KR102298998B1 - Organic coating agent for surface treatment of plating layer containing copper and surface treatment of plating layer using the same - Google Patents

Abstract

The present invention relates to: an organic coating agent having excellent rust prevention, heat resistance, and solderability to prevent corrosion by forming an organic film on the surface of a plating layer containing copper and/or copper alloy through a chemical reaction in order to prevent surface oxidation in corrosive or high-temperature environments due to exposure to the atmosphere, such as copper wiring of printed circuit boards mounted with electronic components, electronic equipment parts, and communication equipment products; and a method for surface treatment of the plating layer using the same.

Description

Organic coating agent for surface treatment of plating layer containing copper and surface treatment of plating layer using the same}

The present invention relates to a plating layer containing copper and/or a copper alloy in order to prevent surface oxidation in a corrosive environment or high-temperature environment by exposure to the atmosphere such as copper wiring of a printed circuit board mounted with electronic components, electronic device parts, and communication device products. It relates to an organic coating agent having a coating excellent in rust prevention, heat resistance, and solderability, which prevents corrosion by forming an organic coating film on the surface by a chemical reaction, and a method for surface treatment of a plating layer using the same.

In order to improve the mounting density of printed wiring boards constituting circuits constituting wiring boards used in electronic device components and communication devices, surface mounting of chip components with paste solder and through-hole mounting of individual components mount), but since the printed wiring board is soldered multiple times, it is exposed to high temperatures and receives a lot of heat at that time. Since the surface of the metal is heated and the formation of an oxide film is promoted, the solderability of the surface of the metal conductive part cannot be maintained satisfactorily.

In order to protect the metal conductive part of such a printed wiring board from oxidation in the air, a process of forming a chemical layer on the surface of the metal conductive part is widely used. It is calculated|required to protect the metal conductive part without it, and to maintain solderability favorable by this.

The circuit constituting the wiring board used in electrical products or electric parts uses copper or copper alloy. It is well known to form an organic film on copper and copper metal alloy parts for this purpose.

However, with respect to the organic coating agent used to prevent oxidation of metal surfaces such as copper, copper alloy, and silver in the metal conductive part, it has excellent heat resistance and causes a chemical reaction with copper and copper alloy parts. It is required to form a film on the

Republic of Korea Patent Publication No. 10-2015-0085542 (published on July 24, 2015)

In order to solve the above problems, an object of the present invention is to provide an organic coating agent having excellent heat resistance, excellent heat resistance of copper and copper alloy by heating, and excellent rust prevention effect of preventing rust on the coated metal surface.

In order to solve the above problems, the organic coating agent of the present invention includes a benzimidazole-based compound represented by the following Chemical Formula 1, an organic acid, a metal compound, an organic solvent, a chelating agent, a wetting agent, a pH adjusting agent, and water.

[Formula 1]

In Formula 1, R ¹ is a C ₁ to C ₁₀ straight-chain alkyl group, a phenyl group, a chlorophenyl group, a 2-ethylphenyl group, a benzyl group, a 2,4-dichlorobenzyl group, a 2,4-dichlorophenoxy group, 2,4 - a dichloronaphthoxy group or a phenylethyl group, and R ² is a hydrogen atom, a halogen atom, or a C ₁ to C ₅ straight-chain alkyl group.

In addition, the present invention relates to a method for surface treatment of a copper and/or copper alloy-containing plating layer, wherein the surface of a metal article including a copper-containing plating layer is coated with the organic coating agent of any one of claims 1 to 9, It can be dried to form a film.

As used herein, the term “copper-containing plating layer” refers to a plating layer including copper and/or a copper alloy.

The organic coating agent of the present invention has excellent heat resistance, provides good heat resistance to copper and copper alloy-containing metal products by heating, and has very excellent coating power, so it has very excellent anti-rust effect and solderability to prevent rust on the metal surface.

Hereinafter, the organic coating agent of the present invention will be described in more detail.

The organic coating agent of the present invention includes a benzimidazole-based compound, an organic acid, a metal compound, an organic solvent, a chelating agent, a wetting agent, a pH adjusting agent, and water.

In the composition of the organic coating agent of the present invention, the benzimidazole-based compound may include a compound represented by the following Chemical Formula 1.

