KR100516682B1 - A method of partially transmitted light plating for polycarbonate constituted resin using the laser engraving - Google Patents

Abstract

The present invention relates to a partial light-transmission plating method of a resin containing a polycarbonate component using laser etching, and its purpose is to have a beautiful appearance by surface treatment of a thick plating layer, and to form an electromagnetic shielding efficiency by forming a copper / nickel plating layer. The present invention provides a partial light-transmission plating method of a resin containing a polycarbonate component using laser etching, in which a portion etched in a predetermined pattern by laser irradiation can have light transmittance upon light irradiation.

The present invention comprises the steps of washing and degreasing polycarbonate or the plated material containing polycarbonate; Etching the washed and degreased plated and neutralizing it, followed by preliminary deposition to impart polarity; Pretreatment by activating the surface of the plated object to which polarity is applied; Forming an electroless copper plating layer on a surface of the pretreated plated object; Electroless nickel plating the plated object on which the copper plating layer is formed to form a copper / nickel plating layer and drying it; The focus of the laser beam is adjusted to selectively diverge the laser beam to the copper / nickel plated layer of the plated object, and the thickness and intensity of the laser beam are adjusted according to the shape of the selected predetermined pattern and the thickness of the coating layer. Irradiating a plating portion of the plated object to remove a portion of the plating layer to form a shape of a predetermined pattern; Through the electroplating of the copper / nickel plating layer of the etched to-be-plated material, the surface-treatment may be provided, and the laser-etched portion may be clearly partially transmitted through the plating layer.

Description

A method of partially transmitted light plating for polycarbonate constituted resin using the laser engraving}

The present invention relates to a partial light-transmission plating method of a resin containing a polycarbonate component using laser etching, and to shield electromagnetic waves or exterior treatment of a composite resin product containing a large amount of polycarbonate or polycarbonate (70% or more) in engineering plastics. For electroless plating as a base plating, the eluting additives added during the production of polycarbonates can be used to relieve stress on the surface to facilitate uniform catalyst application, to allow partial light transmission of the marking, and to process the plating part in threefold. The present invention relates to a partial translucent plating method of a resin containing a polycarbonate component using laser etching having a beautiful appearance.

In general, as the industry is highly developed, the various electronic devices that have appeared to give convenience to life, but no less serious damage.

Among them, the most serious problem is recently caused by various kinds of obstacles caused by electromagnetic waves. Electromagnetic waves are a kind of energy waves generated by various electric and electronic devices, which cause industrial accidents by interfering with various precision instruments and cause various occupational diseases. do.

As civilization develops, industrial devices are gradually becoming computerized, and malfunctions of devices caused by electromagnetic interference cause fatal disasters.

Therefore, developed countries have established related laws regulating various kinds of harmful electromagnetic waves, and are expanding their application to products produced in their home country and products imported from foreign countries. Prohibit production and import of products that do not meet this standard. There is a situation.

Recently, plastics have been widely used in this field due to light weight and miniaturization of various electric and electronic devices. However, since plastic is a non-conductive non-conductive material, in order to shield electromagnetic waves, surface treatment, that is, Patent Publication No. 91-18476 and Plating, conductive coating, and metal fusing are performed as in Patent Application No. 94-4008, but the most effective and stable method is plating (electroless plating) with little change in precision, shielding ability, and resin properties. .

The existing electroless plating method mainly uses the point that the B (butadiene) component among the three components of the ABS resin is easily etched (0.1-2 μm butadiene component on the ABS resin surface is dissolved in acid to form fine holes). It is used only for composite materials containing about 50% or more of ABS resin and ABS resin.

However, ABS resin has a weakness in its physical properties when it is left in its natural state, that is, its weather resistance is weak. Therefore, development of a resin having better physical properties is required, and polycarbonate (PC) having excellent impact resistance and weather resistance is required. ) Is a material that satisfies these conditions to some extent, but its usage has recently increased, but unlike ABS resin, since it is composed of a single component system, it is difficult to etch and has no polarity. It is not possible to use almost no plating, or more than 50% ABS resin compared to its excellent physical properties had a problem.

Due to these problems, polycarbonate was extremely poorly used for plating despite its excellent physical properties.

Polycarbonate resin is a single component, and it is impossible to use a method of removing only some components of the whole product such as ABS to form fine irregularities on the surface of the product. As a result, surface catalysis is difficult, and adhesion to the catalyst nuclei is weak, requiring a process of surface polarization.

