• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a method of color coating a metal surface in a desired color, and more particularly, to a color coating method of a metal surface having excellent stability and chemical resistance while having excellent smoothness and plating effects on a surface of a metal base material. . The present invention is a method of electrodeposition coating using a one-component type electrodeposition paint in the method of coating on the surface of the metal material. The present invention is simply a coating process compared to the prior art, and also after the electrodeposition dye coating Compared to the method, the chemical resistance and weather resistance were excellent.
    公开号:KR19990037756A
    申请号:KR1019990000897
    申请日:1999-01-14
    公开日:1999-05-25
    发明作者:김광순
    申请人:최준기；주식회사 한국하우톤；
    IPC主号:
    专利说明:

    Color coating method for metal surface {Method for Co1or Coating on Metal Surface}
    The present invention relates to a method of color coating a metal surface in a desired color, and more particularly, to a color coating method of a metal surface that has a more stable chemical resistance while attaining effects such as smoothness and plating on the surface of a metal base material. .
    In general, coating (plating) the surface of metal products such as building materials, lighting fixtures, and home appliances with gold, silver, copper, chromium, and zinc is used to prevent discoloration, improve corrosion resistance, improve decorative properties, and improve insulation. It is intended to.
    The problem of plating using a general metal material as described above is that the chemical resistance (corrosion resistance) is low, the discoloration by the oxidation reaction is fast and the color is extremely limited.
    In particular, there is a disadvantage that the plating is hardly performed in the case of minute scratches. Korean Application No. 95-15935 is a method for solving such a problem. However, the coating method is a coating method of coating a transparent resin on the metal base material, and the dye is adsorbed to the color here, but in this case there is a disadvantage that the dye is considerably weak when the dye is exposed to ultraviolet rays, such as discoloration, color coating There is a cumbersome problem that the process of having to go through two steps of electrodeposition coating process, dye coloring process.
    Therefore, in the present invention to solve the problems of the prior art as described above to improve the light resistance, chemical resistance, weather resistance and the like using a pigment rather than using a technical problem.
    In addition, in the present invention, it is a technical problem to simplify the manufacturing step of color coating on the metal base material using the electrodeposition and coloring process steps as a single step.
    1 is a schematic explanatory diagram of electrodeposition coating.
    Hereinafter, the present invention will be described in detail.
    In the present invention, the metal material is treated with ultrasonic waves in an alkaline solution at a temperature of 50 to 80 ° C. for 1 to 5 minutes with an electrolytic density of 2 to 10 Am / dm 2 for 30 seconds to 60 seconds, followed by pickling. The pickled copper was copper plated at 0.5 to 10 Am / dm 2 for 5 to 20 minutes at 15 to 25 ° C. in an aqueous solution of 15 to 30% by weight of copper sulfate, 24 to 45% by weight of nickel sulfate, 3.8 to 6% by weight of nickel chloride, and boric acid. 3 ~ 10-40 minutes in 1 ~ 10 Am / dm ² in the plating solution is 5% by weight to the back 40 ~ 60.C blood conductor pretreatment step of treating the nickel-plated,
    At the same time, 20:80 to 40: 60% by weight of the melamine resin of the following formula (1) and the modified acrylic resin of the following formula (2) are used as an acid catalyst to form a crosslinked polymer of the following formula (3), which is 10 to 15 Emulsifying with 1% by weight of pure water and 1 to 2% by weight of an emulsifier, and then adding 0.1 to 5% by weight of a water-soluble organic dispersion pigment in small amounts to prepare a one-component type electrodeposition paint in which a color is imparted to the resin;
    After the pretreatment in the pretreatment of the object was carried out by hot water treatment for 1 to 5 minutes with pure water, and then neutralized by washing with ultrasonic waves for 1 to 5 minutes, the electrolytic density was applied to the anode in the electrolytic cell containing the one-component electrodeposition paint prepared above. Electrodeposition coating process for coating for 30 seconds to 180 seconds with / dm ² ,
    It is a color coating method of the surface of the metal material which consists of a hardening process which wash | cleans the obtained electrodeposition coating product and thermosets at the temperature of 140-160 degreeC.
    In the above formula, R is a CH 3 group, and m is an integer of 1 or more.
    In the above formula, n is an integer of 1 or more.
    In the above formula, R is a CH ₃ group, m, n is an integer of 1 or more
    Hereinafter, the present invention will be described in more detail.
    That is, the present invention consists of a surface pretreatment process, a process for preparing electrodeposition paint, an electrodeposition coating process, and a curing process, which are described step by step.
    (A) Pretreatment step
    First, the surface is treated as follows to remove various foreign matters attached to the surface of the metal material, to secure smoothness, and to improve adhesion.