[Formula 1]

^{R 1} of Formula 1 is a C ₁ ~ C ₁₀ straight-chain alkyl group, a phenyl group, a chlorophenyl group, a 2-ethylphenyl group, a benzyl group, a 2,4-dichlorobenzyl group, a 2,4-dichlorophenoxy group, 2,4-dichloro naphthoxy group or phenylethyl group, preferably chlorophenyl group, 2,4-dichlorobenzyl group, 2,4-dichlorophenoxy group or 2,4-dichloronaphthoxy group, more preferably 2,4-dichlorobenzyl group group or a 2,4-dichlorophenoxy group.

And, R ² in Formula 1 is a hydrogen atom, a halogen atom, or a C ₁ to C ₅ straight-chain alkyl group, preferably a hydrogen atom or —Cl.

In the composition of the present invention, the benzimidazole-based compound forms a thin film on the metal surface through coordination with copper and/or copper alloy in the metal, and the benzimidazole-based compound represented by the following formula (1) is used. . In addition, the content of the benzimidazole-based compound in the total weight of the preflux of the present invention is 0.5 to 5.0 wt%, preferably 1.5 to 4.5 wt%, and more preferably 2.5 to 3.8 wt%. At this time, if the content of the benzimidazole-based compound is less than 0.5% by weight, the rate of forming a film on the metal surface is slow, and the thickness of the film is thin, so it may not be possible to sufficiently prevent oxidation of the metal surface, and exceeding 5.0% by weight At the very least, the film thickness is formed unnecessarily thick, and on the contrary, solderability may deteriorate and stickiness may occur, so it is preferable to use it within the above range.

In the composition of the organic coating agent of the present invention, the organic acid chlorinates the benzimidazole-based compound and stably dissolves it in water. Acetic acid, formic acid, citric acid, adipic acid ( adipic acid), oxalic acid, lactic acid, and propionic acid may include at least one selected from, preferably citric acid, adipic acid, oxalic acid, lactic acid, and propionic acid. It may include one or more, more preferably, it may include one or more selected from oxalic acid, lactic acid and propionic acid. In addition, the content of the organic acid in the total weight of the organic coating agent is 10.0 to 50.0 wt%, preferably 30.0 to 50.0 wt%, and more preferably 40.0 to 48.0 wt%. At this time, if the organic acid content is less than 10.0% by weight, the solubility may be insufficient and precipitation of the benzimidazole-based compound may occur. If the organic acid content exceeds 50.0% by weight, alkali must be added to adjust the pH, which leads to poor stability of the organic coating agent and reduced physical properties of the formed coating, so it is preferable to use it within the above range.

The metal compound in the composition of the organic coating agent of the present invention is added to increase the film formation rate and heat resistance on metal by controlling the concentration of metal ions. Copper chloride, iron chloride, copper sulfate, iron sulfate, copper oxide, iron oxide, zinc oxide, It may include at least one selected from zinc chloride and zinc sulfate, and preferably includes at least one selected from iron chloride, iron sulfate, and iron oxide. In addition, the content of the metal compound in the total weight of the organic coating agent is 0.2 to 3.0% by weight, preferably 0.6 to 2.2% by weight, and more preferably 1.0 to 1.6% by weight. At this time, if the content of the metal compound in the total weight of the organic coating agent is less than 0.2% by weight, there may be a problem that the heat resistance of the coating is not sufficient, and if it exceeds 3.0% by weight, foreign substances may occur around the coating. good.

In the composition of the organic coating agent of the present invention, the organic solvent is used together with an organic acid to increase the solubility of the benzimidazole-based compound and the pyridine-based compound in water and to improve the solubility stability. Preferably, the organic solvent may include one or more selected from butoxyethanol, ethoxyethanol and ethylene glycol, and preferably, one or more selected from ethoxyethanol and ethylene glycol. And, the content of the organic solvent in the total weight of the organic coating agent is 5.0 to 15.0 wt%, preferably 10.0 to 15.0 wt%, more preferably 12.0 to 15.0 wt%. At this time, if the content of the organic solvent is less than 5.0 wt%, the solubility of the benzimidazole-based compound in water may be poor and the dissolution time may be too long, and if it exceeds 15.0 wt%, it is uneconomical, and rather Since the viscosity is too low, there may be a problem of poor coating properties when forming a film.