In addition, the surface unevenness may be uneven even when etching due to various additives and molding conditions, or the binding force of the catalyst nucleus may be reduced by the influence of additives that suppress polarization even when polarizing. Often appearing, a process is needed to remove their effects.

In the conventional method, there is a method of etching using an organic solvent, but it is difficult to handle such as fire hazards, and as mentioned above, the effect of various additives and molding conditions in the manufacturing of resins is excluded, and the adhesion effect with adhesion is achieved. In order to reap, the strength of the etching must be strong, in this case, surface peeling and cracking of polycarbonate are caused. In addition, the unbalanced surface generated by the molding conditions forms a non-uniform surface state distinguished from other parts even after such an excessive etching, resulting in a decrease in surface uniformity and poor appearance. In addition, when the content of the additive is high and the molding conditions are bad, there is a problem in that the desired adhesion can not be obtained at all by the over-etching as described above.

In addition, conventionally, in order to form a predetermined pattern on the plated resin product, an etching process such as screen printing or photo etching is performed, but the same method is used for the front process, laminating process, exposure process, developing process, corrosion process, and peeling process. There are various problems, such as being complicated, and unable to carry out various, small and precise marking / etching.

The present invention has been made in consideration of the above problems, and its object is to have a beautiful appearance by the surface treatment of a thick plating layer, and to increase the electromagnetic shielding efficiency by forming a copper / nickel plating layer, and to a predetermined pattern by laser irradiation. The present invention provides a partial light-transmission plating method of a resin containing a polycarbonate component using laser etching, in which an etched portion may have light transmittance when irradiated with light.

The present invention comprises the steps of washing and degreasing polycarbonate or the plated material containing polycarbonate; Etching the washed and degreased plated and neutralizing it, followed by preliminary deposition to impart polarity; Pretreatment by activating the surface of the plated object to which polarity is applied; Forming an electroless copper plating layer on a surface of the pretreated plated object; Electroless nickel plating the plated object on which the copper plating layer is formed to form a copper / nickel plating layer and drying it; The focus of the laser beam is adjusted to selectively diverge the laser beam to the copper / nickel plated layer of the plated object, and the thickness and intensity of the laser beam are adjusted according to the shape of the selected predetermined pattern and the thickness of the coating layer. Irradiating a plating portion of the plated object to remove a portion of the plating layer to form a shape of a predetermined pattern; Through the electroplating of the copper / nickel plating layer of the etched to-be-plated material, the surface-treatment may be provided, and the laser-etched portion may be clearly partially transmitted through the plating layer.

That is, according to the present invention, a polycarbonate or a plated material containing a large amount of polycarbonate (more than 70%) is washed for 5 minutes within a range of 50 to 60 ° C, and the washed plated material is about 5% at 40 ° C with 40% nitric acid. Flush after washing for a minute. Subsequently, the nitric acid-treated plated product was diluted with 36 wt% of 1,3-dichloro-2-propanol and 56 wt% of sodium alkyl naphthalene sulfonate in 8 wt% of sodium alkyl naphthalene sulfonate. The pretreatment liquid mixed with% and water was mixed at 4: 6, treated for 100 seconds at a temperature of 43 ° C., followed by washing with water, etching the pretreated plated material, and neutralizing with a neutralizing solution. Give polarity to forbidden things. The polarization was performed for 4 minutes at 40 ° C. in a solution containing 7 wt% of a polarization solution mixed with 80 wt% of ethylenediamine and 20 wt% of distilled water, 7 wt% of 35% hydrochloric acid, and 86 wt% of water. In this way, the surface-polarized plated object is activated and then electroless copper plated to a thickness of 1 micron or less, and the electroless copper plated plated material is nickel plated again. At this time, the formed nickel plating layer to protect the copper plating layer from oxidation and corrosion, and to maximize the electromagnetic shielding efficiency with the copper plating layer has a thickness of less than 0.5 microns. As such, the plated object on which the copper / nickel plated layer is formed is dried and then moved to a laser etching position, and the laser beam is focused on a specific surface of the plated object in consideration of the distance between the plated object and the laser. Adjust the focus. When the focus of the laser beam is adjusted as described above, a predetermined pattern for etching the plated object on which the copper / nickel plating layer is formed is selected, and then the width and intensity of the laser beam are matched to the selected predetermined pattern and the thickness of the copper / nickel plating layer formed on the coated object. Adjust When adjustment of the focus, width, and intensity of the laser beam according to the selected predetermined pattern is completed, the laser beam is irradiated onto the plating portion of the plated object to remove a portion of the plating layer according to the shape of the predetermined pattern. That is, the copper plate / nickel plated layer of the plated material is etched with the laser according to the irradiation of the laser, and the plated object is electroplated again to remain in the unetched portion. A thick plating layer is formed on the copper / nickel plating layer to provide a beautiful plating layer. In this case, the laser-etched portion is a state in which the copper / nickel plating layer is removed, that is, the polycarbonate itself, so that the plating layer is not formed during the electroplating, and is clearly transmitted through light irradiation due to the physical properties of the polycarbonate.

