TW554086B - Method for producing plated molded product - Google Patents

Abstract

A method for producing a plated molded product is provided, in which a surface of a molded product having a thin portion obtained by coinjection molding of resin is subjected to plating. A surface of a molded product having a thin portion obtained by high-speed injection molding of resin is plated by the steps of: (a) forming a metal plating layer on a surface of the molded product by electroless plating; (b) forming a copper plating layer on a surface of the electroless plating layer by electroplating; (c) forming a nickel layer on a surface of the copper plating layer by electroplating; and (d) forming a chromium or chromium alloy layer on a surface of the nickel layer by electroplating. Even for a molded product having a thin portion obtained by high-speed injection molding, a plating which resists removal can be obtained. Further, even when a plating is formed on a satin-finished surface, the plating can reproduce the satin-finished surface.

Description

554086 ^ A7

TECHNICAL FIELD The present invention relates to a method for manufacturing a plated molded article having a thin portion. The present invention also relates to a method for plating a surface of a co-injection molded article having a resin molded article and a surface of an elastic layer on the back side of the molded article. In particular, the present invention relates to a method for plating the surfaces of electrical or electronic components (such as switches, and controlling keyboard surfaces of personal computers), OA equipment (such as personal computers and telephones), and communication equipment (such as DVDs and MDs), and In particular, it relates to a method for manufacturing a cellular phone operation button (keyboard). Technical background For example, there is a growing demand for reducing the thickness of a foldable (clamshell) mobile phone. For this mobile phone, the operation button (keyboard) attached to it must be as thin as possible. Generally, the operation knob is molded from ABS resin (acrylonitrile-butadiene-styrene copolymer), which is easy to plate. However, ABS resin has poor adhesion to the body of a mobile phone. Furthermore, the operation button may have a portion which is not plated for decorative purposes. In this example, a resin other than the ABS resin such as a pc (polycarbonate) resin can be co-injection molded. In addition, bright and foggy surfaces (micro-rough surfaces) can be set on the surface of the operation button for installation purposes. Conventionally, when the operation button of a mobile phone is manufactured in-mold, the obtained operation button will lack an overwhelming and beautiful impression. To avoid this, the surface of the molded article is plated after co-injection molding as described above. When manufacturing thin co-injection moldings, the molding method is used in which the holes and cores are reversed instead of the usual method. Furthermore, when co-injection molding is used to manufacture thin molded products, the resin should be injected into the cavity at a high injection speed. If the resin injection speed is slow, the resin does not enter

This paper is suitable for size @ @ 家 标 ^ X 297 公 玉 554086 A7 B7 5. Description of the invention (2) In the sixth mold, thin molded products cannot be obtained. However, a faster injection speed will cause a problem that the plating layer is easily detached from the obtained molded article. The reason for this problem is that the surface of chess products lacks the ability to anchor the plating on it, depending on the fluidity or orientation of the resin in the mold. In particular, according to the conventional plating, a metal plating layer is formed on the surface of the molded article by electroless plating; a nickel layer is formed from the surface of the electroless plating layer by electroplating; and chromium or Network alloy layer. This coating is easily detached in cross-out adhesion tests, thermal shock tests, and the like. Therefore, it is considered to form a copper plating layer by borrowing electricity after forming a metal ore-layer by electroless plating. The conventional copper plating has a strong flushing effect and causes the following problems. In the conventional plating, even when a slightly rough (smooth polished) surface of the operation knob is generated, the rough surface is uniformly plated to produce brightness and lose roughness. That is, the surface characteristics of the holes formed by the electricity are destroyed. The operation button of the mobile phone may be provided with an elastic layer which is incorporated into the co-injection molded product to provide cushioning on the back surface of the molded product. Furthermore, the surface of the co-injection molded product can be plated. The surface plating of this molded article is typically performed by electroless plating, in which an etching step, a washing step, a catalyst step, and an accelerator step are sequentially performed, followed by electric keys. During the etching step, the molded article is immersed in a chromic acid mixture of chromium-man and sulfuric acid. However, in the last name, the elastic layer is easily soluble in the chromic acid mixture. The dissolved components can agglomerate in a subsequent washing step and diffuse in a later step, so small foreign particles adhere to the plating surface of the molded product, resulting in defective products. -5- This paper size is applicable to SS, AS (CNS) A4 specifications (210X297 public love)

