KR20020059062A - Anti-fingerprint treatment for the copper metal - Google Patents

Abstract

PURPOSE: An anti-fingerprint agent with excellent anti-corrosion and soldering property for copper metal is provided. CONSTITUTION: The anti-fingerprint agent for the copper metal comprises anionic urethane acrylic resin 20 wt.%, anti-corrosion agent 0.1 to 5 wt.%, alcohol 0.1 to 50 wt.% and a balance of water as solvent. Further, anti-fingerprint agent comprises 0.05 to 1 parts by weight of wetting agent, 0.1 to 5 parts by weight of leveling agent, 0.01 to 2 parts by weight of defoaming agent, based on the weight of 100 parts by weight of the anti-fingerprint agent. The anti-corrosion agent is selected from the group consisting of triazole, tetrazole, benzotriazole, benzimidazole and imidazole. In the anti-fingerprint agent, the ratio of the anti-corrosion agent and alcohol is 1:1 to 1:10. The anionic urethane acrylic resin has mean molecular weight of 8000 to 30000, pH 6 to 8 and viscosity(cps) range of 200 to 1000.

Description

Anti-fingerprint treatment for the copper metal

TECHNICAL FIELD The present invention relates to a copper anti-fingerprint agent, and more particularly, can be used for copper used as a building material or an electronic component material, and has excellent anti-fingerprint, corrosion resistance, and solderability, and greatly improves adhesion performance. It relates to an anti-fingerprint agent for copper.

There are many uses of copper in building materials and electronic parts. However, in this use, copper is generally used without separate rubbing treatment. Therefore, the corrosion and discoloration of the copper surface caused by fingerprints and sweat caused by workers during work and the post-treatment manufacturing process of processing copper cause corrosion and discoloration of copper, thereby degrading its value as a commodity. This lowers the required physical properties.

As a method for solving the anti-fingerprint and corrosion resistance of the conventional method has been proposed a method of adhering ethylene acrylic acid resin by injection. It has been proposed that the method of adhering these ethylene acrylic acid resins has a superior anti-fingerprint and corrosion resistance effect than when not treated.

However, since the method of adhering the ethylene acrylic acid resin is an injection method, there are disadvantages in that the coating film is thick, and therefore, the soldering problem and the energy cost are high due to a large amount of heat consumption in order to melt the ethylene acrylic acid resin before injection.

Recently, as a method of solving these problems, a method of using an ethylene acetic acid resin solution which has been accepted has been proposed. These water-soluble resin solutions may be thinner in terms of physical properties than the injection adhesive treatment using conventional ethylene acrylic acid resin, but may be thinner. Corrosion resistance can also be adjusted.

These water-soluble resin solutions are applied to copper and alloys using copper, and as a coating method thereof, the copper wound around the roll is coated with a roll of about 1 μm, so that the material temperature (MT) is controlled at 100-150 ° C. PCM coating method for continuous drying and dip coating method for depositing copper plate directly by putting coating agent in solution bath and drying at 100-150 ℃ is used.

However, since the acid content of the resin (binder) is high in the range of 15 to 20% in order to solubilize the ethylene acrylic acid resin solution, there is a partial defect in corrosion resistance and the like due to lack of water resistance when coated with a dry coating film. . In particular, the high viscosity of the resin solution accommodated still thickens the thickness of the coating film, so that frequent defects occur during the soldering process.

Therefore, the present inventors have approached the direction of using other resins to improve the defects of physical properties obtained by the method of treatment using injection-adhesive or hydrated ethylene acrylic acid resin solutions, which have been enumerated so far, and research and efforts through field application As a result, the energy-environment-friendly copper using the anionic water-based urethane acryl resin of thermoplastic type which is excellent in rubbing and corrosion resistance, excellent in water resistance, solderability and adhesion, and applicable to other metals Solvent-treatment agents have been developed.

Accordingly, an object of the present invention is to provide an anti-fingerprint agent for copper, which is excellent in various properties including copper's anti-fingerprint, corrosion resistance, solderability, etc. used in the manufacture of building materials and electronic component materials. It is.