In addition, the total thickness of the plating layer formed on the plated material is preferably maintained about 40 to 200 microns.

Since the copper / nickel plating layer of the polycarbonate or the plated product containing a large amount of polycarbonate has a thickness of about 1.5 microns or less by electroless plating, it can be easily etched by a laser and is marked by laser etching. Electroplating the formed to-be-plated again to adjust the plating layer to the thickness as necessary, it can have a beautiful appearance and corrosion resistance, wear resistance.

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

Example 1

The plated product to which 50% of polycarbonate or polycarbonate was added was washed for 5 minutes at 50 ° C, treated with 40% nitric acid at 50 ° C for 5 minutes, washed with water, and the surface was swollen, and then 1,3-dichloro- Pretreatment mixture of 56 wt% 2propanol (1,3-dichloro-2-propanol), 8 wt% sodium alkyl naphthalene sulfonate and 36 wt% distilled water, and water at 4: 6 After treatment for 100 seconds at a temperature of 43 ℃ and washed with water to remove the inflated surface layer, the surface layer removed to be recovered twice by etching for 2 minutes at 72 ℃ with 520 g / L and 18 wt% sulfuric anhydride. 4 times and rinsed.

2.5 wt% of the neutralized solution of hydroxylated amine sulfate 18 (weight percent) and distilled water 82 (weight percent) was mixed with the etching-treated plated material, 10 wt% 35% hydrochloric acid, and 8.7 wt% water. After treatment for 5 minutes at a temperature of about 60 ℃ in a liquid, and neutralized by washing with water, and again, polarization solution 7wt%, 35% hydrochloric acid 7wt%, water 80% ethylenediamine and 20wt% distilled water The mixture with 86 wt% was treated at 40 ° C. for 4 minutes to give polarity.

In this way, the polarized plating product 100cc / L and hydrochloric acid 100cc / L with the addition of 0.2 g / L and 520 g / L of palladium chloride (PdCl ₂ ) and cuprous chloride (SnCl ₂ ), respectively After 10 minutes of active treatment and 4 times of water treatment, the first activation treatment, it was treated with 5% sulfuric acid for 2 minutes at 40 ℃ for 10 minutes the second time active treatment.

Copper plated (CuCl2) 12 g / L, formalin (CH ₂ O) 2.03.0 g / L, caustic soda 67 g / L, EDTA (Ethylene Diamine Tetra Acetic ACid) 1520 g / L is mixed with the activated plated, After plating copper copper with an aqueous solution containing a small amount of 2,2-bipyridyl (2,2-bi-pyridyl) and washing with water three times, nickel sulfate 30g / L and sodium hypophosphite (NaH ₂ PO ₂ H ₂ O) The electroless nickel plating is carried out for 10 minutes at a water temperature of about 40 ° C. in which 20 g / L and 20 g / L of sodium citrate are mixed, followed by washing three times. The nickel-plated object was dried at 50 ° C. for about 30 minutes, and the results of testing the coating and adhesion strengths thereof are shown in Table 1.

At this time, the coating force was compared with the plated portion and the non-plated portion, and the adhesion test was performed by attaching a tape with grooves of 1 mm intervals with a sharp knife, etc., to test the adhesion.

Example 2

After the polycarbonate or the plated product to which 70% of the polycarbonate was added, pre-treatment was carried out in the same manner as in Example 1, nickel plating was performed, and coating and adhesion thereto were tested. The results are shown in Table 1 below.

Example 3

100% of the polycarbonate or the polycarbonate-added plated material was pretreated in the same manner as in Example 1, followed by nickel plating, and then the coating and adhesion thereof were tested. The results are shown in Table 1 below.