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554086 _ A7 I ——----_ B7__ V. Description of the invention (3) --- To avoid this problem, consider reducing the concentration of the chromic acid mixture to the extent that the elastic layer can resist dissolution. However, in this example, the plating layer on the surface of the molded article had poor adhesion. In addition, it is considered that the elastic layer is adhered to the back surface of the molded product only after the molded product is applied to the bell. However, in this case, the yield was greatly reduced. When the molded product (such as a mobile phone button, etc.) is plated, the molded product is subjected to pretreatment (chemical process), washing, nickel plating, washing, chrome plating, washing, and drying. In this example, the chromium plating solution used was a plating bath composition containing hexavalent chromium, and hexavalent chromium was ionized and deposited on the surface of the target by electrophoresis to form a metallic chromium coating layer. Although hexavalent or divalent ions and the like are not present in the metallic chromium coating layer, it is necessary to consider the adverse effect of the coating layer on human skin. Furthermore, after this product is discarded, metal chromium corrosion will naturally cause reduction of hexavalent chromium and cause problems. To avoid this problem, conventionally, a treatment method using trivalent chromium in a chromium plating solution has been studied. However, at the beginning of this study, it was understood that, compared to the conventional method of forming a metal coating layer using only a hexavalent path, the method using a trivalent path did not provide adequate coating layer formation and corrosion resistance. -Furthermore, when the mobile phone operation button is a co-injection molded product and is plated with a newly introduced trivalent chromium plating bath, if the plating conditions are set within the standard control value set by the manufacturer, some problems will be caused. The specifications required by the user cannot be well controlled and the standard control values and equipment need to be changed. For example, small ridges and protrusions can be formed on the surface of the product. This cause is thought to be that the dust entering the solution or the impurities generated in the electrolysis are captured in the bellows coating. Furthermore, the launching power is poor. This cause is presumed that when the recording product has an extremely grainy surface, current cannot flow at a standard current density. _'6- Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------) V. Description of the invention (4 Disclosure of the invention One aspect of the invention relates to the manufacture of a plating mold of the invention Method of the product 'The molded product has the surface of the thin part obtained by the high-speed injection molding of the resin to be plated. The method includes the following steps: 0) forming a metal clock coating layer on the surface of the molded product by a Lai electric bell; (b) A copper plating layer is formed on the surface of the electroless plating layer by electroplating; (c) a nickel layer is formed on the surface of the copper plating layer by electricity; and (d) a chromium or chromium alloy layer is formed on the surface of the nickel layer by electric bonds. "High-speed injection molding, high-speed" means the level of velocity in which butadiene molecules change orientation in ABS resin. In particular, butadiene molecules are substantially circularly oriented at conventional injection speeds. When the speed is greater than or equal to At a predetermined speed, the butadiene molecules are oriented in an ellipse. Therefore, it is known that the plating layer is easily detached from the surface of the molded product. In a specific example, the copper plating is performed under the following conditions. The product is immersed in a concentration of 10 to 301 Copper sulfate with a concentration of 70 to 90 g / L and copper sulfate bath with a concentration of 170 to 210 g / L of sulfuric acid and a cathode current density of 1 to 4 A / dm2. In the specific example, a bright surface is provided on the surface of the molded product And rough surface. The plated molded product of the present invention is prepared by any of the methods described above. In a specific example, the molded product is a mobile electric operation button. In a specific example, a metal plating layer formed by electroless plating is used. It is a nickel layer, a copper layer, etc. According to the present invention, even for a molded article having a thin portion obtained by high-speed injection molding, a removal-resistant plating layer can be obtained. Furthermore, even at the bare paper scale It Finance Country National Standard (CNS) A4 Regulation (210) 297 mm) 554086