In order to achieve the above object, the present invention provides an anionic water-based urethane acryl resin of a thermoplastic type and an anti-fingerprinting agent for copper containing an anticorrosive agent and an alcohol and made of predetermined additives.

The composition of the anti-fingerprint agent for copper includes 20% by weight of the anionic aqueous urethane acryl resin of the thermoplastic type, 0.1 to 5% by weight of the corrosion inhibitor, and 0.1 to 50% by weight of the alcohol, and includes the appropriate amount of the additive. By using water as a solvent, the anti-fingerprint agent for copper is comprised.

The additive is a wetting agent, a leveling agent, an antifoaming agent, and the like, and these may use a known material. The amount of the wetting agent is 0.05 to 1 part by weight based on 100 parts by weight of the total treatment agent composition, and the leveling agent is 0.1 to 5 parts by weight. , The antifoaming agent preferably contains 0.01 to 2 parts by weight.

In addition, the thermoplastic type anionic aqueous urethane acrylic resin preferably has a weight average molecular weight of 8000 to 30000, a odor (pH) of 6 to 8, and a viscosity (cps) of 200 to 1000 or less.

As the corrosion inhibitor, at least one selected from the group consisting of triazole, tetrazole, benzotriazole, benzoimidazole and imidazole may be used. This preservative is dissolved with the alcohol and then added to the thermoplastic type anionic aqueous urethane acryl resin, and the preservative is prepared by mixing the preservative and the alcohol in a ratio of 1: 1 to 1:10.

Hereinafter, the present invention will be described in detail.

As described above, the anti-fingerprint agent for copper of the present invention comprises a thermoplastic type anionic aqueous urethane acrylic resin and a corrosion inhibitor and an alcohol, and includes certain additives, and includes a thermoplastic type anionic aqueous urethane acrylic resin. The anionic aqueous urethane acrylic resin of the thermoplastic type that can be used in the present invention is a known material, and the anionic aqueous urethane acrylic resin that can be used in the present invention has a weight average molecular weight of 8000 to 30000 and a pieche (pH) of 6 to It is preferable that it is 8 and viscosity (cps) is 200-1000 or less.

If the weight average molecular weight is less than 800, the coating film becomes difficult to form, the adhesion is poor, and if it is 30000 or more, the workability and the appearance of the coating film are poor. If the odor is less than 6 alkali resistance is lowered, if more than 8 it is less acid resistance. If the viscosity is less than 200, the coating film shape of a certain amount or more during the coating or deposition of the treatment agent during the roll coating operation becomes difficult, and if it is more than 1000, the viscosity occurs and the smoothness is poor during the coating operation. Therefore, it is preferable that the weight-average molecular weight of the thermoplastic anionic aqueous urethane acryl resin is 8000 to 30000, the macular pH (pH) is 6 to 8, and the viscosity (cps) is 200 to 1000 or less.

As the corrosion inhibitor that can be used in the present invention, any one of triazole, tetrazole, benzotriazole, benzoimidazole and imidazole may be used alone or in combination. As a typical corrosion inhibitor, benzotriazole can be used. Its amount is preferably used 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. If the amount thereof is less than 0.1 part by weight, the corrosion resistance of copper is lowered. If the amount is more than 5 parts by weight, compatibility with the aqueous resin becomes poor, which hinders the formation of the coating film.

In using the corrosion inhibitors, the use of alcohols is inevitable. For compatibility between aqueous resins and corrosion inhibitors, dissolve the corrosion inhibitors with alcohols and add them to the resin. Alcohols that can be used may be used alone or in combination of methyl alcohol, ethyl alcohol, propanol, isopropanol, methoxy propanol and butoxy ethanol. Ethyl alcohol can be used as a representative alcohol. In the amount used, the ratio of the alcohol and the corrosion inhibitor is preferably used in a ratio of 1: 1 to 10: 1. If the amount is less than 1: 1, the corrosion inhibitor is not completely dissolved in alcohols, and the compatibility with water-soluble resins is inferior. If it is more than 10: 1, the content of alcohol is increased, which increases the generation of volatile organic compounds, which is harmful to human body and environment. do.