In the composition of the organic coating agent of the present invention, the chelating agent is used to prevent staining of the coating layer formed on the surface of the plating layer and to form a uniform film. Ethylenediaminetetraacetic acid, Tetrahydroxypropylethylendiamine, It may include at least one selected from Nitrilotriacetic acid, Glycine and Glycolic acid, preferably ethylenediaminetetraacetic acid, tetrahydroxypropylethylenediamine and nitrilo It may include one or more selected from triacetic acid, and more preferably, one or more selected from ethylenediaminetetraacetic acid and tetrahydroxypropylethylenediamine. And, the content of the chelating agent in the total weight of the organic coating agent is 0.1 to 5.0% by weight, preferably 0.5 to 4.0% by weight, more preferably 1.0 to 3.0% by weight, in this case, if the content of the chelating agent is less than 0.1% by weight, the amount used Since the amount is too small, it may not be possible to obtain a uniform formation or stain prevention effect of the film, and if it is used in excess of 5.0% by weight, there may be a problem that the film is not evenly formed on the surface of the film, so it is recommended to use it within the above range.

In the composition of the organic coating agent of the present invention, the wetting agent serves to improve the wettability of the surface of the plating layer containing copper and/or copper alloy and the coating power of the organic coating agent. Nonionic surfactants, cationic surfactants and anionic surfactants It may include at least one selected from active agents, preferably, it may include at least one selected from nonionic surfactants and cationic surfactants, and more preferably nonionic surfactants and cationic surfactants. It is advantageous in terms of wettability and coating power improvement to mix and use in a weight ratio of 1:0.30 to 0.80.

The nonionic surfactant may be an ethylene oxide or ester ether nonionic surfactant made by adding ethylene oxide to a diethalolamine, sorbitol, glycerin, or higher alcohol, preferably (C ₈ ~ C ₂₀ straight-chain alkyl)-poly(ethylene glycol-co-propylene glycol)-ether and iso-tridecyl-polyethylene glycol-ether, an ethylene oxide-based nonionic surfactant comprising at least one selected from among ethers can be used. , more preferably one selected from (C ₈ -C ₁₅ straight-chain alkyl)-poly (ethylene glycol-co-propylene glycol)-ether and iso-tridecyl-polyethylene glycol-ether having a weight average molecular weight of 500 to 1200 An ethylene oxide-based nonionic surfactant including the above may be used.

The cationic surfactant is N-dodecyl-N,N'-dimethyl-3-amino-1-propanesulfonate (N-Dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, DDAPS), N -Hydroxyethyl-N-carboxyethyl-N-aminoethyl dodecylamide (Nhydroxyethyl-N-carboxyethyl-N-aminoethyl dodecylamide, IB), Cocamidopropyl betaines, N-dodecyl-N,N -Dimethyl betaine (N-dodecyl-N,N-dimethyl betaine, C ₁₂ -Bet), N-tetradecyloxymethyl-N,N-dimethyl betaine (C ₁₄ -Bet) and (C _12-14 alkyl) may include at least one selected from dimethylbenzylammonium chloride, preferably N-hydroxyethyl-N-carboxyethyl-N-aminoethyl dodecylamide, N It may include at least one selected from -dodecyl-N,N-dimethyl betaine and N-tetradecyloxymethyl-N,N-dimethyl betaine.

In addition, the content of the wetting agent in the total weight of the organic coating agent is 0.1 to 2.0% by weight, preferably 0.25 to 1.50% by weight, more preferably 0.35 to 0.80% by weight, and if the wetting agent content is less than 0.1% by weight, the amount used is too small, so There may be no effect of improving surface wettability and covering power, and when the wetting agent content exceeds 2.0 wt%, the adhesion of the organic film layer formed on the surface of the plating layer is rather reduced, and there may be a problem of staining of the film, so it is recommended to use it within the above range.

The pH adjusting agent in the composition of the organic coating agent of the present invention serves to maintain an appropriate pH of the organic coating agent of about 2.0 to 3.0, and includes ammonium hydroxide, sodium hydroxide, sulfuric acid and hydrochloric acid ( Hydrochloric acid) may include one or more selected from the group consisting of. And, the appropriate content of the pH adjusting agent is 0.05 to 2.00% by weight, preferably 0.40 to 1.50% by weight, preferably 0.70 to 1.25% by weight, and if the pH adjusting agent content is less than 0.05% by weight or exceeds 2.00% by weight, organic Since it may be difficult to maintain an appropriate pH range of the coating agent, it is recommended to use it within the above range.

In addition, water serves as a solvent in the composition of the organic coating agent of the present invention, and the remaining amount is used in addition to the composition described above among 100% by weight of the total preflux.