A plating layer is formed on the smooth polished surface, and the plating can be used to obtain a smooth polished surface. The function of the present invention is as follows. After forming a metal plating layer such as a nickel layer or a copper layer on the surface of the molded article by electroless ore coating, a copper bell cladding layer is formed on the surface of the electroless bell cladding layer. Subsequently, a nickel layer and a chromium or chromium alloy layer are formed on the surface of the copper plating layer by a power boat. Therefore, even for a molded article having a thin portion, the metal plating layer can firmly adhere to the bottom surface (molded article) and resist detachment. Furthermore, the bell cladding layer can be used to obtain the glossy surface and smooth polished surface of the molded mouth. The ease of removing the plating layer on the molded article is measured by the following bars. Cross-peel adhesion test: 1 mm by 1 mm cross-cut Thermal shock test: 85. (: 1 hour and -35t 1 hour repeat cycle. The plating layer needs to be intact after 6 or more cycles. It is known that the plating layer is damaged after 3 cycles. According to the method for manufacturing a plated molded product according to the present invention Another object is to perform a plating treatment on the surface of a molded article obtained by at least partially using the integrally molded elastic layer as a secondary molded article on the surface of the primary molded article. The method includes immersing the molded article in a mixture of chromic acid and sulfuric acid The step of etching the surface of the molded product in an intermediate manner, wherein the etching step is performed under the following conditions: (a) the temperature of the mixture is 65 to 69 ° C; (b) the concentration of chromic acid in the mixture is 370 U / L to 390 g / L And (c) the sulfuric acid concentration in the mixture is 190 to 230 g / l. In a specific example, the method includes a strip washing step, a catalyst step, and an accelerator step in order after the etching step. The accelerator step includes The molded product is immersed in an acidic solution whose pH is closer to neutral than the pH of the acidic solution used in the catalyst step. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 554086 5. Description of the invention (6) And make the acidic solution and active The carbon contact is therefore the impurities contained in the acidic solution are absorbed, and the molded product is subsequently washed. In a specific example, the washing step includes the step of providing a nozzle on the bottom side of the water tank, which blows out tiny air bubbles and air bubbles. Molded products:-In the specific example, the 'elastic layer is composed of thermoplastic polyurethane amino acid: elastomer. The plated molded product of the present invention is made by any of the above methods. The plating The molded product is a mobile phone operation button. / According to the present invention, the 'M coating may be provided on the surface of the co-injection mold-product. The molded product includes a resin molded product and an elastic layer integrally molded on the back surface of the resin molded product. Fineness and coarseness. The function of the present invention is as follows. By etching the co-injection molding under the optimal etching conditions, a bell cladding layer with good adhesion on the molding surface can be provided while suppressing the elution of the elastomer as much as possible. If it is satisfactory, the adhesion of the plating layer is insufficient, causing poor durability. If the etching is excessively performed, the elastic layer is dissolved, causing the surface condition of the molded product to deteriorate. As a result, the production of defective products is increased. According to another object of the method for manufacturing a plated molded product of the present invention, the molded product obtained by injection molding is processed by trivalent chromium plating. The method includes the steps of plating under the following conditions: (a) three in the plating bath Valence chromium concentration is 6 to 40 g / L; (b) the total amount of impurities in the plating bath is 60 ppm or less; (c) the bath temperature is 40 to 50X :; (d) the pH of the plating bath is 3.2 to 3.6; -9- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) binding line 554086 A7 _ B7 V. Description of the invention (7) (e) The cathode current density is 3 to 5 A / dm2; and (f) Anode / cathode ratio is 1.5 to 2: 1. In a specific example, the plating conditions also include: (g) a rectifier ... a person who has the ability to adjust the current as much as three times or more of the total current as much as possible; and (h) the filtration capacity: the entire bath solution is continuous every hour Pass the filter 7 or more times. In a specific example, the molded product is an operation silver button of a mobile phone. According to still another object of the method for manufacturing a plated molded product of the present invention, the molded product obtained by injection molding is processed by trivalent chromium plating. The method includes the steps of plating under the following conditions: (a) the concentration of trivalent chromium in the plating bath is 5 to 10 g / liter; (b) the total amount of impurities in the plating bath is 60 ppm or less; (c) the bath Temperature is 53 to 63 ° C; (d) plating bath pH is 3.2 to 3.6; (e) cathode current density is 3 to 5 A / dm2; and (f) anode / cathode ratio is 1.5 to 2: 1 . In a specific example, the plating conditions also include: (g) a rectifier: someone who has the ability to adjust the current as much as three times or more of the total current as much as possible; and-(h) the filtration capacity: the entire bath solution is continuous every hour Pass the filter 7 or more times. In a specific example, the molded product operates a black button for a mobile phone. The plated molded article is produced by any of the methods described above. -10-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention (8 According to the present invention, + chemical conversion coatings with excellent resistance to corrosion can be treated with hot hexavalent chromium The solution is formed by surface treatment. The function of the present invention is as follows. The following conditions of the plating conditions of the & Mingzhong 1 are changed as follows. () Surface ridges and large rises (attach foreign objects, defects) Qiu improved the filter performance of Qian Shiluo And change the bath impurity control value, resulting in improved particle uniformity in the liquid te (improved filtration accuracy) and reduced attachment of foreign objects. (2) Projection force to adjust the liquid concentration control range, reset the standard value of the liquid temperature and reset pH value. In particular, the metal concentration of the bath is adjusted to be higher than the conventional method, thereby improving the projection force. Moreover, the reaction rate is improved, and therefore the projection force is improved. Furthermore, the pH is set to be higher, thereby increasing the reaction rate. Brief Description of the Drawings Figure 1 is a sectional view of a plated molded article obtained by the manufacturing method of the present invention. Figure 2 is a sectional view of another coined molded product obtained by the manufacturing method of the present invention. Mode (First Invention) As shown in FIG. 1, the thin-molded soil 4 of the present invention includes a thin-molded portion 13 made by co-injection molding. Furthermore, the thin-shaped product 14 includes a resin made of other materials. The main molded product 11 and the secondary molded product molded inside the main molded product 11 by co-injection molding. The secondary molded product 2 may be formed of a transparent resin such as%. -11-Paper silver scale Applicable to China National Standard (CNS) A4 specification (210 X 297¾) 554086 A7