Other additives used in the present invention, that is, wetting agents, leveling agents, antifoaming agents and the like can be used a known material, the amount of each is used in an appropriate amount based on 100 parts by weight of the total composition.

If each is explained, it can be used individually or in mixture as a humectant which can be used by this invention. BYK's 151, 180, 183, 184, 190, 191, 192 Tego's Wet KL 245, wet 450, wet 260, wet265, wet 500, Dispers 715w, Dispers 735w, Dispers 745w and air purifier Duct (Air Product) Surfynol GA etc. can be used. It is preferable to use 0.05 to 1 parts by weight based on 100 parts by weight of the total composition thereof. If the amount thereof is less than 0.05 parts by weight, the treatment agent is not applied to the copper surface, so that the coating film is difficult to form, and if it is 1 part by weight or more, the corrosion resistance and water resistance are lowered.

As the antifoaming agent that can be used in the present invention, any one can be used alone or in combination. BYK's 011, 019, 020, 022, 025, 028 and TEGO's Foamex 800, Foamex 810, Foamex 815, Foamex 825 and Air Product DF 75 are available. Do. It is preferable to use the amount thereof in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total composition. If the amount thereof is less than 0.01 parts by weight, it will not show sufficient anti-foaming properties, and bubbles will remain in the coating film or bubbles will be generated during the operation. If it is more than 1 part by weight, no cratering will occur or wetting.

As the leveling agent that can be used in the present invention, any one can be used alone or in combination. BYK's 375, 380, 385, and Tego's Flow 425 and Glide 435 are available. It is preferable to use the amount thereof in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. If the amount thereof is less than 0.1 part by weight, the surface of the treatment agent may be uneven during hot air or drying after coating on the surface, resulting in poor appearance.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples, and various modifications and changes within the spirit and scope of the present invention are made based on the detailed description and the claims of the present invention. It will be appreciated that applications are possible and that variations and applications are within the scope of the present invention.

Example 1

20 parts by weight of the thermoplastic anionic aqueous urethane acryl resin R-CM was added to a beaker, and a solution of 2 parts by weight of ethanol and 0.3 parts by weight of benzotriazole was gradually added while stirring. After diluting with 76.9 parts by weight of water, 0.4 and 0.2 parts by weight of BYK-380 as a wetting agent BYK-192 and a leveling agent as additives, and 0.2 parts by weight of BYK-020 as antifoaming agent were mixed, and the solid content was 7.5%, pH 7, viscosity. A translucent milky solution was obtained in 12 seconds (Cand Cup No. 4 20 ° C).

Example 2

20 parts by weight of a thermoplastic anionic aqueous urethane acryl resin R-912B was added to a beaker, and then 2 parts by weight of butoxy ethanol and 0.5 parts by weight of benzotriazole were gradually added while stirring. After diluting with 75 parts by weight of water, 0.3 and 0.5 parts by weight of TEGO Dispers 715w as a wetting agent and TEGO Flow 425 as a leveling agent were added, respectively, and 0.05 parts by weight of Surfynol DF 75 as an antifoaming agent. A translucent milky solution was obtained in 11 seconds (Cand Cup No. 4 20 ° C).

Comparative Example 1

17.5 parts by weight of a water-soluble urethane polyester resin R-974 was added to a beaker, and a solution of 2 parts by weight of ethanol and 0.3 parts by weight of benzotriazole was gradually added while stirring. 79.4 parts by weight of water and dilution were added, and 0.4 and 0.2 parts by weight of BYK-380 as an additive and a wetting agent BYK-192 as a smoothing agent were added, and 0.2 parts by weight of BYK-020 as an antifoaming agent. A translucent milky solution was obtained in 12 seconds (Cand Cup No. 4 20 ° C).