    1) alkali ultrasonic treatment
    The metal material is placed in an ultrasonic generating tank and treated for 1 to 5 minutes at a temperature of 50 to 80 ° C. At this time, the grooves deeply dug into the subject or the foreign matter composed of lipids in the surface portion of the micro component are removed.
    As a solvent, in an organic solvent (e.g., trichloroethylene, benzene, toluene, xylene, or derivatives thereof), 3 to 5 wt% of sodium carbonate, 2 to 3 wt% of sodium phosphate, 1 to 2 wt% of caustic soda, and a surface active agent Water-soluble solvents to which 0.1 to 3.0% by weight are added are suitable.
    2) electrolytic degreasing
    Soak the alkali ultrasonically treated metal object in 0.2 to 0.5% by weight of caustic soda, 2-3% by weight of sodium phosphate, 1 to 1.5% by weight of sodium carbonate, and 0.2 to 0.05% by weight of surfactant. Nickel, stainless steel, aluminum or brass is used. Anodizing uses zinc and zinc die casting. In the case of cathodic degreasing, it is treated with an electrolytic density of 5 to 10 Am / dm 2 for 30 to 60 seconds.
    In this case, the oil or the like is oxidized and removed by oxygen gas at the anode, and the oil and the like is removed by the hydrogen gas at the cathode.
    3) acid treatment
    In the case of alkali degreasing or electrolytic degreasing, a fine but oxide film and passivation film remain on the surface of the subject to deteriorate the adhesion of the plating, so to remove it, sulfuric acid, hydrochloric acid, etc. are added to remove the passivated state by adding 5 to 20%. Immersion time is suitable for 30 to 60 seconds.
    4) Copper sulfate plating
    It is a base plating for Nickel plating, to improve smoothness and remove flaws.
    Copper sulfate 15 to 30% by weight sulfuric acid and 4 to screen the material to be 10% by weight aqueous solution 1~10A 5 ~ 20 bungan cathode current density to 20 ~30.C / dm 2, anode current density of 0.5 ~ 5A / dm 2 Copper plating on the surface of the object.
    5) Polished Nickel Plating
    In the aqueous solution containing 24 to 45% by weight of nickel sulfate, 3.8 to 6% by weight of nickel chloride and 3 to 5% by weight of boric acid, the surface was treated with a cathode current density of 1 to 10A / dm 2 at 40 to 60 ° C for 10 to 40 minutes. Make the whole thickness uniform and give the material a gloss. In this case, the anode is nickel plated and blown with an air blower.
    (B) 1-component electrodeposition paint manufacturing process
    1) Synthesis of electrodeposition coating liquid
    A mixed solution of the melamine of formula (1) and the acrylic resin of formula (2) is contained in an electrolytic cell and crosslinked with a sulfonic acid inorganic acid catalyst (0.1 to 2% by weight) to crosslink the formula (3). The route for preparing the polymer is as shown in the following reaction formula (1).
    In the acrylic resin of the modified formula (2) used in the present invention, it is possible to replace the active groups with hydroxy groups (˜0H) instead of carboxyl groups (˜COOH) at both ends. Therefore, the resultant product can also be obtained as a compound of the following formula (4).
    In the above formula, R is a CH 3 group, m, n is an integer of 1 or more.
    In the above formula, R is a CH 3 group, m, n is an integer of 1 or more.
    2) 1-component electrodeposition paint manufacturing process
    One-component type in which the resin component is emulsified with 10 to 15% by weight of pure water and 1 to 2% by weight of an emulsifier, and then added in small amounts while mixing with 0.1 to 5% by weight of a water-soluble organic dispersion pigment. Electrodeposit is prepared.
    The organic dispersion pigment is added to the resin resin blended with the acrylic resin and melamine resin to prepare a one-component type, and induce color development in the desired color during electrodeposition coating. Anything that can be used for attachment can be used. As a solvent, isopropyl alcohol, butyl cellosolve, ethyl cellosolve, etc., and a nonionic surfactant is preferable as a dispersing agent.
    (C) Electrodeposition process
    1) water
    The pretreated metal material subjects are subjected to hot water treatment for 1 to 5 minutes with pure water, followed by neutralization by washing with ultrasonic waves for 1 to 5 minutes.
    2) electrodeposition process
    Hanging the above-mentioned subject to the positive electrode of the electrodeposition vessel containing the one-component electrodeposition paint and the electrodeposition coating is carried out for 30 seconds to 180 seconds at a current density of 40 to 50 A / dm.
    C) curing process
    After the electrodeposition coating is completed, the product is washed with water and left in an oven maintained at a temperature of 140 to 160 ° C. for 30 to 50 minutes to induce curing of the resin.