This floor-like injection molded article u has a thickness of 35 mm or less, preferably a thin portion of 0.15 to 0.30 mm. The ^ ^ ^ 口 口 口 fine injection injection molding and the mold with the fork point and the core system are upside down. Due to π Gu Xiyi ★ J, because of the 又 part of δ, the injection speed is faster than that known. ~ ®, so the resulting molded part with thin portions < 悮 衣. Oral plating was performed by plating the surface of the molded article by the following steps. After washing the molded product, a metal plating layer is formed on the surface of the molded product by plating (chemical plating) or electroless forging copper (chemical plating). The electroless deposit can be performed in the following manner. Etching step: The molded article is immersed in an aqueous solution containing chromic anhydride and sulfuric acid at a predetermined temperature, followed by washing, and the surface of the molded article is roughened. Catalyst (catalyst) step: The molded product is immersed in a water bath containing vaporized palladium, stannous gas and hydrogen gas S: SL, and then the strip is washed, so it is absorbed onto the surface of the molded product. Accelerator step: The molding is immersed in a hydrogen acid solution, followed by washing the strip, so the adsorbed tin is dissolved together with the palladium in the catalyst step and separated with a hydrogen acid solution. Electroless nickel or electroless copper (electroless plating): The molding is immersed in a mixture of nickel or copper, formalin, Rochelle salt, sodium hydroxide, water, sodium hypophosphite, ammonia, etc. (Copper) is deposited on palladium due to the reduction reaction of formalin and sodium hypophosphite. Next, plating was performed on the electroless plated shoulder in the following manner. In the present invention, after mirror-copper or ore-nickel is applied, lacquering or chromium alloy boat coating is performed. (b) The hunting clock forms a copper bond coating on the surface of the non-electric ship coating. The thickness of the copper plating layer is typically 5 to 15 microns. -12- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). The copper and copper conditions are as follows. The drawn product is immersed in a copper sulfate bath at 10-30 ° C (better 20.0) containing a copper sulfate concentration of 70-90 g / L and a sulfuric acid concentration of 170-210 g / L, and at a cathode current density of 1- 4 A / dm2 for bonding. Therefore, in the present invention, non-equal amount of copper sulfate is used. Because copper sulfate has excellent followability (following), it is subject to blasting (roughening) moldings The original surface part becomes ridges and protrusions that are nodular patterns (roughened). Furthermore, the flat surface (bright surface) can show a bright impression as is known. (0 A nickel layer is formed on the surface of the copper plating layer by electroplating -K DO / is treated in a mixture of sulfuric acid, gasified nickel, pentopenic acid, and brightener and under predetermined conditions of voltage and current, followed by washing, thereby forming a nickel coating on the surface of the molded product. d) A chromium or chromium alloy layer is formed on the surface of the nickel layer by electroplating. Subsequently, the molded product is washed and dried. In this way, the molded product includes different resin substance parts (15, ⑻. Therefore, the surface part of the molded product may be transparent. In addition, 'from the surface part of the molded product to the plating layer' The molding agent is tightly adhered to, for example, the silicone rubber sheet of the main body of the mobile phone.: The above-mentioned "coated conventional copper sulfate provides a coating layer with high hooking ability ... the nodular part of the bottom layer (rough,)" And smooth polished due to the plating layer.: ^ &Quot;) Hook two According to the present invention, non-equal amount of sulfuric acid steel can provide a ridge-and-protrusion pattern with an excellent following portion (roughening). Bottom / flat bottom / Layer of nodularity * s + sliding part (bright surface) -13- 554086 A7

554086 A7 B7

V. Description of the invention For this step, the preferred conditions are as follows: The temperature of the chromic acid mixture used is preferably 65 to 69 ° C and more preferably 66 to 68. (:. The chromic acid concentration of the chromic acid mixture is preferably 370 g / l to 390 g / l. The sulfuric acid degree is preferably 190 g / l to 230 g / l. The processing time of the engraving step is typically 8 To 12 minutes. When the concentration of chromic acid is far outside the above range, the elastic layer 22 is disadvantageously decomposed and impurities are dissolved in the mixture. When the concentration of sulfuric acid is much higher than the above range, crystals develop and hinder continuous manufacturing. The reason is that The high sulfuric acid concentration causes the complex acid to saturate in the chromic acid mixture. The preliminary name engraving step can be performed before the above money engraving step. In this example, the name engraving conditions are as follows. Preliminary etching step: The temperature of the chromic acid mixture used is preferably 66 to 68. (:. The chromic acid concentration of the complex acid mixture is preferably 135 to 65 g / l. The sulfuric acid concentration is preferably 180 g / l to 220 g / l. The processing time of the rice carving step is typically 2 to 4 minutes. A-2. Washing step In order to remove the chromic acid mixture from the surface of the molded article, washing. The washing step can be rinsed with water. After washing, if necessary, neutralize and then wash again. 、 A-3 · Catalyst (catalyst) The above molding is immersed in an aqueous solution of palladium chloride, stannous gas, and hydrogen acid, followed by washing, so that palladium is adsorbed on the surface of the molding. In the catalyst step, 'soaking is performed under the following conditions. -15-This paper scale ㈣ 中 @ @ 家 料 (CNS) A4 specifications (21G X tear off