Comparative Example 2

7 parts by weight of ethylene acrylic acid resin 5980 was solubilized in 0.3 parts by weight of ammonia water and 89.5 parts by weight of water, and then charged into a beaker and slowly added a solution of 2 parts by weight of ethanol and 0.3 parts by weight of benzotriazole. 0.5 and 0.2 parts by weight of BYK-381 as a wetting agent Surfynol GA and a smoothing agent as additives and 0.2 parts by weight of BYK-011 as antifoaming agent were mixed and then semi-transparent in 7.5% of solid content, pH 8.5 and viscosity 14 seconds (4 cups 20 ℃). A milky solution was obtained.

Comparative Example 3

17.5 parts by weight of 4983-40R, an ethylene acrylic acid resin solution, was added to a beaker and a solution of 2 parts by weight of butoxyethanol and 0.5 parts by weight of benzotriazole was gradually added while stirring. 18 parts by weight of water and dilution were added, followed by adding 0.3 and 0.4 parts by weight of BYK-381 as a wetting agent, Dispers 815W as an additive, and 0.2 parts by weight of BYK-020 as an antifoaming agent, and a solid content of 7.5%, pH 8, and viscosity. A translucent milky solution was obtained in 15 seconds (cup 4 times 20 ° C.).

Experimental Example Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 R-CM ^{(Note 1)} R-912B ^{(Note 2)} R-974 ^{(Note 3)} 5980 resin solution ^{(Note 4)} 4983-40R ^{(Note 5)} Ethanol butoxyethanol benzotriazole water BYK-192 ^{(Note 6)} TEGO Dispers 715 \ ^{(Note 7)} Surfynol GA ^{(Note 8)} BYK-380 ^{(Note 6)} TEGO FLOW 425 ^{(Note 7)} BYK-381 ^{(Note 6)} BYK-020 ^{(Note 6)} Surfynol DF75 ^{(Note 8)} BYK-011 ^{Note 6} 20 ---- 2-0.3750.4--0.2--0.2-- -20 ---- 20.576.6-0.3--0.5--0.1- --17.5--2-0.379.40.4--0.2--0.2-- --- 96.8-2-0.3 --- 0.5--0.2--0.2 ---- 17.5-20.579.1-0.3 --- 0.40.2-- Sum 100.0 100.0 100.0 100.0 100.0

Note 1) Thermoplastic anionic aqueous urethane acryl resin of Korea Bokwang Chemical (solid content 35%)

Note 2) Thermoplastic anionic water-based urethane acrylic resin of Korea Gwanggwang Chemical (solid content 35%)

Note 3) Thermoplastic nonionic water-soluble urethane polyester resin manufactured by Genca, Switzerland (35% solids)

4) 7 parts by weight of Primacor 5980 resin, 0.3 parts by weight of ammonia water and 89.5 parts by weight of water

Note 5) Prime resin (40% solids) of Mychem, USA

Note 6) product made by Germany

Note 7) Tegosa Products, Germany

Note 8) US Air Products Company

Psalm Fabrication

Degreased 70 × 150 × 0.05 mm sized copper plate was deposited in a coating bath by immersion coating method, and then immersed for 30 seconds, then extracted and dried at room temperature for 1 minute, and then dried in a forced hot air circulation oven to have a surface temperature of 100 ° C. .

In order to find out the characteristics of each of the treatment agents shown in Table 1, the characteristics of the coating film after coating were tested by the test method of the following specimens by the method of manufacturing the specimens mentioned above.

Coating film property test

Appearance test

Evaluate the appearance of the painted specimens, with no foreign matter and no unpainted area.

(◎: No abnormality, ○: Tee slightly, △: Cratering, ×: Unpainted)

Anti-fingerprint test

Wipe off after 5 minutes after applying petroleum jelly to the coated area to observe the coating state.