The pH of the preflux of the present invention composed of the above-described composition and composition ratio is preferably 2.0 to 3.0, preferably about 2.4 to 3.0, in view of formation of an appropriate film thickness and liquid stability of the preflux. When treating the surface of a copper-containing plating layer, it is very important and sensitive to the pH of the preflux, and since the pH changes over time, it is important to continuously check the acidity to maintain an appropriate pH.

With the organic coating agent of the present invention described above, a coating film is formed on the surface of the copper-containing plating layer to prevent rust.

For example, the surface of a metal article including a copper-containing plating layer may be coated with the organic coating agent of any one of claims 1 to 9, and then dried to form a coating film.

The coating may be performed by a general coating method performed in the art, such as a spray method, an immersion method, and a top coating method.

The copper-containing plating layer may be a surface of a metal conductive part constituting a circuit part of a printed wiring board for electronic components or the like.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are not intended to limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[Example]

Example 1: Preparation of organic coating agent

3.0 wt% of a benzimidazole-based compound represented by the following formula 1-1, 45.0 wt% of an organic acid containing lactic acid and propionic acid in a weight ratio of 1: 1.10, 1.30 wt% of iron chloride as a metal compound, ethoxyethanol and ethylene glycol 1 : 15.0 wt% of an organic solvent including 0.88 wt%, 1.5 wt% of tetrahydroxypropylethylenediamine as a chelating agent, 0.5 wt% of a wetting agent containing a nonionic surfactant and a cationic surfactant in a weight ratio of about 1:0.56, pH An organic coating agent having a pH of 2.6 to 2.8 was prepared by mixing 1.0 wt% of ammonium hydroxide as a modifier and the remaining amount of water.

At this time, when the nonionic surfactant includes (C ₁₂ linear alkyl)-poly(ethylene glycol-co-propylene glycol)-ether having a weight average molecular weight of 800 to 900, the cationic surfactant N-hydroxy ethyl-N-carboxyethyl-N-aminoethyl dodecylamide.

[Formula 1-1]

In Formula 1-1, R ¹ is a 2,4-dichlorobenzyl group, and R ² is a hydrogen atom.

Example 2

An organic coating agent was prepared with the same composition and composition ratio as in Example 1, but an organic coating agent was prepared using a benzimidazole-based compound represented by the following Chemical Formula 1-2 instead of the benzimidazole-based compound represented by Chemical Formula 1-1. .

[Formula 1-2]

In Formula 1-2, R ¹ is a 2,4-dichlorophenoxy group, and R ² is a hydrogen atom.

Example 3

An organic coating agent was prepared with the same composition and composition ratio as in Example 1, but an organic coating agent was prepared using a benzimidazole-based compound represented by the following Chemical Formula 1-3 instead of the benzimidazole-based compound represented by Chemical Formula 1-1. .

[Formula 1-3]

In Formula 1-3, R ¹ is a 2-ethylphenyl group, and R ² is a hydrogen atom.

Examples 4 to 9 and Comparative Examples 1 to 10

An organic coating agent was prepared using the same composition as in Example 1, but the organic coating agent was prepared by varying the content of the composition as shown in Tables 1 to 3 below, and Examples 4 to 9 and Comparative Examples 1 to 10 were carried out, respectively.

Category (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 it's benzimi
sol compound Kinds chemical formula
1-1 chemical formula
1-2 chemical formula
1-3 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 content 3.0 3.0 3.0 4.3 1.8 3.0 3.0 organic acid 45.0 45.0 45.0 45.0 45.0 45.0 45.0 metal compound 1.3 1.3 1.3 1.3 1.3 1.3 1.3 organic solvent 15.0 15.0 15.0 15.0 15.0 15.0 15.0 chelating agent 1.5 1.5 1.5 1.5 1.5 4.7 0.5 wetting agent nonionic
Surfactants 0.32 0.32 0.32 0.32 0.32 0.32 0.32 cationic
Surfactants 0.18 0.18 0.18 0.18 0.18 0.18 0.18 pH regulator 1.0 1.0 1.0 1.0 1.0 1.0 1.0 water The remainder of 100% by weight