    According to the above process, the present invention is crosslinked by adding a pigment to an acrylic resin and melamine resin having excellent durability, and shows a coating structure having excellent light resistance and weather resistance chemical resistance than conventional dye coloring.
    Hereinafter, the present invention will be described in more detail with reference to Examples.
    Example 1
    1) Pretreatment of the subject
    An 8 cm × 30 cm × 30 cm steel small panel was taken and sonicated at 60 ° C. for 3 minutes in an aqueous solution containing 30 g of sodium carbonate, 20 g of sodium phosphate, 7 g of caustic soda, and 3 g of surfactant in 1 liter of water.
    The iron plate was hung on the negative electrode, immersed in an alkaline aqueous solution in which 3 g of caustic soda, 10 g of sodium phosphate, 10 g of sodium carbonate, and 0.5 g of surfactant was dissolved, and then energized for 1 minute at an electrolytic density of 10 A / dm 2 .
    Subsequently, after immersing for 30 seconds in an aqueous 10% sulfuric acid solution, an iron plate was placed on a negative electrode of a 1 L aqueous solution containing 20 g of copper sulfate and 100 ml of sulfuric acid, and treated with 10 A / dm 2 for 25 minutes to obtain brown copper plating. Subsequently, 350 g of nickel sulfate, 50 g of nickel chloride, and 40 g of boric acid were dissolved in a 1 liter aqueous solution, and a nickel plated steel plate was applied to the negative electrode and treated with nickel for 25 minutes with a current density of 5 A / dm 2 .
    After the pretreatment was washed with water for 3 minutes at a temperature of 50 ~ 60 ° C and lowered to 30 ° C to oscillate the ultrasonic wave, followed by air blow washing in hot water for 5 minutes at room temperature with a pure water of 250,000 Ω-cm or more.
    After washing with water, the electrodeposition treatment was carried out while adjusting with ammonia water to bring the pH solvent 7 ml to 8 ml in the vessel where the ester solvent was remixed.
    2) Electrodeposition solution value
    The resin solution was blended with the melamine resin of the formula (1) and the modified acrylic resin of the formula (2) in a ratio of 30 to 70, and then emulsified by the addition of a water-soluble organic dispersion pigment (3% by weight). It is listed in Table 1 below.
    3) Electrodeposition solution working condition
    The working conditions of the electrodeposition resin solution are summarized in Table 2 below.
    4) Electrodeposition Resin Electrodeposition Value
    The electrodeposition characteristics of the electrodeposition resin solution are summarized in Table 3 below.
    ※ When solvent was insufficient in electrodeposition resin solution, it was replenished with butyl cell solution.
    ① Electrodeposition equipment
    Rectifier: A rectifier having a fill deviation of three-phase direct current less than 5% was used.
    ② Counter electrode: Material SUS 316
    Counter area: 25% of treated area
    As a counter electrode material, pure iron or chromium-based iron is not good, and the size of the counter electrode area is to prevent defects caused by overcurrent during operation.
    ③ Ultra filter
    Pump pressure: 2 to 5 kg / cm 2 , 50 l / min
    Filtrate outflow: 7ℓ / HR
    One tank is installed per 100Okg.
    ④ Precision paint circulation pump capacity
    Liquid flow rate: 5 to 8 times / hour
    5) Basic Characteristics of Organic Disperse Pigments
    Basic characteristics of organic pigments are summarized in Table 4 below.
    6) mechanism of electrodeposition
    ① Anion Electrodeposition Coating Overview
    An electrode electrodeposition phenomenon was shown in which two electrodes were immersed in an electrodeposition bath made of a resin aqueous solution such as an resin emulsion or an alkali salt of a high acid resin, connected to a DC power source, and a current difference was applied between the anodes. A schematic illustration of electrodeposition coating is shown in FIG. 1. In this case, the mechanism of all reactions taking place in the bath or in the active interface is complex.
    Iii. Electrophoresis
    Iii. Electrolysis (Electro1ysis)
    ㉢. Deposition of resin on anode
    삼 .Electrosmosis
    ② Anionic
    Coating film formation in electrodeposition
    The paint precipitates when the object is immersed in the electrodeposition liquid and a current is passed.
    In general, the NV of the deposited paint is about 80%, and the remainder contains water, a solvent, and some neutralizing agent, and the surface of the coating is washed with water to form a rough surface of sand pepper. When the precipitated film is heated, the viscosity of the film is lowered and flows, thus finally forming a flat plane.
    At the same time, curing of the resin starts and a strong crosslinked film is formed.
    As described above, the copolymerized resin between the modified acrylic resin and the melamine resin is electrodeposited on the nickel-plated substrate at the anode part of the electrolytic cell.