(◎: No abnormality, ○: Less than 10% of petrolatum remains, △: Less than 50% of petrolatum remains Loss cratering, ×: All of petrolatum remains)

Adhesion test

A total of 100 coated specimens are to be 1 mm in width, 3M Scotch tape is attached, and then peeled off to evaluate the adhesion of the coating film.

(◎: No abnormality, ○: 10 or more dropouts, △: 50 or more dropouts, ×: complete dropouts)

Solvent resistance test

Methyl ethyl ketone was applied to the gauze and rubbed in a reciprocating direction with a constant force.

(◎: no abnormality (more than 20 times), ○: less than 20 times, △: 5 times or less, ×: 1 time or less)

Corrosion resistance test

The painted specimens were sprayed continuously with 5% saline solution at 35 ° C and 95% humidity to evaluate the initial degree of rust.

(◎: No more than 72 hours, ○: Initial call after 48 hours △: Initial call after 24 hours, ×: Initial call before 24 hours)

Solderability test

Adhesion was evaluated by soldering a 0.1 mm diameter copper wire onto the painted specimen

(◎: 0.4 kg / cm 2 or more, ○: less than 0.4 kg / cm 2, △: 0.1 kg / cm 2 or less, ×: not attached)

The physical property test results of the obtained coating film are shown in Table 2 below.

Experimental Example Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Exterior ◎ ◎ ○ ◎ ◎ Anti-fingerprint ◎ ◎ ◎ ◎ ◎ Adhesion ◎ ◎ ○ △ △ Solvent resistance ◎ ◎ ◎ ◎ ◎ Corrosion resistance ◎ ◎ ◎ X X Solderability ◎ ◎ △ △ △

Table 2 shows that the compositions obtained in Examples 1 and 2 exhibited superior effects compared to the compositions of Comparative Examples in terms of appearance and fingerprint resistance, corrosion resistance, adhesion, solvent resistance, solderability, and the like. Could.

As described above, when a thermoplastic type anionic aqueous urethane acryl resin and a corrosion inhibitor, and a treatment agent prepared using an alcohol, a humectant, a leveling agent, an antifoaming agent, etc. are used in copper or a copper alloy, excellent anti-fingerprint, corrosion resistance, and physical properties A coating film can be obtained. In addition, the use of water-based urethane acrylic resin as a main raw material has the advantage of reducing energy saving problems, environmental pollution problems, work hygiene stability problems and fire risk.

Claims (6)

An anionic aqueous urethane acryl resin of a thermoplastic type, and an anti-fingerprint agent for copper comprising a corrosion inhibitor and an alcohol, and comprising certain additives. According to claim 1, wherein the anti-fingerprint agent for copper, 20% by weight of the anionic aqueous urethane acrylic resin of the thermoplastic type, 0.1 to 5% by weight of the corrosion inhibitor, 0.1 to 50% by weight of the alcohol, the additive An anti-fingerprint agent for copper, comprising a suitable amount, and using water as a solvent. The method of claim 2, wherein the additive is a wetting agent, a smoothing agent, an antifoaming agent, the wetting agent is 0.05 to 1 part by weight, the leveling agent is 0.1 to 5 parts by weight, the defoaming agent is 0.01 to about 100 parts by weight of the total treatment agent composition An anti-fingerprint agent for copper, comprising 2 parts by weight. The method of claim 1, wherein the thermoplastic type anionic aqueous urethane acryl resin has a weight average molecular weight of 8000 to 30000, a odor (pH) of 6 to 8, and a viscosity (cps) of 200 to 1000 or less. Anti-fingerprint agent for copper. The anti-fingerprint agent for copper according to claim 1, wherein at least one selected from the group consisting of triazole, tetrazole, benzotriazole, benzoimidazole and imidazole is used as the corrosion inhibitor. The method of claim 5, wherein the corrosion inhibitor is dissolved in the alcohol and added to the anionic aqueous urethane acrylic resin of the thermoplastic type, the corrosion inhibitor and the alcohol is mixed in a ratio of 1: 1 to 1:10. Anti-fingerprint agent for copper to be used.