KR20090051583A - Etching and surface treating material for mg and mg alloy - Google Patents

Etching and surface treating material for mg and mg alloy Download PDF

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Publication number
KR20090051583A
KR20090051583A KR1020070118043A KR20070118043A KR20090051583A KR 20090051583 A KR20090051583 A KR 20090051583A KR 1020070118043 A KR1020070118043 A KR 1020070118043A KR 20070118043 A KR20070118043 A KR 20070118043A KR 20090051583 A KR20090051583 A KR 20090051583A
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KR
South Korea
Prior art keywords
magnesium
acid
etching
surface treatment
treatment agent
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KR1020070118043A
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Korean (ko)
Inventor
김병욱
김성배
이성현
허현
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주식회사 동진쎄미켐
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Priority to KR1020070118043A priority Critical patent/KR20090051583A/en
Publication of KR20090051583A publication Critical patent/KR20090051583A/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/22—Acidic compositions for etching magnesium or alloys thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The present invention relates to etching and surface treatment agents of magnesium and magnesium alloys, in particular, exhibits etching performance on the surface of magnesium and magnesium alloys, does not generate black smut during etching, easy to control the surface etching rate, etching At the same time it can improve the metal gloss of the surface of magnesium and magnesium alloy, easy to control the surface gloss and texture of the surface, and relates to magnesium and magnesium alloy etching and surface treatment agent does not generate harmful heavy metals to the environment.

Magnesium, magnesium alloy, etchant, surface treatment agent, photolithography

Description

 Etching and Surface Treatment Agent of Magnesium and Magnesium Alloy {ETCHING AND SURFACE TREATING MATERIAL FOR Mg AND Mg ALLOY}

The present invention relates to etching and surface treatment agents of magnesium and magnesium alloys, in particular, exhibits etching performance on the surface of magnesium and magnesium alloys, does not generate black smut during etching, easy to control the surface etching rate, etching At the same time it can improve the metal gloss of the surface of magnesium and magnesium alloy, easy to control the surface gloss and texture of the surface, and relates to magnesium and magnesium alloy etching and surface treatment agent does not generate harmful heavy metals to the environment.

Magnesium (Mg) is the eighth most abundant element in the earth's crust and the third richest in seawater and can be extracted from ore and seawater.Mg alloys are lightweight, have high specific strength, exhibit excellent dimensional stability, and workability. It has good heat, high electrical conductivity and vibration absorption, and excellent electromagnetic shielding effect, so that it is widely used in various fields such as home appliances, automobile parts, computers, aircraft parts, communication devices, office equipment, and sporting goods. In particular, the interest in magnesium and magnesium alloys are increasing as a substitute for aluminum having poor mechanical properties, poor recycling, poor electromagnetic shielding, and poor workability.

Magnesium and magnesium alloys have low corrosion resistance and are corroded by water or chemicals. For this reason, magnesium and magnesium alloys are subjected to surface treatment such as chemical conversion or anodization for the purpose of corrosion protection. However, such a surface treatment is helpful in improving the corrosion resistance, but had a problem of significantly lowering the original gloss of magnesium and magnesium alloy.

In addition, in order to design a pattern or shape on the surface of magnesium and magnesium alloy, when the surface is etched by applying a photolithography process, black smuts are severely generated. There was a hassle of having to go through a separate process such as a surface treatment agent disclosed in Japanese Patent Laid-Open No. 2004-149911 to improve the glossiness or to improve the glossiness.

In order to solve the problems of the prior art as described above, the present invention shows the etching performance for the magnesium and magnesium alloy surface, does not generate black smut during etching, easy to control the surface etching rate, at the same time magnesium And it is to provide a magnesium and magnesium alloy etching and surface treatment agent to improve the metal gloss on the surface of the magnesium alloy, easy to control the surface gloss and texture, and does not generate heavy metals harmful to the environment.

Another object of the present invention is to provide a method for treating the surface of magnesium and magnesium alloy by applying the surface treatment agent.

In order to achieve the above object, the present invention

a) 0.5 to 25 weight percent dicarboxylic acid;

b) 0.1 to 10% by weight of inorganic acid;

c) 0.1 to 10 wt% peroxide; And

d) remaining water

It provides an etching and surface treatment agent of magnesium and magnesium alloy comprising a.