554086 A7 '' B7

V. Description of the invention (13 Temperature: 31 to 35 ° C Concentration (catalyst): 53-67 g / l Concentration (hydrochloric acid): 280-320 g / l Roller (chromium concentration): 150 ppm or less Washing It can be carried out by leaching. A-4. Acceleration is the step of immersing the molded product in aqueous hydrochloric acid solution, followed by washing, so that the tin adsorbed with the palladium in the catalyst step is dissolved and separated with hydrochloric acid. It is better in the accelerator step. The soaking conditions are as follows.

Temperature: 36 to 40 ° C Impurity (tin): 100 ppm or below In this step, if the molded product is directly washed with water, the pH of the acidic solution used in the catalyst step (normally pH 1) quickly drops to neutral Therefore, impurities such as hydroxides are generated and seem to adhere to the surface of the molded article. To avoid this, the pH of the acidic solution is preferably about 1.5 and the acidic solution adsorbs impurities through activated carbon. As far as the washing step is concerned, a nozzle for blowing out minute air bubbles is provided at the bottom of the water tank, thereby washing the elastic layer 22. Air bubbles impact the surface of the molded product (especially the elastic layer 22), so the impurities and residual medicines attached to the surface of the molded product can be effectively removed. A-5. Electroless nickel plating or copper plating (chemical plating) Moulded products are immersed in a mixture of nickel or copper, formalin, genchelle salt, sodium hydroxide, sodium hypocarbonate, ammonia, water, etc., and then washed . As a result, nickel (copper) was deposited on the period by the degenerative reaction of formalin and subfilled sodium. Subsequently, plating was performed on the electroless plating layer as follows. In the present invention, after nickel plating or copper plating, nickel plating, chromium keying, and encapsulation are performed. -16- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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554086 A7 ___ _ Έ7 V. Description of the invention (U ^-—- Gold plating, gold plating or other alloy plating. (Third invention) The following steps are used to perform trivalent chromium on the surface of the above-mentioned molded product having a thin portion. Plating. '(A) Washing of molded products. Metal plating is formed on the surface of molded products by electroless nickel plating (electroless plating) or electroless copper plating. Electroless chain coating can be performed as follows. Etching step: dipping of molded products In a mixture of chromic anhydride and sulfuric acid at a predetermined temperature, followed by washing, and the surface of the molded product becomes rough. Catalyst (catalyst) step ·· The molded product is immersed in gaseous palladium, stannous gas and hydrogen chloride In the aqueous solution of acid, the palladium is adsorbed on the surface of the molded product. The accelerated step · The molded product is immersed in the hydrogen acid aqueous solution and then washed, so the tin adsorbed with the palladium in the catalyst step can be dissolved and dissolved in hydrochloric acid The solution is separated. Electroless nickel plating or copper plating (electroless plating): The molded product is immersed in a mixture of nickel or copper, formalin, Rochelle salt, sodium hydroxide, sodium hypophosphite, ammonia, water, etc., and then washed , So nickel ( ) Deposited on the surface due to the reduction reaction of formalin and sodium hypocarbonate. Subsequently, plating is performed on the electroless plating layer as follows. In the present invention, after nickel plating or copper plating, chromium plating or chromium alloy recording is performed. (B) Gu plating layer is formed on the electroless plating layer by electroplating. The thickness of the copper plating layer is typically 5 micrometers to 15 micrometers. The copper and copper conditions can be as follows. The molded product is immersed in 10-3 0 ° C ( Better at 20 ° C) Concentration of copper sulfate containing 70-90 g / -17- This paper size applies Chinese National Standard (CNS) A4 (210 χ 297 mm) 554086 A7 —B7

And in the cathode current dense and brightener mix and then wash the bar, so the fifth, the invention description (15 liters and sulfuric acid Mm_2l ... two copper baths with a moderate 1-4 A / dm2 for electric boat. (C) by electroplating on copper A nickel layer is formed on the surface of the plating layer. The molded article is immersed in nickel sulfate, gasified nickel, boric acid, and treated under predetermined voltage and current conditions to form a coating layer on the surface of the molded article. In the wire step after electroplating, water It is better to use special means to vibrate the water supply, so the main and secondary moldings are penetrated and co-injected!