    Electrodeposition time is suitable for about 30 second-3 minutes, and about 4-10 micrometers is suitable for a resin layer.
    7) Electrodeposition hardening process
    After the electrodeposition coating was completed, the product was washed with water and cured for about 30 to 50 minutes in an oven maintained at a temperature of 140 to 160 ° C to obtain a brass color development coating product.
    Examples 2-7
    The coating product was prepared in the same manner as in Example 1, except that the pigment color of each of the following Examples was set as the color shown in Table 5 below.
    Test the physical properties of each coating product prepared in the above embodiment summarized in Table 6
    ※ Measurement condition of each characteristic test
    Hardness: pencil hardness (uni), corrosion resistance: 35 ° C 1% NaC1 Salt Spray, accelerated weather resistance: humidity 55 ± 5%, test piece irradiation temperature: 63 ± 3 ° C (light; ultraviolet), spray (pure); 120 minutes 18 minutes spray repeat test, impact test: (1/4 ") × 50,000 g (Dupont method), Rubbing test: aceton solvent
    Comparative Example 1
    It is similar to Example 1 except that the electrodeposition coating is performed on the metal to be coated instead of the electrodeposition coating using the one-component electrodeposition coating of the present invention, and then immersed in an alkaline dye solution to use dye coating. Coating to obtain a coating product of Comparative Example 1.
    Test Example
    The properties of the one-part pigment coating product of Example 1 and the dye coating product of Comparative Example 1 according to the present invention were measured and summarized in Table 7 below.
    As described above, the present invention has a simpler coating process compared with the prior art, and also has excellent light resistance chemical resistance and weather resistance compared to the method of dye coating after electrodeposition.
    权利要求:
    Claims (3)
    [1" claim-type="Currently amended] Electrode density of 2 to 10 Am / dm was obtained by treating a metal-based object with an ultrasonic solution in an alkaline solution at a temperature of 50 to 80 ° C for 1 to 5 minutes.2And pickling after electrolysis for 30 seconds to 60 seconds, and the pickling was carried out at 0.5 to 10 Am / dm for 5 to 20 minutes at 15 to 25 ° C in an aqueous solution of 15 to 30% by weight of copper sulfate.2Copper plating is carried out in a plating solution of 24 to 45% by weight of nickel sulfate, 3.8 to 6% by weight of nickel chloride, and 3 to 5% by weight of boric acid, again at 40 to 60 ° C for 1 to 10 Am / dm for 10 to 40 minutes.2in Nickel plated material pretreatment process,
    At the same time, 20:80 to 40: 60% by weight of the melamine resin of the following formula (1) and the modified acrylic resin of the following formula (2) are used as an acid catalyst to form a crosslinked polymer of the following formula (3), which is 10 to 15 Emulsifying with 1% by weight of pure water and 1 to 2% by weight of emulsifier, and then adding 0.1 to 5 weight percent of the water-soluble organic dispersion pigment in small amounts to prepare a one-component type pre-paint that imparts color to the resin;
    After the pretreatment in the pretreatment of the object was carried out by hot water treatment for 1 to 5 minutes with pure water, and then neutralized by washing with ultrasonic waves for 1 to 5 minutes, the electrolytic density was applied to the anode in the electrolytic cell containing the one-component electrodeposition paint prepared above. electrodeposition coating process to coat for 30 seconds to 180 seconds with / dm 2 ,
    The color coating method of the surface of the metal material which consists of a hardening process of wash | cleaning the said electrodeposition coating product obtained by heat and thermosetting at the temperature of 140-160 degreeC.
    (One)
    In the above formula, R is a CH 3 group and m is an integer of 1 or more.

    In the above formula, n is an integer of 1 or more.

    In the above formula, R is a CH 3 group, m, n is an integer of 1 or more.
    [2" claim-type="Currently amended] The method of claim 1, wherein the modified acrylic resin of the formula (2) is a hydroxy group (-OH) in place of the carboxyl group (-COOH) active group at the terminal, characterized in that the color coating method of the metal material surface.
    [3" claim-type="Currently amended] 2. The color coating method according to claim 1, wherein the compound of formula (3) is the following formula (4).
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    同族专利:
    公开号 | 公开日
    CA2270845A1|2000-07-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-01-14|Application filed by 최준기, 주식회사 한국하우톤
    1999-01-14|Priority to KR1019990000897A
    1999-05-25|Publication of KR19990037756A
    优先权:
    申请号 | 申请日 | 专利标题
    KR1019990000897A|KR19990037756A|1999-01-14|1999-01-14|Method for Co1or Coating on Metal Surface|
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