Category (wt%) Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 it's benzimi
sol compound Kinds chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 content 3.0 3.0 5.2 0.4 3.0 3.0 3.0 organic acid 45.0 45.0 45.0 45.0 45.0 45.0 45.0 metal compound 1.3 1.3 1.3 1.3 1.3 1.3 1.3 organic solvent 15.0 15.0 15.0 15.0 15.0 15.0 15.0 chelating agent 1.5 1.5 1.5 1.5 5.3 0.05 1.5 wetting agent nonionic
Surfactants 1.0 0.20 0.32 0.32 0.32 0.32 1.7 cationic
Surfactants 0.56 0.12 0.18 0.18 0.18 0.18 1.1 pH regulator 1.0 1.0 1.0 1.0 1.0 1.0 1.0 water The remainder of 100% by weight

Category (wt%) Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 it's benzimi
sol compound Kinds chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 chemical formula
1-1 content 3.0 3.0 3.0 3.0 3.0 organic acid 45.0 52.0 45.0 45.0 45.0 metal compound 1.3 1.3 3.2 0.1 1.3 organic solvent 15.0 15.0 15.0 15.0 4.2 chelating agent 1.5 1.5 1.5 1.5 1.5 wetting agent nonionic surfactant 0.08 0.32 0.32 0.32 0.32 cationic surfactant 0.01 0.18 0.18 0.18 0.18 pH regulator 1.0 1.0 1.0 1.0 1.0 water The remainder of 100% by weight

Experimental Example 1: Solder flow-up rate property and solder spreadability performance evaluation

Solder improvement and solder improvement tests of the organic coating agents of Examples 1 to 9 and Comparative Examples 1 to 10 were measured as follows, and the results are shown in Table 4 below.

(1) Solder improvement test

As the test piece, a printed wiring board made of a glass epoxy resin having 300 copper through-holes having an inner diameter of 0.80 mm and having a size of 120 mm (length) × 150 mm (width) × 1.6 mm (thickness) was used. The test piece was degreased, soft etched, washed with water, immersed in an organic coating agent maintained at a predetermined liquid temperature for a predetermined time, and then washed with water and dried to form a coating film with a thickness of about 0.40 μm on the copper surface. formed.

Next, about the test piece to which the surface treatment was performed, using an infrared reflow apparatus (MULTI-PRO-306 of Vetronix Co., Ltd.), reflow heating with a peak temperature of 240 degreeC was performed 3 times. Then, soldering was performed using a flow soldering apparatus (conveyor speed: 1.0 m/min).

In addition, the solder used was a tin-lead type eutectic solder having a composition of 63 wt% of tin and 37 wt% of lead, the flux used for the solder was JS-64 MSS (Koki Co., Ltd.), and the solder temperature was 240°C. did.

Then, with respect to the soldered test piece, the number of through-holes in which the solder was raised (soldered) up to the upper land portion of the copper through-holes was counted, and the ratio (%) to the total number of through-holes (300 holes) was calculated.

The greater the wettability of the solder with respect to the copper surface, the easier it is for the molten solder to penetrate the copper through-hole and rise to the upper land portion of the through-hole. That is, as the ratio of the number of through-holes in which the solder to the upper land portion was raised to the total number of through-holes was larger, the solder wettability to copper was excellent, and it was determined that the solderability was good.

(2) Solder diffusivity test

As a test piece, a printed wiring board made of a glass epoxy resin of 50 mm (length) x 50 mm (width) x 1.2 mm (thickness) (as a circuit pattern, a circuit portion of 0.80 mm in width and 20 mm in length made of copper foil, with an interval of 1.0 mm 10 in the width direction) was used. The test piece was degreased, soft etched, washed with water, immersed in an organic coating agent maintained at a predetermined liquid temperature for a predetermined time, and then washed with water and dried to form a coating film with a thickness of about 0.40 μm on the copper surface. formed.

And about the test piece which surface-treated, the reflow heating whose peak temperature is 240 degreeC was performed once using the infrared reflow apparatus (Product name: MULTI-PRO-306, the Betronics company make). Then, using a metal mask having an opening diameter of 1.2 mm and a thickness of 150 µm, tin-lead paste solder was printed in the center of the copper circuit part, and reflow heating was performed under the above conditions to perform soldering.

The tin-lead-based paste solder used was a tin-lead-based eutectic solder having a composition of 63% by weight of tin and 37% by weight of lead, and the reflow heating performed before and after printing of the paste solder was set so that the peak temperature was 240°C. did.