The water can be completely removed. · S (D) forms a chromium or chromium alloy layer on the surface of the nickel layer by electroplating. In the present invention, trivalent chromium plating is performed. The composition of the plating solution is, for example, chromium sulfate (trivalent), chromium acetate (trivalent), chromium nitrate (trivalent), vaporized chromium (trivalent), or chromium hydrogen hydrogen (divalent) (see Japanese Patent Publication) 2000 ～ 54 丨 57). In this example, the conditions for silver plating are as follows. U) Trivalent chromium concentration in the plating bath: 6 to 10 g / l (preferably 7 to 9 g / l) (b) Total impurities in the cooling of the plating: 60 ppm or less (preferably 35 卯 ㈤ or less) Below) (c) Bath temperature · 40 to 50. (: (Preferably 47 to 49. (:) (d) Plating bath pH · 3.2 to 3.6 (preferably 3.35 to 3.45) (e) Cathode current density: 3 to 5_1112 (preferably 3.5 to 4.5 // ( 11112) (0 anode / cathode ratio: 1.5 to 2: Γ (g) rectified state · one who has the ability to adjust the current as much as 3 times or more of the total current as much as possible; (h) over / consider this force · whole Bath solution passed every hour; 7 or more baths-18540540 A7 B7

. This filtration is performed continuously. Specifically, the amount of Xinde ring bath solution is conventionally about 2 times per hour ', while the present invention is 7 to 10 times per hour. The filter (filter cloth) used preferably has a mesh size of 5 to 10 micrometers (conventionally about 50 to 100 micrometers). Furthermore, it is preferable that the above-mentioned current is often applied to the plating bath. In order to obtain a black molded article, the processing conditions were changed only by the following points. (a,) The trivalent chromium concentration in the plating bath is 6 to 10 g / l (preferably 6 to 9 g / l). (c) The bath temperature is 53 to 63. (3 (preferably 57 to 59 ° C) (d ') Bunara pH ··· 3.2 to 3.6 (preferably 3.45 to 3:55) Therefore, the chromium concentration and liquid temperature increase by about 2%, and the pH decreases by about 2% 〇2, and the filtering capacity increased by 25 times or more relative to the standard plating conditions recommended by the manufacturer, so that impurities can be reduced. (Example 1) Main molded products made from ABS resin and thermoplastic polyurethane The secondary molded article made of the elastomer is molded by co-injection to obtain a molded button product for a mobile phone. This molded article is etched under the following conditions. After the etching, the molded article is washed twice with water. Each washing The water passed through the filter membrane (# 2) and the residue adsorbed by the filter paper were visually observed and evaluated (the factor ranged from the worst 50 to the best 0). Furthermore, the washed molded products were plated and molded by conventional methods. The plating layer of the product is visually observed. A. Test target: In the second step (the second step of the second invention), the thermoplastic water-based amino acetic acid elastomer is dissolved, and the liquid is cured by a lotion, etc. And the cured elastomer is dispersed in subsequent steps, resulting in defective products. • 19- Paper-like ㈣ 财 guan household materials (CNS ^ Specifications (咖 χ 撕 公 爱)-554086 A7 B7 5. Description of the invention (17) Whether it is chromic acid or sulfuric acid of chromic acid mixture. B. Test conditions chromic acid The mixture is prepared by combining three amounts of chromic acid concentration (350 to 410 g / L, stepwise change of 30 g / L) and three amounts of sulfuric acid concentration (180 to 240 g / L, stepwise change of 30 g / L). C. Test method Pour each of the complex acid mixtures prepared above into a 1 liter flask. Six of the above moldings are immersed in this mixture and etched for 8 minutes. This etching process is repeated twice. D. Evaluation method is in the mold etched in paragraph C The product was washed twice. Each wash water passed through the filter membrane (# 2), and the residue adsorbed by the filter paper was visually observed and evaluated (the factor range was from the worst 50 to the best 0). Furthermore, the visual observation was attached to the filter paper E. Results are shown in Table 1. Table 1 No. Etching Concentration First Washing Second Washing Plating Product Test Results Chromic Acid Sulfuric Acid Residue Oil Film Residual Oil Film n = p =% Protrusion Size Protrusion Area 1 410 G / l 180 g / l 50 slightly 3 no 40 23 58% greatly 2 380 g / l 180 g / l 50 more 3 more 48 45 94% greatly 3 350 g / l 180 g / l 40 more 10 more 80 80 100% large 4 410 g / l 210 g / l 20 more 1 slightly 48 6 13% moderate 5 380 g / l 210 g / l 1 slightly 2 no 40 8 20% moderately small 6 350 g / l 21 () g / l 5 more 3 slightly _ 96 4 4% medium Moderate Moderate 7 410 g / liter 240 g / liter 2 Slightly 1 Slightly 48 32 67% Small Moderate S 380 g / liter 240 g / liter 1 None 1 Slightly 48 27 56% Moderate Moderate 9 350 grams 240g / L1 No 1 No 48 34 71% Moderate Moderate -20- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Pretend

