based coupling agent or containing a silane-based coupling agent and a zirconium-based coupling agent;
5 to 20% by weight of at least one inorganic metal sol selected from the group consisting of silica sol, alumina sol, titania sol and zirconia sol;
0.05 to 1.0% by weight of at least one rust inhibitor selected from the group consisting of phosphoric acid-based rust inhibitors, aluminum salt-based rust inhibitors, molybdenum salt-based rust inhibitors, fluorine-based rust inhibitors, vanadium salt-based rust inhibitors, cerium salt-based rust inhibitors and selenium salt-based rust inhibitors; And
A surface treatment agent for magnesium and magnesium alloy materials, which comprises an excess of water. delete The method of claim 1, wherein the silane-based coupling agent is a silicon-containing metal compound selected from the group consisting of Vinyltrimethoxysilane, Vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane, 3-Glycidoxypropyl-trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- wherein the titanium-based coupling agent is at least one selected from the group consisting of aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy silane, 3-Mercaptopropyl trimethoxysilane and (3-ACRYLOXYPROPYL) TRIMETHOXYSILANE, 2-propanolato, tris isooctadecanoato-O, Titanium IV bis 2-methyl-2-propenoate-O, Tetecanoato-O 2-propanolato, Titanium IV 2-propanolato, tris (dodecyl) benzenesulfanato-O, Titanium IV 2-propanolato, tris (dioctyl) phosphato-O, Titanium IV, tris , methoxydiglycolylato, Titanium IV 2-propanolato, tris (dioctyl) pyrophosphato-O, Titanium IV, tris (2-propenoato-O), methoxydiglycolylato-O, Titanium IV is (dioctyl) pyrophosphato-O, oxoethylenediolato, (2-propenolatomethyl) butanolato, tris (dioctyl) phosphato-O, Titanium IV bis (butylmethyl) pyrophosphato-O, hexafluoro titanic acid, IV bis 2,2 (bis 2-propenolatomethyl) butanolato, tris (dioctyl) pyrophosphato-O, propenolatomethyl) butanolato, tris (3-amino) phenylato, Titanium IV bis octanolato, cyclo (dioctyl) pyrophosphato-O, O, Titanium IV bis cyclo Wherein the zirconium-based coupling agent is selected from the group consisting of Zirconium IV 2. 2-dimethyl 1,3 propanediolato, bis (dioctyl) pyrophosphato-O, (adduct) 2 moles N, N-dimethylamino- alkyl propenoamide, Zirconium IV (2-ethyl, 2-propenolatomethyl) 1,3-propanediolato, cyclo bis 2-dimethylamino pyrophosphato-O, adduct with 2 moles of methanesulfonic acid, Zirconium tetrakis 2,2 , adduct with 2 moles of di-tridecyl, hydrogen phosphite, hexafluoro zirconic acid, Zirconium IV 2-ethyl, 2-propenolatomethyl 1,3-propanediolato, cyclo di 2,2 bisnitrophenolato- , Zirconium IV bis 2-ethylhexanolato, cyclo (di 2-ethylhexyl) pyrophosphato, Zirconium IV 2,2 bis-2-propenolatomethyl butanolato, tris neodecanolato- dodecyl) benzenesulfonato-O &lt; / RTI &gt; Surface treatment of magnesium and magnesium alloy material according to Jing. delete delete The surface treatment agent for a magnesium and magnesium alloy material according to claim 1, further comprising 1 to 10% by weight of an alcohol-based or glycol-based organic solvent. The surface treatment agent for a magnesium and magnesium alloy material according to claim 1, wherein the pH is 0.5 to 6.0. Preparing a magnesium and magnesium alloy material subjected to a degreasing process and a coating film for removing oxides present on the magnesium and magnesium alloy material by using a surface treatment agent to maintain the gloss of the material, Forming step,
The surface treatment agent may contain 1 to 10% by weight of two kinds of metal complex compounds containing a silane-based coupling agent and a titanium-based coupling agent or containing a silane-based coupling agent and a zirconium-based coupling agent, silica sol, alumina sol, titania sol and zirconia sol 5 to 20% by weight of at least one inorganic metal salt selected from the group consisting of at least one rust inhibitor selected from the group consisting of a phosphoric acid-based rust inhibitor, an aluminum salt-based rust inhibitor, a molybdenum salt-based rust inhibitor, a fluorinated rust inhibitor, a vanadium salt- 0.05 to 1.0% by weight, and an excess of water. The surface treatment method of magnesium and magnesium alloy material according to claim 1, The surface treatment of magnesium and magnesium alloy according to claim 8, wherein the surface treatment of the workpiece is performed by impregnating the workpiece with the surface treatment agent having a temperature of 15 to 30 캜 for 5 to 60 seconds. Way. The surface treatment method of claim 8, wherein the surface treatment agent further comprises 1 to 10% by weight of an alcohol-based or glycol-based organic solvent.

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