Example 4

After pre-treating the plated product to which polycarbonate or polycarbonate is added 70% in the same manner as in Example 1, copper plating 1 micron, nickel plating 0.5 micron, and the copper / nickel plated layer formed by laser etching the marking Electroplating was again performed, and the degree of appearance and the clearness of the marking were tested. The results are shown in Table 2.

Comparative Example 1

After plating 50% of the polycarbonate or the polycarbonate-added material by nickel plating by the conventional ABS resin plating method, the coating and adhesion strengths thereof were tested. The results are shown in Table 1 below.

Comparative Example 2

After coating the plated product to which the polycarbonate or polycarbonate is added to 70% by nickel plating by the conventional ABS resin plating method, the coating and adhesion strengths thereof were tested. The results are shown in Table 1 below.

Comparative Example 3

100% of polycarbonate or polycarbonate-coated material was nickel plated by the conventional ABS resin plating method, and then the coating and adhesion thereof were tested. The results are shown in Table 1 below.

Comparative Example 4

The plated material to which 70% of polycarbonate or polycarbonate was added was nickel plated by the conventional ABS resin plating method, and the mark was etched by screen printing, and then electroplated again, and the beautifulness of the appearance and the sharpness of the mark were applied. Was tested and the results are shown in Table 2.

Comparative Example 5

After pre-treatment of the plated product to which the polycarbonate or polycarbonate is added 70% in the same manner as in Example 1, copper plating 1 micron, nickel plating 0.5 micron, and etching the mark on the formed copper / nickel plating layer by screen printing This was again electroplated, and the degree of appearance and the sharpness of the marker were tested. The results are shown in Table 2.

Coverage Adhesion Example 1 100% 97-100% Example 2 100% 97-100% Example 3 100% 97-100% Comparative Example 1 100% 97-100% Comparative Example 2 40-60% Less than 70% Comparative Example 3 30% less than 40% less than

In this way, when electroless plating of a resin product containing at least 70 polycarbonates and polycarbonates is carried out through the above process, a large amount (more than 70%) of polycarbonates and polycarbonates is contained by the conventional plating method of ABS resin. When plating one resin product, it can be seen that the plating is impossible or non-plating at least 60 sites, while the present invention is capable of 100% plating.

Exterior Clarity (Transparent) Example 4 100 100 Comparative Example 4 80 80 Comparative Example 5 100 80

As described above, the plated layer is formed by electroless plating and electroplating, and the plated layer is formed by conventional techniques and the plated layer is formed by etching, and the etching layer is formed by screen printing and photoetching. When contrasting the appearance and sharpness of the plated object, it can be seen that the object according to the present invention has a beautiful appearance and excellent sharpness.

As described above, the present invention can easily perform electroless plating on a polycarbonate and a resin product containing 70% or more of polycarbonate, thereby replacing the weak physical properties of the existing ABS resin.

In addition, the present invention is to use a laser to etch a predetermined pattern on a polycarbonate or a resin product containing a polycarbonate plated layer, it is very small and fine from several centimeters to several micrometers to etch very complex and sophisticated characters, marks, figures, etc. It can be easily and quickly etched, which can be mass-produced, and can greatly contribute to industrial development such as minimizing time and effort.

Claims (2)

Washing and degreasing the polycarbonate or the plated material containing the polycarbonate; Etching the washed and degreased plated and neutralizing it, followed by preliminary deposition to impart polarity; Pretreatment by activating the surface of the plated object to which polarity is applied; Forming an electroless copper plating layer on a surface of the pretreated plated object; Electroless nickel plating the plated object on which the copper plating layer is formed to form a copper / nickel plating layer and drying it; The focus of the laser beam is adjusted to selectively diverge the laser beam to the copper / nickel plated layer of the plated object, and the thickness and intensity of the laser beam are adjusted according to the shape of the selected predetermined pattern and the thickness of the coating layer. Irradiating a plating portion of the plated object to remove a portion of the plating layer to form a shape of a predetermined pattern; The surface treatment is performed by electroplating the copper / nickel plated layer of the etched plated object, and having a beautiful plating layer, the laser-etched portion is partly transparently transmitted using laser etching. Partial translucent plating method of resin containing polycarbonate component. The method of claim 1; Wherein the copper plating layer is less than 1 micron, the nickel plating layer has a thickness of less than 0.5 microns, the partial translucent plating method of the resin containing the polycarbonate component using laser etching.