Line 554086 A7 _B7 V. Description of the invention (18) In Table 1, η represents the total number of tests, p represents the number of defective products, and% represents the percentage of defective products. The size and area of the protrusions were measured visually. As can be seen from Table 1, the best results occurred at a chromic acid concentration of 380 g / l and a sulfuric acid concentration of 210 g / l. In the test in which the sulfuric acid concentration was 240 g / L, liquid crystals developed around the liquid surface at the rupture site, indicating that this condition is not suitable for the actual manufacturing process. This reason is considered to be due to the high sulfuric acid concentration causing saturation of chromic acid in the mixture. (Example 2) A molded product treated with nickel plating was subjected to trivalent chromium plating under the following conditions to obtain a silver button for a mobile phone. (a) Trivalent chromium concentration in the plating bath ... 9 g / l (b) Total impurities in the plating bath ... 35 ppm or less

(c) Bath temperature: 48 ° C (d) Plating bath pH: 3.4 (e) Cathode current density: 4.0 A / dm2 (f) Anode / cathode ratio of 1.5: 1 (g) Rectifier: one with adjustable current amount Capable of 3 times or more of the total current. (h) Filtration capacity: The entire bath solution continuously passes through the filter 7 times or more per hour. _ As a result, a mobile phone silver button with good electron microscope coverage ^ 7 without coarse M degrees was obtained. (Example 3) Trivalent chromium plating was performed on a molded product treated with nickel plating under the following conditions, and obtained -21-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 554086 A7 _ B7 V. Description of the invention (19) 'There is a black button for a mobile phone. (a) Trivalent chromium concentration in the plating bath: 9 g / l (b) Total impurities in the plating bath: 35 ppm or less

(c) Bath temperature: 58 ° C (d) Plating bath pH ·· 3 · 5 (e) Cathode current density · 4.0 A / dm2 (f) Anode / cathode ratio of 1.5 to 1 (g) Rectifier ·· One who has the ability to adjust the current as much as three times or more of the total current. (h) Filtration capacity: The entire bath solution continuously passes through the filter 7 times or more per hour. As a result, a black button for a mobile phone having good plating power without roughness is obtained. (Comparative Example 1) A molded product treated with nickel plating was subjected to trivalent chromium plating under the following conditions to obtain a silver button for a mobile phone. (a) Trivalent chromium concentration in the plating bath: 5 g / l (b) Total impurities in the plating bath: 600 ppm

(c) Bath temperature · 40 ° C (d) Plating bath pH: 3.2 Two (e) Cathode current density · 7.0 A / dm2 (f) Anode / cathode ratio of 1.5 to 1 (g) Rectifier: One who has the ability to adjust the current as much as 1 times the total current. -22- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554086 A7 B7 Five inventions description (20 (h) filtration capacity: the entire bath solution continuously passes through the filter 2 times per hour. Result 'Obtained a mobile phone silver button with poor electric boat coverage and no coarseness. (Comparative Example 2) A nickel-plated molded product was subjected to trivalent chromium plating under the following conditions to obtain a black button for a mobile phone. (a) Trivalent chromium concentration in the plating bath: 8 g / l (b) Total impurities in the bell bath · 64 0 ppm or less

(c) Bath temperature · 5 (TC (d) Plating bath pH: 3.4 (e) Cathode current density: 7.0 A / dm2 (f) Anode / cathode ratio of 1.5 to 1 (g) Rectifier: One with adjusted current (H) Filtration power. The entire bath solution passes through the filter twice per hour continuously. As a result, a black cell phone button with poor plating coverage and no roughness is obtained. The surface roughness is judged as follows: visual observation of adhering foreign objects, cracks, etc. from centimeters or less, and products with foreign objects with a size of 02 mm or more are judged to be incompatible.-^ The plating coverage is judged as follows Carry out: evaluate whether the plating is uniform and whether B is discolored, stained, etc. & Products with discoloration, stained, etc. are judged to be not: Industrial applicability-23- 554086 A7 B7 V. Description of the invention (21) ~ " ^ --- According to the first invention, even for a molded article having a thin portion obtained by high-speed molding, a removal-resistant plating layer can be obtained. Furthermore, even when a plating layer is formed on a smooth polished surface, the The plated layer can then be made into this smooth surface. The second invention can provide a good adhesion plating layer on the co-injected molded product by etching the surface of the molded product, and the elastic layer can avoid dissolution as much as possible. Therefore, the development of protrusions on the surface of the molded product can be avoided, thereby reducing defects. Product production. According to the second invention, a treatment solution containing no hexavalent chromium can be used to provide a metal coating layer with excellent corrosion resistance through surface treatment. Furthermore, the chromium concentration and liquid temperature increase by about 2 ° /., And the pH decreases It is about 0.2, and the filtering capacity is increased by 2.5 times or more compared to the standard plating conditions recommended by the manufacturer, so it can reduce impurities. -24- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)