The length (mm) of the wetted and diffused solder on the surface of the copper circuit portion of the obtained test piece was measured. It is judged that it is excellent in solder wettability and solderability is so good that this length is long.

division Solder improvement (%) Solder diffusivity (mm) Example 1 96.2 4.24 Example 2 94.5 4.18 Example 3 88.1 3.69 Example 4 97.3 4.12 Example 5 80.5 3.06 Example 6 95.8 4.14 Example 7 89.8 3.79 Example 8 96.5 4.42 Example 9 92.2 3.97 Comparative Example 1 94.3 4.07 Comparative Example 2 30.3 1.78 Comparative Example 3 94.2 4.10 Comparative Example 4 84.4 3.25 Comparative Example 5 96.4 4.40 Comparative Example 6 88.5 3.02 Comparative Example 7 78.9 3.28 Comparative Example 8 96.0 4.23 Comparative Example 9 94.9 4.28 Comparative Example 10 95.4 4.01

In the case of Examples 1 to 9, it was confirmed that overall excellent solder improvement and diffusion properties were obtained. However, in the case of Example 3, the solder improvement and diffusivity tended to be lower than those of the other examples.

And, in the case of Comparative Example 1, in which the content of the benzimidazole-based compound exceeds 5.0% by weight, there was a problem in that the solderability was rather decreased compared to that of Example 4, and the content of the benzimidazole-based compound was 0.4% by weight. In the case of Example 2, when compared with Example 5, the solderability was very poor.

In the case of Comparative Example 3 in which the content of the chelating agent was used in excess of 5.0% by weight, compared with Example 6, the solder improvement and solder diffusivity were slightly decreased, and in the case of Comparative Example 4 in which the content of the chelating agent was less than 0.1% by weight, the implementation Compared with Example 7, the results showed that the solder improveability and the solder diffusivity were sharply decreased, because a uniform coating layer was not formed.

In the case of Comparative Example 5, in which the wetting agent content was greater than 2.0 wt%, there was no solder-improving wetting agent or solder diffusivity improvement effect compared to Example 8, and in Comparative Example 6 in which the wetting agent content was less than 0.1 wt%, Example 9, there was a problem that the solderability was significantly lower.

In the case of Comparative Example 7 in which the organic acid was used in excess of 50% by weight, there was a problem in that the solderability was rather reduced, compared with the other examples.

And, in Comparative Example 8 using more than 3.0 wt% of the metal compound and Comparative Example 9 using less than 0.2 wt% of the metal compound, there was no significant difference in solderability compared to other Examples.

In the case of Comparative Example 10 using less than 5% by weight of the organic solvent, there was no significant difference in solderability as compared to Example 1, but there was a problem that the dissolution time of the composition was too long.

Experimental Example 2: Measurement of physical properties such as rust prevention

After the specimen treated with the coating film of about 0.40 μm with the organic film agent of each of the Examples and Comparative Examples was subjected to oxidation treatment in an oven at 270 to 280 ° C. for 30 minutes, the rust prevention properties were measured to the extent of discoloration, and the results were It is shown in Table 5 below. And, the antigrease (Antigrease) observed the degree of fingerprints by hand rubbing the surface of the specimen treated in the oven, that is, the specimen for which the anti-rust property was measured. The film uniformity and the degree of staining were visually judged whether the film surface was uniformly formed and whether staining occurred on the film surface.

division rust prevention antigrid heat resistance Film uniformity, degree of staining Example 1 ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ○ ◎ ○ Example 4 ◎ ○ ◎ ◎ Example 5 ○ ○ ◎ ◎ Example 6 ◎ ◎ ◎ ○ Example 7 ○ ○ ○ ○ Example 8 ◎ ◎ ◎ ◎ Example 9 ◎ ○ ○ ○ Comparative Example 1 ○ △ ◎ ◎ Comparative Example 2 △ X △ ○ Comparative Example 3 ○ ○ ○ △ Comparative Example 4 ○ ○ ○ X Comparative Example 5 ○ ○ ○ △ Comparative Example 6 △ ○ ○ ○ Comparative Example 7 △ △ ○ ◎ Comparative Example 8 ◎ ◎ ◎ △ Comparative Example 9 ◎ ○ △ ◎ ◎=Very good, ○=Excellent, △=Normal, X=Poor

It was confirmed that Examples 1 to 9 showed overall excellent rust prevention, anti-grease, and heat resistance, and showed no or very few stains on the surface while having film uniformity.