The present invention also provides an etching and surface treatment agent of magnesium and magnesium alloy, characterized in that it further comprises 0.1 to 50 parts by weight of the glycol compound with respect to 100 parts by weight of the etching and surface treatment agent of magnesium and magnesium alloy.

In another aspect, the present invention provides a surface treatment method of magnesium or magnesium alloy, characterized in that using the etching and surface treatment agent.

In another aspect, the present invention provides a magnesium or magnesium alloy characterized in that the surface treatment by the surface treatment method.

Magnesium and magnesium alloy etching and surface treatment agent of the present invention exhibits etching performance on the surface of magnesium and magnesium alloy, does not cause black smut during etching, easy to control the surface etching rate, and at the same time etching and magnesium It can improve the metal gloss of the alloy surface, it is easy to control the surface gloss and texture of the surface, and does not generate heavy metals harmful to the environment can be very useful for the surface processing of magnesium.

Hereinafter, the present invention will be described in detail.

The etching and surface treatment agents of magnesium and magnesium alloys of the present invention include: a) 0.5 to 25% by weight of dicarboxylic acid; b) 0.1 to 10% by weight of inorganic acid; c) 0.1 to 10 wt% peroxide; And d) residual amount of water.

In the present invention, the a) dicarboxylic acid acts to improve the surface etching and glossiness of magnesium and magnesium alloy, less black spots occur during etching, and it is easy to control the glossiness and etching rate. Preferably, the dicarboxylic acid may be a substance selected from the group consisting of succinic acid, oxalic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, maleic acid and fumaric acid, more preferably oxalic acid. Good to do.

In the present invention, the dicarboxylic acid is preferably included in an amount of 0.5 to 25% by weight. When the content of the dicarboxylic acid is less than 0.5% by weight, the etching rate is slow, there is a fear that the glossiness of the metal surface may fall, and when it exceeds 25% by weight, it may be difficult to control the etching rate. Preferably it is included 1 to 10% by weight.

  In addition, in the present invention, the b) the inorganic acid is very difficult to control the etching rate of the black spots when used alone, it is very difficult to control the etching rate, when used in combination with the dicarboxylic acid to improve the etching and glossiness, the etching and glossiness It is easy to adjust. The inorganic acid is preferably used at least one substance selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid, more preferably sulfuric acid.

In the present invention, the inorganic acid is preferably included in an amount of 0.1 to 10% by weight. When the content of the inorganic acid is less than 0.1% by weight, the etching rate is lowered, the surface gloss may be lowered, and when the content of the inorganic acid exceeds 10% by weight, it may be difficult to control the etching rate. Preferably from 1 to 5% by weight.

In the present invention, the peroxide (peroxide) to form a film on the surface of the magnesium and magnesium alloy to increase the gloss and at the same time to control the etching rate, the microscopic stain not observed with the naked eye or visible To remove the role. In the present invention, the peroxide is preferably at least one selected from the group consisting of hydrogen peroxide, alkyl peroxide having 1 to 10 carbon atoms, benzyl peroxide and urea hydrogen peroxide, more preferably It is recommended to use hydrogen peroxide.

In the present invention, the peroxide is preferably included in an amount of 0.1 to 10% by weight. When the content of the peroxide is less than 0.1% by weight, the metal surface may be blurred, the glossiness may not be removed, and black stains may not be removed. When the content of the peroxide is greater than 10% by weight, the etching rate may be slow and the surface gloss may be degraded. . It is preferable to use 1 to 5% by weight.

The present invention also includes d) water in the residual amount together with the above components of the etching and surface treatment agents of magnesium and magnesium alloys. As the water, it is preferable to use ultrapure water.

In addition, the etching and surface treatment agent of the magnesium and magnesium alloy of the present invention may further comprise e) glycol compound with the above components. When the glycol compound is included, the etching and surface treatment agents of the magnesium and magnesium alloys of the present invention increase the etching rate, and the glossiness is further improved.

The glycol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether And diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether.

Preferably, the glycol compound may be included in an amount of 0.1 to 50 parts by weight, and more preferably 5 to 40 parts by weight, based on 100 parts by weight of the etching and surface treatment agent of the present invention. Within the above range, the etching and glossiness is excellent, and the etching rate is easily controlled.

In addition, the etching and surface treatment agents of the magnesium and magnesium alloy of the present invention may further include additives commonly used in etching and surface treatment agents in the art.