Claims (1)

The method of making plated molded products' where the molded product is plated with a thin part obtained by injection molding and the following steps are performed for plating: (a) forming a metal plating layer on the surface of the molded product by electroless plating (B) forming a copper plating layer on the surface of the electroless plating layer by electroplating; (c) forming a nickel layer on the surface of the copper plating layer by electroplating; and (d) forming a chromium or chromium alloy layer on the surface of the nickel layer by electroplating. 2. As the oldest method in the scope of patent application, copper plating is performed under the following conditions: • The molded product is immersed in 10 to 3 (TC containing 70 to 90 g / l of copper sulfate and Π0 to 2 10 g / L concentration of copper sulfate bath with sulfuric acid and cathodic current density of 1 to 4 A / dm2. 3. ^ The method of applying for the scope of the patent item !, wherein a bright surface and a rough surface are provided on the surface of the molded product. For example, the plated molded products produced by the method of applying for the scope of the patent item No. 1. For the plated molded products of the scope of the patent application No. 4, the molded product is the operation button of a mobile phone. A method in which the surface of a molded article having a thin portion obtained by rapid co-injection molding is subjected to plating, and the method includes the following steps: (a) forming a metal plating layer on the surface of the molded article by electroless plating; (b) ) Forming a copper plating layer on the surface of the electroless plating layer by electroplating; (c) forming a nickel layer on the surface of the copper plating layer by electroplating; and This paper is suitable for national materials (_domain weaving and management) 554086 patent application scope ⑷ Chromium or chromium alloy layer is formed on the surface of nickel layer by electroplating. =: = Making method: The method in which two layers of m are applied on the surface of the main molded product to the surface of the molded product as a secondary molded product, and the molding method includes immersing the molded product in chromium = acid. The step of engraving the surface of the molded article in the mixture is carried out under the following conditions: The temperature of the hydrazone mixture is 65 to 69. ;; The chromic acid concentration in the rhenium mixture is from 37 g / L to 390 g / L. And the sulfuric acid concentration in the ⑷ mixture is from 190 g / L to 230 g / L. For example, the method of the seventh item in the patent scope of patent application, which includes a washing step, a catalyst step, and an accelerator step after the etching step. Lizhong = device step: including immersing the molded product in a pH ratio catalyst: = near the mouth Acidic solution, and the acidic solution and the molded product. (1) The step of “baking the quilt and collecting it, and then washing it as described in item 8 of the scope of patent application.” The step of providing a nozzle at the bottom side, “:” step includes blowing in a water tank to the mold. The method of blowing out tiny air bubbles and emptying the air 10.:= item 7 of the patent scope, wherein the elastic layer is composed of a thermoplastic melamine based formate elastomer.丨 1. A kind of recording die mouth made by the method of applying for the scope of patent application item 7 ° — 12.::::Key scope of the scope of application " Push the operation button of the phone. 7. 8. Acid-coated live perilla 9. Gas-polymerized products 26 A4 ^ (21〇x297 ^) A method for manufacturing a plated molded product. The surface of the product is subjected to a plating process by trivalent chromium plating: wherein the mold is obtained by injection molding. The method includes the following conditions: the concentration of trivalent chromium in the plating bath. 6 to 10 g / L; (b) total amount of impurities in the plating bath or below; (C) bath temperature of 40 to 50 t: (d) pH of the plating bath is 3.2 to 3.6; (e) the cathode current density is 3 to 5 A / dm2; and (f) the anode / cathode ratio is 1.5 to 2: 1. Among them, the obtained mold is co-injected. The method includes a method of manufacturing a plated molded product under the following conditions. The surface of the surface product is processed by trivalent chromium plating, and the steps of plating are: (a) trivalent in a plating bath The chromium concentration is 5 to 10 g / L; (b) the total amount of impurities in the plating bath is go ppm or less; (c) the bath temperature is 53 to 63 ° C; (d) the coin bath pH is 3.2 to 3.6 (e) the cathode current density is 3 to 5 A / dm2; and (f) the anode / cathode ratio is 1.5 to 2: 1. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)