On the other hand, in the case of Comparative Example 1, in which the benzimidazole-based content exceeds 5.0% by weight, compared to Example 4, rather poor rust prevention and anti-grease results, and the benzimidazole-based content was 0.5% by weight In the case of Comparative Example 2, which is less than %, when compared with Example 5, all of the anti-rust property, anti-grease, and heat resistance showed poor results.

In the case of Comparative Example 3 in which the chelating agent was used in excess of 5.0% by weight, compared with Example 6, physical properties such as rust prevention properties were rather poor, which is because the film was not formed evenly due to excessive use of the chelate. And, in the case of Comparative Example 4 using less than 0.1% by weight of the chelating agent, compared with Example 7, the film uniformity was very poor, and there was a problem in that a large amount of unevenness was generated on the surface of the film.

In the case of Comparative Example 5, in which the wetting agent content was more than 2 wt%, there was a problem in that the film was stained and the adhesion of the film layer was rather reduced, thereby reducing physical properties such as rust prevention, and the wetting agent content was less than 0.1 wt%. In the case of 6, there was a problem that the rust prevention property was greatly reduced.

In the case of Comparative Example 7 in which the organic acid was used in excess of 50% by weight, the film stability was poor, and the physical properties of the film were rather deteriorated.

In the case of Comparative Example 8, in which the metal compound was used in excess of 3.0 wt%, a lot of stains occurred on the film, which is judged to be due to the presence of a large amount of foreign substances. There was no problem.

The embodiments according to the present invention described above are merely exemplary, and those of ordinary skill in the art to which the present invention pertains will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, it is to be understood that the present invention is not limited to the form recited in the detailed description, but includes all modifications, equivalents and substitutions falling within the scope of the present invention.

Claims (10)

delete As an organic coating agent having a pH of 2.0 to 3.0,
1.8 to 5.0 wt% of a benzimidazole-based compound represented by the following formula (1), 10 to 50.0 wt% of an organic acid, 0.2 to 3.0 wt% of a metal compound, 5 to 15 wt% of an organic solvent, 0.1 to 5.0 wt% of a chelating agent, 0.1 wt% of a wetting agent to 2.0% by weight, 0.05 to 2.0% by weight of a pH adjusting agent, and water;
The chelating agent includes tetrahydroxypropylethylenediamine (Tetrahydroxypropylethylendiamine),
The wetting agent includes a nonionic surfactant and a cationic surfactant in a weight ratio of 1: 0.30 to 0.80,
The nonionic surfactant has a weight average molecular weight of 500 to 1200 (C ₈ -C ₁₅ straight-chain alkyl)-poly (ethylene glycol-co-propylene glycol)-ether and iso-tridecyl-polyethylene glycol-ether selected from Containing an ethylene oxide-based nonionic surfactant containing at least one,
The cationic surfactant is N-hydroxyethyl-N-carboxyethyl-N-aminoethyl dodecylamide, N-dodecyl-N,N-dimethyl betaine and N-tetradecyloxymethyl-N,N-dimethyl An organic coating agent for surface treatment of a copper-containing plating layer comprising at least one selected from betaine;
[Formula 1]

In Formula 1, R ¹ is a chlorophenyl group, 2,4-dichlorobenzyl group, 2,4-dichlorophenoxy group or 2,4-dichloronaphthoxy group, and R ² is a hydrogen atom or a halogen atom. According to claim 2, wherein the organic acid is acetic acid, formic acid, citric acid, adipic acid, oxalic acid, lactic acid, and propionic acid ( Propionic acid), an organic coating agent for surface treatment of a copper-containing plating layer, characterized in that it contains at least one selected from among. The surface of claim 2, wherein the metal compound comprises at least one selected from among copper chloride, iron chloride, copper sulfate, iron sulfate, copper oxide, iron oxide, zinc oxide, zinc chloride and zinc sulfate. Organic coating agent for treatment. The organic coating agent for surface treatment of a copper-containing plating layer according to claim 2, wherein the organic solvent comprises at least one selected from butoxyethanol, ethoxyethanol and ethylene glycol. delete delete The copper-containing plating layer according to claim 2, wherein the pH adjusting agent comprises at least one selected from ammonium hydroxide, sodium hydroxide, sulfuric acid and hydrochloric acid. An organic coating agent for surface treatment of delete Copper-containing, characterized in that the surface of a metal article including a copper-containing plating layer is coated with the organic coating agent according to claim 2, 3, 4, 5 or 8, and then dried to form a coating film. A method for surface treatment of the plating layer.