In another aspect, the present invention provides a method of surface treatment of magnesium or magnesium alloy and the magnesium or magnesium alloy surface-treated by the method, characterized in that using the etching and surface treatment agent.

The surface treatment method of the magnesium or magnesium alloy of the present invention is made by contacting the etching and surface treatment agent to the magnesium or magnesium alloy, and the surface of the magnesium or magnesium alloy is etched in a single treatment and at the same time exhibits excellent glossiness. . In particular, when the photolithography process is applied to form a specific pattern or design on the surface of magnesium or magnesium alloy, etching and polishing may be performed in one step, and thus may be usefully used.

In the surface treatment method of the present invention, the metal to be treated is magnesium or a magnesium alloy. The magnesium alloy may include, for example, Mg-Al-Zn-based alloys, Mg-Zn-Zr-based alloys, Mg-Al-based alloys, Mg-rare earth element-based alloys, and the like.

In addition, the contact method of the metal and the surface treatment agent in the surface treatment method of the present invention is not particularly limited, and may be used, such as dipping, spraying by spray, coating by a roll coater, and the like, and preferably by dipping.

In addition, it is possible to further improve the glossiness when combined with ultrasonic treatment, bubbling treatment, and agitation during surface treatment following immersion.

Referring to the surface treatment method including a photolithography process to form a specific shape in the magnesium or magnesium alloy in the present invention as a specific example as follows.

Apply a photoresist on the surface of magnesium or magnesium alloy to form a specific shape, dry it (soft baking) at 90 to 120 ° C., expose it by irradiation with ultraviolet rays, develop it, and perform hard baking at 110 to 140 ° C. Then, the etching and surface treatment agent of the present invention is etched according to the desired shape, and the photosensitive liquid remaining on the metal surface is stripped. The hard baking process may be skipped in some cases and may be treated with the etching and surface treatment agent of the present invention immediately after exposure.

The surface treatment method of the present invention can improve the etching and glossiness of magnesium and magnesium alloy in one treatment, and thus can be used very usefully in the industry. In particular, the electronic products and communication requiring ultra-light weight, electromagnetic shielding and dimensional stability It can be usefully used in the outer frame of a device, a computer, or a vehicle.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

Magnesium etching and surface treatment agents were prepared by mixing 4% by weight of oxalic acid, 1.5% by weight of sulfuric acid, 3% by weight of hydrogen peroxide and the balance of ultrapure water.

Example 2-15

According to the ingredients and contents shown in Table 1 below, magnesium etching and surface treatment agents were prepared. In Table 1, the unit is dicarboxylic acid, inorganic acid, and peroxide is the weight%, dicarboxylic acid, inorganic acid, peroxide and ultrapure water is 100% by weight in total, the units of glycol compounds 1 and 2 are the dicarboxylic acid, inorganic acid, peroxide and It is weight part with respect to a total of 100 weight part of ultrapure water.

TABLE 1

Example Dicarboxylic acid  Inorganic acids peroxide Ultrapure water Glycol Compound 1 Glycol Compound 2 2 Oxalic acid 4 Sulfuric acid 1.5 H 2 O 2 2 Remaining amount EG 10 3 Oxalic acid 6 Sulfuric acid 2.5 H 2 O 2 2 Remaining amount EG 20 4 Oxalic acid 8 Sulfuric acid 4 H 2 O 2 2 Remaining amount EG 30 5 Oxalic acid 4 Sulfuric acid 1.5 H 2 O 2 3 Remaining amount EG 30 BDG 5 6 Oxalic acid 4 Sulfuric acid 1.5 H 2 O 2 5 Remaining amount EG 30 BDG 5 7 Oxalic acid 4 Sulfuric acid 1.5 H 2 O 2 5 Remaining amount EG 30 TEG 5 8 Oxalic acid 4 Sulfuric acid 1.5 H 2 O 2 3 Remaining amount EG 30 MDG 5 9 Malonic acid 4 Sulfuric acid 1.5 H 2 O 2 3 Remaining amount EG 10 10 Succinic acid 4 Sulfuric acid 1.5 H 2 O 2 2 Remaining amount EG 10 11 Oxalic acid 4 nitric acid 1.5 H 2 O 2 2 Remaining amount EG 10 12 Oxalic acid 4 Hydrochloric acid 1.5 H 2 O 2 2 Remaining amount EG 10 13 Oxalic acid 4 Phosphoric Acid 1.5 H 2 O 2 2 Remaining amount EG 10 14 Oxalic acid 4 Sulfuric acid 1.5 MP 2 Remaining amount EG 10 15 Oxalic acid 4 Sulfuric acid 1.5 UHP 2 Remaining amount EG 10

In Table 1, EG is ethylene glycol, BDG is diethylene glycol monobutyl ether, TEG is triethylene glycol, MDG is diethylene glycol monomethyl ether, MP is methyl hydrogen peroxide, and UHP is urea hydrogen peroxide. Indicates.

For Examples 1 to 15, the etching rate, the gloss, and the degree of smut generation for the magnesium alloy were tested. Experimental method was washed with magnesium alloy (AZ31B rolled plate, 10 cm × 5 cm × 0.6 mm) to remove foreign substances such as organic matter, and then immersed for 5 minutes at room temperature with the etching and surface treatment agents of Examples 1 to 15. After washing with pure water and drying with nitrogen gas, the etching rate, surface gloss, and smut occurrence were determined and shown in Table 2 below. In Table 2, staining was confirmed by rubbing with the naked eye and by hand, and the criterion of etching rate and gloss was as follows.

-Etch Speed Criteria

Slow: less than 500 μm / min

Somewhat slow: 500-800 μm / min

Medium: 800-1400 μm / min

Fast: 1400-2000 μm / min

Very fast> 2000 μm / min

-Gloss criteria

×: Glossiness not recognized

△: gloss very cloudy

○: gloss slightly cloudy

◎: Very good gloss

TABLE 2

Example Etching speed Polish smut One Somewhat slow ◎ radish 2 usually ◎ radish 3 speed ◎ radish 4 Very fast ◎ radish 5 Very fast ◎ radish 6 Very fast ○ radish 7 Very fast ◎ radish 8 Very fast ◎ radish 9 usually ◎ radish 10 usually ○ radish 11 usually ○ radish 12 usually ○ radish 13 usually ○ radish 14 usually ○ radish 15 usually ○ radish

As shown in Table 2, the etching and surface treatment agents of Examples 1 to 15 of the present invention were confirmed to exhibit the etching and gloss on the surface of the magnesium alloy without smut generation in one treatment.

Claims (9)

a) 0.5 to 25 weight percent dicarboxylic acid; b) 0.1 to 10% by weight of inorganic acid; c) 0.1 to 10 wt% peroxide; And d) remaining water Etching and surface treatment agent of magnesium and magnesium alloy comprising a. The method of claim 1, Etching and surface treatment of magnesium and magnesium alloys, characterized in that it further comprises 0.1 to 40 parts by weight of the glycol compound with respect to 100 parts by weight of the etching and surface treatment agent of magnesium and magnesium alloy. The method of claim 1, The dicarboxylic acid is an etching and surface treatment agent of magnesium and magnesium alloys, characterized in that at least one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, malonic acid, maleic acid and fumaric acid. The method of claim 1, The inorganic acid is an etching and surface treatment agent of magnesium and magnesium alloys, characterized in that at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid. The method of claim 1, The peroxide is an etching and surface treatment agent of magnesium and magnesium alloys, characterized in that at least one selected from the group consisting of hydrogen peroxide, alkyl peroxide having 1 to 10 carbon atoms, benzyl peroxide and urea hydrogen peroxide (urea hydrogen peroxide) . The method of claim 2, The glycol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether And at least one member selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether. Treatment agent. The surface treatment method of magnesium or magnesium alloy using the etching and surface treatment agent of any one of Claims 1-6. Magnesium or magnesium alloy characterized in that the surface treatment by the surface treatment method of claim 7. The method of claim 8, The magnesium or magnesium alloy is magnesium or magnesium alloy, characterized in that the outer frame of the electronics, communication devices, computers, or automobiles.
KR1020070118043A 2007-11-19 2007-11-19 Etching and surface treating material for mg and mg alloy KR20090051583A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109112543A (en) * 2017-06-22 2019-01-01 三星显示有限公司 Etching composition and method for forming wiring using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109112543A (en) * 2017-06-22 2019-01-01 三星显示有限公司 Etching composition and method for forming wiring using the same
US11384437B2 (en) 2017-06-22 2022-07-12 Samsung Display Co., Ltd. Etchant composition and forming method of wiring using etchant composition

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